DCN 80-202-187-54-23
Radian Contract //202-187-54
EPA-6oo/7-r.n-i ssp
August 1980
TRACE METALS AND STATIONARY CONVENTIONAL
COMBUSTION SOURCES
Volume 1
Technical Report
by
Larry 0. Edwards (Project Director)
Charles A. Muela
Ralph E. Sawyer
Carol May Thompson
Damon H. Williams
R. Dean Delleney (Program Manager)
Radian Corporation
Austin, Texas 78703
EPA Contract //68-02-2608
Chuck Chatlynne, Project Officer
Industrial Environmental Research Laboratory (IERL/RTP)
U.S. Environmental Protection Agency
Research Triangle Park, N.C. 27711
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DISCLAIMER
This report has been reviewed by the Environmental Research Laboratory
U.S. Environmental Protection Agency, Athens, Georgia, and approved for publ
cation. Approval does not signify that the contents necessarily reflect the
vievs and policies of the U.S. Environmental Protection Agency, nor does men
tion of trade nar.es or comercial products constitute endorsement or recorr.en
dation for use.
ii
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ABSTRACT
This is the principal volume of a two-volume report that gives results of a
search of U.S. literature to identify published information about trace
metals and Stationary Conventional Combustion Processes (SCCPs). The
search was initially computerized with later cross referencing from identi-
fied reports. The report summarizes the information found in the literature
and includes specific references. It summarizes what has been published
about ambient trace metals in air, water, and soils. A survey, reporting
the trace metal concentration in combustible fuels, identifies coal as the
fuel of most concern; generally, trace metal levels in coal are similar to
their crustal abundances. It reviews conventional combustion technology.
It discusses trace metal flows and partitioning around various types of boi-
lers and pollution control devices, and reports data from cited studies. In
addition to coal, the report gives data for oil, municipal refuse, and wood.
It also covers emissions to air, water, and soil, including trace metal
leaching. It documents the health and environmental effects of trace metals.
Where possible, it assesses specific contributions from SCCPs. It covers
environmental transport systems, as well as special problems associated
with radioactive metals and SCCPs.
iii
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CONTENTS
Section Page
1 INTRODUCTION 1_1
1.1 DEFINITIONS 1-2
1.2 LITERATURE SEARCH 1-5
1.3 FORMAT AND ORGANIZATION 1-9
1.4 SUMMARY OF FINDINGS 1-9
REFERENCES I"1*
2 AMBIENT TRACE METAL CONDITIONS 2-1
2.1 AMBIENT TRACE METAL CONCENTRATIONS 2"1
2.2 NATURAL SOURCES OF TRACE METAL POLLUTANTS 2-12
2.3 ANTHROPOGENIC SOURCES OF TRACE METAL POLLUTANTS 2-13
2.4 RESEARCH NEEDS. 2-24
REFERENCES 2-25
3 TRACE METALS IN FUELS 3-1
3.1 COAL 3-1
3.2 FUELS OTHER THAN COALS 3-16
3.3 COAL PREPROCESSING 3-21
3.4 FLY ASH FORMATION MECHANISMS 3-23
3.5 MISCELLANEOUS TOPICS 3-26
3.6 RESEARCH NEEDS 3-27
REFERENCES 3"29
4 CONTROL TECHNOLOGY 4-1
4.1 TRACE ELEMENTS FROM SUBSYSTEMS 4-1
4.2 FINE PARTICLES AND TRACE ELEMENTS FROM THE COMBUSTION
PROCESS 4-8
4.3 AIR POLLUTION CONTROL SYSTEMS 4-20
4.4 COST OF FINE PARTICULATE AND TRACE ELEMENT CONTROL PRO-
CESSES 4-60
4.5 COMBINING CONTROL PROCESSES TO INCREASE COLLECTION EFFI-
CIENCY 4-66
4.6 EMERGING CONTROL TECHNIQUES 4-73
4.7 UNAVAILABLE DATA 4-76
REFERENCES 4-78
5 TRACE ELEMENT EMISSIONS FROM SCCP 5-1
5.1 TRACE ELEMENT EMISSIONS TO THE ATMOSPHERE FROM COAL-FIRED
POWER PLANTS IN TERMS OF HEATING VALUE OF COAL 5-3
5.2 ATMOSPHERIC TRACE ELEMENT EMISSIONS FROM COAL-FIRED POWER
PLANTS; VALUES NOT BASED ON HEATING VALUE IN COAL 5~16
5.3 TRACE ELEMENT EMISSIONS VIA SOLID WASTES OR AQUEOUS
EFFLUENTS FROM COAL-FIRED FACILITIES 5-22
5.4 SECONDARY EMISSIONS OF TRACE ELEMENTS FROM SOLID MATERIALS
ASSOCIATED WITH THE COMBUSTION OF COAL 5-37
5.5 VARIABLE DISTRIBUTION OF TRACE ELEMENTS BETWEEN BOTTOM
ASH AND FLY ASH AND AMONG VARIOUS SIZE FRACTIONS IN
FLY ASH 5-52
iv
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CONTENTS (continued)
Section Page
5.6 EMISSIONS FROM COMBUSTION OF OIL AND GAS .5-73
5.7 TRACE ELEMENT EMISSIONS FROM INCINERATION OF SOLID
WASTE MATERIALS
5.8 TRACE ELEMENT EMISSIONS FROM WOOD BURNING FACILITIES 5-87
5.9 NEEDS FOR FURTHER STUDY CONCERNING TRACE ELEMENT
EMISSIONS FROM SCCP 5-87
REFERENCES 5-92
6 ENVIRONMENTAL AND HEALTH EFFECTS :>~1
6.1 ELEMENTS OF SPECIFIC CONCERN S"2
6.2 ENVIRONMENTAL TRANSPORT MECHANISMS 6-5
6.3 ECOLOGICAL EFFECTS 6-14
6.4 HUMAN HEALTH EFFECTS 6-21
6.5 RESEARCH NEEDS 6-34
6.6 SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS LITERATURE 6-35
REFERENCES 6-70
7 RADIOLOGICAL EMISSIONS FROM SCCP'S 7-1
7.1 CONCENTRATIONS IN FUELS 7-2
7.2 EMISSION LEVELS 7-3
7.3 HEALTH AND ENVIRONMENTAL EFFECTS 7-6
7.4 COMPARISON OF COAL AND NUCLEAR POWER 7-10
7.5 REGULATIONS AND AMBIENT LEVELS 7-11
7.6 MISCELLANEOUS TOPICS 7-12
7.7 RESEARCH NEEDS 7-12
REFERENCES 7-14
8 ACCURACY OF DATA AND ANALYTICAL TECHNIQUES 3-1
8.1 TYPES OF TRACE ELEMENT SAMPLING .3-2
8.2 ANALYTICAL TECHNIQUES USED IN TRACE ELEMENT ANALYSIS 3-4
8.3 EVALUATION OF VARIOUS ANALYTICAL TECHNIQUES 3-8
8.4 AREAS WHERE FURTHER EVALUATION IS REQUIRED 3-13
REFERENCES 3-22
9 REGULATIONS 9-1
9.1 FEDERAL ENVIRONMENTAL REGULATORY ACTS SINCE 1970 9-2
9.2 STATE ROLE IN COMPLIANCE WITH FEDERAL ENVIRONMENTAL
REGULATIONS 9-12
9.3 IMPACT OF ENVIRONMENTAL REGULATIONS ON SCCP's 9-14
9.4 STATUS OF ENVIRONMENTAL COMPLIANCE 9-17
REFERENCES 9-19
V
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CONTENTS (continued)
SECTION Page
10 FUTURE RESEARCH 10-1
10.1 SOURCES OF INFORMATION 10-2
10.2 ANALYTICAL TECHNIQUES 10-4
10.3 ALTERNATE FUELS 10-5
10.4 HEALTH AND ENVIRONMENTAL EFFECTS. 10-7
10.5 TECHNOLOGY ASSESSMENT 10-8
REFERENCES 10-10
GLOSSARY G-l
vi
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LIST OF TABLES
TABLE Page
1-1 Classical Definitions of Non-Trace Metal Elements 1-3
1-2 Databases Searched in Literature Review 1-5
1-3 Terms Used in Initial Literature Search 1-6
1-4 Terms Used in Third Literature Search 1-7
2-1 Atmospheric Metal Concentrations in U. S., 1966-1967 2-3
2-2 Ambient Trace Element Concentrations Based on Five Northern
Great Plains' Sites 2-6
2-3 Comparison of Ambient Trace Element Data for Sacramento, Cali-
fornia (January, 1974) Based on Multiday Impactor Samples
With Model Results 2-7
2-4 Ambient Trace Metal Concentrations Often Used for Reference.... 2-8
2-5 Concentration of Elements in Air Particulate Matter in Texas... 2-9
2-6 Average Amount of Trace Elements in Selected California Cities. 2-10
2-7 Chadron, Nebraska Rainfall Analysis, 1973 2-11
2-8 Compliance Status of National Priority Sources 2-17
2-9 Cadmium Emission Rates 2-21
3-1 Mean Analytical Values for 23 Whole Coal Samples from the
Eastern United States 3-3
3-2 Mean Analytical Values for 114 Mid-Continent Whole Coal
Samples 3-4
3-3 Mean Analytical Values for 28 Whole Coal Samples from the
Western United States 3-5
3-4 Explanation of Abbreviations Used in Tables 3-1, 3-2, and 3-3.. 3-6
3-5 Average Trace Element Content in Ash of Coal From Three Areas
as Weight Percent 3-8
3-6 Range of Trace Elements in U.S. Coals and Ashes 3-10
3-7 Trace Metals in Coal and Fly Ash 3-11
vii
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LIST OF TABLES (continued)
TABLE Page
3-8 Trace Elements, Mineral Correlations 3-14
3-9 Trace Element Contents of Some Crude Oils by Neutron Activation
Analysis 3-17
3-10 Proximate Analysis of Coal and Combustible Fraction of Urban
Refuse 3-19
3-11 Concentrations of Elements in Coal, Paper Products and the
Combustible Fraction of Urban Refuse 3-20
4-1 Various Utility Plant Wastestreams and Their Source 4-2
4-2 Constituents of Coal Pile Runoff 4-5
4-3 Typical Anount and Size of Fly Ash Emissions from Various
Boilers i-10
4-4 Partitioning Behavior of Trace Elements at Allen Steam Plant... 4-17
4-5 Ash and Trace Element Partitioning Observed in Three Western
Power Plants Utilizing Pulverized Coal and Cyclone Boilers 4-18
4-6 Typical Cyclone Particle Collection Versus Particle Size 4-28
4-7 Actual Trace Element Collection Exhibited by Cyclone Separator. 4-30
4-8 Particle Collection Efficiency Exhibited by an ESP (Cold-Side). 4-36
4-9 Trace Element Collection Efficiency of ESP's at Several Coal-
Fired Power Plants 4-37
4-10 Collection Efficiencies Exhibited by Various Wet Scrubbers for
Trace Elements Distributed on Fly Ash 4-46
4-11 Comparison of Trace Element Removal Efficiencies of an SO2
Scrubber on a Coal or Fuel-Oil Fired Boiler 4-48
4-12 Baghouse Installations 4-51
4-13 Dust Removal Efficiencies Obtained During Pilot Plant Tests.... 4-53
4-14 Trace Element Collection Efficiencies Exhibited by Baghouse
Collectors 4-55
viii
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LIST OF TABLES (continued)
TABLE Page
4-15 Estimated Future Use of Various Control Processes 4-58
4-16 Bag Cost as a Percent of Installed Cost 4-60
4-17 Capital Costs Associated With Installation of Baghouse at Nucla
Power Plant 4-62
4-18 Estimated Cost of Operating Baghouses at the Nucla Power Plant... 4-63
4-19 Investment Costs of ESP's on Various Utility Boilers 4-64
4-20 Annualized Operating Costs of ESP's on Various Utility Boilers... 4-65
4-21 Venturi Scrubber Design Parameters 4-67
4-22 Estimated Costs of a Particle Venturi Scrubber 4-67
4-23 Capital Cost Comparison for Baghouse and ESP's for a 500 MW
Utility Boiler 4-68
4-24 Comparison of Annual Operation and Maintenance Costs for Bag-
house and ESP's for a 500 MW Utility Boiler 4-69
4-25 Capital Cost Comparison of an ESP and a Venturi Scrubber 4-70
4-26 Predicted Overall Collection Efficiency for a Cyclone and ESP
Combination 4-71
4-27 Approximation of Venturi Scrubber's Copper Collection Efficiency. 4-74
5-1 Atmospheric Emissions of Trace Elements from Coal-Fired Plant
Plants with Cold-Side or Hot-Side Electrostatic Precipitators
for Particulate Controls 5-4
5—2 Atmospheric Emissions of Trace Elements from Coal-Fired Power
Plants with Wet Scrubbers or Cyclones for Particulate Control.— 5-6
5-3 Characteristics of Units at Western Power Plant Studied by
Ondov, et al 5-9
5-4 Operating Conditions for the T.A. Allen Steam Plant 5-11
5-5 Percentages of Elements Entering with the Coal which were
Emitted to the Atmosphere from Two Western Coal-Fired Power
Plants 5-12
!x
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LIST OF TABLES (continued)
TABLE P.ige
5-6 Concentration of Trace Elements in Particulate Emissions to
the Atmosphere from a Coal-Fired Power Plant in Illinois 5-21
5-7 Constituents of Coal Pile Runoff 5-26
5-8 Summary of Concentrations of Trace Elements Sludge Liquors and
Elutriates 5-27
5-9 Trace Element Concentrations in Coal, Ashes, and Aqueous Samples
Associated with a Western Coal-Fired Power Plant (Station I)...... 5-29
5-10 Trace Element Concentrations in Coal, Sluice Ash, and Aqueous
Samples from a Western Pulverized Coal-Fired Power Plant
(Station II) 5-30
5-11 Trace Element Concentrations in Coal, Ash, and Aqueous Streams
from a Western Cyclone Type Coal-Fired Power Plant (Station
III) 5-31
5-12 Flow Rates for Streams Around Station I 5-32
5-13 Flow Rates for Streams Around Station II 5-33
5-14 Flow Rates for Streams Around Station III 5-34
5-15 Trace Element Concentrations in Water Entering and Leaving a
Western Coal-Fired Power Plant 5-35
5-16 Trace Element Concentrations in Precipitator Ash and Percentage
of Trace Element Content of Ash Extracted by Several Extracting
Solutions 5-36
5-17 Average Concentrations of Trace Elements in Liquors from Ash
Ponds at Coal-Fired Power Plants Operated by the Tennessee
Valley Authority 5-38
5-18 Average Concentrations of Trace Elements in Liquors from Com-
bined Ash Ponds at Coal-Fired Power Plants Operated by the
Tennessee Valley Authority 5-39
5-19 Concentrations of Trace Elements in Liquors from Combined Ash
Ponds at Coal-Fired Power Plants Operated by the Tennessee
Valley Authority 5-40
x
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LIST OF TABLES (continued)
TABLE Page
5-20 Trace Elements of Most Environmental Concern in Leachates from
High-Sulfur Illinois Basin Coal Refuse 5-43
5-21 Equilibrium Concentrations of Trace Elements in Coal Ash
Leachate 5-45
5-22 Concentration of Potential Problem Species in Selected Fly Ash
and Sludge Leachates 5-4 7
5-23 Average Concentrations and Surface Enrichment of Trace Elements
for Eleven Fly Ashes 5-48
5-24 Mass Median Aerodynamic Diameters (MMAD) of Elements in Aerosols
Emitted from Two Coal-Fired Electrical Generating Units 5-54
5-25 Enrichment Factors for Elements in Aerosols Emitted from Several
Coal-Fired Power Plants 5-55
5-26 Surface Predominance of Elements in Fly Ash Particles 5-68
5-27 Leaching of Fly Ash 5-69
5-28 Summary of Analytical Results - Surface Characterization of
Fly Ash Particles 5-70
5-29 Concentration of Major Trace Elements in Oil 5-76
5-30 Emission Factors and Mass Emission Rates of Trace Elements
During Oil-Firing Test 5-77
5-31 Inorganic Content of Scrubber Cake from Oil Firing (Dry
Basis) 5-78
5-32 Representative Composition of Conventional High Sulfur Residual
Oil Derived from Venezuelan Crude 5-79
5-33 Partial Composition of Particulates Emitted from Oil-Fired
Furnace Burning High Sulfur Residual Fuel Oil Derived from
Venezuelan Crude 5-79
5-34 Compositions of Particles Emitted from Three Municipal In-
cinerators 5-82
5-35 Composition of Hogged Fuel (Wood and Bark) Ash and Cal-
culated Atmospheric Emissions from Hogged Fuel Boilers 5-88
xi
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LIST OF TABLES (Continued)
TABLE Page
6-1 Major Trace Metal Pathways and Transport Mechanisms li-6
6-2 Probable Available Form, the Average Composition Range for Selec-
ted Agronomic Crops, and Suggested Tolerance Levels of Heavy
Metals in Agronomic Crops when Used for Monitoring Purposes <>-19
6-3 Trace Element Concentrations in Fresh Water and Fresh Water
Organisms (>-22
6-4 Trace Element Concentrations in Seawater and Marine Organisms fi-23
6-5 Particle Size Distribution in Fly Ash (>—26
6-6 Toxicity-Based Estimated Permissible Concentrations (i-33
6-7 Summary of Ecological and Health Effects f»—36
7-1 Range of Uranium and Thorium Concentrations and Geometric Means
(Expected Values) for Coal Samples from Various Regions of the
United States *'-2
7-2 Radionuclide Concentrations in Western Coals V-2
7-3 Radioactive Iosotope Releases to the Atmosphere from Electric
Power Plants ''-5
7-4 Maximum Individual Radiation Dose Commitment Levels from Typical
1,000 Megawatt Coal and Nuclear Power Plants j—8
7-5 Regulations for Limiting Radiation Dose Commitments to Indivi-
dual Organs by the U.S. Nuclear Regulatory Commission ',-9
8-1 Coal Analysis for Trace Elements-Comparison of Methods {'.-10
8-2 Fly Ash Analysis for Trace Elements-Comparison of Methods {i—11
9-1 National Ambient Air Quality Standards 9-5
9-2 National Standards of Performance for New Stationary Sources Sr—7
xii
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LIST OF FIGURES
rig"re ?£££
2-1 Enrichment factors relative to aluminum for elements
on particles collected in the atmospheres of Boston,
northwest Indiana, and San Francisco 2-19
4-1 Simplified schematic of a typical power plant 4-3
4-2 Particle-size distribution of particles emitted from un-
controlled power plants utilizing stoker coal-fired
boilers 4-12
4-3 Particle-size distribution of particles emitted from un-
controlled power plants utilizing pulverized coal-
fired boilers 4-13
4-4 Particle-size distribution of particles emitted from un-
controlled power plants utilizing cyclone coal-fired
boilers 4-14
4-5 Particle-size distribution of particles emitted from un-
controlled industrial power plants (coal-fired) 4-15
4-6 Particle-size distribution of particles emitted from un-
controlled municipal incinerators (Bahco data) 4-16
4-7 Plot of surface area to volume ratio as a function of
particle size 4-19
4-8 Concentration of nickel vs_ particle size 4-21
4-9 Concentration of chromium v£ particle size 4-22
4-10 Concentration of vanadium v£ particle size 4-23
4-11 Concentration of copper vb particle size 4-24
4-12 Concentration of lead vs_ particle size 4-25
4-13 Schematic of simple dry cyclone separator 4-26
4-14 Plate-type electrostatic precipitator 4-31
4-15 Fly ash resistivity variations with temperature 4-33
4-16 Fractional efficiency data for electrostatic precipi-
tators 4-35
zlii
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LIST OF FIGURES (continued)
Figure Page
4-17 Diagram of cyclone scrubber 4-40
4-18 Schematic of venturi scrubber 4-42
4-19 Schematic of spray tower scrubber. 4-43
4-20 Fractional efficiency data for wet scrubbers 4-45
4-21 Fabric filter (collection outside bags) 4-52
4-22 Fabric filtration collection efficiency V£ particle dia-
meter 4-54
4-23 Median fractional efficiency for 22 tests 4-56
4-24 Anticipated use of various particulate control devices in the
utility industry 4-59
6-1 Relative accumulation (ppm) of the most plentiful elements
in the most abundant representatives of the food chain in
all sampling sites.... 6-15
6-2 Fraction of particles deposited in the three respiratory
trace compartments as a function of particle diameter 6-29
6-3 Retention of particulate matter in lung relation to parti-
cle size 6-30
9-1 Boundaries of air quality control regions 9-4
xiv
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SECTION 1
INTRODUCTION
The role that trace metals play in the environment has been a subject
of increasing interest. Three factors have combined to provide much of the
impetus behind this growing concern:
• Increasing energy demands are being met by the increasing use
of fossil fuels, particularly coal. Coal contains essen-
tially all the trace metals in roughly the same abun-
dance as in the earth's crust. Massive burning of coal
has become a major anthropogenic mobilization pathway
by which these trace metals enter the biosphere.
• Improved analytical technology in the 1970's has provided
a higher quality and quantity of data on trace metals.
Only with these improved data can the impact of trace
metal emissions be assessed. Indeed, many effects of
trace metals in the environment are yet to be identified.
• There is a growing awareness and concern about environ-
mental factors influencing health. More and more, statis-
tical studies are implying a relationship between diseases
and factors in the environment such as trace metals.
To meet the need for a comprehensive assessment of the environmental
effects of stationary conventional combustion processes, the Environmental
Protection Agency's Industrial Environmental Research Laboratory at Research
Triangle Park (EPA/IERL-RTP), N.C., established a Conventional Combustion
Environmental Assessment (CCEA) program in February 1977. This CCEA program
was chartered to assess comprehensively the effects of pollutants released
from conventional combustion processes and associated control technologies
on human health, the ecology, and the general environment, and to recommend
measures for controlling adverse effects to within acceptable limits. The
program concentrates upon Stationary Conventional Combustion Processes
(SCCP) in the utility, industrial, residential, and commercial use sectors.
1-1
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In 1977 IERL-RTP initiated the CCEA program. Initially Kenkeremath
et al¦ (1) wrote a report to assist in the implementation of the program and
Thompson and Harrison (2) published a survey of projects supported or conduc-
ted by EPA relevant to the CCEA program, including current research as of
July 1978. These studies reported that some data already existed, although
dispersed and of uneven quality. They recommended an information search to
establish a database needed to implement the CCEA program. In 1978, EPA
contracted with Radian Corporation to bring together all relevant informa:ion
on trace metals that are emitted from stationary conventional combustion
processes/equipment and produce a detailed summary environmental assessment
report. In addition to this main report, which will establish the information
database, a short technical sumnary and a separate bibliography have also been
published.
1.1 DEFINITIONS
The exact definition that was used in this study for an SCCP (Stationary
Conventional Combustion Process) was taken from Thompson and Harrison (2)
and consultations with the project officer. The sources specifically con-
sidered were:
• utility boilers (coal, oil, gas),
• packaged boilers,
• residential heaters,
• refuse and wood boilers, and
• turbines.
The majority of the literature on trace metals and fuels or emissions concerns
coal, and the number of pages devoted to coal in this report reflects that
proportion. Almost nothing was found relating to residential heating and
turbines. The details of the literature search are given in Section 1.2.
Types of sources specifically not covered under the SCCP definition were:
• fluidized-bed combustion,
• coal gasification or liquefaction,
• oil shale retorting,
1-2
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• industrial process heating,
• refineries,
¦ mobile combustion sources, and
¦ nuclear.
In certain sections, reference to or comparison with some of these types of
processes has been made, but in general, they have not been considered.
The directive for this work specified that trace metals only were to be
considered. However, most researchers, in performing trace analysis, report
many elements including the trace metals. Trace elements are often defined
as elements whose concentrations are less than 100 ppm. But some concentra-
tions vary widely, and no precise definition is possible. Frequently used
classifications from a variety of environmentalists and chemists appear in
Table 1-1.
TABLE 1-1. CLASSICAL DEFINITIONS OF NON-TRACE METAL ELEMENTS
Minor Elements
Semi-Metals
Non-Metals
Al
B
H
Ca
Si
C
CI
As
N
Fe
Se
0
Mg
Te
F
P
I
P
K
At
S
Si
CI
Na
Br
S
Inert gases
Ti
Zn
All other elements (about 60) are almost always classified as metals or
trace metals. In fossil fuel ash, Si, Al, Fe, Mg, Ca, and Ti are sometimes
considered as major elements, but not universally.
1-3
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In this study, non-metals were not specifically considered, but when in-
cluded in a table or report, they were not deleted. Some of the semi-metals
are of high environmental concern (especially As and Se) and were given full
trace metal status; others were included when available. The major or minor
metals, or those frequently classified as such in the coal literature, be-
come trace elements in certain systems such as cooling tower blowdown ef-
fluent or the ambient environment. Hence, all metals are usually referred
to as trace metals for general use. The terminology trace element is used
when the table or report includes some non-metals. The term trace metal
may be used almost interchangeably in cases where the definitions are amb:Lg-
guous.
Finally, the relationship between particles, particulate size and tr.ice
metals must be introduced. Concentrations of trace metals in the atmosphere
are normally defined as the amount of trace metals in or on the particulate
matter suspended in the air. Usually high-volume filtration is used to trap
the solids and the "catch" is analyzed. Similarly, the trace metals in stack
emissions frequently refer only to those associated with the particulates.
The trace metals exiting the stack as vapors are seldom included. However,
since the vast majority of trace metals are condensed and remain with the
fly ash, trace metals are closely associated with the particulate matter in
emissions or ambient air.
In certain sections of this report, a good deal of effort is devoted to
particles, specifically fine particulate matter. While trace metals may not
be frequently mentioned in these sections, the discussion is germane to trace
metals. For example, control mechanisms are not designed for control of trace
metals, but rather, are designed to control particles. Thus, trace metals
are controlled only by controlling the particulate matter. This relation-
ship is exercised frequently (in Sections 3, 4, 5, 9), and the reader should
be aware of the dependence. The details of the relationship are developed
in the sections mentioned above.
1-4
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1.2 LITERATURE SEARCH
One of the major purposes of this project was to conduct an extensive
literature search and to publish a bibliography covering trace metal emissions
from SCCP's. Since much of the data gathered before 1970 is of variable
quality due to the technology of the times, and computer data bases were
established at about that same time, a computerized search was chosen as the
principal search method. To convey the extent of the search and to inform
anyone interested in extending the search (see Section 10.1), a complete
review of the strategy used follows.
Three data base vendor systems were searched for information: Lockheed
Retrieval Services (DIALOG®), National Library of Medicine (MEDLARS), and
Department of Energy (DOE/RECON). Specific data bases searched are given
in Table 1-2.
TABLE 1-2. DATABASES SEARCHED IN LITERATURE REVIEW
DOE/RECON MEDLARS DIALOG®
Energy Data Base Cancer proj
Energy R&D Projects Toxline
Medline
Chemical condensates (Chemical Abstracts)
NTIS (U.S. Government reports and
announcements
SSIE (Smithsonian Science Information
Exchange)
Excerpta Medica
APTIC (Air Pollution Technical
Information Center)
Dissertation Abstracts
Magazine Index
Environmental Periodicals Bibliography
Energyline
BIOSIS (Biological Abstracts)
Compendex (Engineering Index)
Pollution
Enviroline
Monthly Catalogue
1-5
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The search was run three times based on three requests. The first search
included only coal combustion. The list of terms used appear in Table 1-3.
TABLE 1-3. TERMS USED IN INITIAL LITERATURE SEARCH
Coal Trace Metals
Trace Elements
Heavy Metals
Carcinogens
Baghouse
Dust
Illness
Electrostatic Precipitators
Health
Fly Ash
Filtration
Scrubber
Toxic
Liquefaction
Gasification
Fluidized Bed Combustion
S0X, N0X, S02
Desulfurization
Mines
Mining
NOTE: A, B, and C are conceptual categories which may be
combined or excluded.
A was "anded" with B; therefore each abstract had to have the word "coal"
and one of the terms from column B. C was "notted" from A and B, which
means if any term from column C was in an abstract that contained terms
from A and B, the abstract was not printed.
The second search was broadened to include all combustion terms,
using the word "COMBUSTION" in column A. The same terms in column B were
used, but column C was expanded to include coal, mobile sources, ships,
aircraft, automotive fuels, automobiles and miners.
1-6
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The third request was a search on trace element or metal concentrations
in ambient air, water, and soil. The strategy is listed in Table 1-4.
TABLE 1-4. TERMS USED IN THIRD LITERATURE SEARCH
A
B
C
Trace elements
Ambient
Air
Trace metals
Water
Soil
Note: A, B, and C are conceptual categories which
may be combined or excluded
Each column was "anded" together, meaning at least one term in each
column had to be included in the final abstract. Databases searched for
this request included: COMPEMDEX, NTIS, CHEM condensates, Monthly catalog,
APTIC, Conference papers, ENVIROLINE, and Pollution.
These searches produced about 20,000 titles and abstracts. The cita-
tions were reviewed and only English language articles published in the
United States and specifically referring to some aspects of trace metals
and SCCP's were retained. This procedure lowered the number of relevant
citations to about 2000. These abstracts were subsequentaly categorized
by subject and the most useful articles obtained. About 400 documents
were fully reviewed, with the balance being used only in abstract form.
It was difficult to assess the quality of foreign articles not obtained.
About 20,000 English language citations were identified, with an additional
6000 foreign language articles which were not used. In the course of the
study, many references were made to articles, particularly review articles,
published in Britain. These have not been included.
1-7
-------
Many of the foreign articles were in Eastern European languages or
Russian. Based on the data and spot checking abstract files, it may be con-
cluded that a considerable volume of energy-related literature exists in
Eastern Europe, mostly on coal, but the quality of the research and its
relevance to trace metals and SCCP's could not be determined without addi-
tional effort. A recent Southern Research Institute publication (3) reviews
recent Russian literature on particulate emissions from SCCP's.
With the large volume of published works available, a manual literature
search is impractical. Information retrieval from computerized information
sources is the state-of-the-art. However, it was discovered that some
important articles were not picked up. This was particularly true of fed-
eral government publications (such as EPA), in spite of the claims made by
the data base vendors. The problem probably lies in the strategy used
herein and the shortcomings of the "key wording" of the reports.
Some articles of interest were picked up from references listed in
reports that were reviewed, particularly older articles. Ideally, 100 per-
cent closure of the references was sought (that is, all key references in
articles refer to already identified reports), but this was not quite
achieved. It is reasonable to assume that all major articles, through at
least 1977, are included within the references of this report and closure is
95 percent complete.
Some non-bibliographic references were included in the list of 2000
relevant citations, such as reports of ongoing research and research pro-
posals. Some of these research groups were contacted to confirm the nature
and the stage of the research; these data are included in the text, but not
referenced in the bibliography. As a prelude to this report, EPA published
in July 1978, a survey of projects relating to the CCEA program (2). In-
cluded in that report were tables of current research activities. That
publication should serve as a complement to the non-bibliographic citations
discussed in this report.
1-8
-------
1.3 FORMAT AND ORGANIZATION
The report has been divided into nine sections following the introduc-
tion. Each section is designed to be read independently; that is, if a sub-
ject is encountered which is fully developed elsewhere in the report, those
aspects of immediate concern are treated, but the more complete section is
referenced. This leads to some duplication of references, but a complete,
pertinent reference list is given at the end of each section. The references
are numbered sequentially as they appear in the section.
A complete bibliography accompanies this report as a separate document.
It is divided into subjects paralleling the sections. All of the referenced
citations recur in the bibliography along with additional citations added
for completeness. The citations under each subject category in the biblio-
graphy are alphabetized by first author's last name.
1.4 SUMMARY OF FINDINGS
Coal is our most abundant fossil fuel resource. Uncertainties in the
petroleum supply and delays in the expansion of the nuclear power industry
have led planners to project coal to fill the United States' ever-increasing
gap between energy demand and supply. Coal reserves in the U.S. are esti-
mated to total nearly 500 billion tons (4).
Consequently, the major emphasis of this report has been on emissions
from coal-fired utilities. Not only is coal the source from which a large
fraction of the SCCP-related trace metal emissions are generated, but it is
also the sector that has been most studied. Oil, the other major fossil fuel
energy source, annually produces less than one percent of the ash generated
by coal. But because oil-fired facilities are often considered "clean"
sources, particulate control may not be as efficient. The pollution con-
tribution of oil-fired plants is probably greater than the coal-to-oil ash
ratio would imply. It should not be inferred that trace metals from oil
combustion are not of concern, but rather that they have not been as exten-
sively studied as coal. The number of pages in this report concerning each
type of fuel approximately reflects the proportionate amount of space in the
literature devoted to that topic.
1-9
-------
Before the SCCP trace metal contribution can be assessed, the natur.il
or background levels of trace metals need to be determined. This is approx-
imated by measuring ambient levels in rural locations, or locations far ::rom
any major pollution source. There is considerable doubt if any place is
unaffected by anthropogenic (man-generated) trace metal pollution, but
isolated locations present the only alternative. As reported in Section 2,
an ambient air monitoring network has been established under the auspice:;
of the EPA. Data are regularly fed into the SAROAD (Storage and Retriev.il
of Aerometric Data) database, but most of these data are on criteria pollu-
tants. Criteria pollutants are SO2, NOxi CO, hydrocarbons and particulate
matter. In general, the particulate matter data gives little information
about trace metal concentrations. However, for some 400 stations trace
metal data averaged over three months are also fed into the SAROAD database.
Two recently published reports (5, 6) have summarized non-criteria
pollutant data through 1975. Additional information may be available from
state offices or regional EPA offices, but each case is individual. With
lead's becoming a criteria pollutant (7), the data on trace metals are
expected to increase.
Outside of this SAROAD network, data are fragmented geographically .and
of uneven quality. Most measurements were taken to serve some specific our-
pose, frequently in an urban area or around a major pollution source. Seldom
is the information of high enough quality to specifically identify any pol-
lutant source, such as an SCCP. The data on water and soil trace metal
levels are too locale specific to attempt any generalization.
Turning to SCCP pollution sources, the first consideration is the fuel
itself. Section 3 quantitatively reviews the trace metal levels in coal
(the main anthropogenic pollution source), oil, gas, refuse and wood. I:i
general, the trace element levels in coal are about the same as they are in
the earth's crust. The burning of coal concentrates them about tenfold, but
releases some to the atmosphere with the rest remaining in the ash (solii waste)
from the combustion processes. Oil has less than 0.1 percent ash with tie
1-10
-------
most abundant trace metals being vanadium and nickel. Natural gas has
essentially no trace metals. Municipal refuse has about the same ash
content as coal (-10 percent) and has concentrations of many trace metals
comparable to levels in coal. Little has been studied for trace elements
associated with combustion of wood.
Section 4 discusses the details of various types of SCCP's. It is
necessary to understand how different combustion processes function in order
to understand the nature of the problem they create. All the potential waste-
streams and their usual contents are reviewed. Although solid and liquid
wastes do contain trace metals, the wastestream of greatest concern is the
flue gas and fly ash, particularly from coal and refuse. Therefore, the major
emphasis of the section is on control technologies. They have the largest
impact on the atmospheric emissions and also offer the greatest range of
alternatives. Several control technologies have been developed to control
criteria pollutants: SO2, NO^ and particulates. Control of the particu-
lates also represents control of the trace metals. However, many of the trace
metals are known to be highly concentrated in the very fine fly ash particles,
the "fines." These particles are commonly defined as the fraction smaller
than one micron. They present problems for several reasons: (1) they are
most mobile and have the longest residence times in the atmosphere; (2) they
contain higher concentrations of trace metals; and (3) they are easily
inhaled and difficult for the lungs to eliminate.
Section 5 quantitatively reviews the literature on point-source emissions.
Again the main emphasis is on coal. Data are presented from several studies
which follow trace metals through a combustion process from source through
burning through scrubbing to emission. What is known about how and why the
trace metals partition as they do is documented. The emissions in all effluent
streams from coal, oil, gas refuse, and wood combustion in a variety of
processes are presented and discussed. The efficiencies of different control
technologies discussed qualitatively in Section 4 are quantified in Section 5.
Section 6 is devoted to the health and environmental effects of trace
metals. Specific notice has been made where effects can be directly related
1-11
-------
to SCCP's trace metal emissions. More generally, however, the literature
reports health and environmental effects due to trace metals independent of
source. A large table gives the specific health and environmental effects
caused by each trace element. Environmental pathways and transport mechanisms
are also discussed.
Section 7 deals with the radiological trace metals from SCCP's. Th:.s
section reviews source, emission and health data related specifically to
the radionuclides. The consensus of research is that, while coal burning
plants emit higher levels of radiation than nuclear power plants, the levels
are still so small as to be of minor concern compared with the criteria
pollutants and other trace metals.
Section 8 addresses the accuracy of data. The quality of data was ex-
tremely variable before 1976, when an NBS standard coal and coal ash greatly
aided researchers in establishing the validity of their data. Part of the
reason for the uneven quality of data was the variety of analytical techniques
used. Each method has its strong and weak points, and one must use extreme
caution when comparing data from different laboratories. Very recently, the
advent of large computers has enabled researchers to use neutron activatr.on
analysis and X-ray fluorescence with a high degree of accuracy. Neither
of these methods requires sample preparation, and the results are remarkably
consistent among different laboratories. New simultaneous, multi-element:
analysis techniques should also serve to greatly increase the quality and
quantity of trace metal data.
Section 9 reviews the current status of regulations that pertain to
trace metals. The net finding is that there are essentially no regulations
for trace metals, per se. The closest any regulations come to controlling
trace metal emissions are the regulations for particulate emissions. Very
recently, states are beginning to promulgate regulations so detailed as 1:o
set specific emissions limits for different sized fly ash particles. In some
instances, control of fine particles is synonymous with trace metal control.
This is in part directed at better trace metal control. The recent designa-
tion of lead as a criteria pollutant indicates the increased interest in
regulation of trace metal emissions.
1-12
-------
Section 10 reports on needs for future research recommended in the lit-
erature. Also some research needs are apparent from obvious gaps in the
literature. At the end of each of the other sections (except Section 1)
is a subsection which deals specifically with the research needs identified
in that subject area. These research needs are of two general types: (1)
to fill in data gaps (for example in ambient air monitoring), and (2) to
expand or explore our knowledge of trace metal processes (for example in the
particle size or health field). A summary of the discussion of research
needs found near the end of each of the eight subject areas sections, com-
bined with Section 10, should represent a survey of the more important future
research topics.
1-13
-------
REFERENCES
1. Kenkereraath, D. C., C. G. Miller, and J. B. Truett. A Program for the
Environmental Assessment of Conventional Combustion Processes.
EPA-600/7-78-140, Research Triangle Park, North Carolina, 1978.
2. Thompson, W. E., and J. Vi. Harrison. Survey of Projects Concerning
Conventional Combustion Environmental Assessments. EPA 600/7-78-139,
Research Triangle Institute, Research Triangle Park, North Carolina,
1978.
3. Southern Research Institute. Recent USSR Literature on Control of
Particulate Emissions from Stationary Sources. EPA 600/2-77-084.
Research Triangle Park, North Carolina, 1977.
4. Boulding, R. What is Pure Coal? Environment, 18(1):12-17,35-36,
1976.
5. U.S. Environmental Protection Agency. National Air Trends in Trace
Metals in Ambient Air, 1965-1974. EPA/450-1-77/003. PB-264 906/9BE,
Research Triangle Park, North Carolina, 1977. 4lp.
6. U.S. Environmental Protection Agency. Air Quality Data for Non-
Criteria Pollutants - 1971 Through 1975. EPA-450/2-78-001. Research
Triangle Park, North Carolina, 1978.
7. U.S. Environmental Protection Agency. National Primary and Secondary
Ambient Air Quality Standards for Lead. Fed. Reg.,
43(194):46246-46277, 1978.
1-14
-------
SECTION 2
AMBIENT TRACE METAL CONDITIONS
Perhaps the first point to be addressed in the assessment of the impact
of trace metal emissions from SCCP's is the present ambient levels. The
atmosphere is the medium of greatest concern, and the individual can do little
to protect himself from its pollutants. These pollutants may be widespread
and long lasting; they also may have a significant impact on human health.
The water and soil are also of concern, but in these media the impact
of a pollutant source may be much more localized and more readily identified.
Any data on trace metals in the water or soil are so dependent upon local
factors such as population, industry, and geographical and meteorological
conditions that comparisons are very difficult. These media are of great
concern, but because the problems, the studies, and the solutions are
usually local issues, no general statements can be made.
The atmosphere provides a large ballast for pollutions. Trace metal
pollutants may have long residence times, undergo mixing and move far from
their source. Although the atmosphere is also very dependent upon local
factors, boundaries are more gradual, and monitoring over regions provides
useful information on pollution sources, build-up and the effectiveness of
control strategies. Such data may also prove useful in public health studies.
2.1 AMBIENT TRACE METAL CONCENTRATIONS
For some time, the United States has had an air pollution monitoring
network. However, its chief concern has been the criteria pollutants: N0x,
SO2, CO, hydrocarbons and particulates. Until very recently, no direct
attention was paid to trace metals.
2-1
-------
Atmospheric trace metals concentrations are measured by pulling a
high volume of air through a filter ("HiVol" sampling) to trap out the
suspended particulates. These filter catches are then analyzed for the
amount of trace metals, and by knowing the volume of air sampled, the trace
metal concentration in the atmosphere is calculated.
EPA receives information from an air monitoring network with about 10,000
stations (1). However, this network was established to gather data on c riteria
pollutants, and only a few trace metal data have been included. About ^00
stations report trace element data on about 27 elements, 21 of which may be
considered as trace metals (2). While these data are not dense enough t;o
allow construction of regional isopleths, they do provide a good overview of
the ambient concentrations of trace metals in the U.S. atmosphere. And;, al-
though the data are averaged and condensed before being fed into the nauional
database, and although the results are relatively uniform because all analyses
are done by EPA-RTP, the results are not analyzed or interpreted on a regular
basis. The resulting publications merely display the data.
In 1957, the National Air Sampling Network (NASK), later called the
National Air Surveillance Network, consisted of 185 urban and 48 rural
stations. By 1971, there were 1141 urban, 66 source-oriented (i.e., associa-
ted with a specific point source) and 49 rural stations in the network. As
mentioned above, the prinicipal function of the network is to monitor cri-
teria pollutants, but some trace metal data have resulted. In 1972, ths EPA
published the data from NASN for the years 1964 through 1968, including the
non-criteria data (3). They reported as many as 16 trace metals, but 5
elements are incomplete (antimony, bismuth, copper molybdenum, and tin).
The ranges and most common values for the other 11 are given in Table 2-1.
Since 1968 most of the nation's air pollution monitoring has been
carried out by three NASN's: high volume-network, gas sampling network
and the CAMP (Continuous Air Monitoring Program) station network. This
total program, operated under the auspices of the EPA, consisted of soma
7,000 air samplers (1).
2-2
-------
TABLE 2-1. ATMOSPHERIC METAL CONCENTRATIONS IN U.S., 1966-1967
Urban
(UR/m3)
Non-urban
(yg/m3)
Element
Value
Detected
Range
Detection
Limit
% Below
Detection
Limit
Most
Common
Value
Detected
Range
Detection
Limit
% Below
Detection
Limit
Be
.0003
0-.0007
.0002
85
.00007
0-.0004
.0007
95
Cd
.01
0-.09
.01
73
.004
0-.03
.004
93
Cr
.006
0-0.1
.006
62
.003
0-.03
.002
70
Co
.006
0-.045
.006
99
—
—
.002
99.5
Fe
1.5
0.1-6.1
.2
3
.2
.02-1.5
.05
17
Pb
.8
0.1-5.0
.1
1
.08
.03-0.8
.03
28
Mn
.03
0-.81
.01
6
.01
.002-.07
.004
21
Ni
.01
0-.187
.006
30
.002
0-.03
.002
36
Ti
.02
0-.13
.001
51
.002
0-.03
.003
28
V
.02
0-.905
.003
AO
.003
0-.01
.001
55
Zn
.5
0-1.7
.1
60
.1
0-0.6
.04
56
SOURCE: (1)
-------
Monitoring and data analysis are carried out within the Office of ALr
and Water Programs at RIP, which, with its Air Pollution Technical Inforna-
tion Center, is a subdivision of the EPA. Processing of the huge amounts
of data is handled by an automatic system for the Storage and Retrieval
of Aerometric Data (SAROAD). The SAROAD system is part of the AtmospherLc
and Emissions Reporting System (AEROS). The collection and dissemination of
aerometric data to and from the National Aerometric Data Bank (NADB) are
handled through the National Aerometric Data Information Service (NADIS).
Again, it should be emphasized that these data are mainly for criteria
pollutants, and trace metal data are reported for only about 400 stations.
Quarterly reports are issued for criteria pollutants, but only infrequent
summary reports for non-criteria pollutants have been forthcoming. Informa-
tion on trace element concentrations in the atmosphere is not required by
any Federal agency (4).
The Monitoring and Data Analysis Division of EPA has recently published
two reports that present air quality data for non-criteria pollutants; the
first covers the years 1965-1974 (5) and the second covers the years 1971—
1975 (2). Both of these are vast data compilations, without comment. They
cover about 400 reporting stations from all 50 states and include rural and
urban stations. These data are averaged over three month periods and pro-
cessed at the state or EPA regional offices before being submitted into the
SAROAD system. Thus, more complete or detailed data may exist at the local
offices, but each case would require individual attention. The data are
so voluminous that no representative one-page table is possible. Again, it
should be noted that the bulk of data in the SAROAD system are for criteria
pollutants, and customized retrieval is required to access the latest
trace metal data.
Studies outside of AEROS more often present some data analysis and com-
mentary, but are very spotty and uneven. The methods of sampling and analysis
are not uniform, and the studies were usually generated for some specific
reason.
One such study was an EPA supported project that measured the trace
elements in ambient air at five selected stations in the Northern Great
2-4
-------
Plains (6). Table 2-2 summarizes these data; however, 5 data points over
about 100,000 square miles is only dense enough to give an overview of this
essentially rural area. The study was commissioned because of suspected
ambient trace metal increases due to industry, coal burning and coal pro-
cessing in the area. One of the results was the confirmation that glass
substrate filters mask low level trace metal concentrations (due to trace
metals in the substrate); cellulose filters are now preferred.
Representative of urban studies is one reported for Sacramento,
California (7). These data, taken on sized aerosols, are presented for
particulates below 3.6 vim, those sizes most respirable; see Table 2-3.
Urban air concentrations are being studied by the International Decade
of Ocean Exploration. Their values for the concentration of trace elements
in U.S. urban air are presented in Table 2-4. The values in Table 2-4 rep-
resent an averaged value of U.S. urban air concentrations from over 20 urban
locations around the U.S. (8). Other research teams have reported back-
ground trace element concentrations in urban aerosols for Miami, Florida
(10), Fresno, California (11), New York City (12), northwest Indiana (13),
and several Texas gulf coast cities (14). Typical of some states, Texas
has established an air particulate monitoring system with trace element anal-
ysis. While this program is focusing on the major urban areas, a few smaller
cities were included. Table 2-5 gives an analysis for up to 17 elements
at various sites around the state (14). Also see Table 2-6 for a similar
California study (7).
One isolated study did try to establish background levels for atmos-
pheric trace metals (15). It was remote from any large fossil fuel power
plant, and the researchers hoped to determine "natural" ambient (background)
levels before coal-fired plants began operation in adjacent states. The
site chosen was rural Chadron, Nebraska, 480 km north-northeast of Denver,
Colorado. Rather than collect particulates by high-volume sampling, they
collected and analyzed rain and snow for seven metals. Their results are
reproduced in Table 2-7.
2-5
-------
TABLE 2-2. AMBIENT TRACE ELEMENT CONCENTRATIONS BASED ON FIVE NORTHERN GREAT
PLAINS' SITES
Element
Annual Range yg/m3
Annual Average yg/m'
Arsenic
4E-3/4E-5
4.32
E-4
Barium
3E-2/9E-4
9.10
E-3
Beryllium
5E-5/4E-6
1.68
E-5
Calcium
3E-0/2E-5
5.55
E-l
Cadmium
2E-4/2E-5
6.95
E-5
Chlorine
3E-1/1E-5
5.66
E-2
Cobalt
6E-4/8E-6
1.34
E-4
Copper
3E-2/3E-3
1.54
E-2
Chromium
4E-2/2E-3
1.03
E-2
Fluorine
4E-1/4E-3
6.26
E-2
Iron
4E-1/6E-3
1.14
E-l
Lead
5E-2/2E-3
1.66
E-2
Lithium
2E-3/2E-5
1.66
E-2
Magnesium
6E-1/8E-3
1.99
E-l
Manganese
2E-2/7E-4
3.88
E-3
Nickel
5E-3/2E-5
1.32
E-3
Phosphorus
3E-1/2E-2
8.70
E-2
Selenium
5E-4/2E-5
1.59
E-4
Silicon
3E-0/9E+1
3.56
E+l
Silver
2E-4/2E-6
3.41
E-5
Sodium
2E-0/3E-2
5.44
E-l
Zinc
3E-2/4E-3
1.21
E-2
SOURCE:
(6)
2-6
-------
TABLE 2-3. COMPARISON OF AMBIENT TRACE ELEMENT DATA FOR SACRAMENTO, CALIFORNIA (JANUARY, 1974)
BASED ON MULTIDAY IMPACTOR SAMPLES WITH IMPACT MODEL RESULTS
Stage 2 Filter Stage 3 Filter
Concentration (pg/ms) Concentration (ug/m9) Combined Concentration (lig/m')
0.65
-3.6 inn
0.1-
0.
65 po
0.1
-3
.6 vim
Element
Size Range
Slze
Range
Size Range
Ba
1.0
x 10"'
0
.0
1.0
X
10"'
Ca
6.5
t*
1
o
K
3.9
X
10"2
1.0
X
10"1
CI
1.87
x 10"'
0
.0
1.9
X
10_I
Cr
0.0
1.0
X
10"'
1.0
X
IO-1
Cu
3.0
x 10"®
1.4
X
10"*
1.7
X
io"1
Fe
8.6
x 10~*
1.0
X
10"'
1.9
X
io-1
Mg
2.0
x 10"*
3.0
X
10"'
2.3
X
IO-2
Mn
3.0
x 10"1
1.0
X
io"3
4.0
X
10"'
Na
1.06
X
M
o
1
5.7
X
10"*
1.6
X
10"1
N1
0.0
2.0
X
10"'
2.0
X
10"'
Pb
1.64
1
O
K
7.22
X
10"'
8.9
X
10"1
SI
•• 1.66
x lo"1
— t
1.56
X
io"1
3.2
X
10"'
Zn
1.6
x 10
2.6
X
10"*
4.2
X
10~*
SOURCE: (7)
-------
TABLE 2-4. AMBIENT TRACE METAL CONCENTRATIONS OFTEN USED FOR REFERENCE
Crustal3 Open U.S. Urban
Abundance Ocean Air Average
Element (ppm) (ppm) (yg/ra3)
Aluminum
81,300
1,000
1,500
Antimony
0.2
200
20
Arsenic
1.8
2,000
20
Beryllium
2.8
5
].
Cadmium
0.2
20
20
Cesium
60
300
L
Chromium
100
300
40
Cobalt
25
30
I.
Copper
55
2,000
20C<
Gallium
15
20
].
Iron
50,000
5,000
2,00C
Lanthanum
30
10
:i
Lead
13
20
1,000
Manganese
950
300
200
Mercury
0.08
100
Molbydenum
1.5
10,000
10
Nickel
75
2,000
30
Scandium
22
1
1
Selenium
0.05
100
4
Silver
0.07
10
2
Tantalum
2
20
0.2
Tin
2
20
2C
Titanium
4,400
1,000
10C
Tungsten
1.5
100
c
Uranium
1.8
3,000
C .1
Vanadium
135
1,000
20C
Zinc
70
3,000
70C
aSOURCE: (9)
bSOURCE: (8)
2-8
-------
TABLE 2-5. CONCENTRATION OF ELEMENTS IN AIR PARTICULATE MATTER IN TEXAS
Location
Ca
Ti
V
Cr
Element
Mn
(Ug/m°)
Fe
Co
Ni
Cu
Zn
Hg
Statewide
7.73
0.
.19
0.03
0.05
1.3
<.018
_
0.12
0.13
_
(range)
(0.6-
(¦
.02-
(c.004)
(<•05-
(.01-
(0.1-
(<¦
.018-
(<
.01)
(<.01-
(<-005-
(<•02-
29.9)*
1.
33)
1.1)
.17)
10)
.05)
•96) .
1.77)
.05)
Amarlllo
2.7
0.
34
<.006
0.01
0.05
1.5
<0.
.02
<0.
.01
0.12
0.15
<0.03
Clute
29.9
0.
22
<•007
0.01
0.01
1.0
<0.
.02
<0,
.01
0.01
0.11
<0.03
Corpus Chrlstl
21.9
0.
29
<.008
1.10
0.09
10.0
<0.
,02
<0.
.01
0.16
1.77
<0.03
Dallas
4.8
0.
08
<0.004
0.01
0.01
0.7
<0.
01
<0.
.01
0.02
0.01
<0.02
El Paso
13.7
0.
34
<.008
<0.06
0.11
3.4
<0.
02
<0.
.01
0.96
1.66
<0.03
Houston
6.6
0.
11
<0.008
0.05
<0.03
0.6
<0.
03
<0.
.01
0.22
0.14
<0.03
Harllngen
11.8
0.
20
<0.G06
<0.05
<0.03
1.2
<0.
02
<0.
.01
0.02
0.02
<0.03
San Antonio
3.5
0.
12
<0.004
<0.04
<0.02
0.1
<0.
.01
<0.
.01
<0.01
0.07
<0.02
* Valves In parenthesis are ranges
SOURCE: (14)
-------
TAHI.R 2-6. AVERAGE AMOUNT OF TRACF. F.I.EMF.NTS IN SELECTED CAI.IFORNIA CITTF.S.
Site +
Sacramento
Nn
A1 SI
CI
_ ELEMENTS » (ppb)
K Ca Tl
Mn Fc Cu Zn Br Ph
617 13 J 869 3372 1016 336 *>11 577 94
36 1215 8 30 158 704
Richmond
1692 122 1 34 1058 llHl 1948 296 417 40
22
634
4 75 175 557
1. Ivermore
302 92 357 2382 609 244 331 454 64
30 934 5 60 65 361
Oakland
1710 137 115 1339 1758 2014 313 528 72 26 36 764 26 132 221 984
Ran Joro
732 197 597 3145 869 891 470 836 91
30 1182 5 58 288 1058
N>
I
S.i linns
715 89 196 1134 532 1048 219 285 24
12 440
35 179
Bnkersf lelil
169
77 1420 4566 1507 18 1043 1252 146 19 27 1819 14 47 252 1072
Lor Alamltos
825 173 472 2149 3879 366 451 642 79 71 27 973 6 73 115 940
l,os Angeles 696
98
443 2418 4013 173 473 751 134 25 31 1006 17 183 252 1498
Aztisa
478 167 1137 3751 3084 97 913 1063 242 43 49 2009 20 190 217 1407
RlverslHe
274
94 1024 4019 288/, 107 793 1266 143 15 36 1793 7 95 370 1697
Indlo
320 182 2434 7864 3409 99 155/. 2619 312 35 70 3387 14 108 119 789
F.l Cajon
890 193 875 3680 2663 296 560 772 139 24 33 1327 7 39 166 1041
~Nominal error, 115%
Source: (7)
+ for months July, August, September (1973)
-------
TABLE 2-7. CHADRON, NEBRASKA RAINFALL ANALYSIS, 1973
Concentration
Element g/cm3
Ag
8.4
X
10"11
A1
3.5
X
10" 7
Cd
3.1
X
10~10
Cu
U.U
X
10"9
Mn
5.2
X
10"3
Pb
4.8
X
10~9
Zn
1.0
X
10"8
SOURCE: (15)
2-11
-------
The study of trace metal concentrations in aqueous systems is currently
hindered by the lack of a convenient or obvious reference or standard.
Therefore, some authors (8) have chosen the trace element concentrations of
the open ocean as an universal reference point, much like the crustal abundances
are used for terrestrial comparisons. Trace element concentrations in oceans
and crustal abundances are given in Table 2-4. Another set of values used
for comparison are the Multimedia Environmental Goals (MEG's). These are
concentrations of pollutants, including trace metals, thought to be safe
for human health or non-deleterious to the environment. Values are given
for both emission goals, Minimum Acute Toxicity Effluents (MATE's), and
Ambient Goals, Estimated Permissible Concentrations (EPC's); see Section 9
(Table 9-6). In addition, another value often used as a guideline in
estimating permissible effluent stream concentrations is the U.S. Department
of Agriculture irrigation standards for water considered safe for agricul-
tural irrigation (17). The trace metal concentrations of our surface
waters (which show great fluctuations both in location and time) and
groundwaters remain largely unknown.
In general, the aqueous trace metal concentrations are so dependent upon
local population, industry and geological factors, as well as the amount of
water moving through a region, that it is futile to even present typical
or representative values because none can be defined.
No general statements can be made about trace metal concentrations in
soils. The average crustal abundances are well known (the Clarke values)
and often used as a standard for comparison (see Table 2-4); however, local
factors are so variable and significant that ambient soil concentrations must
be measured for each individual case. Several such studies are discussed
in Sections 6.2.2 and 6.2.3 (18-24). As with aqueous systems, typical or
representative values cannot be presented.
2.2 NATURAL SOURCES OF TRACE METAL POLLUTANTS
A natural source may be defined as any source not man-made or man
caused (not anthropogenic). Wind, rain, flowing water and other meteoro-
logical factors are examples of natural emission pathways. In some rural
2-12
-------
areas, such as West Texas, the majority of airborne trace elements are due
to windblown particles (25, 26). Another indirect but significant pathway
of trace metals into the biosphere is uptake by plants. The trace metal may
be mobilized by the action of the plant (e.g., respiration, spores), or the
vegetation may be consumed by animals including, directly or indirectly, man.
Pathways through living systems are dealt with extensively in Section 6.2 of
this report.
Background concentrations of trace elements in streams, rivers, and
lakes have not been well quantified (27). One reason for the lack of more
complete information is simply the magnitude of the task; however, several
studies do exist on watersheds near large electrical utility boilers (28-30)
in which quantification of trace elements in air, soil, and water are con-
sidered. In most of these studies, attempts were made to determine the back-
ground levels and the amounts of trace metals mobilized via natural pathways
and man; also see Section 6.2 and 6.3.
2.3 ANTHROPOGENIC SOURCES OF TRACE METAL POLLUTANTS
The escalating concern about the environment over the last several
decades has been due, in part, to the increasing generation of electric
power (31-34). More recently, the use of coal, which produces two to three
orders of magnitude more ash than oil or gas for the same Btu output, has
increased; see Sections 3 and 5 of this report for quantification. The
continuing growth of urban areas and industry have also contributed to the
environmental problems.
The trace metals emitted by the burning of fossil fuels and urban
refuse are predominantly associated with the ash. Trace metals such as
mercury, molybdenum, beryllium and lead and trace (non-metallic) elements
such as selenium, arsenic, fluorine and chlorine may be emitted at least
partially in the vapor phase, and present unique problems. However, in most
cases, extensive evidence exists showing that the trace metals are intimately
bound to the bottom ash and aerosol fly ash. In fact, many of the trace
metals are concentrated in the submicron ash particles (35); see Sections
3.A, 4.8.3 and 5.5.
2-13
-------
Determination of the relationship between trace metals and ash particles
is still evolving, and in general, not enough is known about the location,
quantity, mobility and environmental and health effects of trace metals l;o
fully characterize the relationship. Thus, in the past, most attention was
focused on particulate emissions which could easily be quantified. Withr.n
the last decade, the trace metals themselves have begun to be studied. Still,
most of the control technology and regulations are designed to moderate or
curtail particulate emissions. Of course, a decrease in particulate emis-
sions means a concomitant decrease in trace metal emissions, but not neces-
sarily proportionately so. In fact, the current trend in regulations is to
establish limits on fine particulate emissions in an attempt to reduce trace
metal emissions. For example, New Mexico now has regulations limiting the
release of sub-2.0 yin particles from coal-fired power plants (36). Today,
only two trace metals are classified as hazardous emissions; mercury and
beryllium (37), and very recently (October 1978) lead has been declared as
a criteria pollutant (38); see Section 9. Thus, essentially all our know-
ledge about atmospheric trace metal levels comes from studies of particulate
matter.
Although coal burning does not produce a liquid effluent directly,
aqueous effluent streams do result from coal combustion processes. The
main sources are either from the sluicing of ash or from the wet SO2 scrub-
bers. In both cases, ash contacts water and the trace elements may be leached
into the aqueous phase. See Section 4 for a full description of all process
streams. These liquid effluents are normally cleaned to some extent and
either reused, released or ponded where the water may soak into the soil.
Also, buried ash may be leached by natural waters and release trace metals.
Any of these processes may generate aqueous trace metal effluents (39).
These sources are usually rather visible (except underground leaching) and
easily traced to the source. As a result, they have been fairly well iden-
tified. Some states now do not permit aqueous discharge from new power 'slants.
2-14
-------
Concentrations of trace elements in soils have been determined only in
widely scattered regions of the U.S. In studies of SCCP's, trace element
concentrations of soils have been measured around large SCCP's to determine
long term soil effects of emitted trace elements (18, 27,30, 40, 41). For
example, in one study done in conjunction with a trace element balance around
Mohave Generating Station in Southern Nevada, the concentration of specific
trace elements in soil was determined (41). The sampling was done on speci-
fied soil types up to 20 kilometers downwind of the smokestack. Soil profiles
up to 20 centimeters deep were determined and all trace metals studied,
except strontium, were found to be greater in the surface soils (0-2 cm).
Sulfur, copper and strontium were found to decrease in surface soils with
increasing distance from the plant. Estimations of the deposition during
the lifetime of the plant showed that the emission rates were inadequate,
except for sulfur, to account for the measureable increases that were
found in soil concentrations. Two other studies were recently performed
in conjunction with the establishment of trace element balances around
watersheds near large SCCP's (18, 30). In one study performed in Tennessee,
a six-month mass balance indicated that the watershed under study efficiently
retained lead, cadmium, and copper; however, less than 70 percent of mag-
nesium, chromium, zinc, and mercury introduced to the watershed could be
retained by the soil (18).
Combustion of fossil fuels and wood in smaller SCCP's (e.g., industrial
boilers, commercial package boilers, residential heating) contributes to the
anthropogenic emissions, but very little data were found for these processes.
The paucity of data on residential units was particularly obvious. Some
emission studies have been done on package or self-contained boilers, but
rarely were trace metals included within the scope of these studies. Once
again, studies principally concerned with particulate loading represent the
main source of trace metal data. See Section 5 for a report of these studies.
The Air Pollution Control Act was promulgated in 1955 by the Congress.
The major provisions of the act stipulated that the Federal government would
provide research funds and technical assistance for studying the causes of
pollution. The states and local governments would be responsible for
2-15
-------
pollution control at the source (1). By 1976 over 200,000 anthropogenic
sources of pollution had been identified as being subject to emissions
limitations (42). Of the 200,000 sources of emissions, about 20,000 are
classified as major emitters (emissions greater than 100 tons/yr) and are
projected to produce 85 percent of all stationary source air pollution. Table
2-8 shows the degree of compliance attained by the major emitters and pri-
ority sources (see table for definition) as of 1975 (42).
Thus, although this act applies only to criteria pollutants (S02, NC^,
CO, hydrocarbons, and particulate matter), it is representative of the lf.ws
and regulations that limit emissions. Until the level of knowledge about, trace
metals is improved, regulations and control strategies will continue to spply
only to criteria pollutants. Lead is the first example of a specific trace
metal that is being regulated (38).
There are other anthropogenic sources of trace metals, but most of
these do not fall under the definition of SCCP sources (e.g., mobile sources,
process heating, coal gasification, refineries). Although urban refuse is
comparable to coal in ash content per Btu, far less is burned, and coal
remains as the primary source of trace metal emission from SCCP's.
2.3.1 Urban Environments
Current background trace element concentrations are, at best, difficult
to ascertain for most urban areas. For example, Ca, Ti, V, Mn, Fe, Ni, Zn,
Br, and Pb, have all shown order of magnitude fluctuations in a two-hour
sampling time (11). Most atmospheric trace metal studies use high-volume:
filtration sampling methods. They result in the collection of suspended
particles or aerosols. These filtrate "catches" are then analyzed and re-
present the atmospheric trace element concentrations; however, the collection
and analysis of aerosols is deceptively complex, and the quality of the
data is often suspect.
2-16
-------
TABLE 2-8. COMPLIANCE STATUS OF NATIONAL PRIORITY SOURCES3
Total Status with Respect to Emission Limitation
(Type of Source/ Number and/or Compliance Schedule
Primary Pollutant) Identified In Compliance In Violation Unknown Status
I. All Major Sources 19,360 16,190 (84%) 2,136 (11%) 1,035 (5%)
(e.g. sources capable
of emitting 100+ tons/yr
of a pollutant)
II. Priority Major Sources
A.
Power Plants (SO^)
383
276
(72%)
60
(16%)
47
(12%)
B.
Smelters (S0x)
25
5
(20%)
4
(16%)
16
(14%)
C.
Steel Processes (Particulates)
1,177
449
(38%)
301
(26%)
427
(36%)
D.
Municipal Incinerators
230
110
(48%)
85
(37%)
35
(15%)
E.
Petroleum Refineries (HC)
260
173
(67%)
34
(13%)
53
(20%)
F.
Kraft and Sulfite Pulp Mills (S0t»)
150
87
(58%)
34
(23%)
29
(19%)
3
Numbers represent facilities rather than emission points for all source categories.
SOURCE: (42)
-------
For example, it has been reported that the size distribution of urban
aerosols often has two modes separated by a particle-deficient region at
approximately 1-2 microns. This deficiency may be in part caused by emission
from SCCP's. The removal efficiency of modern electrostatic precipitators
frequently used with large coal-fired boilers decreases rapidly for particles
smaller than one micron. Thus, they emit primarily small particles and may
be a significant contributor to the modal distribution below one micron found
in many urban aerosols (35); also see Section 4 of this report. Particle
sizes below three microns are known to be easily respired by humans, and
such particles tend to reside for long periods in the lungs; see Section 6.4
of this report for a detailed discussion.
Another theory that has been advanced is that the bimodality of urban
aerosols may be the result of different formation processes for the two-
size modes (43). Hence, any attempt to identify aerosol sources by means
of elemental composition "fingerprinting" should therefore include measure-
ments of aerosol composition as a function of particle size (44, 45).
Many reported studies of urban aerosols have not done this.
Since much of the particulate matter in the atmosphere is derived
ultimately from crustal material (e.g., particles from wind erosion of
soil and rocks, fly ash particles released in coal combustion), a common
method of reporting urban trace element concentrations is the use of enrich-
ment factors. As reported by Gordon and Zoller (46), an enrichment factor of
a particular element is determined by first comparing its urban concentra-
tion to its crustal abundance. This ratio is then compared to a non-volatile
element whose concentration is known to be quite stable. Gordon and Zoller
chose aluminum. Numbers greater than one are then concentrated relative to
aluminum. Figure 2-1 shows such enrichment factors obtained from concentra-
tions of elements measured on atmospheric particles collected in Boston,
northwest Indiana, and San Francisco (13, 46, 47).
2-18
-------
10,000
1000
on
o
o
«x
100
~ 10
1.0
0.1
1 1
_T—
I 1 1 ! 1 1 | J | I I I
1 "IJ
1—r
" 1 f" li
_ URBAN ENRICHMENT FACTORS 4
1
O
X
.7 X 10^-
—
BOSTON
—
SAN
FRANCISCO
N.W
. INDIANA
—
-
-
-
-
_
* -
~ —
——X~~
—
-
=*="
-
*=
—
-
, i 1
J
1 , 1 ! L 1 . I 1 1 ! 1
1 1 I
-J L
1 1 1
A1 5c Th RE Mg U V Cr Mn Fe Co H\ Cu Zn As Cd Sn Sb Pb Se S Na CI Br
Figure 2-1. Enrichment factors relative to aluminum for elements on particles
collected in the atmospheres of Boston, northwest Indiana, and
San Francisco. In this figure "RE" represents an average of four
rate-earth elements.
SOURCE:
(46)
2-19
-------
Some programs which measure ambient levels of trace metals are designed
to identify large fluctuations. Few of these programs are designed to iden-
tify the source(s). One project by Giauque, et^ (11) which did use this
approach studied Fresno, California. They sized the urban aerosols before
measuring the trace metal concentrations. Some of their conclusions were:
• Seventy-five percent of lead and bromine and 50 percent
of zinc were found on particles less than 0.5 ym in
diameter. The lead and bromine were predominantly from
automobiles; zinc was probably derived from incineration
of tin cans and tires.
• Diurnal concentration fluctuations were noted for Pb, Br, Ca,
Zn, Cr, Fe, K, Ti, Mn. The last four of these showed fluc-
tuations similar to total particulate loading cycles and are
probably derived from windblown dust.
• Calcium was found predominantly on large particles. Its
source is most likely the cement industry.
Also, the Sacramento study reported earlier, see Table 2-3, performed
limited particle sizing before trace element analysis (7).
The current interest in this area is to attempt to use emissions data
and modeling to "predict" the reported ambient trace metal levels. Research
in this direction requires a system capable of inputing emission rates for
all local point sources (available from source emission inventories such as
the National Environmental Data System, NEDS) and modeling their distribution
to predict trace metal ambient concentration patterns. Comparison with meas-
ured ambient isopleths could then be used to improve the modeling unti] a
full understanding of the pollution pattern was achieved. In general, the
state-of-the-art has not reached this level. Local studies of many cities
have been made, but few were published and/or identified by this information-
literature search. Among those areas studied where the researchers speculate
to some degree about the sources of trace metal pollutants are studies of
Miami, Florida (10), New York City (12), northwest Indiana (13), Bostor (46),
and several Texas (14) and California cities (7). Data from the Texas and
California studies were given in Tables 2-5 and 2-6.
2-20
-------
2.3.2 Rural Situations
The influence of SCCP's on trace element concentrations of the rural
United States is also difficult to assess. One reason is that the impetus
for determining most of the rural data has been the study of large fossil
fuel power plants located in a particular rural area (15, 48-52). Seldom
was any preliminary or background study done. Thus, a study commenced after
the plant has been in operation cannot accurately determine the contribution
due to the SCCP. Also, much of the particulate matter in rural areas is due
to windblown oust, and the contribution of the fly ash is sometimes rela-
tively small. Finally, the far smaller number of people affected in rural
areas by SCCP emissions is a contributing factor, both financially and
politically, to the lack of motivation to study rural regions.
The Chadron, Nebraska study was mentioned above in Section 2.1. Another
study in rural Colorado (50) reported background beryllium levels of 0.4 Ug/m3
in air. The study projected that if coal combustion were increased four-fold,
airborne beryllium levels would rise to 1-2 pg/m3. This beryllium concentra-
tion level is a normal background level experienced in industrial areas of
the United States. Another study looked at emissions of cadmium and attempted
to identify the sources (53). The results of the study appear in Table 2-9.
TABLE 2-9. CADMIUM EMISSION RATES
Source
Emission (1000 lbs/yr)
Metal Extraction
Concentration and Metal Production
0.5
2,100.
Conversion of Metal to Products
33
36
Product Use
Metal Recycle and Disposal
Fossil Fuel Combustion
Phosphate Fertilizer Production
2,200
200-700
50.
SOURCE: (53)
2-21
-------
The Texas study also included several small, non-urban towns (14), see
Table 2-5, as did the California study, see Table 2-6.
2.3.3 Nonspecific Sources
The specific contribution of SCCP's to background trace element cor.cen-
trations is an area that is currently experiencing increased interest ar,.d
investigation. However, under the current regulatory climate, there is no
law that specifically requires the reporting of trace element emissions from
SCCP's. Therefore, we are only able to report on how well plants with fossil-
fueled boilers have responded to other requirements under current regulations.
Of special interest should be their compliance with requirements for total
suspended particulate standards. Of 20,000 major emitters of particles identi-
fied in 1974, less than 400 were coal-fired power .plants (42). Data for
compliance of SCCP's with regards to total suspended particulate standards
was not available as a separate category in 1975. By comparison, with regard
to regulatory SO2 laws in 1974, some 72 percent of coal-fired power plants
were in compliance (42).
Many studies have been done that considered particular trace elements
such as boron, beryllium, bronine, copper, manganese, lead, selenium and zinc
emissions into the biosphere. Some of these studies also estimated the amounts
of a particular element emitted by coal combustion (50, 63-65). In a similar
vein, the 1969 copper emissions to the atmosphere in the U.S. amounted to
13,680 tons. The combustion of coal was responsible for only 15% of the total
copper emissions (56,57). In 1972, boron emissions to the atmosphere in
the USA totaled 11,003 tons. Nearly 22% of the emissions resulted from the
processing of boron compounds, more than 34% from the manufacture and use
of various end products, and about 43% from the combustion of coal (55).
For manganese, normal background levels range from 0.01 - 0.02 yg/m3. At
power stations using methylcyclopentadienyl manganese tricarbonyl as a suoke
suppressant for stack emissions, air concentrations of manganese 1000 fe=t
downwind were 0.1 - 0.2 pg/rn3. At a site burning fuel oil containing 125 ppm
manganese, air concentrations 1,500 feet downwind were 0.03 - 0.05 Ug/m3 (53).
2-22
-------
In another study selenium emission rates from the Allen Steam Plant
study were used to calculate the minimum mobilization of selenium from coal
consumption in the United States and the world. Calculations indicate that
1.5 to 2.5 times as much selenium is mobilized by man through coal burning
as by natural weathering (58).
The mass balance of trace elements in Walker Branch Watershed in rela-
tion to nearby coal-fired steam plants was investigated (18). The watershed,
which is on the ERDA reservation at Oak Ridge, is within 20 km of three coal-
fired steam plants, two in the TVA system and one belonging to ERDA. In
conjunction with this program, there is an ongoing, well instrumented
program monitoring a forested catchment (located within 15 km of two large
coal-fired power plants). Measurements of selected trace contaminants in
air, rain, on leaf surfaces and in stream water are made on a basis designed
to elucidate transport, deposition, and cycling of these contaminants on
the landscape (18, 30).
Yet these two studies, and others like them, highlight a number of
problems. Uniform sampling methods were not employed, nor were methods of
analysis of the samples documented. A computer simulation model was made
of the trace metal flow around the Allen Steam Plant and compared with the
measured data. Results were inconclusive (66), and the modeling and moni-
toring computer program did not interface with the SAROAD system used by
EPA to monitor emissions.
In summary, the contribution from SCCP's to the trace metal mix in
the environment is largely undetermined. In those spotty instances where
studies have been made, for either specific locales or certain trace metals,
no general conclusions may be drawn. That is, in certain cases the SCCP
contribution is dominant, as selenium around the Allen Steam Plant (58).
While in other cases, such as rural areas with high dust levels or for
total copper emissions (56) , the SCCP contribution is small to insignifi-
cant. In most cases, even the approximate contribution of a specific SCCP
is unresolvable. But the chief reason for the incompleteness of the data
is not primarily anthropogenic. Rather, it is the constraints imposed by
2-23
-------
available technology and costs, coupled with the sheer magnitude of the
task, that have led to the current status.
2.4 RESEARCH NEEDS
The National Aerometric Data Bank (NADB) has provided a good beginning
to assess the atmospheric trace metal levels. However their data are uneven
and not of sufficient quantity to sketch out national or regional isopleths
for each element. The regional and state offices have more data, but nuch
of it is unpublished. Also, locally sponsored programs sometimes produce
data of variable quality. More monitoring stations reporting trace metal
information into the SAROAE system would be very desirable.
The evolution of such data may be forthcoming. With lead being declared
a criteria pollutant in October 1978 (38) , and State Implementation Plans
due in July of 1979 for compliance by October of 1982, states will have to
establish a lead monitoring network. With the task of HiVol atmospheric
sampling being done and the catches analyzed for lead, small additional
effort would produce data for other trace metals. This is particularly
true with the newly developed multi-element analytical instruments beginning
to proliferate (X-ray fluorescence, SSMS/ID and plasma fluorescence; see
Section 8). More analysis and interpretation of the data would be highly
beneficial. Interpretive reports such as those by Gordon and Zoller (46)
and Hall et al. (67) are needed as much as more trace metal data.
The number of trace metal studies on water and soil are expected to in-
crease with improving technology, and more and better data will be produced;
however, local factors remain so variable and influential that only studies
restricted to a locale for specific reasons appear to be warranted at this
time.
2-24
-------
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States. Honolulu, Hawaii, Oriental, 1975.
2. U.S. Environmental Protection Agency. Air Quality Data for Non-
Criteria Pollutants - 1971 Through 1975. EPA-450/2-78-001. Research
Triangle Park, North Carolina, 1978.
3. U.S. Environmental Protection Agency, Office of Air Programs. Air
Quality Data for 1968. APTD 0978. Research Triangle Park, North
Carolina, 1972.
4. Hunt, W. F. Jr., et al. National Air Quality and Emission Trends
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2-25
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11. Giauque, R. D., L. Y. Goda, and N. E. Brown. Characterization of
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In: Nuclear Chemistry Annual Report 1973. Lawrence Berkeley Labora-
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13. Dams, R. J., J. A. Robbins, K. A. Rahn, and J. W. Winchester. Quanti-
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Lindgren. Energy Dispersive X-Ray Fluorescence Analysis of Air Par-
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15. Struempler, A. W. Trace Metals in Rain and Snow During 1973 at
Chardron, Nebraska. Atmos. Environ., 10(1):33-37, 1976.
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Utility Solid Wastes. EPRI FP-878, EPRI TPS 78-779, Fred C. Hart
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18. Lindberg, S. E., A. W. Andren, R. J. Raridon, and W. Fulkerson. Mass
Balance of Trace Elements in Walker Branch Watershed: Relation to
Coal-Fired Steam Plants. Environ. Health Perspect., 12:9-18, 1975.
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20. Wagenet, R. J., W. J. Grenney, and J. J. Jurinak. Environmental
Transport Model of Heavy Metals. ASCE J. Environ. Eng. Div.,
104(1):61-76, 1978.
21. Anderson, W. L., and K. E. Smith. Dynamics of Mercury at Coal-Fired
Power Plant and Adjacent Cooling Lake. Environ. Sci. Technol.,
11(1):75-80, 1977.
22. Klein, D. H., and P. Russell. Heavy Metals: Fallout Around a Power
Plant. Environ. Sci. Technol., 7(4):357-358, 1973.
2-26
-------
23. Roffman, H. K., R. £. Kary, and T. Hudgins. Ecological Distribution
of Trace Elements Emitted by Coal-Burning Power Generating Units
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from the Symposium on Coal Mine Drainage Research, 1977. National
Coal Association, Washington, D.C., 1977. pp.192-215.
24. Glass, G. E. Ecological Effects of Coal-Fired Steam-Electric Gene-
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Washington, D.C., 1978.
25. Struempler, A. W. Trace Element Composition in Atmospheric Particu-
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26. Palomba, J. Jr., and R. F. Wromble. An Appraisal of Air Pollution in
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27. Wagenet, R. J., W. J. Grenney, and J. J. Jurniak. Erosion Model for
Arid Wildland Watersheds. Paper 77-2510. Presented at the ASAE
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28. Heit, M. Review of Current Information on Some Ecological and Health
Related Aspects of the Release of Trace Metals into the Environment
Associated with the Combustion of Coal. HASL-320, U.S. Energy Re-
search and Development Administration, New York, 1977. 53pp.
29. Tullar, I. V. , and I. H. Suffet. The Fate of Vanadium in an Urban Air
Shed: The Lower Delaware River Valley. APCA J, 25(3):282-286, 1975.
30. Moore, W. W. Reduction in Ambient Air Concentrations of Fly Ash-
Present and Future Prospects. In: Proceedings of the 3rd National
Conference on Air Pollution, Public Health Service, 1966.
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31. King, R. B., J. S. Fordyce, A. C. Antoine, H. F. Leibecki, H. E.
Neustadter, and S. M. Sidik. Elemental Composition of Airborne Par-
ticulates and Source Identification: An Extensive One Year Survey.
APCA J., 26(11):1073, 1976.
32. Eisenbud, M-, and T. J. Kneip. Trace Metals in Urban Aerosols.
EPRI-117-FR, PB-248 324, New York University, New York, 1975. 440pp.
33. Morgan, J. J., W. Bach, E. Eriksson, H. Flohn, K. Fraedrich, E. D.
Goldberg, R. E. Hamilton, G. Haury, W. Jacobi, et al. Source Func-
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and Heat. Group Report. Presented at the Workshop on Global Chem-
ical Cycles and Their Alterations on Man, Dahlem, Germany.
2-27
-------
34
35
36
37
38
39
AO
41
42
43
44
45
Hilst, G. R. Detection of Large-Scale Effects of Air Pollution.
Paper 26d. Presented at the 64th Annual American Institute of Chem-
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Davison, R. L., D. F. S. Natusch, J. R. Wallace, and C. A. Evans, Jr.
Trace Elements in Fly Ash. Dependence of Concentration on Particle
Size. Environ. Sci. Technol., 8(13):1107-13, 1974.
New Mexico, Health and Environment Department. Implementation Plan
for the Attainment and Maintenance of National Ambient Air Quality
Standards. Santa Fe, New Mexico, 1979.
U.S. Environmental Protection Agency. Proposed National Emission
Standards for Hazardous Air Pollutants: Asbestos, Beryllium,
Mercury. Research Triangle Park, North Carolina, 1971.
U.S. Environmental Protection Agency. National Primary and Secondary
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43(194):46246-46277, 1978.
Coltharp, W. M., N. P. Meserole, B. F. Jones, K. Schwitzgebel, R. S.
Merrill, G. L. Sellman, C. M. Thompson, and D. A. Malish. Review and
Assessment of the Existing Data Base Regarding Flue Gas Cleaning
Wastes. Radian Corp., Austin, Texas,
Pezzetta, J. M., and I. K. Iskandar. Sediment Characteristics in the
Vicinity of the Pulliam Power Plant, Green Bay, Wisconsin. Env.
Geology, 1(3):155, 1975-1976.
Strojan, C. L., and F. B. Turner. Trace Elements and Sulfur in Soils
and Plants Near the Mohave Generating Station in Southern Nevada.
Presented at the 4th Joint Conference on Sensing of Environmental
Pollution, New Orleans, Louisiana, 1977.
U.S. Environmental Protection Agency. State Air Pollution Implemen-
tation Plan Progress Report, Janaury 1 to June 30, 1975. Washington,
D.C., 1975.
Lee, R. E. Jr., H. L. Crist, A. E. Riley, and K. E. MacLeod. Concen-
tration and Size of Trace Metal Emissions from a Power Plant, a Steel
Plant, and a Cotton Gin. Environ. Sci. Technol., 9(7):643-647, 1975.
Hammerle, R. H., and W. R. Pierson. Sources and Elemental Composition
of Aerosols in Pasadena, California, by Energy Dispersive X-Ray
Fluorescence. Environ. Sci. Technol., 9(12):1058-1068, 1975.
Lee, R. E. Jr., and D. J. von Lehmden. Trace Metal Pollution in the
Environment. APCA J., 23(10):853-857, 1973.
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46. Gordon, G. E., and W. H. Zoller. Normalization and Interpretation of
Atmospheric Trace Element Concentration Patterns. CONF-730802. In:
Proceedings of the 1st Annual NSF Trace Contaminant Conference, 1973.
National Technical Information Service, Springfield, Virginia, 1974.
pp.314-325.
47. Martens, C. S., J. J. Wesolowski, R. Kaifer, W. John, and R. C.
Harriss. Sources of Vanadium in Puerto Rican and San Francisco Bay
Area Aerosols. Environ. Sci. Technol., 7(9):817-820, 1973.
48. Edwards, H. A., C. Hill, and W. 0. Ursenbach. Application of Scanning
Electron Microscopy to Identification and Estimation of Natural and
Man-Made Dusts in Arid Regions. Chemosphere, 1(3):107-112, 1972.
49. Winchester, J. W. Natural and Pollution. Sources of Trace Elements in
Atmospheric Particulates. AIChE Symp. Ser. 71(149):16-18, (1975).
50. Phillips, M. A. Investigations into levels of Both Airborne Beryllium
and Beryllium in Coal at the Hayden Power Plant near Hayden,
Colorado. Environ. Lett., 5(3):183-188, 1973.
51. Ross, W. D., J. L. Pyle, and R. E. Sievers. Analysis for Beryllium in
Ambient Air Particulates by Gas Chromatography. Environ. Sci.
Technol., 11(5):467, 1977.
52. Ethyl Corp., eds. A Consideration of the Public Health Aspects of
Manganese in the Environment. New Orleans, Louisiana, 1971. 3pp.
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Organometallic Compounds. Vol. 2, International Agency for Research
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54. Moore, H. E., E. A. Martell, and S. E. Poet. Sources of Polonium-210
in Atmosphere. Environ. Sci. Technol., 10(6):586—591, 1976.
55. Davis, W. E. National Inventory of Sources and Emissions. Barium,
Boron, Copper, Selenium, and Zinc 1969. Boron, Section II.
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1972. 51pp.
56. Davis, W. E. National Inventory of Sources and Emissions. Barium,
Boron, Copper, Selenium, and Zinc 1969. Copper, Section III.
APTD-1129, PB-210 678, Davis (W.E.) and Associates, Leawood, Kansas,
1972. 74pp.
2-29
-------
57. Lagerwerff, J. V., D. L. Bower, and G. T. Biersdorf. Accumulation of
Cadmium, Copper, Lead and Zinc in Soil and Vegetation in the Prox-
imity of a Smelter. In: 6th Annual Conference on Trace Substances
and Environmental Health Proceedings, University of Missouri, 1972.
pp.71-78.
58. Andren, A. W. , D. H. Klein, and Y. Talmi. Selenium in Coal Fired
Steam Plant Emissions. Environ. Sci. Technol., 9(9):856-858, 1975.
59. McKnight, J. S. Effects of Transient Operating Conditions on Steam-
Electric Generator Emissions. EPA 600/2-75-022, PB'247-701, Research
Triangle Institute, Research Triangle Park, North Carolina, 1975.
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Burdens Due to Projected Coal Utilization in the Illinois River
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the Environment, American Institute of Chemical Engineers,
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61. Greifer, B., and J. K. Taylor. Pollutant Analysis Cost Survey.
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Pollutant Emissions. MRC-DA-692, PB-270 550, Monsanto Research
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the Range Resource in the Vicinity of Colstrip, Montana: Progress
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66. Lyon, W. S. Trace Element Measurements at a Coal-Fired Steam Plant.
CRC Press, Cleveland, Ohio, 1977.
67. Hall, E. H., C. M. Allen, D. A. Ball, J. E. Burch, H. N. Conkle, W.
T. Lawhon, T. J. Thomas, and G. R. Smithson, Jr. Comparison of Fossil
and Wood Fuels, Final Report. EPA 600/2-76-056, PB 251 622,
Battelle-Columbus Laboratory, Columbus, Ohio, 1976.
2-30
-------
SECTION 3
TRACE METALS IN FUELS
The most influential factor in trace metal emissions from SCCP's is,
of course, the fuel. "What goes in must come out," is a self-evident
statement. Various design alternatives can do no more than shift the burden
of trace metal emissions from one stream to another. Such tradeoffs are
frequently desirable and usually the object of control technology design.
How various designs influence the ultimate fate of trace metals is treated
in Sections 4 and 5. In this section, the concentrations of trace metals in
different source fuels will be reviewed, and the influence of the fuel charac-
teristics on the destiny of trace metals will be discussed.
3.1 COAL
The most extensively analyzed and reported fuel source is coal.
Most trace metal analyses of coals are carried out for one of four
reasons: (1) to determine the trace metal concentrations and add to the
building nationwide database; frequently this will cover a wide variety of
coals; (2) as part of a study of one particular power plant to determine the
fate of trace metals during the combustion and clean-up processes; this ana-
lysis will usually be only for the single coal used during the testing;
(3) to determine the concentration, partitioning and behavior of one or two
specific elements in the combustion process; while a variety of coals may
be analyzed, only the element(s) of interest is considered; and (4) to deter-
mine the accuracy of a certain analytical procedure; the emphasis here is on
comparing analytical techniques and the trace metal concentrations are
usually given incidentally for a few different, often non-identified coals.
The first class of analyses is the most useful for providing an understanding
of the fuel source problems and alternatives; however, the method of reporting
is not consistent. Frequently the reports are given in terms of major, minor
3-1
-------
and trace element concentrations (see Section 1, Introduction, for defini-
tion of these terms). Less extensive efforts result in only proximate or
ultimate analysis. Many authors report the Btu value as part of the analysis,
but the seldom reported trace element per Btu ultimately may be the most
useful format (1). The most common unit remains percent by weight, usually
in ppm for trace elements.
3.1.1 Whole Coals by Region
Since coals found in a local region are frequently similar, many data
bases break up United States coal fields into geographical classes; for
example, Eastern, Mid-continent, and Western. In general, Eastern coals
are high sulfur, high Btu and low ash (anthracite and bituminous) whereas
Western coals are often low sulfur, low Btu and high ash (subbituminous
and lignite). Mid-continent coals are usually intermediate in these quali-
ties. Anthracite coals are generally defined by percent of fixed carbon
(about 86% or greater); some bituminous coals are also judged by their
fixed carbon (between 69% or 86%), while others are judged by their caloric
content (about 11,500 Btu/lb or greater). Subbituminous (8,300-11,500
Btu/lb) and lignite (less than 8,300 Btu/lb) are usually defined strictly
by their caloric content. Most often, moisture and Btu values are reported
on an "as received" basis. All other properties are referred to as a "dr>"
basis.
Tables 3-1, 3-2 and 3-3 list the trace element concentrations found
in whole coal (contrasted with coal ash) for Eastern, Mid-Continent (Illinois
Basin) and Western coals; they are representative of other data compilations
for whole U.S. coals (2); also see references (3-7).
Although they are lowest in ash (the bulk of which is aluminosilicates),
Eastern coals are generally highest in trace metal concentrations. Mid-
continent coals are intermediate and Western coals are lowest in trace
metals despite their higher overall ash content. In general, however,
the variations are not large (less than X3). Exceptions include: (1)
Western coals are highest in Ba, P, Sr, Ca, Na and (2) Illinois Basin coals
(typical of Mid-Continent coals are highest in B, Be, Br, Cd, Ge, Mn, Ni, Pb,
3-2
-------
tABLS 3-1. KEAJt A*ALTTICAL ?ALDK5 POI 23 UK)U COAL SAMPLES FUH TSX I4STEBK
UNITS) STATES
(Appalachian Coal Fields)
Eloaenc Arithmetic Geonetrlc MIelIbibb NixlaiB Standard Wimber
Heaa Haas Deviation Saaples
Ag
0,02
PP®
0.02
PP®
0.01
0.06
0.01
13
A£
25
p pm
15
PP®
0.8
100
27
23
B
62
PP®
28
ppa
5.0
120
32
23
Ba
200
ppa
170
PP"
72
420
110
14
fie
1.3
ppm
1.1
PP®
0.23
2.6
0.56
23
Br
12
PP®
8.9
PP*
0.71
26
7.6
23
Cd
0.24
PT»
0.19
ppn
0.10
0.60
0.18
23
Ca
25
ppa
23
PP"
11
42
9.1
14
Co
9.8
ppa
7.6
ppm
1.5
33
7.8
23
Cr
20
PP®
18
ppn
10
90
16
23
Ca
2.0
ppa
1.6
PP"
0.40
6.2
1.6
14
Cu
18
PP®
16
PPm
5.1
30
7.3
23
Dy
2.3
PP®
2.0
ppn
0.74
3.5
0.94
14
Eu
0.52
ppn
0.47
PP®
0.16
0.92
0.22
14
F
89
PP®
84
PP®
50
150
31
23
Ca
5.7
PP®
5.2
PP®
2.9
11
2.6
23
Ce
1.6
ppn
0.87
PP®
0.10
6.0
1.7
23
Hf
1.2
PP®
1.1
ppn
0.5B
2.2
0.45
14
Hg
0.20
PP®
0.17
PP"
0.05
0.47
0.12
23
I
1.7
PP®
1.4
PP®
0.33
4.9
1.1
14
Id
0.23
PP®
0.22
PP®
0.13
0.37
O.OB
14
La
15
PP®
14
ppm
6.1
23
5.3
14
Lu
0.22
PP®
0. IB
PP"
0.04
0.40
0.12
14
to
ie
PP™
12
PP®
2.4
61
16
23
HC
4.6
PP®
l.B
PP®
0.10
22
6.3
23
Ni
15
p?n
14
PP®
6.3
2B
5.7
23
P
15C
PP®
81
PP®
15
1500
300
23
Pb
5.9
PP®
4.7
ppn
1.0
18
4.0
23
Rt>
22
ppa
19
ppn
9.0
63
15
14
Sb
1.6
PP«
1.1
PP"
0.25
7.7
1.7
23
Sc
5.1
PP®
4.5
PPn
1.6
9.3
2.4
14
Se
4.0
ppa
3.4
PP"
1.1
8.1
2.0
23
SB
2.6
PP®
2.4
PP®
0.87
4.3
1.0
14
So
2.0
PP®
0.97
PP®
0.20
8.0
2.4
19
Sr
I3C
PP®
100
PP®
28
550
130
14
Ta
0.33
PP®
0.26
ppn
0.12
1.1
0.28
14
TO
0.*4
PP®
0.28
PP"
0.06
0.63
0.17
14
Ti
4.5
PP®
4.0
PP®
1.8
9.0
2.1
14
V
1.5
ppc
1.3
PP®
0.40
2.9
0.73
14
V
36
ppn
35
PP®
14
73
14
23
y
0.69
PP®
0.62
PP"
0.22
1.2
0.31
14
rt
0.83
PP®
0.73
PP®
0.18
1.4
0.35
14
Zn
25
PP®
19
PP®
2.0
120
24
23
Zi
45
PP®
41
ppn
8.0
88
IB
19
A1
1.7
Z
1.6
z
1.1
3.1
0.56
23
Ca
0.47
I
0.34
z
0.09
2.6
0.51
23
CI
0.17
z
0.10
z
0.01
0.80
0.21
23
re
1.5
X
1.3
z
0.50
2.6
0.69
23
K
0.25
z
0.21
w
0.06
0.68
0.14
23
Mg
0.06
z
0.05
•
4
0.02
0.15
0.03
23
Ka
0.04
I
0.03
z
0.01
0.08
0.02
23
ii
2 . B
2.6
z
1.0
6.3
1.1
23
Ti
0.09
X
0.09
I
0.05
C.16
0.04
23
Adl
1.2
I
0.99
z
0.50
4.0
0.89
14
Mela
2.7
I
2.4
z
1.0
6.8
1.5
23
Vol
*33
X
32
z
17
42
8.0
23
Fi*C
55
I
54
z
45
72
7.2
23
Aah
12
Z
12
z
6.1
25
4.3
23
Btu/lb
13111
13093
11374
13816
696
14
C
72
z
72
z
63
80
5.3
22
U
4.9
z
4.9
z
4 .0
6.0
0.44
22
N
1.3
z
1.3
z
0.94
1.8
0.27
22
0
8.0
t
7.0
z
2.5
IB
4.3
22
Hca
12
2
12
z
6.2
25
4.3
23
Lea
15
z
15
z
7.6
26
4.9
23
OrS
0.92
z
0.82
z
0. 35
2.5
0.48
23
PyS
1.3
z
0.81
w
0.04
2.6
0.91
23
SuS
0.10
*
0.06
z
0.01
0.42
0.10
22
ToS
2. 3
*
1.9
9
0.55
5.0
1.3
23
Srrf
2.1
z
1.8
z
0.74
4.8
1.1
23
SOURCE: (2) Sec Table 3-4 for explanation of abbreviation*.
3-3
-------
tabu 3-2. heas aialttical values k>i ii* kls-qjujiak*i umli <*m
CAMPLES
(Fr-oa the_U llnol. B..ln Ccjl Fleld^
Elcaent
irltlMdc
CioMtrlc
Minima
Nulaa
Standard
¦ob«i
Ma ad
Ha an
Deviation
Swin
Ai
0.03
PPB
0.03
ppm
0.02
0.08
0.02
37
As
It
ppa
7.4
ppm
1.0
120
20
113
B
110
ppm
98
ppm
12
230
50
99
Ba
100
PP®
75
ppm
5.0
750
110
56
Be
1.7
PP"
1.6
ppm
0.5
4.0
0.82
113
Br
13
ppa
10
ppB
0.6
52
7.4
113
Cd
2.2
PP"
0.S9
ppm
0.1
65
7.4
93
Ce
14
ppa
12
ppm
4.4
46
7.5
56
Co
7.3
PPO
6.0
ppm
2.0
34
5. 3
113
Cr
18
Ppm
16
ppm
4.0
60
9.7
113
Ca
1.4
ppa
1.2
ppm
0.5
3.6
0.73
56
Cu
14
PP»
13
ppm
5.0
44
6,6
113
Dy
1.1
PP«
1.0
ppm
0.5
3.3
0.42
56
Eu
0.26
?pm
0.25
ppm
0.1
0. B7
0.12
56
T
67
ppm
63
p pm
29
140
26
113
Ga
3.2
ppm
3.0
Ppm
0.8
10
1.2
113
Q%
6.9
ppc
4.8
p pm
1.0
43
6.4
113
Hf
0.54
ppm
0.49
p pm
0.13
1.5
0.25
56
Hg
0.2
ppm
0.16
ppm
0.03
1.6
0.19
113
I
1.7
ppa
1.2
ppm
0.24
14
2.0
56
IQ
Q. 16
ppm
0.13
ppm
0.01
0.63
0.11
56
La
6.8
ppm
6.4
ppm
2.7
20
2.8
56
Lu
0,09
Ppn.
0.08
Ppm
0.02
0.44
0.06
56
Kd
S3
ppm
40
p pm
6.0
210
41
113
Hs
8.1
PpB
6.2
ppm
0.3
29
5.4
111
KL
21
ppa
19
ppm
7.6
68
10
113
P
64
ppm
45
ppm
10
340
60
113
Pb
32
PpD
15
ppm
o.e
220
42
1L3
Rb
19
ppjB
17
ppm
2.0
46
9.9
56
Sb
1.3
ppm
0.81
ppm
0.1
8.9
1.4
113
Sc
2.7
pptfi
2.5
ppm
1.2
7.7
1.1
56
Se
2.2
ppD
2.0
ppm
0.4
7.7
1.0
113
So
1.2
ppm
1.1
ppa
0.4
3.8
0.55
56
Sa
3.8
ppa
0.94
ppm
0.2
51
B.B
60
Sr
35
ppm
30
ppm
10
130
23
56
Ta
0. 15
ppm
0.14
ppm
0.07
0.3
0.06
56
Tb
0.22
ppm
0.1B
ppm
0.04
0.65
0.14
41
Th
2.1
ppm
1.9
ppm
0.71
5.1
0.87
56
T1
0.66
?pm
0.59
ppa
0.12
1.3
0.31
25
U
1.5
ppm
1.3
ppm
0.31
4.6
0.93
56
V
32
ppm
29
ppm
11
90
13
113
u
0.82
ppm
0.63
ppn
0.04
4.2
0.69
56
Yb
0.56
ppm
0.53
ppn
0.27
1.5
0.21
56
Zn
250
?Ptt
87
ppn
10
5300
650
113
Zr
47
ppm
41
ppn
12
130
27
88
Ai
1.2
1.2
0.43
3.0
0.39
113
Ca
0.67
0.51
0.01
2.7
0.46
113
CI
0.14
0.08
0.01
0.54
0.13
113
Fe
2.0
1.9
0.45
4.1
0.63
113
R
0.17
0.16
0.04
0.56
0.07
113
me
0.05
0.05
0-01
0.17
0.02
113
h'a
0.05
0.03
0.2
0.04
113
51
2.4
2.3
0.58
4.7
0.7
113
Tl
0.36
0.06
0.02
0.15
0.02
113
Adl
7.3
6.4
1.4
17
3.4
9B
Hoi s
9.4
. 8.1
0.5
18
4.3
112
Vol
40
40
27
46
3.1
111
TtxC
49
49
41
61
3.6
111
Ash
11
11
4.6
20
2.3
112
Btu/lb
127L2
12702
11562
14362
470
107
C
70
70
62
80
3.0
110
H
5.0
5.0
4.2
6.0
0.31
110
K
1.3
1.3
0.93
1.8
0.19
110
0
6.2
8.0
4.2
14
1.8
109
Hca
11
11
3.3
20
2.5
112
Lta
15
15
3.8
24
3.3
112
OrS
1.6
1.4
0.37
3.2
0.6
112
Pys
2.0
1.8
0.29
4.6
0.7B
111
SuS
0.1
0.05
0.01
1.1
0.16
109
To 6
3.6
m
3-4
I
0.56
6.4
1.1
113
Sxrf
3.i
*
3.2
X
0.79
6.5
1.1
112
SOIT.CE : (2) See Table j-4 for crpl«n*tlcro of abbreviation®.
3-4
-------
TAJ LI 3-3. tOAh ANALYTICAL VALUES FOE 26 WLI COAL SAMPLES FVOH TEE
WESTEBH UNITED STATES
Elcmeot Arithmetic Geonaerlc mIaIbub Maxims Standard N\»b«r
Meao Hcbd Deviation Suxplea
A*
0.03 ppm
0.02 ppm
0.01
0.07
0.02
22
AJ
2.3 ppo
1.5 ppm
0.34
9.8
2.6
29
3
56 ppm
4 8 ppm
16
140
32
27
S«
300 ppm
430 ppm
160
1600
320
22
Bl
0.46 ppm
0.35 ppm
0.10
1.4
0.34
29
Br
4.7 ppo
2.1 ppm
0.50
25
7.3
29
Cd
0.18 ppm
0.15 ppn
• 0.10
0.60
0.13
29
Ce
11 ppn
9.1 ppm
2.8
30
8.0
22
Co
1. B ppo
1.5 ppn
0.60
7.0
1.5
29
Cr
9.0 ppa
8.1 ppm
2.4
20
4.2
29
Cs
0.42 ppm
0.16 ppm
0.02
3.8
0.B2
22
Cu
10 ppa
8.5 ppn
3.1
23
S .9
29
oy
0.63 ppm
0.57 ppm
0.22
1.4
0.32
22
Eu
0.20 ppn
0.16 ppa
0.07
0.60
0.17
22
F
62 ppm
57 ppn
19
140
28
29
Ca
2.5 pps
2.1 ppa
0.B0
6.5
1.4
29
G«
0.91 ppm
0.50 ppn
0.10
3.0
0.92
29
Rf
0.78 ppa
0.70 ppm
0.26
1.3
0.33
22
Hg
0.09 ppn
0.07 ppm
0.02
0.63
O.U
29
I
0.52 ppm
0.46 ppm
0.20
1.0
0.25
22
In
0.10 ppm
0.07 ppa
0.01
0.25
0.07
22
La
5.2 pps
4.5 ppm
1.8
13
3.0
22
Lu
0.07 ppa
0.05 ppn
0.01
0.43
0.09
22
Hn
49 ppm
26 ppm
1.4
220
49
29
Mr
2. i ppn
0.59 ppm
0.10
30
5.6
29
Ni
5.0 ppm
4.4 ppm
1.5
18
3.2
29
P
130 ppm
62 ppa
10
3 10
130
29
Pb
3.4 ppm
2.6 ppn
0.70
9.0
2.3
29
Rb
4.6 ppc
2.4 ppm
0.30
29
6.6
22
Sb
0.5B ppa
0.45 ppm
0.13
3.5
0.61
29
Sc
1.8 ppc
1.5 ppm
0.50
4 .5
1.1
22
S€
1.4 ppc
1.3 ppm
0.40
2.7
0.59
29
Sa
0.6L ppa
0.56 ppm
0.22
1.4
0.29
21
So
1.9 ppm
0.4 3 ppm
0.10
15
3.8
26
Sr
260 pps
220 ppm
93
500
140
22
Ta
0.15 ppc
0.12 ppm
0.04
0.33
0.08
22
Tb
0.21 ppm
0.17 ppm
0.06
0.5B
0. 15
18
Th
2.3 ppc
1.8 ppm
0.62
5.7
1.5
22
I*
1.2 ppm
0.99 ppc
0.30
2.5
0.65
22
V
14 ppm
12 ppm
4.8
43
10
29
w
0.75 ppm
0.58 ppn
0. 13
3.3
0.65
22'
Yb
0.38 ppm
0.34 ppc
0.13
0.7B
0.17
22
Zn
7.0 ppm
5.0 ppm
0.30
17
4.9
29
Zr
33 ppm
26 ppm
12
170
31
26
Ai
1.0 Z
0.88 X
0.31
2.2
0.56
29
Ca
1.7 S
1.5 I
0.44
3.8
0.93
29
CI
0.03 X
0.02 X
0.01
0.13
0.03
29
F«
0.53 z
0.49 x
0.30
1.2
0.24
29
K
o.o5 z
0.03 X
0.01
0.32
0.06
29
*8
o.K :
0.12 Z
0.03
0.39
0.09
29
Na
o.i4 :
0.06 X
0.01
0.60
0.16
29
Si
1.7 I
1.3 X
0.38
4.7
1.2
29
Ti
o.oj :
0.05 I
0.02
0. 13
0.02
29
Adl
14 I
12 Z
4.5
31
7.3
21
Hols
is ;
16 Z
4. 1
37
8.9
29
Vol
44 :
44 z
33
53
3.8
29
rixc
46 x
46 Z
35
55
5.3
29
Ash
9.6 X
8.9 Z
4.1
20
3.7
29
Btu/Ifc
11409
11377
10084
12901
872
22
C
67 X
87 X
58
74
4.2
29
H
4.7 I
4.6 Z
3. 8
5.8
0.48
29
N
1.0 I
0.98 Z
0.59
1.5
0.22
29
0
17 J
17 X
8.8
22
3.2
29
Rta
9.6 X
8.9 Z
4.1
20
3.7
29
Lta
12 I
11 X
4.7
26
5.1
29
OrS
0.53 x
0.50 X
0.25
1.1
0.19
29
PyS
o.i9 x
0.10 Z
0.01
1.2
0.24
29
SuS
0.04 I
0.03 Z
0.01
0.22
0.04
27
loS
0.76 I
0.70 Z
0.34
1.9
0.33
29
Sxrf
0.73 Z
o.70 :
0.40
1.2
0.20
29
501T.CI: (*) See table 3-4 for explanation of abbreviations
3-5
-------
TABLE 3-4. EXPLANATION OF ABBREVIATIONS USED IN
TABLES 3-1, 3-2, AND 3-3
Adl Air-dry loss
FixC Fixed Carbon
Hta High Temperature Ash
Lta Low Temperature Ash
Mois Moisture, as received
OrS Organic sulfur
PyS Pyritic sulfur
SuS Sulfate sulfur
Sxrf Sulfur by X-Ray Fluorescence
ToS Total sulfur
Vol Volatile matter
3-6
-------
Zn, Fe, and S. Finally, only four elements In coals significantly exceed
the average crustal abundance: boron, chlorine, selenium and arsenic.
3.1.2 Elemental Composition in Ashed Coal
More frequently, especially In the past, analyses have been done on
"ashed" coal rather than on whole coal. In this procedure the coal is
burned in an oven, and the resulting ash is digested In acid and analyzed.
This procedure, high-temperature ashing at about 750*C, assumes that metal
oxides compose the ash, but the method is not able to analyze for the volatile
elements: Hg, Se, Be, F, As and sometimes Fb. Recently, several methods
have been developed to overcome this difficulty. Low-temperature ashing
(150°C), using ozone or oxygen radicals to "burn" the coal, has been one
approach. Another approach has been to trap and analyze the off-gases from
high-temperature ashing. Neutron analysis methods require no sample pre-
paration and can accurately measure the concentration of the volatile ele-
ments in the whole coal. Ruch £t^ al.- (5-7) have evaluated the accuracy of
elemental determinations for volatile elements, reporting trace elemental
concentrations for a large number of whole coals and their ashes. Also
see Lee et_ al_. (8), Pollock (9) and Cowherd et_ al^ (10) for similar
studies. Hence, concentrations for these volatile elements, especially in
older analytical data, reflect a degree of uncertainty. Ashing remains as
the most common method of analysis for trace metals in coals, and much of the
elemental data for coal are presented as ash concentrations.
Although certain regions are higher in trace elements, an overview
shows that most U.S. coals contain similar amounts of total trace elements
in a coal ash (about 0.65% in ash), however, large variations may occur
for each element. Following Ctvrtnicek £t^ al^. (11), Table 3-5 shows that
barium, strontium and zirconium levels are higher in Western ashes; boron,
germanium, lead and zinc are highest in Mid-continent ashes; and Eastern
ash is noticeably higher in copper and lithium. Cadmium, mercury and sele-
nium are not usually included because of their volatility; approximate
values based on Western coal are (in ppm): Cd, 0.1-0.8; Hg, 0.1-0.2;
3-7
-------
ruL! M. attiagk ma CLKmrr umiimi
auas, i] vtiofT rouTDrr*
l^prei* lut rrcvloc* lofrioi Frovlac# Wttfm Sf ui
ImU rw- lv«ri|« rw- Aviri|t Pit* Awrqt
)Mr tuntf trie* fvncy iriei futacy tttet
CrvatAl Halt of of «l«Mat of «UaMt of olrant
ituc- iiuc- coomt iitte* ratnt ittie- ccemt
u rfttacted, «ic«pt thai mrtifl in
pircrt'irtti ««rt calculated for ill of the mt*(! uilni uro for 9l«i*et cootvat* b< 1^
Jlcit of datftciioB.
SOURCE: (|i)
3-8
-------
Se, 0.5-5.0. They also reported that do correlation could be found (for
Western coals) relating the percent of ash in coal to the individual or
total trace metal content.
Altschuler (12) has recently (1978) reported on the distribution and
nature of about four trillion tons of coal. Vhile his main interest was
sulfur, he does comment on the trace metals content. He notes that cer-
tain elements In coal are enriched over crustal abundances, and those
elements are commonly associated with organic fixation or sulfides. Of
the ten elements most enriched in coals, nine of them are potentially hazar-
dous to humans or the environment: Sb, As, Be, Cd, Pb, Mo, Se, S, and U.
Ray and Parker (15) give tables of coal ash analyses for various U.S.
coals broken dovn by type; i.e., anthracite, volatile bituminous, etc.
Weverks e_t a^. (16) also gives tables of both whole coals and coal ash '
broken into coal types (or rank). Table 3-6 gives ranges of elements found
In U.S. coals and coal ashes. Table 3-7 is another author's compilation
of similar data for comparison (17); this table in addition gives the average
values of trace elements and the percent of each element found in the re-
sulting fly ash.
There are numerous publications giving analytical trace element data
for specific coal fields, coal seams or regional and area coals; many are
included in the bibliography accompanying this report. Recently, an ex-
tensive compilation of U.S. coal data has been gathered together and stored
in a computerized database at Pennsylvania State University. This database
Includes all types of data available for coal: whole coal, low temperature
ash, ultimate and proximate analysis, etc. It is organized by county, and
the data are specific to each seam. The Information is readily available
for a nominal fee associated with the service (18).
Many other articles exist that have reviewed or summarized data on trace
element in coal. Work done before 1970 is likely to be Imprecise or inac-
curate owing to the poorer technology of the times and the (then) lack of a
coal standard. Some frequently cited and useful papers on elemental analy-
sis not referred to elsewhere include: (19-24).
3-9
-------
TABLE 3-6. IABGE OF TRACE ELIMENTS IK D.6. COALS MS ASHES
Eleaent VboX* Coal Coal Aah
(Major) (X) (t)
Xi
0-0.20
0.71-2.72
*«
0.1-0.25
0 -2.4
A1
0.43-3.04
S.3-21.2
SI
0.58-6.09
9.3-28
a
0-0.56
-
i
0.02-0.43
0.66-1.32
Cm.
0.05-2.67
0.58-14
T1
0.002-0.32
0.1-2.6
re
0.32-4.32
2.09-24.4
2c
0-0.56
0-1.6
Sr
-
0.009-0.96
Ba
-
0.01-1.39
Hlnori
(ppo)
(ppa)
LI
<20-3100
B«
0-31
0-1100
B
1.2-356
30-6500
F
10-295
-
P
5-1430
<440-3360
Sc
10-100
2-155
V
0-1281
6-3800
Cr
0-610
<1-1800
Mn
6-181
30-1800
Co
0-43
0-600
HI
0.4-104
0-1200
Cu
1.8-185
10-*0l0
Ca
0-61
0-540
Ce
0-819
0-1500
As
0.5-106
21-570
Sc
0.4-8
-
Br
4-52
-
B>
-
<91-1100
7
<0.1-59
0-620
Zr
8-133
100-1650
Ho
0-73
0-2900
*8
-
<1-64
Cd
0.1-65
-
Sn
0-51
0-4250
Sb
0.2-9
<40-230
La
0-98
0-820
Tb
-
<2-23
V
-
<10-182
Hg
0.01-1.6
<70-259
Tb
4-218
10-1420
B1
-
1-900
0
<10-1000
-
SOURCE; (16)
3-10
-------
TABU 3-7. TRACE METALS II COAL AND FLY ASH
Average
Conceo.
Concen.
Z Remaining
Concen.
Range
Remaining In
Is Fly Aah
In Coal
In Coal
Flj Ash
after Combustion
Eleaeat
(ppa)
(ppn)
(ppn)
¦t 500*C
At
—
0.1-2
0.4-3
790
As
5
0.5-93
2.8-200
35-50
B
55
5-224
-
795
Ba
64
2-500
110-700
-
Be
2
0.2-4
1-7
82
M
-
0.1-65
2-100
38
Co
12
1-43
25-70
790
Cr
20
4-54
80-500
795
Cu
12
5-61
33-300
795
F
-
25-220
10-100
-
Tc
-
1800-8000
-
790
Ce
8
1-43
-
795
Bg
2
0.2-5
0.1-18
0-10
In
0. IB
-
0.2
-
Hn
30
6-181
150-500
795
Ho
6
1-30
34
67
Ni
20
3-80
45-300
76
Fb
9
4-218
95-440
37
Ra
-
-
-
-
Rb
25
-
180
790
Sb
-
0.2-8.9
5.6-100
50
Sc
8
-
29.5
790
Se
3
0.45-7.7
0.77-40
24
So
2
1-51
1.9-100
795
Sr
85
46-160
69-1000
-
Te
0.5
-
-
36
Th
3.47
-
17.1
790
T1
0.125
<0.2-0.7
5-76 •
-
0
-
10-160
-
-
V
33
11-78
180-2000
70
V
0.93
-
2.7
790
Zo
329
6-5350
70-1000
795
SOURCE: (17)
3-11
-------
3.1.3 Elemental Forms in Coal
The widespread geographical trends of trace metals in coals discussed
above are not Intended to give specific details. Local geological factors
more frequently influence the concentrations of trace metals. Hall, Magee,
and Varga (25-27) have reported that certain elements tend to be concentrated
near the edges of a coal seam (Ge, Be, Ga, B); other elements may be enriched
if the seam is close to an ore deposit (Mo, Sn, Pb, Hg, CI being typical ex-
amples) . But their basic conclusion vas that only a few trace metals vary
appreciably depending upon geography, and that elemental concentrations
in coal are near their average crustal abundance (their Clarke values).
That is, most trace elements are between 1-100 ppm in all regions, with some
20 trace metals generally between 5-10 ppm. Boron and fluoride are usually
higher, mercury, commonly lower. Concentrations near crustal abundances are
not considered toxic. Hall et^ al. (25) also reported, as did Altschuler (12),
that those elements that are concentrated in coals and whose concentrations
fluctuate most widely have generally been associated with the organic ph«se
(S, Ge, Be, B, Ga).
Gluskoter (28) has addressed the form of trace metals in coal. He
has used density separations to define the organic (lighter) and inor-
ganic (denser) phases of the coal. The fractions were then analyzed for
comparative amounts of trace metals. He defined four groups: strong
organic affinity (Ge, Be, B); organic association (P, Ga, Sb, Ti, V);
Inorganic association (Co, Ni, Cr, Se, Cu); strong inorganic affinity (Hi;,
Zr, Zn, As, Cd, Pb, Km, Mo). There are exceptions to these classes for
individual coal samples, but other workers are in general agreement.
Gluskoter reports that Horton and Aubrey (29), using a similar technique,
concluded Be, Ge, Va, Ti, and B were largely organically combined in coal,
while P, Mn and Sn were inorganically combined. Zubovic (30) has compiled
a list based on percentage or organic affinity: Ge (87), Be (82), Ga (79),
Ti (78), B (77), V (76), Ni (59), Cr (55), Co (53), Y (53), Mo (40), Cu
(34), Sn (27), La (3), Zn (0). And he concluded that this series was
related to the chelating properties of the metals. The fate of a trace
3-12
-------
metal during combustion is believed to be partially influenced by its degree
of organic association; see SectioD 3.4.
Gluskoter (28) and others have further studied the chemical form of
trace metals in the inorganic phase of coal. They state that the over-
whelming majority of the minerals in coal are in one of four groups:
• Aluminosilicates, or clay minerals, are most abundant
Most common among them are illite [(OH)UK2(Sle*Al2)
A1i«02o] and kaolinite [(OH) eSit,Ali»Oi oj • About 52% of
Illinois Basin inorganic material are alurainosilicates.
• Sulfides and sulfates show a considerable range of
variation. Pyrite is the dominant sulfide mineral
in coal; marcasite is also common. These are different
crystal forms of FeS. Significant amounts of sphalerite
(ZnS) and galena (PbS) are also found in coals. Sul-
fates are not common and are often absent in unweathered
coal. When found, they are most commonly an iron sulfate.
About 25% of Illinois Basin inorganic materials are sulfur
minerals.
• Carbonates vary widely in composition. Frequently re-
ported forms are calcite (CaCOj), siderite (FeCOa),
dolomite (CaCO3*MgCO3) and ankerite (2CaC03'MgCOj*FeC03).
These carbonates make up about 9% of Illinois Basin
inorganic matter.
• Silica, or quartz, is found in all coals. For Illinois
Basin samples, silica represents about 15% of all minerals.
Quartz is the only mineral of those mentioned that is
stable and persists in high-temperature ashing at 750 C.
Gluskoter further reports that Goldschmidt (31) has classified ele-
ments on their affinities to occur in certain mineralogical groups. The
chalcophile elements commonly form sulfides (Zn, Cd, Hg, Cu, Pb, As, Sb,
Se, and others). The lithophlle elements generally occur in the silicate
phases (Si, Al, Ti, K, Na, Zr, Be, Y). Mg, Fe and Mn are usually associated
with the carbonates. The mineral form of the trace metal will have an effect
on its fate during preprocessing and combustion; Bee Sections 3-3 and 3-4.
Miller (32) has looked for correlations of trace metals with mineral
types. He studied 15 Illinois coals, and the elements for which he found
correlation coefficients greater than 0.5 are given in Table 3-8; also see (4).
3-13
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TABLE 3-8. TRACE ELEMENTS, MINERAL CORRELATIONS1
As, Be, Cu, Sb
B, Cd, Zn, Hg
B, Cd, Mn, Se, Mo, V
B, Cr, Mn, Cd, Mo, Se, V, Zn
B, Cu, F, Hg, Sn, V
Pyrite
Sphalerite
Calclte
Quartz
Clays
1Correlation coefficient >0.5
SOURCE: (32)
3.1.4 Incidentally Reported Elemental Studies in Coals
Another body of data on fuel source concentrations is associated with
studies in which trace element pathways through power plants were studied..
This type of research usually involves measuring the total amount of each
element entering the process and the total leaving in each effluent strean.
This necessarily involves a trace metal analysis of the fuel. The data
are specific to the fuel being used at the time of the study. Section 5
reports complete details on a number of these studies.
Lyon (35), in a recent book, has summarized most aspects of a three
year study of the Allen Steam Plant in Memphis, Tennessee. This study, wiich
was funded through Oak Ridge National Laboratory, generated many papers.
Included in this work were several coal and coal ash analyses.
Ray and Parker (15) have reviewed several studies of trace metal parti-
tioning; contained in this review are references to each study. They have
reviewed work done at the following facilities:
• Illinois Power Plant (36),
• Midwestern Power Plant (37),
• Chalk Point Station (38-41),
• Valraont Power Station (42-44),
• Allen Steam Plant (35, 45-53),
• Canadian Steam Plant (54),
• three Northern Great Plains Plant (13, 14, 55-57), and
• Widows Creek Power Plant (10).
3-14
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Other authors reporting source fuel, trace metal concentrations as
part of a larger study include Block and Dams (58), Gasper and Dauzvardia
(59), Cato (60), Fancher (61), Coutant et al. (62), Ondov et al. (63)
and Ragaini and Ondov (64), Rancitelli (65), Wangen and Wienke (66).
In a similar vein, analysis of one or several coals have been reported
in papers whose principal concern was the analytical methodology. Often
the results of several labs are compared, and the NBS standards are fre-
quently included. An explanation of the analytical techniques involved
will be found in Section 8.3. A partial list of these primarily analytical
studies which incidentally reported concentrations of trace metals in coals
is given below, classified by analytical technique:
• Instrumental Neutron Activation Analysis (INAA) - (67-79),
• Atomic Absorption Spectrometry (AA) - (80-81),
• Mass Spectrometry:
Spark source only - (82-86),
With Isotope dilution - (87, 88),
• X-ray Fluorescence - (72, 73, 89-92), and
• Comparisons - (71-73, 81, 82, 93).
Babu (94), in reviewing all the major analytical techniques, reports several
trace element analyses of various coals.
There are several articles that deal specifically with NBS standard trace
metal coal sample. In 1973 von Lehmden e£ al^ (72, 73), had several identi-
cal coal samples analyzed at about 50 different labs around the United States
for trace metal content. The range of results was very broad, being greater
than an order of magnitude for many elements. He thus demonstrated the
need for a standard sample. NBS responded and by 1975, a comparative
analysis of' the NBS standard by four labs using INAA produced very similar
results (71). Other works have continued to measure and confirm the trace
metal concentration in the NBS coal standard (70, 95).
Another type of analysis, forcusing on one or two elements only, has
also resulted in some trace metal information on fuels. This type of paper
or book is frequently long and extensively treats many aspects of a parti-
cular element. Trace metals for which this approach has been used include:
3-15
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mercury (96-100); lead (101-102); uranium and thorium (103); boron (104);
cadmium (105); chromium (106); beryllium (107); lead and cadmium (108,
109); lead, chromium, cadmium, zinc, and mercury (110). Also, Babu (94)
devotes a chapter in his book exclusively to mercury.
3.2 FUELS OTHER THAN COALS
By far, the vast majority of trace metal literature concerns coal,
and with justification. Indeed, coals run from a few to thirty percent
inorganic material, and that material contains roughly the crustal abundance
of trace metals. When the coal is burned, these elements are released and,
if they do not escape the facility, are concentrated in the ash. Oil on
the other hand usually is less than 0.1 percent ash, and the trace metal
environmental impact is generally believed to be less. Natural gas burns
essentially without ash. It is worthy of note that urban refuse, with a
total ash content comparable to coal, is remarkably free of sulfur.
3.2.1 Petroleum
The most abundant metals in oil are vanadium and nickel, but iron,
zinc, chromium, copper, manganese and cobalt and others are almost always
present in concentrations ranging from less than 1 ppb to more than 100
ppm (111). Other metals that have been identified in oils include; U, Zr,
Sr, Sn, Pb, Nd, Mo, La, Ga, Ca, Ce, Ba, B, As, K, Na, Mg, Tl, A1 (112).
Table 3-9 gives typical trace metal concentrations values for several crude
oils analyzed by neutron activation (113). Oil normally does contain some
fine inorganic sediment; however, the trace metals do not seem to be associa-
ted with this phase. If the oil is filtered, the fine black filtrate de-
posits show no unusual levels of any trace metal (111).
The metals are usually associated with the liquid phase and believed
to be chelated or complexed with ligands; however, the heavier oils typi-
cally have higher levels of trace metals that are concentrated in the
asphaltenes. On the molecular level, V and Ni are usually classified either
as metalloporphyrins or non-porphyrin Ni and V. Widely varying ratios of
the two forms have been reported. This may be due in part to some metallo-
porphyrins being strongly associated with the asphalt phase (114).
3-16
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TABLE 3-9. TRACE ELEMENT CONTENTS OF SOME CRUDE OILS
BY NEUTRON ACTIVATION ANALYSIS
CONCENTRATION IN CRUDE OIL (ppm)
California Venezuela Alberta
Element (Tertiary) Libya (Boscan) (Cretaceous)
V
7.5
8.2
1100.
0.682
CI
1.47
1.81
—
25.5
1
—
—
—
1.36
s
9.90
4694.
—
1450.
Na
13.2
13.0
20.3
2.92
K
—
4.93
—
—
Mn
1.20
0.79
0.21
0.048
Cu
0.93
0.19
0.21
—
Ga
0.30
0.01
—
—
As
0. 655
0.077
0.284
0.0024
Br
0.29
1.33
—
0.072
Mo
—
—
7.85
—
Cr
0.640
0.0023
0.430
—
Fe
68.9
4.94
4.77
0.696
Hg
23.1
—
0.027
0.084
Se
0.364
1.10
0.369
0.0094
Sb
0.056
0.055
0.303
—
Ni
98.4
49.1
117.
0.609
Co
13.5
0.032
0.178
0.0027
Zn
9.76
62.9
0.692
0.670
Sc
.0088
.0003
.0044
—
U
——
0.015
—
—
SOURCE: (113)
3-17
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A book by Yen (115) has been published (1975) dealing with trace
metals in petroleum. The reader is referred to that book and the references
therein for a detailed exposition of the subject. The reader is also ad-
vised to see Mezey ££ al_. (116) who treat the contaminants (including
trace metals) in liquid fuels and their removal (117); that report draws
heavily from Yen.
Given et al. (118) have looked at trace metal concentrations in a
coal and compared them to the solids and oils resulting from catalytic
hydrogenation of that coal. Titanium appears to be somewhat enriched in
the oils relative to other elements. Also, Knauer and Milliman (119)
have reported analyzing petroleum products to mercury. Finally, Goldstein
and Siegmund (120) have looked at the influence of fuel oil composition on
particulate mass loading and size distribution. While they do not explicitly
deal with trace metals, many of their results have implications relevant
to the understanding of trace metal behavior in fuels.
3.2.2 Urban Refuse
Urban refuse is growing in use as a fuel source, often combined with
a fossil fuel. It has been estimated that by 1980, energy from refuse
burning will be equivalent to 40,000 barrels of oil per day (121). The
trace element content of urban refuse has been studied by a team at College
Park Metallurgy Research Center at College Park, Maryland (Bureau of Mines;
support), and a series of papers have resulted (122-126). The following
discussion draws largely on data developed by this group.
Urban refuse has a lower Btu content than coal, but it is also low
in sulfur. The proximate analysis of refuse is compared with coal in Table
3-10. It should be noted that when discussing urban refuse as a fuel, oni
generally means processed refuse, or the combustible fraction thereof.
3-18
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TABLE 3-10. PROXIMATE ANALYSIS OF COAL AND COMBUSTIBLE FRACTION OF
URBAN REFUSE
Coal
Refuse
Moisture, %
3.5-7.0
15-30
Ash, %
9-12
5-25
Volatile, %
35-40
30-60
Fixed Carbon, %
50-55
1-15
Btu/lb, as received
10,000-12,600
2,000-5,000
Btu/lb, dry
11,000-13,300
6,000-9,000
Sulfur, %
1-2.5
0.1-0.3
Chlorine, %
<0.1
0.3-1.5
Source: (122)
Chlorine is of interest in refuse because of the higher potential
amounts introduced by plastics and chloride salts; however, the inorganic
forms usually are high melting solids and remain in the bottom ash. While
it is true that trace elements in refuse can vary widely depending upon its
source, the elemental content is remarkably constant from one geographic
region to another. Apparently mass production and distribution of consumer
goods leads to a corresponding uniformity of refuse (125).
Table 3-11 lists minor and trace element concentrations for refuse,
paper, magazines and coal. Prominant differences exist, and the presumed
sources of the differences between coal and refuse include: aluminum
(foil, food wrapping), chlorine (plastics, salts), silicon (sand, glass,
clay), titanium and zinc (pigments). Silver, cadmium, chlorine, copper,
mercury, lead, and zinc are an order of magnitude higher in the combustible
fraction of urban refuse than in coal; titanium is also noticeably higher.
Sulfur, conversely, is an order of magnitude less than in coal. The paper
by Haynes et^ al. (125) gives the greatest exposition of data and analytical
techniques of the series, and the reader is referred there for a more ex-
tensive breakdown and analysis of the data.
3-19
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table >-ii. GONCDmiATiais or elements i* coal, pape* pkhjdcts and the combustible fraction op dubak
REFUSE (TTTICAL VALUES W PAXEKIHISIS)
Major alraaota
(cone. In pet)
Urban
Refuse
Selected
Paper Product*
Meiailnea
Coal
Alialma
0.3-1.6 (1.1)
0.1-3.0 (1.0)
1.0-6.0
©
M
1
H
(.14)
Calcium
.21-1.0 (0.5)
.04-2.7 (0.5)
.04-1.1
.007-. 50
(.03)
Chlorioa
.1-1.5 (0.4)
.05-2.5 (0.1)
-
0-.1 (.01)
Iron
.05-.7 (0.2)
.01-.06 (.03)
.04-.5
.01-1.0
(0.1)
Magneaiufc... •.
.05-.8 (0.1)
.002-.2 (.05)
.005-.3
.01-.4 (.02)
Phosphoroua...
.001-.7 (0.1)
-
-
<•03
Pottfilua
.03-.2 (0.07)
.01-.10 (.03)
r-t
O
1
rl
o
.01-.60
(0.2)
Silicon.......
1.-10 (4)
-
-
.08-4.1
(0.2)
SodlUfi
.15-.9 (0.5)
.01-3.J (0.3)
.01-.1
.01-.35
(0.2)
Sulfur
• 1-.3 (0.2)
<¦3
-
1.-2.5
(1.2)
Tltanlua
.07-1.7 (0.2)
.01-1.7 (1.0)
.>-1.8
.003-.18
(.006)
Zinc
.04-.8 (0.1)
.005-.02 (.008)
.001-.04
.001-.10
(.003)
Minor alefeanta
(cone, in pp»)
X«re earths.,.
-
<600.
-
<50
Act lsny
20-80 (45)
.02-250. (3)
•
1-1,800 (20)
Arsenic
<3
.001-9
-
1-70
(45)
Barlua
35-100 (50)
1-10.200 (1)
1-300
20-1.600 (80)
Beryllluts.....
<2
<4
<2
.4-90
(25)
Blssuch
1-45 (22)
-
<15
.02-3 (0.2)
Botod.
5-70 (15)
.1-20 (1)
-
1-270
(100)
Cadtalus
3-70 (15)
.01-19 (0.3)
0-2
.2-5 (0.5)
Cesiun
<20
<35 (6)
-
.1-9 (0.J)
Chronlun
10-175 (30)
.4-330 (20)
70-260
.3-400
(1)
Cobalt
2-17 (5)
1-4
10-20
.3-135
(25)
Copper
30-450 (195)
.04-100 (12)
4-100
1-180
<7)
C«roar.luB
<6
<15
-
.03-1,000 (45)
Gold
<2
.01-90 (.03)
-
.02-.5
(0.1)
Lead
110-1,300 (230)
.3-250 (10)
20-1,400
1-100
(7)
Llthlua.......
2-10 (3)
2-200 (10)
5-15
1-165
(20)
Manganest
50-480 (85)
.5-500 (25)
1-50
20-240
(25)
Hercury
-
.1-9C (0.3)
-
.07-.6
(.15)
MolyWenua....
10-30 (20)
3-330
-
1-20
(5)
Nickel........
4-50 (15)
1-100 (5)
10-20
3-900
(65)
Niobium.......
<6
<15
-
3-40
(4)
Plat Ijillb
<10
<35
-
<¦06
Rubidium
< 6
9-60
-
1-450
(25)
Scandlus
-
1-18 (1)
-
0-36
(6)
Sliver
.1-16 (2)
.03-6 (0.2)
<7
.01-8 (0.2)
St ronrlua
20-70 (50)
5-100 (30)
5-40
15-1.000 (135)
Tantalua......
<4
.15-203 (3)
-
<1
(6)
Tin.
20-95 (50)
.1-20 (2)
<30
1-50
(20)
Tungsten
<30
<70
-
.5-40
(20)
Vanadius
5-70 (15)
.1-20 (10)
-
2-80
(20)
Zlrcpnlurc.....
1-70 (10)
.05-25 (5)
-
25-450
(70)
Source: (122, 132)
3-20
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There have been a number of articles on urban refuse incinerators,
primarily involving auxiliary power generation. Of all the reports Iden-
tified in this literature search, only the series cited above deals directly
with trace metal analysis of refuse. The others are concerned with various
aspects of particulate and pollution control, refuse-fossil fuel mixtures,
fouling, safety, noise, aqueous pollutants or non-trace metal chemical compo-
sition of refuse (127-132); these reports relate to trace metal content only
by inference. See Section 5.7 for a quantitative discussion of the emissions
from urban refuse.
3.2.3 Wood
During the 1970's, there have been a smattering of articles analyzing
the use of wood as an alternate fuel. They generally claim that wood has
a greater Btu content per dollar than coal or oil. In certain areas of
the country, wood could substantially reduce the reliance on other fuels.
Use of timber scraps would also encourage growth in a logged area. How-
ever, none of these articles report any trace metal results, and the con-
spicuous absence of such data implies that they do not exist. For example
see (133).
An EPA sponsored study by Battelle (Hall £t al_., 134) reported a com-
parison of wood and fossil fuels. This report probably represents the most
definitive document available on wood used as fuel, including a brief dis-
cussion of trace metals in wood. Brown (135) has also studied the role of
trace elements in wood combustion and published a table (reproduced in Hall,
et al.) of trace metals in ashed wood. That data are included in Table 5-35
of this report. See Section 5.8 for a discussion of trace metals in emis-
sions from wood.
3.3 COAL PREPROCESSING
In discussions on the form of trace metals in coal, the effects of pre-
combustion preparation cannot be neglected. The principal objective of these
procedures is to separate out as much of the mineral matter as possible
before burning. This is done mechanically by exploiting the greater density
3-21
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of the non-organic phases. After grinding, much of the mineral matter is
separated by differential Bettling or Bome form of centrifugation. This
is usually done to a large extent at the mine site and results In large
piles of primarily mineral debris called gob piles and culm banks. This
crude processing, not occurring at the combustion site, is not to be con-
sidered as part of an SCCF process. However, finer grinding, sizing, and
further separation is sometimes done at the plant site. The mineral debris
generated at the site is usually combined with the combustion ash or dis-
posed of in similar manner.
Effective preprocessing can considerably reduce the particulate loading
and the potential atmospheric emissions. The pyrites, being quite dense
(about 5 g/cc) and containing much of the sulfur, are usually the major
components removed. Of course, other trace elements are removed as well,
but in general, the details are poorly understood. Miller (32) has reported
that the following elements in Illinois coals are reduced by more that 50%
when 20% of the total raw coal is removed by float-sink, separations: Al,
As, Ca, Cd, Co, Cr, Cu, Fe, Ga, Hg, K, Mn, Mo, Ni, Pb, Sb, Se, Si, Ti, Zn,
and Zr.
Since weathering leads to oxidation of sulfide to form sulfate, sink-
float separations, particularly for pyrites, are more efficient before the
coal is ground and stored for a long time. The effluent from the sink-
float operation and the runoff from the debris piles present problems, but
they are preferable to those emissions created by combustion of the sulfates
and pyrites. A very exhaustive review of the whole subject of coal preparation
and the resulting wastes has been made by Wewerka et al. (136). They consid-
ered over 4400 references (through mid-1975) and have compiled a periodically
updated computerized database which is available upon request at Los Alamos
Scientific Laboratory. While their main concern was washing at the mine sit:e,
much of the data and many of the citations apply as well to preparation at l:he
combustion site. The full report is an ERDA publication, and a useful summitry
may be found in Torrey (16).
3-22
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In 1976, Mezey et al. (117) reviewed the technology, results and
problems of coal washing and separation. They also included a 214 entry
citation list on coal cleaning, and 82 references on contaminant removal
from petroleum.
Preprocessing will improve the quality of coal. Not only is inorganic
material partially removed, but the Btu-per-ton value is increased as the
coal is upgraded by removal of noncombustibles. If fewer trace metals
enter the boiler, certainly less are emitted. Besides those already men-
tioned, other articles which discuss preprocessing, its benefits and trade-
offs relating to trace metals, include: Ford (137), Manahan (138),
Schultz et al. (139-140), Stambaugh et al. (141), Williams et al. (142,
143), Cavallaro et al. (144), Uewerka et al. (145), Wewerka et al. (146),
and Capes et_ al. (147) .
3.4 FLY ASH FORMATION MECHANISMS
In recent years, several studies have considered how fly ash parti-
cles form. Of principal concern is the effect of the form of the element
in the fuel upon its ultimate fate. The experimental approach used in most
of these inquiries was to measure elemental concentration as a function of
fly ash particle size. The idea, following Natusch (148, 149), is that the
smaller, spherical fly ash particles have a greater relative surface area
than larger particles. Thus, elements which tend to be volatilized in com-
bustion will condense in the off-gas stream on any available surfaces and
thereby be enriched in the small particle fraction. Natusch predicts a sim-
ple inverse dependence (concentration, C, is inversely proportional to size,
CaD where D is diameter). Flagan and Friedlander (150), using a more
complex theory involving a dependence upon the gas viscosity (the Knudsen
number), predict a CaD 2 dependence in regions where the Knudsen number is
less than 1 (the coninuum regime). Results vary from one study to another,
but the Natusch model appears to be in better agreement with the data (151).
Although agreement is not universal, the consensus of several studies
(36, 37, 40, 44, 45, 151-158) is that the more volatile elements show a
3-23
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preference for small fly ash particles (e.g., As, Zn, Sb, Se, Pb, Ga, Cd,
Cr, Hg, Ni, Tl, V, Co). Various studies include other trace metals in their
enrichment lists. The "volatility" of an element seems to be best corre-
lated with the melting point of the oxide, although there are prominent
exceptions. Most other metals show no enrichment versus particle size and
some even decrease with decreasing particle size. Gladney et al. (AO)
show a decrease for Fe and Ce; they postulate the Fe concentration decrease
is due to most of the Fe being introduced in a pyrite form which behaves
differently from the organic phase during combustion; nowever, the same
speculation will not account for the decrease in Ce. Smith, Campbell and
Nielson (151, 153) point out that the fly ash matrix is composed mostly of
Al, Mg and Si, and for very small particles a slight decrease in these
elements is to be expected. That is, the increasing concentration of trace
metals "dilutes" the matrix elements. Indeed, they observe a significant
dilution of Si for smaller particle sizes, although not for Al, Fe or Mg.
Ondov et_ al. (159) also report a decrease for silicon.
Campbell £t_ al. (153) observed that fly ash is not homogenous, and
that some particles are selective enriched only in certain elements.
They have also observed more complex curves of concentration versus size,
some with local maxima and minima indicating a more subtle behavior than
predicted by the Natusch model. Almost al 1 authors agree on the need for
additional and more direct research on this problem. No model has been
positively confirmed. And this subject is of great concern because the
smaller particles, which do seem to have higher concentrations of certain
trace elements, pass more readily through most types of control devices,
are most mobile and long-lived in the atmosphere, are most active in the
environment, and have the greatest residence time in the lungs (37).
All of these effects are treated specifically elsewhere in this report.
Results pertaining to sink-float separation of ground coal have been
discussed elsewhere, see Section 3.1.3. The primary consideration in that
work was the separation of inorganic material. It has also been proposed
(see references in that paragraph and 37, 151) that the location of the trace
element in the coal plays a key role in its fate upon combustion. The idea
3-24
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Is that trace elements bound In the organic phase are atomized during combus-
tion, whereas those occluded with the mineral matter in the coal are less
likely to be vaporized. If the "condensation on the fly ash surface" theory
is valid, then those elements shoving a high degree of organic affinity ought
to show a more prominent inverse dependence of concentration with size.
However, the correlation is not supported by the evidence. For example, of
the 13 elements usually found to be enriched in the small particle fraction
(see above), four are in Gluskoter's (29) list of high inorganic affinity
(Hg, Cd, Pb, Zn) and four more are in the inorganic association category
(Co, Ni, Cr, Se). Furthermore, none of his strong organic affinity elements
made the list of commonly enriched elements (Ge, Be, B). Although the ideas
seem plausible, they do not account for the behavior of the elements. Again,
the metal oxide boiling point seems to provide the greatest degree of empir-
ical correlation.
Zimmerman _e£ al. (160) have studied the formation of metallic aero-
sols from different sources, one of which was combustion. They paid parti-
cular attention to mechanism of nucleation and particle size characteris-
tics. Hulett et al. (49), as part of the continuing ORNL study at the Allen
Steam Plant in Memphis, have looked at fly ash particles with a scanning
electron microscope (SEM) and photoelectron spectroscopy. They found particle
(matrix) composition to vary greatly as a function of size. Distinct compo-
sition differences were found when they compared the outside to the inside
of fly ash particles. They reported sulfates concentrated on the particle
surface, and that the surface of urban aerosols was higher in trace metals
than aerosols collected in a steam plant.
Work on the trace metal concentration and particle size is continuing
at Battelle's Pacific Northwest Laboratory in Richland, Washington; at
Lawrence Livermore Laboratory in Livermore, California; and at the Universi-
ty of New Hampshire. At New Hampshire, Ulrich is carrying on a more direct
approach in the study of fly ash formation. With Ulrich, French (161) has
reported a combination of experimental and theoretical studies that show
larger fly ash particles are formed from molten minerals in the boiler.
3-25
-------
They further report that the lov concentrations of netal oxides in boiler
flue gas indicate that the more volatile oxides appear to participate direct-
ly In the condensation, nucleation and growth of sub-micron fly ash
particles in the boiler. They conclude that, while the surface area pheno-
menon may be operative, one cannot neglect the possibility of different
formation mechanisms for smaller particles which entrap larger concentrations
of the trace metal oxides.
3.5 MISCELLANEOUS TOPICS
This section describes a series of unrelated articles on rather
isolated topics that do not fit conveniently into any of the above categories.
All of these articles are relevant to a study of trace metal emissions from
SCCP's, but their emphasis is on fuel characteristics.
Bolding (1) emphasizes that the trace element concentrations of coal
should be classified by amount of pollutant per Btu, the true measure of t.
fuel source. Furthermore, he analyzes the future increase in coal use and
warns that the trend toward larger power plants may exacerbate the pollu-
tion problem beyond current predictions.
Joyce and Higer (162) at NASA have found that remote sensing of coal
fields (via satellite) is able to classify fossil fuels by several quali-
ties: organic and inorganic sulfur, ash content, coking qualities, detailed
petrology and trace element content. Hence, a more accurate survey of the
pollutant content of our coal reserves is possible. This remote sensing
is also useful for establishing baseline data for many types of pollution,
and would be useful in siting studies.
Metal-containing additives are used in many oil-fired SCCP's to
improve boiler cleanliness, to reduce corrosion, to reduce stack emissions
and plumes by improving flue gas and ash handling characteristics, and to
help maintain design steam temperatures. These additives nearly always
are oxides or hydrates of magnesium, manganese, or mixtures of the two with
smaller amounts of aluminum. The use of these additives necessarily
increase the potential emissions of these metals. Kukin (163) has reviewed
the subject of such additives to oil-fired furnaces. Harker £t^ _al. (164)
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at Lawrence Berkeley Laboratory have reported (although in a foreign journal)
on the use of methyl cyclopentadienyl manganese tricarbonyl (MMT) in gas
turbine combustoxs. They find that there is an optimum level to control
particulate emissions, and that the manganese is intimately bound in the
effluent particulate matter as manganese monoxide. They report a similar
behavior for oil burning furnaces and power generation turbines.
Walker et _al_. (165) have written a report concerned with the catalysis
of coal conversion to liquid or gaseous fuel. While this process does not
fall under the definition of the SCCP constraint, they found it necessary
to review the subject of minerals and trace elements in coal in order to
understand catalytic behavior, Although much of the information they de-
veloped has also been reported elsewhere by Gluskoter, (28; see Section 3.1.3
of this report), a coauthor with Walker on this project, the work, referen-
ces, and recoTrjnended research programs are worthy of note.
Zimmerman et_ _al/ (160) with the EPA have prepared a review report on
metal aerosols. While much of the report is not germane to emissions
from SCCP's, metal aerosol formation from combustion and metallic vapor
condensation, both of which are relevant to fly ash formation processes,
are reviewed.
3.6 RESEARCH NEEDS
By and large, the generalized characterization of coals is one of the
areas where research has been sufficient. The only area deficient in data
would be low temperature ashing and whole coals, yet these areas are fairly
well represented in the literature. Of course, variations in individual coals
preclude the use of generalized trace metal concentrations with any specific
coal. Trace metals in petroleum show even wider individual variances, and
for many purposes, each crude oil must be considered separately. The prob-
lem is even greater with residual oils, where trace metal analyses are sel-
dom made. The team at Maryland has studied urban refuse and produced suffi-
cient data to characterize the fuel; a corroberative study would be reassuring.
Trace metals in wood have been little studied, but conventionally, the
organic pollutants have attracted far more attention.
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Although the form of the trace elements in coal have been studied, see
Section 3.1.3, the importance of the inorganically versus organically bound
trace metals on their fate during and after combustion remains uncertain.
Various theories have been proposed and certain studies seem to report data
relating trace metal concentrations to various parameters, but the data vary
from one experiment to another and no theory is supported unanimously. Ihe
theory of Natusch, which presumes that the volatile metals condense on the
fly ash surfaces, seems to be most popular; however, some of the evidence
does not support it. Thus, a greater understanding of the fly ash formation
processes, particularly due to the influence of the trace metal forms in the
coal, is needed. This nay be accomplished, in part, by a more detailed study
of the location of the trace metals on or in the fly ash particles,
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114. Yen, T. F. Preprints, Division of Petroleum Chemistry. ACS,
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115. Yen, T. F. The Role of Trace Metals in Petroleum. Ann Arbor Science,
Ann Arbor, California, 1975.
116. Mezey, £. J., S. Singh, and D. W. Hissong. Fuel Contaminants:
Volume I, Chemistry. EPA/600/2-76/177a, PB 256 020,
Battelle-Columbus Labs., Columbus, Ohio, 1976. 177pp.
117. Mezey, E. J., S. Singh, and D. W. Hissong. Fuel Contaminants: Volume
2. Removal Technology Evaluation. EPA 600/2-76/177b, PB-260 475,
Battelle-Columbus Labs., Columbus, Ohio, 1976. 318pp.
118. Given, P. H., R. N. Miller, N. Suhr, and W. Spackroan. Major, Minor
and Trace Elements in the Liquid Product and Solid Residue from
Catalytic Hydrogenation of Coals. Adv. Chem. Ser., 188-191, 1975.
119. Knauer, H. E., and G. E. Milliman. Analysis of Petroleum for Trace
Metals. Determination of Mercury in Petroleum and Petroleum Prod-
ucts. Analy. Chem., 47(8):1263-1268, 1975.
120. Goldstein, H. I., and C. W. Siegraund. Influence of Heavy Fuel Oil
Composition and Boiler Combustion Conditions on Particulate Emis-
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121. U.S. Environmental Protection Agency. Third Report to Congress:
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124. Campbell, W. J. Metals in the Wastes we Burn? Environ. Sci.
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125. Haynes, B. W., S. L. Law, and W. J. Campbell. Metals in the Com-
bustible Fraction of Municipal Solid Waste. RI-8244, U.S. Bureau of
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127. Ball, D. A., P. R. Beltz, P. Smith, R. B. Engdahl, and W. T. Reid.
Annotated Bibliography on Supplemental Firing of Municipal Solid
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Labs., Columbus Ohio, 1978.
128. Johnson, R. L. Energy Recovery from Municipal Solid Waste, an En-
vironmental and Safety Mini-Overview Survey. ATR-76(76l8)-7, Aero-
space Corp., Germantown, Maryland, 1976.
129. Kilgore, J. D. , L. J. Shannon, and P. Gorman. Environmental Studies
on the St. Louis-Union Electric Refuse Firing Demonstration. In:
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Symposium Papers. Institute of Gas Technology, Chicago, Illinois,
1976. pp. 413-426.
130. MacAdam, W. K. Design and Pollution Control Features of the Saugus,
Massachusetts Steam Generating Refuse Energy Plant. Resour. Recovery
Conserv., 1(3)235-243, 1976.
131. Niessen, W. R., and A. F. Sarofim. Incinerator Air Pollution: Facts
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132. Law, S. L., H. E. Marr III, and W. J. Campbell. Concentration and
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E. Aleshin, ed., 1976. pp.251-252.
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134. Hall, E. H., C. M. Allen, D. A. Ball, J. E. Burch, H. N. Conkle, W.
T. Lawhon, T. J. Thomas, and G. R. Smithson, Jr. Comparison of Fossi!.
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135. Brown, 0. D. Energy Generation from Wood Wastes. Presented at the
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137. Ford, C. T. Coal Cleaning to Remove Trace Elements Prior to Utili-
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138. Manahan, S. £. Cleaning Coal with Coal: Coal Humix Acids for Removal
of Acid, Iron, Heavy Metals, and Organic Pollutants Associated with
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139. Schultz, H., £. A. Hattman, and W. B. Booher. Fate of Some Trace
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140. Scbultz, H., E. A. Hattman, and W. B. Booher. Fate of Some Trace
Elements During Coal Fretreatment and Combustion. Adv. Chem. Ser.,
141:139-153, 1975.
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146. Wewerka, E. M., J. M. Williams, P. 0. Wanek, and J. D. Olsen. Envi-
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148. Natusch, D. F. S., C. F. Bauer, H. Matusievicz, C. A. Evans, J.
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A86-A169.
3-43
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SECTION 4
CONTROL TECHNOLOGY
A typical coal-fired power plant includes a combustion unit and various
support or subsystems. Fine particles and/or trace elements are emitted
from the combustion unit as well as from some of the subsystems (1,2). This
analysis is primarily focused on the emission of pollutants from the com-
bustion process to the atmosphere; a discussion of the emissions from utility
subsystems is Included for completeness. The sources of major power
plant wastestreams (listed in Table 4-1 and shown schematically in Figure
4-1) are discussed in the following sections. The techniques used by the
utility industry to control or treat the wastestreams are also described.
4.1 TRACE ELEMENTS FROM SUBSYSTEMS
The utility subsystems which may emit trace elements include: (1)
coal storage and preparation, (2) raw water treatment, (3) metal cleaning,
(4) cooling water system, (5) floor and yard drainage, and (6) ash handling
and disposal. Each of these topics is discussed below.
4.1.1 Coal Storage and Preparation
Before coal is utilized in a combustion process, It is normally sized
and as much ash (Inert materials) and pyritlc sulfur as possible are removed
(3). Although a large portion of this coal preparation procedure Is con-
ducted at the mining site, the coal may undergo further preparation at the
plant site before being stored in piles.
4.1.1.1 Waste Characterization and Control —
Environmentally unacceptable wastestreams are generated by various
phases of the coal storage and preparation system. Fine dust 16 generated
4-1
-------
TABLE 4-1. VARIOUS UTILITY PLANT WASTESTREAMS AND THEIE SOURCE
Source
Aqueous
Vaste Streams
Gaseous
Solid
Cool storage and
preparation
Raw water treating
Combustion process
Ash handling
Coal pile runoff,
Drainage
Sludge
Boiler
Blow Down
Sluiced Ash
Flue gas and
fly ash aero-
sols
Particulate
Matter
Botton ash
Dry Ash
Metal cleaning
Cooling system
Floor and Yard
Drain
Air pollution
control
Cleaning vaste-
strees
Cooling tover
Blow Down
Wastewater
SOz sludge,
sluiced particles
4-2
-------
to AtMnsPtnnr
~
.e-
i
u
Mill ro*
ruimic a (Ming
r
Msir milt in
A\H IMMR ING
SIMIH
SUM
r *---1
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1110 Will
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,, , OKI IHMUGN
tnw IK IMItR
wciwww ik toouw mm
rwi —~
rWIMIIOH AIR
C0*1E»SATTW1I*
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Wtl -UPJM]
wsc. wm(
MIIR SIRIMISl
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*0111* iimi
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i iRisii* t
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HRMIIW.S
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(OIIIR
VMM ART KM ICS.
IROORfttORf t SWTI IK
IMSItS. INIMI SCHIIR
¦At WASH. ClOSIU
Cin INT. tMIIR STSHNS
CONS IRIKI ION AC 11V It T
* Wastewater that may be reused In plant or mist be treated
before being discharged to environment.
Figure 4-1. Simplified schematic of a typical power plant.
Source: (4)
-------
during the coal sizing operation, but these emissions can be adequately
controlled with the use of water sprays. This, however, converts an air
pollution problem into a water pollution problem. The resulting waste-
water is combined with the runoff from the coal storage piles.
In many sections of the country, the runoff from coal processing wastes
or mining activities has become a serious problem (1). Because of the
similarities between these wastes and coal storage in piles at the plant
site, it is anticipated that runoff from these piles could also be a serious
problem. The actual volume of coal pile runoff as well as Its composition
is affected by the composition of the coal, surface area of the pile, anc
amount of rainfall (2). In general, the coal reacts with rain and oxyger.
to convert metal sulfides to sulfuric acid (2, 4-6). The acid can, in turn,
dissolve many other complex metallic sulfides, sulfates, and sulfites, re-
leasing some or all the following trace metals: aluminum, zinc, copper,
cadniun, beryllium, nickel, chromium, vanadium, silver, and lead. Major
checical constituents of coal pile runoff and their composite range of con-
centrations are presented in Table 4-2 (2). Because of the various con-
taminants in and the volume of runoff (approximately 17-26 million gallons
per year based on 43-60 inch of rain per year), coal pile runoff represents
a serious threat to waterways or aquifers (4). In some plants, impervious
liners are normally used in these ponds as well as underneath the coal piles
in order to prevent seepage that could contaminate groundwater aquifers
(4). Coal pile runoff, which typically has a pH of 2-6 and high dissolved
solids content, is normally routed to an evaporation pond. Runoff having
a pH of 6-5 and low dissolved solids content can be routed, along with
other wastestreams, to an ash pond depending on available pond area (4).
4.1.1.2 Gaseous Emissions—
Under certain conditions, the oxidation of the coal or other mineral,
matter can produce sufficient heat to ignite the interior of the pile. As
a result, coal piles may also be the source of noxious odors and vaporous
trace metal emissions whenever the coal piles spontaneously ignite. One
study has shown that trace element emissions from burning coal piles are
4-4
-------
TABLE 4-2. CONSTITUENTS OF COAL PILE RUNOFF
Range
Conventional Measures of Pollution
pH
2.1 -
6.6
(ag/1)
Total Suspended Solids
22.000 -
610.000
Total Dissolved Solids
720.000 -
26,970.000
Turbidity
2.770 -
505.000
Total Hardness
130.000 •
1.851.000
Major Chemical Constituents
Amoonla
0.000 -
1.770
Nitrate
0.300 -
1.900
Phosphorus
0.200 -
1.200
Sulfate
130.000 -
20,000.000
Chloride
3.600 -
481.000
Aluminum
66.000 -
1,200.000
Iron
0.060 -
4,700.000
Manganese
90.000 -
180.000
Sodium
160.000 -
1,260.000
Trace Element Constituents
Arsenic
0.005 -
0.600
Beryllium
<0.010 -
0.070
Cadmium
<0.001 -
0.003
Chromium
0.000 -
16.000
Cobalt
0.025 -
Copper
0.010 -
3.900
Magnesium
0.000 -
174.000
Mercury
<0.0002-
0.007
Nickel
0.240 -
0.750
Selenium
<0.001 -
0.030
Zinc
0.006 -
12.500
Source: (2)
-------
a potentially serious environmental problem, particularly at the local level,
and concluded that this possibility needs to be comprehensively assessed (5).
A.1.2 Raw Water Treatment
Good quality water Is required for the generation of steam in a utility
plant. The quality of boiler feed water can vary as is required by the
boiler's operating pressure (4). Today's high pressure, high-temperatura
boilers require a controlled stream of high quality water which can be
achieved by various treatment processes. Among these processes are clari-
fication, lime-soda softening, ion exchange, and filtration (2.4). Oper-
ation of the softening, clarification, and filtration processes results in
the generation of a "sludge" which consists of 0,5-5.0 percent suspended
solids and contains chemical additives such as phosphate, caustic soda, lime,
and alum. Treatment of these sludges typically involves hydraulic thickening
to a content of 15-20 percent solids. After thickening, the sludges are
devatered and the solids disposed of in a landfill (2, A).
When an ion exchange process is used, a wastestream containing waste
regenerants (sulfuric acid and sodium hydroxide) and rinse water is gener-
ated. This stream is normally collected in a neutralization tank and its
pH adjusted to the range of 6.0-9.0. Any precipitates formed upon neutrali-
zation are separated from the liquid by settling or filtration and then
disposed of in a landfill. The overflow can be reused or discharged to the
environment (A).
4.1.3 Metal Cleaning
Because the efficiency of a power plant is dependent on the cleanli-
ness of the various heat transfer surfaces in the plant, these surfaces are
cleaned regularly. Equipment that must be cleaned Includes the boiler,
boiler fireside, air preheater, stack cooling tower basin, as well as mis-
cellaneous small equipment. Strong chemicals are normally utilized in uhe
cleaning process and ideally, the surfaces are cleaned to the "bare metal."
Consequently, some of the metal is dissolved in the cleaning solution. Iron,
copper, nickel, zinc, and chromium are the metals commonly found in the waste-
stream from this treatment process (2) .
4-6
-------
Many utilities discharge their cleaning wastes vlth once-through
cooling water, relying on the resulting high dilution ratio to minimize the
adverse effects of discharge. Other utilities collect this wastestream in
storage basins or ash ponds and adjust the pH to the neutral range. The
less soluble compounds precipitate from the water, and "clean" water is
discharged from the plant. The settled Bolids are periodically cleaned from
the pond and disposed of in landfills (A, 7).
4.1.A Cooling Water System
The cooling water used in a power plant must be free of biological
growth in order to prevent fouling of the heat transfer surfaces. Various
chemicals can be used to control biological growth In the cooling water.
For instance, chlorine and/or organic chemicals are normally used for
biological control in a once-through cooling system (2, A). Consequently,
the discharge from such a system would contain these components. Since
once-through cooling water may contain some dissolved trace metals such as
copper, they could also be expected to be present in the effluent. The
level of residual chlorine in the effluent can be controlled by employing
an intermittent program of chlorine or hypochlorite addition. Another
technique that can be used to reduce the level of residual chlorine dis-
charged is to employ chlorination at periods of low condenser flow (2, A).
In a closed, recirculating, cooling system a blowdown is required to
prevent scaling of the condenser. The blowdown stream contains dissolved
solids, residual chlorine, and chromates (A, 7). Reducing the level of
residual chlorine being discharged can be achieved by the same techniques
employed in a once-through system. An end-of-pipe treatment for reducing
chlorine levels Is the addition of a reducing agent such as sodium bisulfite;
however, an excess of this chemical creates an oxygen demand, thus trading
one potential water problem for another (A).
A.1.5 Floor and Yard Drainage
Floor and yard drainage from a coal-fired power plant generally con-
tains dust, fly ash, coal dust, and floor scrubbing detergent (A). This
wastestream may also contain lubricating oil or other oils resulting from
A-7
-------
pump seal leakage or oil spills. This wastestream can be combined vlth ccal
pile runoff and treated accordingly (7).
A.1.6 Ash Handling and Disposal
Bottom ash generated by the combustion process Is rejected by this
process and sent to final disposal via the ash handling system. Disposal
of the ash is achieved by a water sluicing system to an ash pond or by a
pneumatic conveying system to a landfill site (2). In both of these disposal
methods, the possibility of trace metals leaching from the ash and contamina-
ting local groundwaters should be considered (6). Several alternatives to
these disposal techniques have been found and include use of ash as a:
• source for recovering various metals,
• skid-retardant aggregate in highways, and
• replacenent for a portion of the cement in concrete mix
(9-15).
Efforts for the utilization of ash in the areas of sanitary landfills, agri-
culture and land reclamation, and coal mine fire control are being explored
(12, 16).
4.2 FINE PARTICLES AND TRACE ELEMENTS FROM THE COMBUSTION PROCESS
A.2.1 Boiler Blowdown Characterization
The coal combustion process is the source of three vastestreams: boiler
blowdown, bottom ash, and flue gases vlth suspended particles. Boiler blowdown
is the result of an attempt to control the scaling of dissolved solids in the
boiler feed water on to the boiler surfaces. Boiler blowdown is principally a
source of soluble salts, but it commonly contains iron and copper (2, 7).
Normally, this stream is of high enough quality to be reused in various
portions of the plant. The most desirable reuse of boiler blowdown is as
makeup to the demineralizer system (7).
I*.2.2 Bottom Ash Characterization
Coal-fired combustion processes generate two types of ash, fly ash t.nd
bottom ash. Fly ash exits the boiler with the flue gas and will be discussed
4-8
-------
later; bottom ash exit* at the bottom of the boiler. Bottom ash varies
In quantity and composition depending on the type of fuel utilized, method
of combustion, and point in the boiler from which It is obtained (2). Typi-
cally, the bottom ash contains various metals such as arsenic, cadmium,
cesium, cobalt, chromium, copper, mercury, magnesium, manganese, sodium,
nickel, lead, tin, selenium, titantium, iron, aluminum, gallium, germanium,
vanadium, and uranium (2, 9, 11, 17, 16). The bottom a6h is disposed of
via the ash handling system as described above.
4.2.3 Flue Gas Characterization
The flue gas from all fossil-fuel combustion processes (except those
fired with natural gas) contain SO2, NO^, particles, and various trace
elements that are present in the fuel. Particulate emissions from combus-
tion processes can vary depending on the composition of the fuel, type of
combustion process used, quantity of excess air used for combustion, as
veil as other operating practices (19). Typical loadings and particle size
distributions for fly ash discharged from various types of coal-fired boilers
are presented in Table 4-3. The data in this table show that pulverized
coal boilers produce the heaviest dust loadings. The finest particulate
emissions are generated by cyclone boilers (3). The results of a test in
which the emissions generated by an oil-fired and coal-fired Industrial
boiler were compared shoved that the quantity of particles from oil firing
is considerably less than from coal firing (20). However, the particles from
oil firing are generally smaller and more difficult to remove from the flue
gas (20).
Although the data in Table 4-3 do not characterize the distribution of
particles that are less than 10 microns (ym) In diameter, these particles
(particularly, those less than 5 urn) have been reported to significantly
contribute to all major adverse aspects of air pollution (21). For instance,
visibility reduction associated with air pollution is primarily a result
of 0.1-1.0 lim diameter particles in the atmosphere (21, 22). Several re-
searchers have also shown that the greatest pulmonary deposition is exhlbiteS
by the smallest particles emitted from a combustion or incineration process
(23-2B). More complete distribution data for particles from various boilers
4-9
-------
TABLE 4-3. TYPICAL AMOUNT AND SIZE OF FLY ASH EMISSIONS FROM VARIOUS BOILERS
Pulverized Coal
Underfeed
Stoker
Spreader
Stoker
Dry1
Bottom
Slag1
Tap
Cyclone
Furnace
Carry-over, fraction of ash
in coal, ZJ
20-30
30-80
60-85
45-55
10-15
Combustible content, Z
10-50
20-60
5-10
5-10
5
Dust loading, lb/1000 lb gaB*
0.5-4
1.5-10
6-9
4-6
0.6-1.5
Typical size consist, cumulative
percent
Microns Mesh
< 10
7
11
40
86
< 20
15
23
70
91
< 44 325
30
42
80
95
< 74 200
38
56
97
98
<149 100
57
73
100
100
'Ash exits furnace as a dry solid
2Ash exits furnace as molten liquid
1Includes combustibles
*Based on coal having 15Z ash content dust in gas leaving furnace before any collectors.
Corrected to 50Z excess air.
Source: (3)
-------
are presented in Figures 4-2, 4-3, and 4-4. The data presented Is Figure
4-2 reflect data obtained from nine stoker-fired boilers, while Figures 4-3
and 4-4 summarize data from 300 pulverized coal and seven cyclone boilers, re-
spectively (4). Particle size distribution data for emissions from Indus-
trial coal-fired boilers and municipal incinerators are presented in Figures
4-5 and 4-6. Comparison of these data shows that, while the details of
each distribution are unique, the bulk of particles from all boiler types
fall Into similar size ranges for all types of sources. If the flue gas
subsequently pass through an ESP, which removes particles above 2 ym
quite efficiently, the final emissions compare even more closely.
Upon combustion, the trace metals in the coal are partitioned among
the fly ash, bottom ash, and flue gas exiting the boiler. The presence of
the various trace metal6 in the boiler effluents is dependent on their
respective volatilities (29). A trace metal mass balance and partitioning
study in which 37 trace elements were considered was conducted at the
Allen Steam Plant (30). During this study the various trace elements were
categorized into three groups according to their partitioning behavior;
these groups are presented in Table 4-4. Although the data In Table 4-4
are the results observed in one plant, similar partitioning behaviors have
been reported by other sources (23, 30-33). The partitioning of 27 trace
elements between bottom and fly ash was also quantified for three power
plants as shown In Table 4-5 (33).
These elements that vaporize Bt operating temperatures In the boiler
(approximately 1500°C) may condense on the fly ash in the flue gas as the
flue gas cools (5, 23, 29, 32, 34). These "condensable" trace elements
(Class I and II elements in Table 4-4) are believed to condense on any
available surface (17, 23, 29). Since the largest surface areas per unit
of mass are exhibited by those particles having the smallest diameters
(see Figure 4-7), the greatest trace element concentrations (mass basis)
have been found on the smallest fly ash particles (23, 29, 30, 32, 35).
There has been some speculation that trace element deposition on small
particles is the result of adsorption of the trace element; however, Linton,
et al. have reported that 80 percent of the trace elemental mass in particles
4-11
-------
100.00
10.00
5
DC
u
0.01
STOKE* FIRED ELECTRIC UTILITY
BOILER CYCLONE INLET
ARITWETIC MEAN
JLX
U_JL
0.01 i i 1 S 10 10 90 95 99 99.9 99.99
WEISHT S LESS THAN STATED SIZE
Figure 4-2. Particle-size distribution of particles eaitted
from uncontrolled power plant# utilizing stoker
coal-fired boiler*.
Source: (17)
4-12
-------
100.00« t'i i i i i i i i i i i i i i i i i >
10.00
1/1
1~Q
-r-r
//
• UNCONTROLLED POWER PLANTS,
PULVERIZED UNITS, EXTREMES
OF BAHCO DATA
a UNCONTROLLED POWER PLANTS.
PULVERIZED UNITS, ARITHMETIC
MEAN OF BAHCO DATA
Q.01' ' » ' ii i
¦ ¦ ¦ * ¦ 1 1 ¦*
t. i i
0.01 .1 .51 5 10 50 90 95 99 99.9 99.99
WEIGHT S LESS THAN STATED SIZE
Figure 4-3. Particle-size distribution of particles
emitted from uncontrolled power plants
utilizing pulverized coal-fired boilers.
Source: (17)
4-13
-------
100.00
10.0
E
ec
i
1.0
o
Ui
—I
o
as
c
a.
0.1
* CYCLONE FIRED ELECTRIC
UTILITY BOILER
• ARITHMETIC MEAN.
0.01 t'ii i—l.
0.01 J JS 1 5 10
50
90 95 99 99.9 99.99
WEIGHT % LESS THAW STATED SIZE
Figure 4-4. Particle-size distribution of particles
emitted from uncontrolled power plants
utilizing cyclone coal-fired boilers.
Source: (17)
4-14
-------
100.00
10.00 -
S 1.00
0.10 -
TRAVELING GRATE
® SPREADER STOKER
UNDERFEED STOKER
a PULVERIZED COAL
CYCLONE FURNACE
0.01
O-Ol J. il 5 10 50 90 95 99 99.9 99.99
WEIGHT X LESS THAN STATED SIZE
Figure 4-5. Farticle-gize distribution of particles
emitted from uncontrolled industrial power
plants (coal-fired)
Source: (17)
4-15
-------
100 > r t t i " ¦¦r,,r
10
LTt
O
(->
5
3
a.i
a.01 1 i 1 5 10
• EXTREMES
~ ARITHMETIC MEAN
90 95 99 99.9 99.99
WEIGHT S LESS THAN STATED SIZE
Figure 4-6. Particle-size distribution of particles emitted
from uncontrolled municipal incinerators (Bahco
data).
Source: (17)
4-16
-------
TABLE 4-4. PARTITIONING BEHAVIOR OF TRACE ELEMENTS AT ALLEN STEAM PLANT
Partitioning Trace Element
Group Behavior Symbol
Class I Elements partition
about equally between
slag and fly ash
exiting boiler
A1, Ba, Ca, Ce, Co, Eu, Fe,
Hf, K, La, Mg, Ma, Rb, Sc,
Si, So, Sr. Ta, Th, Ti
Class II Elements are concentrated
in boiler fly ash compared
with the slag
As, Cd, Cu, Ga, Pb, Sb,
Se, Zn
Class III Elements remain essentially
in the gas phase
Hg, Ce, Br
Note: (1) Elements, Cr, Cs, Na, Ni, D, and V appear to be between Classes I
and II
(2) Cyclonic boilers used at Allen Steam Plant
Source; (30)
4-17
-------
TABLE 4-5. ASH AND TRACE ELEMENT PARTITIONING OBSERVED IN THREE WESTERN POWER
PLANTS UTIL1ZINC PULVERIZED COAL AND CYCLONE BOILERS
in ¦i ii i
Pulverized Coal
Bollera
Cyclone
Boiler
Plant A1
Plant
B*
Plant
c'
Boiler
Boiler
Boiler
Bottoa
Aah
Fly Ash
Bottoa Ash
Fly Aah
Bottoa Aah
Fly Aah
Coap often t
(X of Total)
(X of Total)
(X of Total)
(X of Total) (X of Total)
(X of Total)
Ash
22.2
77.8
21.3
78.7
73
36.3
Alualnua
20.5
78.5
18.0
82.0
67
32.8
Antiaony
2.7
97.3
9.9
90.0
15
84.1
Arsenic
0.8
99.0
5.0
95.1
16
83.1
Barlun
16.0
83.9
15.4
64.4
64
34.9
Berylllua
16.9
82.0
15.7
84.4
56
41.5
Boron
12.1
87.9
7.9
92.1
21
78.9
Cadnlin
IS.7
64.3
8.9
91.1
26
73.5
Calclua
18.5
81.5
15.1
84.9
60
39.7
Chlorine
16.0
84.0
8.3
91.7
12
87.6
Chroalua
13.9
86.1
10.7
89.3
44
55.7
Cobalt
IS.6
84.4
15.5
84.4
48
53.9
Copper
12.7
87.3
12.4
87.6
34
66.1
Fluorine
1.1
98.9
0.0
100.0
1
98.9
Iron
27.9
72.1
20.4
80.6
61
38.2
Lead
10.3
89.7
3.1
96.8
7
92.3
Magneslua
17.2
82.8
17.7
82.3
62
37.9
Manganese
17.3
82.7
13.6
66.3
62
37.7
Mercury
2.1
97.9
0.8
99.3
0
99.2
Holybdenua
12.8
87.2
8.4
91.6
16
83.9
Nickel
13.6
86.4
16. 3
81.6
22
77.1
Selenium
1.4
98.6
0.0
100.0
2
97.8
Sliver
3.2
96.8
9.5
91.7
22
78.1
Sulfur
3.4
96.5
0.0
100.0
0
99.9
Ti tanlun
21.1
78.9
20.6
79.3
69
30.9
Uranlua
18.0
82.0
50.1
49.8
29
70.0
Vanadl iia
IS. 3
84.9
16.3
83.6
60
39.1
Zinc
29.4
70.6
4.4
95.5
13
86.9
'Plant A Is
a 3S0 HU
unit
with a tangentlally-flred, pulverized coal
boiler.
'Plant B la
a 330 HU
unit
with a tangentlally-flred, pulverized coal
boiler.
'Plant C la
a 2S0 HU
unit
with a cyclonic boiler. In which lignite la
burned.
Source: (33)
-------
Surface To Volume Ratio
A
10'
Number Distribution
10°
0.06 0.1 0.2
0.02
0.6 1.0 2.0
10
PARTICLE DIAMETER (um)
Figure 4-7. Plot of surface area to volume ratio as a function
of particle size. The lower curve is typical of
number distributions (of particles) found in fly
ash.
Source: (35)
4-19
-------
of 1 Mm is present on the surface of the particle (32, 36). Several investi-
gators have studied the variation in the concentrations of trace element!;
vith respect to particle size (23, 29, 30, 35-37). Some of their observji-
tions are presented in Figures 4-8 through 4-12. The various processes
that are normally used to control particulate emission from combustion
processes and their effectiveness in controlling trace element emissions
are discussed in the next section.
4.3 AIR POLLUTION CONTROL SYSTEMS
Until recently, the air pollutants with which the utility industry has
been most concerned were particles, SO2 and NO^. Consequently, the primary
purpose of the air pollution control system in the utility industry has
been the reduction of gaseous (SO2, N0X) and particulate emissions. Sinc.e
little concern has been given specifically to trace element emissions, nc>
direct effort has been made to control these emissions (5, 21, 38-46);
however, some reduction in trace element emissions is achieved by particle
control processes due to the presence of trace elements on the fly ash (^3,
47). The reduction that could be expected is difficult to quantify because
the higher trace element concentrations are present on the smallest part:.cles
and control processes become less effective as the particles decrease in
size (17, 36, 38, 40, 43, 48).
The four basic technologies that have been used in the utility industry
to reduce gaseous and particulate emissions include: dry mechanical separa-
tors, electrostatic precipitators, wet scrubbers, and baghouses. These
technologies are briefly described and their impact on trace element emis-
sions are discussed below.
4.3.1 Dry Mechanical Separators
4.3.1.1 Process Description —
Cyclone (centrifugal) separators are one of several dry, mechanical
collection devices that have been developed for particulate control. In most
cases, the flue gas enters the separator tangentially at the top of the
cylinderical section and spirals downward into a conically-shaped bottom;
see Figure 4-13 (48). The particles, which have a greater applied centr:lfu-
4-20
-------
250
200
I. 150
a.
s
° 100
50-
10
20
30
0
40
50
70
60
PARTICLE SIZE (um)
Figure 4-8. Concentration of nickel vs particle size.
Source: (37)
4-21
-------
250
200
150-
u
s
O 100-
50-
30
0
20
10
50
60
70
PARTICLE SIZE (pm)
Figure 4-9. Concentration of chromium vs^ particle size.
Source: (37)
4-22
-------
500
300-
200-
100-
10
20
30
40
0
50
60
70
PARTICLE SIZE (um)
Figure 4-10. Concentration of vanadium vs particle size.
Source: (37)
4-23
-------
400
300-
z
o
200-
100-
0
10
20
30
40
50
60
70
PARTICLE SIZE (ym)
Figure 4-11. Concentration of copper vs particle size.
Source: (37)
4-24
-------
250 -g>
200-
150-
s.
Q.
5
b-
5
»—
bJ
100-
50-
PARTICLE SIZE (ym)
Figure 4-12. Concentration of lead vs particle size.
Source: (37)
4-25
-------
CLEAN GAS
£
TANGENTIAL INLET
DUST
DISCHARGE
Figure 4-13. Schematic of simple dry cyclone separator.
Source: (48)
4-26
-------
gal force than the flue gas, accumulate at the wall and are carried down,
against the wall, by the gas. The dust Is discharged through the bottom
while the flue gas flows back up in a small spiral vortex and exits at the
top.
Cyclones can efficiently remove particulates of approximately 5 ym at
dust loadings of 1-100 grains/ft3 with only a moderate pressure drop (42,
48). Because of their ability to handle high dust loadings, cyclones seem
to be best suited as a precleaning device for other processes. These
separators are, generally, low in cost, have no moving parts, and can be
constructed of materials that can withstand temperatures as high as 980°C
(42, 48). The major disadvantage of cyclone separators is their relative
inability to collect fine particles (<2 ym) without incurring substantial
pressure drops (42, 48-50). Because of this disadvantage the utility in-
dustry is moving away from using cyclones; a survey conducted by Schwieger
showed that 43 percent of recent or proposed boiler installations are not
using or planning to use cyclones (51).
4.3.1.2 Impact on Trace Element Emissions —
Because data showing the trace element collection efficiency of a cy-
clone separator are scarce, and a relationship is known to exist between
trace element concentrations and particle size, it is important to know how
effectively a cyclone can collect particles of various sizes. Although a
cyclone's collection efficiency is case specific, the collection efficiency
with respect to particle size for a "typical" cyclone is presented in Table
4-6. These data show that a typical cyclone can remove particles down to
the 5 ym size range with relatively high efficiencies; however, the collec-
tion efficiency is significantly less for respirable particles (approxi-
mately 2 ym) and is relatively ineffective for particles in the 0.1-1.5 ym
size range.
As was previously stated, data about a cyclone separator's ability to
remove trace elements from the flue gas has not been well characterized;
however, the trace element removal efficiency of a cyclone separator was
calculated from data reported for a 250 MW power plant (33). The various
4-27
-------
TABLE 4-6. TYPICAL CYCLONE PARTICLE COLLECTION
VERSUS PARTICLE SIZE
Particulate Collection
Particle Size Typical Collection
(Urn) Efficiency1 (%)
20
95
10
85
5
70
4
70
3
58
2
20-55
1.5
10-33
1.0
6-23
0.8
8-18
0.6
2-15
0.5
1-10
0.4
.5-7.5
0.3
.25-.45
0.2
.06-3.0
0.1
-V0-.5
'Low and high ends cf range reflect expected collection of low and high
efficiency cyclones, respectively.
Source: (17, 40, 42, 58)
4-28
-------
trace elements for which data were reported and the collection efficiencies
calculated are presented in Table 4-7.
4.3.1.3 Waste Streams Generated —
Operation of a cyclone separator results in a solid wastestream that
must be disposed of. In many cases, this stream is combined with bottom
ash from the combustion process and transported to a final treatment area
such as an ash pond or a metal recovery process. In those cases where
these ashes have been disposed of in an ash pond, the fly ash has been
reported to form a gray scum on the pond's surface due to its buoyancy.
This buoyancy is a result of the carbon dioxide trapped inside tiny sili-
cate spheres that make up the fly ash (52). The gray scum can be con-
trolled by skimming devices (23).
The pollutants in the flue gas exiting the cyclone are normally not
at low enough levels to allow discharge of the gas into the atmosphere.
In most cases making this effluent environmentally acceptable would require
the removal of SO2 and perhaps N0X as well as further reduction of its parti-
culate content.
4.3.2 Electrostatic Precipitator
4.3.2.1 Process Description —
The utility industry has utilized electrostatic precipitator (ESP) for
more than 50 years to reduce particulate emissions, and they are still very
popular in this industry (49, 53-55). This popularity has spread to other
combustion processes such as municipal incineration and industrial boilers
(1, 56-58). Operation of an ESP (Figure 4-14) is based on the generation
of a high voltage, direct current corona. This corona is generated by a
non-uniform electric field which occurs when a small diameter wire is used as
one electrode and a plate or cylinder is used as the other electrode (53,
59). The corona ionizes the flue gases, and the ions become attached to
the particles, thereby, charging them. The charged particles migrate toward
the collection electrodes and are subsequently removed. Removal of the
4-29
-------
TABLE 4-7. ACTUAL TRACE ELEMENT COLLECTION EXHIBITED
BY A CYCLONE SEPARATOR
Collection
Trace Element Efficiency (2)
Total Ash
65.0
Aluminum
66.0
Antimony
7.4
Arsenic
75.3
Barium
95.4
Beryllium
84.3
Boron
31.4
Cadmium
44.0
Calcium
54.8
Chlorine
8.7
Chromium
27. 7
Cobalt
45.1
Copper
56.8
Fluorine
25.3
Iron
54.2
Lead
30.0
Magnesium
61.0
Manganese
66.8
Mercury
3.2
Molybdenum
24.9
Nickel
18.6
Selenium
33.1
Silver
79.6
Sulfur
1.8
Titanium
74.4
Uranium
60.6
Vanadium
36.2
Zinc
39.4
Source: % Collection derived from (33)
4-30
-------
COLLECTING
PLATES
FLUE GAS
ST ADC GAS
¦ HIGH TENSION
WIRE ELECTRODE
FLY ASH DISPOSAL
DRY OR WET SLUICING
Figure 4-14. Plate-type electrostatic precipitator.
Source: (58)
4-31
-------
accumulated dust may be achieved by washing the collection electrodes or
rapping the electrodes to dislodge the dust, allowing it to drop Into a
hopper (48, 53). Major advantages of an ESP are their:
• relatively high collection efficiencies, with modern
precipitators capable of achieving particulate effi-
ciencies of greater than 99 percent, and
• relatively low pressure drop, which is particularly
advantageous when large volumes of gases are handled
(48, 53, 58).
The primary disadvantages of ESP's are the sensitivity of the collection
efficiency to variations in fly ash resistivity or changing gas flow rates
and the relatively high energy requirements (53, 58). Fly ash resistivity
is very site and fuel specific, but generally the maximum in collection
efficiency is for a fly ash resistivity of about 2 x 1010 ohm-cm. Fly ash
with a higher resistivity (<2 x 101 c ohm-cm) reduces an ESP's collection
efficiency; this type of ash is found in low sulfur coals. Lower resisti-
vity ash, (>2 x 1010 ohm-cm) also decreases the collection efficiency of an
ESP due to the easy reentrainment of this ash in the flue gas (53). The
ash resistivity can be made more favorable by the addition of chemical
agents (S03 or NH3) to the flue gas, or operating the ESP at an elevated
temperature as is shown in Figure 4-15 (50, 53, 60-62).
This elevated temperature concept is the basis of the "hot" electro-
static precipitator. The hot ESP is located ahead of the air heaters
instead of in its normal downstream position (cold ESP) (60). Although the
hot ESP operates at a condition of optimum ash resistivity, Thoem reports
results of a study that indicate that for a given total particulate contiol
efficiency, a cold ESP appears to be a better fine particulate and there-
fore trace element collector than the hot ESP (61). The cold ESP also has
the advantage of handling a smaller volume of gas because a gas at 150°C
is about 25 percent less in volume than the same gas at 315°C (60). Mesich
et al. compared the total particle collection efficiencies of hot-side
and cold-side ESP's; their results showed that there was no difference ir.
the collection efficiencies of these ESP's (63).
4-32
-------
FLY ASH FROM LOW SULFUR COAL
FLY ASH FROM HIGH SULFUR COAL
20Q
700
500
0
100
300
600
TEMPERATURE *F
Figure 4-15. Fly ash resistivity variations with temperature.
Source: (53)
4-33
-------
4.3.2.2 Trace Element Collection Efficiency —
The ability of an electrostatic precipitator to collect particles and
trace elements condensed on fly ash particles is highly dependent on particu-
late size. Several investigators have studied the impact of particulate size
on ESP collection efficiency; their results are graphically summarized in
Figure 4-16 (17, 64-68). From these data it is apparent that these re-
searchers did not consider submicron particles; however, control of sub-
micron particles was considered in studies by Shannon _et al_. and Ondov
et al. (41, 69). The results of these studies are in good agreement and
are summarized in Table 4-8. Although the data in this table indicate that
ESP's exhibit high collection efficiencies for submicron particles, Paulson
et al. reported that when the proportion of particles smaller than 5 ym
reached a level that exceeded 45 percent (by weight), the ESP collection
efficiency was unacceptably low (less than 98.5 percent) (70).
Like other control technologies, little data regarding the ability of
an ESP to control trace element emissions from combustion processes are
available; however, sufficient data to allow the calculation of the trace
element removal efficiencies of four commercial-scale ESP's have been
reported. These ESP's were utilized in facilities that varied in size fram
105 MW to 62 5 MW. The trace element collection efficiencies calculated far
the ESP's at the various facilities are presented in Table 4-9. Although
some differences in the calculated efficiencies could be expected due to
differences in the operation of the utility plants or the ESP's or their
respective design capabilities, in many cases these efficiencies were in
relatively good agreement.
4.3.2.3 Wastestreams Generated —
Two streams that are of concern exit ESP's. The first stream is the
collected fly ash. Since this effluent is the same as the ash discharged
from a cyclone separator, it can be disposed of in the manner discussed in
Section 4.1.6. The second stream is the effluent flue gas, which contains
SO2 and N0x. In most cases, the level of these contaminants must be re-
duced before the flue gas can be discharged to the atmosphere.
4-34
-------
u>
Ul
99.99
99.9
99.8
99.0
9S.0
90.0
i i i i 11 i 1—i—i i i i ¦ i
i I 11 1 1 1—i—i i r r
ELECTROSTATIC PRECIPITATORS
B STAIRMAND. DRY ISP
• STAIKMANU, IRRIGATED ESP
~ WLIL CONDITIONED OUST, PARTICLE SIZING BY ELECTRON MICROSCOPE
¦ WLT ESI>. HIGH RESISTIVITY OUST, PARTICLE SWING BY ELECTRON HICROSCOPE
• NO INFORMATION EXCEPT 99.9S EFFICIENT
~ NO INFORMATION EXCEPT 99.9X EFFICIENT
» PILOT SCALE ESP ON COAL -FIRED BOILER; GAS VELOCITY 2.62 FT/SEC
A "TYPICAL" CURVE
0.01
O.OS
0.1
0.2
0.5
1.0
2.0
S.O
10.0
20.0
>-
u
s
»-«
u
u.
\h
S
~-»
t
ioj 99 99
100.0
PARTICLE DIAMETER - MICRONS
Figure 4-16. Fractional efficiency data for electrostatic precipitators.
Source: (17)
-------
TABLE 4-8. PARTICLE COLLECTION EFFICIENCY
EXHIBITED BY AN ESP (COLD-SIDE)
Particle Size
(Win)
ESP Collection Efficiency
(Z)
20
10
5
4
3
2
1.5
1.0
0.3
0.6
0.5
0.4
0.3
0.2
0.1
0.05
0.01
>99.9
>99.9
99.7
99.7
99.2
98.0
97.0
96.0
94.0
93.0
92.0
90.0
92.0
96.0
,57.0
94.0
90.0
Source: (41,69)
4-36
-------
TABLE 4-9. TRACE ELEMENT COLLECTION EFFICIENCY OF ESP'S
AT SEVERAL COAL-FIRED POWER PLANTS
ESP Collection Efficiencies (%)
Trace Elements Plant A Plant B Plant C Plant D
Aluminum
99.2
ND
99.6
98.9
Antimony
96.0
99.1
77.5
92.3
Arsenic
99.9
ND
97.5
88.5
Barium
99.9
ND
99.5
96.0
Beryllium
97.6
ND
ND
99.1
Boron
94.7
ND
ND
ND
Bromine
ND
ND
ND
99.8
Cadmium
95.5
98.8
96.7
91.2
Calcium
99.0
ND
99.6
98.7
Cerium
ND
ND
99.4
98.7
Cesium
ND
ND
99-0
98.8
Chlorine
4.5
ND
ND
ND
Chromium
85.6
99.8
98.6
96.2
Cobalt
98.2
ND
99.3
97.5
Copper
99.1
ND
99.3
ND
Dysprosium
ND
ND
ND
98.6
Euroqium
ND
ND
99.6
98.7
Fluorine
92.3
ND
ND
ND
Gallium
ND
ND
100.0
95.6
Hafnium
ND
ND
99.3
98.7
Inqiua
ND
ND
ND
94.6
Iron
98.6
99.6
95.3
98.7
Lead
91.6
99.3
96.6
94.5
Lanthanum
ND
ND
99.3
98.7
Lutetium
ND
ND
ND
98.6
Magnesium
99.0
ND
100
98.8
Manganese
98.6
100
99.1
98.4
Mercury
0.0
ND
ND
ND
(continued)
4-37
-------
TABLE 4-9. CONTINUED
ESP Collection Efficiencies (7.)
Trace Elements Plant A Plant B Plant C Plant D
Molybdenum
89.2
ND
ND
94.9
Neodynium
ND
ND
ND
98.7
Nickel
78.5
99.7
99.4
ND
Potassium
ND
ND
99.4
99.0
Rub idlum
ND
ND
99.4
94.5
Samarium
ND
ND
99.6
98.6
Scandium
ND
ND
99.5
98.5
Selenium
61.8
94.3
95.7
92.3
Silver
98.7
ND
ND
ND
Strontium
ND
ND
100
ND
Tantalum
ND
ND
99.3
98.7
Terbium
ND
ND
ND
98.6
Thorium
ND
ND
99.3
98.7
Titanium
99.2
ND
99.1
98.5
Tungsten
ND
ND
ND
92.8
Uranium
98.2
ND
98.6
96.3
Vanadium
92.2
99.9
98.7
96.3
Ytterbium
ND
ND
ND
98.7
Zinc
96.3
99.6
98.2
93.7
Zirconium
ND
ND
ND
98.6
Total Ash
99.1
99.7
99.5
97.0
ND - No data.
Bases:
1) Plant
A - 350
MW
unit with hot-
side ESP;
source: (40)
2) Plant
B - 105
MW
unit; source:
(73)
3) Plant
C - 290
MW
unit; source:
(19)
4) Plant
D - 625
MW
unit, source:
(27)
4-38
-------
4.3.3 Wet Scrubbers
4.3.3.1 Process Description —
Wet scrubber technology has been widely used to control gaseous (SO2,
NO^) and particulate emissions from combustion processes (1, 17, 53, 71,
72). This technology is made up of four basic types of scrubber: cyclone,
venturi, spray tower, and packed bed, or variations of these scrubbers (53).
The cyclone and venturi are best suited to remove particulates from the
flue gas, while turbulent contact scrubbers like the spray tower and packed
bed scrubbers are used principally to control gaseous pollutants (48, 53,
73). Regardless of its primary function, a wet scrubber can be expected
to reduce, to some degree, the level of trace element emissions from the
combustion process on which it is utilized (47).
4.3.3.2 Particle Scrubbers —
The cyclone and venturi scrubbers have been used primarily to remove
particles from the flue gas. These scrubbers characteristically exhibit
relatively high flue gas pressure drops as well as high energy requirements.
Wet cyclone scrubbers can have several configurations; however, in each con-
figuration the gas is set into rotary motion by being tangentially intro-
duced into the scrubber or by vanes in the scrubber (53). The particles
adhere to the liquid droplets and both are forced to the vessel's walls by
centrifugal forces (48, 53). The liquid is discharged at the bottom, and
the "clean" gas exits at the top. An illustration of a wet cyclone scrubber
is presented in Figure 4-17. Typical liquid-to-gas ratios in cyclone scrub-
bers range from about 5 to 15 gallons/1000 actual cubic feet of gas (48).
Collection efficiency is typically 96 percent for 2-3 ym particles at a
pressure drop of 1.3-2.3 inches of water (53). The primary advantages of
a wet cyclone separator are its enhanced particulate collection due to the
addition of a liquid, and its simplicity. Disadvantages associated with the
cyclone scrubber include: (1) increase in a plant's water and utility
requirements (2) significantly increased energy consumption when higher
removal efficiencies are desired, and (3) generation of a wastewater (48, 53).
4-39
-------
ClMn-gis outlet
Scrubbing liquor sprays
.ruboing liquor Inlet
ScniDbing liauor »nd
recs*tr*s Suit outlet
Figure 4-17. Diagram of cyclone scrubber.
Source: (48)
4-40
-------
Venturi scrubbers are often used when very high collection efficiencies
are required and where most of the particulates are smaller than 2 ym in
diameter (71). The venturi-type scrubber (Figure 4-18) achieves a relatively
high collection efficiency by introducing the scrubbing liquid at right
angles to the high velocity gas flow in the venturi throat. Gas in the
throat of a venturi typically attains a velocity of 200-600 ft/sec (53). The
velocity of the gases alone causes the atomization of the liquid; When the
venturi scrubber is primarily used to remove particles, it may be placed
in a vertical arrangement. This arrangement is claimed to produce turbu-
lent mixing of gas and liquid which results in a lower scrubbing liquor re-
quirements, as well as a lower pressure drop (53). Liquid rates for this
type of scrubber typically range from 5-20 gallons per thousand actual
cubic feet of gas. Gas-side pressure drop in Venturis typically ranges
from 5-15 inches of water (48). Venturi scrubbers are capable of over 99
percent removal of particles that are 2-5 vim in size (40, 48) . Primary ad-
vantages of venturi scrubbers are their relatively high removal efficiencies
for smaller particles and ability to remove particulate and gaseous pollu-
tants without requiring any physical modification. A venturi's main disadvan-
tage is the relatively high pressure drop and the corresponding energy
requirement necessary to attain a high removal efficiency. As with any
wet collection device, a wastewater is generated by a venturi scrubber.
4.3.3.3 Gas Scrubbers —
A schematic of a turbulent contact (spray tower) scrubber is presented
in Figure 4-19. In this type of scrubber, liquid is sprayed into the top
of the scrubber. The falling droplets encounter a countercurrent flow of gas
and collect particles by impaction and interception. Because of its rela-
tively low particle collection efficiency, this type of scrubber is primari-
ly used to remove gaseous pollutants (53). The primary advantages exhibited
by this scrubber are its:
• simplicity,
• dual removal of gaseous and particulate pollutants,
• relatively low pressure drop and corresponding low energy
requirements,
4-41
-------
G&S
IN
wmmmmmi
LIQUI0
IH
\
(J6 » LXQUJB
% tSTRMNWeNt
StPARAW
, veotUri B«ubbet
,q Schematic °
figure V18-
rre" (53)
Source•
4-42
-------
CLEAJMaAS OUTLET
SCRUBBING-MEOIUH
SPRAYS
SCRUBBER BODY
DIRTY-OAS
INLET
SCRUBBING LIQUOR AND
RECOVERED DUST OUTLET
Figure -4-19. Schematic of spray tower scrubber.
Source: (48)
4-43
-------
• minimization of dust reentrainment, and
• ability to be retrofitted to an existing plant.
Disadvantages associated with this scrubber are:
• relatively low collection efficiency of small particles,
• significantly high power requirements associated with increased
collection efficiencies,
• potential requirement of a mist eliminator due to significant
liquid entrainment, and
• generation of a wastewater that must be treated before it can
be reused or discharged (48, 53).
4.3.3.4 Trace Element Collection Efficiency —
As with other control devices, the ability of a wet scrubber to reduce
trace element emissions is expected to be correlated with its efficiency
for removal of snail particles. Shannon summarized collection efficiency
versus particle size data from a number of sources for various wet scrut-
bers (17). His results are shown in Figure 4-20. Three studies have con-
sidered the impact of wet scrubbers on trace elements emitted from coal-
fired utility boilers. Trace element collection efficiencies were calcu-
lated from this data and are presented in Table 4-10.
TRW, Inc. conducted some tests in which the ability of a pilot-scale
flue gas desulfurization scrubber to control trace element emissions frcm
a boiler that could be fired with coal or fuel oil was measured (20). The
trace element removal efficiencies exhibited by this scrubber are delineated
in Table 4-11 on the basis of the type of fuel fired in the boiler. These
data show that the trace element removal efficiency of an SO2 scrubber which
is applied to a coal-fired boiler is comparable to the removal efficiencies
exhibited by a particulate scrubber such as a venturi. The removal effi-
ciencies of the SO2 scrubber are generally lower for the oil-fired appli-
cation than for the coal-fired case. These results reflect the smaller
sizes of particles from the oil-fired boiler, and the subsequent diffi-
culty involved in capturing these particles (20).
4-44
-------
i 1—i—r-»
SCMMBERS
o SltlnunJ, brevity Sprey toner, 1m Ihm I U.Q p
O Stilntnd, laplngment Scrubber
• Stelminil, Or trie* Scrubber
T Stilnund, Venturl Scrubber
* Spriy lower, Soluble Duit (He..SO.), Optical t
flaeAly 0.0) rt
Counter, liquid llowrt Appro
~ Venturl Scrubber 'typical * Curve
Venturl Scrubber, HjW). Plant Hlft,
AprroalMtely JO In.AP
0.01
19.99
PARIICII DIMCKR - MICRONS
Figure 4-20. Fractional efficiency data for wet scrubbers.
Source: (17)
-------
TABLE A-10.
COLLECTION EFFICIENCIES EXHIBITED BY VARIOUS
WET SCRUBBERS FOR TRACE ELEMENTS DISTRIBUTED
ON FLY ASH
Collection Efficiencies ('/.}
Venturi (1) Venturi (2) Horizontal (3)
Trace Elements Scrubber Scrubber Scrubber
A1
99.5
99.7
ND
Ag
ND
9a.8
ND
As
96.3
92.1
98.0
B
ND
93.6
ND
Ba
99.5
99.0
6.0
Ee
ND
99.2
55.0-82.0
Br
ND
ND
ND
Ca
99.7
99.0
99.6
Cd
ND
92.3
46.0
Ce
>99.9
ND
ND
CI
98. a
ND
ND
Co
> 99.8
96.9
ND
Cr
96.1
88.9
ND
Cs
> 99.9
ND
NT)
Cu
ND
99.3
ND
Dy
> 99.9
ND
ND
Eu
> 99.9
ND
ND
F
ND
98.0
98.9
Fe
> 99.9
99.2
ND
Ga
99.5
ND
ND
Hf
> 99.9
ND
ND
Hg
ND
12.6
22.2
In
99.3
ND
ND
K
>99.9
ND
ND
La
> 99.9
ND
ND
Lu
> 99.9
ND
ND
Mg
99.9
98.5
ND
(continued)
4-46
-------
TABLE 4-10 . CONTINUED
Collection Efficiencies (2)
Venturi (1) Venturi (2) Horizontal (3)
Trace Elenents Scrubber Scrubber Scrubber
Mo
98.4
52.8
92.2-95.8
Mn
99.2
99.6
ND
Na
99.9
ND
ND
Nd
> 99.9
ND
ND
Ni
ND
95.0
90.8-98.0
Pb
ND
98.0
62.8-97.1
Rb
ND
ND
ND
S
ND
37.3
ND
Sb
95.5
99.3
83.0-50.0
Sc
> 99.9
KD
ND
Se
85.0
97.3
60.9-79.0
5 m
> 99.9
ND
ND
Sr
99.8
ND
ND
Ta
>99.9
ND
ND
Tb
ND
ND
ND
Th
> 99.9
ND
¦ ND
Ti
> 99.9
99.6
99.2
U
99.5
96.0
ND
V
99.2
97.0
89.0
w
97.4
ND
ND
Yb
>99.9
ND
ND'
Za
99.3
97.4
ND
Zr
> 99.9
ND
ND
ND - No Data
(1) Source: (34) (2) Source: (32)
(3) Data questionable because scrubber had not attained steady state opera-
tion. Horizontal scrubber is siailar in some respects to spray tower;
However, it has a lower power consumption. Source: (75)
4-47
-------
TABLE 4-11. COMPARISON OF TRACE ELEMENT REMOVAL EFFICIENCIES OF AN S02
SCRUBBER ON A COAL OR FUEL-OIL FIRED BOILER
Removal Efficiencies (")
Trace Fuel Oil- Coal-Fired
Element Fired Boiler Boiler
Be
Unknown
98
Hg
87
55
Ca
83
99
Mg
91
99
Sb
91
99
As
81
97
B
93
88
Cd
77
99
Cr
90
95
Co
89
99
Cu
99
99
Fe
95
99
?b
94
99
Mn
87
98
Mo
89
99
Ni
83
95
V
71
98
Zn
90
98
Se
87
97
Sr
98
99
Ai
92
99
Zr
94
99
Total
87
99
NOTE: SO2 scrubber is a double alkali unit.
Source: (20)
4-48
-------
4.3.3.5 Wastestreams Generated —
The operation of any wet scrubber results in the generation of an aqueous
wastestream. If particulate scrubbing is the only function performed, the
wastestream will be a wastewater containing suspended solids. This stream
can be combined with the bottom ash and treated or disposed of accordingly.
If SO2 is the primary function of the scrubber and the scrubbing process
is a "throwaway" system, a sludge is generated. The waste sludge, which is
approximately 55-60 percent solids and represents the largest volume of
solid waste generated by a coal- or oil-fired power plant, is sent to an
evaporative pond (usually with the bottom ash and fly ash slurries) or
mechanically dewatered. In many cases the solids are ultimately used as
landfill (2, 4, 7) .
Spent scrubber sludges principally contain calcium sulfate, calcium sul-
fite, sodium chloride, magnesium chloride, as well as detectable quantities
of trace elements (2, 7, 74). Disposal of these sludges in temporary or
permanent ponds or landfills may result in contamination of groundwaters and
is, therefore, of concern. In many cases, utilities minimize the potential
contamination of groundwaters by lining the disposal pond with an impervious
liner (4, 75). Holland, et al_. tested the leachability of trace elements
from waste sludges in unlined ponds (76). These researchers used waste
sludges from five operating power plants and found that selenium, boron,
and chromium pose the greatest threat to groundwaters; however, they also
found that typical soils can protect groundwaters to some degree from selen-
ium, boron, and chromium contamination. Clay was found to prevent the
occurrences of any contamination, while sandy soils provided the least pro-
tection .
4.3.4 Baghouses (Fabric Filters)
4.3.4.1 Process Description —
Although baghouses have not been widely utilized to control particulate
emissions from coal-fired utility boilers in the past, it has been estimated
that U.S. utilities will spend five billion dollars for baghouse systems
by 1985 (77, 78). This projected use of baghouses reflects the anticipated
extensive use of low sulfur, high-ash coal as well as the need to achieve
4-49
-------
greater control of particulate emissions. The first full-scale baghouse
application to a coal-fired power plant was installed at the Sunbury Steam
Electric Company in 1973 (79). Currently, several plants use baghouses 1:0
control particulate emissions. These companies, the type fuels and boilers
used, as well as the capacities of their baghouses are summarized In Table
4-12 (80). It has also been reported that the largest power plant in the
U.S. (Shawnee Power Plant in Kentucky) has committed $80 x 106 for the in-
stallation of 10 baghouse units (81).
A baghouse (Figure 4-21) removes particles by filtering the gas through
a fabric. As the dust cakes the fabric surface, the collection efficiency
of the baghouse increases. However, the pressure drop through the baghouse
also Increases until it reaches a point where the fabric must be cleaned.
Baghouses are normally classified by the techniques employed to clean the
fabric. The shaker-type baghouse is supported by a structural framework
which is free to oscillate when driven by a small electric motor. Period-
ically, one compartment is isolated so that no gas flows through it. During
this time, the isolated compartment is shaken for a specified period of
time to dislodge the cake into the hopper below.
In the reverse-flow type baghouse, individual compartments are again
isolated and an auxiliary fan forces air through the bags in the direction
opposite to the normal flow of gas. When the bag is reinflated, the cake is
dislodged and falls into the hopper. Reverse jet baghouses employ a mani-
fold which surrounds the bag and travels the length of the bag in a cycle.
A jet of high pressure air is shot from the manifold and blows the dust off
the filter.
In the reverse pulse type baghouse, a short pulse of compressed air
is sent through a venturi directed from the top to bottom of the filter.
The resulting air mass expands the bag and removes the dust cake (82).
Some of the more important design considerations for baghouses are:
(1) air-to-cloth ratio (filtering velocity), (2) filter drag, and (3) pres-
sure drop. The following sections discuss in detail the operating princi-
ples, applicability, design considerations, and operating costs for fabrilc
4-50
-------
TABLE 4-12. BAGIIOUSE INSTALLATIONS
Case
No.
Plant and Location
Fuel
Fuel Firing Equipment
Plant Capacity
on Bagliouscs t
8
9
10
1L
Alainltos, CA
Sunhury
Sliamokln, PA
Carborundum
Niagara Falls, NY
Amal. Sugar
NYSSA, OR
Amal. Sugar
Nampa, ID
Colorado UTE
ilo It wood, PA
Winston-Salem, NC
Winston-Salem, NC
du Pont
du Pont
No. 6 Oil
1.5-1.7% S
0.8% S anthracite
and up to 6% S
petroleum coke
(75/25 mixture)
Bituminous Coal
7% ash 2.3% S
Coal
Coal
0.6-1.9% S Coal
12% ash
Anthracite, fines
and petroleum coke
0.8% S Coal
0.8% S Coal
Coal
Coal
Source: (80)
+ Capacity rated In either
Source: (80)
Tangential tilting
return flow burners
Spreader
Spreader
Spreader
Pulverized coal
Spreader
Spreader
Spreader
Spreader
2,305,000 lb/lir
175 MW
75,000 lb/hr
200,000 lb/hr
150,000 lb/hr
3 units each
132,000 lb/hr
50% of 80 MU unit
75,000 lb/hr
40,000 lb/hr
megawatts (MW) of electrical power or pounds per hour lb/hr) of steam.
-------
COLLECTED DUST
Figure 4-21. Fabric filter (collection outside bags).
Source: (55)
4-52
-------
filters (82). The primary advantages of baghouses are their high collection
efficiencies for small (submicron) particles and insensitivity to changes
in coal ash content or ash characteristics (48, 53, 77, 79). Major disadvan-
tages of baghouse control devices are the temperature and chemical limita-
tions of fabrics that have been used, relatively short life of the filter
fabrics used and relatively high pressure drop and correspondingly high
energy requirements (19, 48, 80).
4.3.4.2 Particle Collection Efficiency—
Unlike most of the control devices that have been previously discussed,
baghouses are capable of controlling submicron particles with approximately
99 percent efficiency. The differences between the collection efficiencies
exhibited by baghouses and other control devices for small particles are
largely due to the mechanisms that control the collection of these particles
(81). The collection of the larger particles (>1 van) is controlled by impac-
tion and electrostatic attraction, while Brownian diffusion becomes the
controlling factor for particles that are smaller than 0.2 ym (40, 81).
Brownian diffusion is proportional to gas velocity and will, conse-
quently, be dependent in a baghouse on the air-to-cloth ratio (48, 88).
The air-to-cloth-ratio relates the volume of flue gas to the surface area
of the filter fabric. The impact of this ratio on the collection effi-
ciency of particles ranging in size from 0.1 to 10 ym is illustrated in
Figure 4-22. Based on a pilot plant test, McKenna ££ al_. (81) reported
the particulate collection efficiencies presented in Table 4-13.
TABLE *-13. DOST IOUTaL OTIC1DKIKS OSTALIED
Km Lie pilot ruurr tuts
Noki Felt Filter Media With
/U.r-co-Cloth l»dlo of %6
Fartlda Diuacer
Eaooval
X
<9.5
(
99.84
99.74
95.78
99.69
98.03
99.21
99.16
96.88
98.98
2.8
1.75
D.9
0.54
0.36
<0.36
¦same (n>
4-53
-------
96
99
99.9
99.S9
o
KEY AIR/CLOTH
J 1 I I I I I
1 i I i i i i
0.1
Figure 4-22.
Source: (81)
1.0
PARTICLE DIAMETER (MICRONS)
Fabric filtration collection efficiency vs
particle diameter.
10
4-54
-------
The particulate collection efficiencies of a commercial-scale baghouse
that is being utilized at the Nucla Power Plant (a western coal-fired spread-
er stoker power plant) are presented graphically in Figure 4-23. As this
figure shows, the baghouse's median overall collection efficiency was con-
sistently above 99.4 percent; there is, however, an obvious lack of data
regarding the collection efficiency of submicron particles.
4.3.4.3 Trace Element Collection Effiency —
Data reflecting the trace element collection efficiency of a baghouse
is very limited. Yeh et al. reported that a baghouse was superior to an
ESP in reducing toxic trace element emissions from a coal-fired combustion
(83). In this study, the collected fly ash and slag retained an average of
91 percent of arsenic in the coal, 77 percent of the Be, 55 percent of the
Cd, 82-100 percent of the Hg, 63 percent of the Pb, and 87-100 of the Se
at optimum conditions. Additional trace element collection data was ob-
tained from application of baghouses at a coal-fired power plant and
steel mill (46, 73). These collection efficiencies are presented in Table
4-14.
TABLE 4-14.
TRACE ELEMENT COLLECTION EFFICIENCIES
EXHIBITED
BT BAGHOUSE
COLLECTORS (X REMOVAL)
POWER PLANT
Steel
Trace Eleaenc
11 HV Load 12
W Load
Mill
Al
100
100
__
Ca
100
100
—
Cr
—
—
99.9
Cu
—
100
100
r«
>99.9
100
—
—
—
99.8
Pb
>99.9
100
—
Hi
—
100
100
S
>99.9
55.2
—
SI
100
100
—
Ti
100
100
—
U
—
—
100
Zn
100
100
—
Source (31, 46)
4.3.4.4 Wastestreams Generated —
Two wastestreams exit the baghouse, the collected fly ash and flue gas.
Collected fly ash will contain those trace elements that are condensed on
4-55
-------
io. a
90.0
1 2 3 4 5 6 7 8 9 10 11 12 13 14
PARTICLE SIZE, urn
o
Ui
3
99.9
Figure 4-23. Median fractional efficiency for 22 tests,
Source: (45)
4-56
-------
the fly ash. Because this stream is dry, it may be an excellent source for
the recovery of valuable metals (9, 43). However, the economics of this
procedure may be prohibitive and must be carefully analyzed. In a typical
facility, the collected ash is combined with boiler bottom ash and sent to
a final disposal process (4). The flue gas normally contains relatively
little fly ash; however, the gas could contain significant levels of gaseous
pollutants. The levels of these pollutants might require further reduction
before the flue gas could be discharged to the atmosphere.
A.3.5 Anticipated Future of Trace Element and Fine Particulate Control
Processes
Mcllvaine reported in a study to the EPA that 66,000 Mw of high sulfur
coal burning boilers and 67,000 Mw of low sulfur coal burning boilers will
be ordered by 1982 for installation by 1985(81). Because low sulfur coal
has a relatively high ash content and high ash resistivity (which makes use
of electrostatic precipitators difficult), baghouses are expected to be
utilized in 45 percent of these facilities, either singly or combined with
another control process (such as an SO 2 scrubber). It has also been esti-
mated that baghouses will not be used in any of the future high sulfur, low
ash installations. Precipitators are anticipated to be used in 45 percent
of the low sulfur facilities and 85 percent of the high sulfur installations.
Wet particulate scrubbers will be used for 10 percent of the low sulfur
installations and 15 percent of the high sulfur installations. In addition
to new units, about 8,000 Mw yearly of existing capacity will have to be
brought into compliance with particle regulations; of these retrofitted
installations, 20 percent are expected to be baghouses, 10 percent scrubbers,
and 70 percent ESP's. A summary of these projections for future use of
control processes is presented in Table 4-15. The predicted increase (based
on installed costs) of particulate control equipment in the utility sector
from 1976 to 1982 is depicted in Figure 4-24. Overall, in the industrial
and utility sectors, it is predicted that between 1976 and 1982 the total
air pollution control equipment market will increase 500 percent - from 1.7
to 5.2 billion dollars (81).
4-57
-------
TABLE 4-15. ESTIMATED FUTURE USE OF VARIOUS CONTROL PROCESSES
New Installations New Installations
Low Sulfur High Sulfur
(67,000HW) (66.000MW)
Retrofit
Inctallat j.on:
(8.000MV)
ESP's
Baghouses
Wet, Particle
Scrubbers
45%
45%
10%
85%
0%
15%
70 %
20 %
10 %
Source: (81)
4-58
-------
1.500
z 1.GDC
v*--
0.?
fm«: F'lTl*s
1377 i;-73
1579
rws
1361
l?c2
Figure A-24. Anticipated use of various particulate control
devices in the utility industry.
Source: (81)
4-59
-------
4.4 COST OF FINE PARTICULATE AND TRACE ELEMENT CONTROL PROCESSES
Since it has been speculated that baghouses, ESP's, and particulate
scrubbers will be used extensively by the utility industry for particle
control, it is germane to examine and compare the costs associated with
these devices.
4.4.1 Baghouse Costs
Although baghouses are currently being used in the utility industry on
a commercial scale and are expected to become more popular for controlling
particles, little cost information is available for this control device.
The capital costs of baghouses are dependent on the filter media used
and the air-to-cloth ratio. Mycock estimated the installed costs of a
baghouse designed to handle a 150,000 ACFM slipstream from a 250,000
lbs/hr pulverized coal boiler (81) . These costs were developed for throe
different filter media and air-to-cloth ratios on the bases of actual
bag manufacturer quotes obtained in 1978. Table 4-16 shows the costs o:
the bags as a percentage of the installed costs.
TABLE
4-16. tiC COST AS
A PERCENT OF
INSTALLED COST
Instilled
Bag Coat
X of Inatallad Coat
Filter Media
Coat (»)
($)
Due to Bag Coat
Woven Glass
2/1
1,387,530
97,200
7.0
4/1
784,900
51,(40
6.6
6/1
338,860
34,560
6.4
Teflon Felt
2/1
1.568,970
343,440
21.9
4/1
SSI,668
183,168
20.8
6/1
626,412
122,112
19.5
Teflon Woven
2/1
1,400,490
174,960
12.5
4/1
791,812
93,312
11.8
6/1
566,506
62,208
11.0
Source: (61)
4-60
-------
Ensor et_ al. present a detailed review of the capital and operating
costs of the retrofitted baghouse installation at the Nucla Power Generator
Station in their report (46). Three baghouses were retrofitted to three
12,650 Kw spreader stoker boilers In 1973-1974; capital costs associated
with these Installations are delineated in Table 4-17. Also presented In
this table are the approximate 1978 installed system and unit costs which
were estimated using the Marshall and Stevens (M&S) cost Indices (84).
Ensor also reported operating costs which reflected only new or additional
expenses incurred by the plant as a result of the baghouse operation.
These costs were reported on the basis of 1976 dollars and are presented
in Table 4-18.
4.4.2 ESP Costs
Electrostatic precipitators are highly sensitive to fly ash character-
istics such as fly ash resistivity. The capital costs are a function of
collector area which is in turn a function of parameters such as fly ash
loading, fly ash resistivity, and flue gas flowrate. Detailed capital costs
for ESP's were developed by the Industrial Gas Cleaning Institute (IGCI) for
the EPA (85). These costs were developed for various types of coal,
boiler sizes, emission limits, and types of ESP's (hot-side and cold-side).
The capital costs IGCI developed for the following cases are presented in
Table 4-19:
• Case 1 - a cold-side ESP on a 200 Mw boiler and a .03
lb/106 Btu emission level,
• Case 2 - a hot-side ESP on a 200 Mw boiler and a .05 lb/106
Btu emission level,
• Case 3 - a hot-side ESP on a 200 Mw boiler and a .03 lb/10s
Btu emission level, and
• Case 4 - a hot-side ESP on a 700 Mw boiler and a .03 lb/106
Btu emission level.
In all these cases, the coal composition was the same; consequently, the
data in Table 4-19 show the impact of ESP size and location and emission
level on capital costs of ESP's on utility boilers. Annualized operating
costs for the cases presented in Table 4-19 are given in Table 4-20.
4-61
-------
TABLE 4-17.
CAPITAL COSTS ASSOCIATED WITH INSTALLATION
OF BAGHOUSE AT NUCLA POWER PLANT
Baghouse Equipment and Installation Coat
Earthwork
Concrete - foundation
Structural - stairways, handrails
Process Equipment
Baghouse (material only) $631,000
Ductwork (material only) $113,000
Labor & Other Equipment $347,000
Total Process Equipment
Piping - drainage and air
Electrical
Painting
Iastruaentat loo
Insulation
Fly Aah Conveyor System Equipment and Installation Cost
Earthvorlt
Concrete - foundation!
Equipneot - controls, valves
blowers
Pneumatic conveyor Haas
Electrical
Painting
Inat ruments
Retrofit Equipment and Installation Cost
Earthwork
Demolition - ductwork, concrete
Modifications
Ash system
Rebuild and balance I.D. fans
Stacks, rebuild tops and relocate
Condensate and compressed air piping
Air preheater bypass
Electrical
Instruments
Painting
Insulation
TOTAL FIELD COST
Indirect Owner Cost
AdsinistratIon
Engineering and Supervision
All Risk Insurance
Interest During Construction
Travel. Vehicle, Office, Miscellaneous
Engineering and Fee
1973/19 74 nSTALLED SYSTEM COST
APPROXIMATE 19 78 INSTALLED SVSTE1 COST
1978 I'nlt Costs - S100/leu
- S15/ACFY
- Sil.b/ft1 ci filter
39,000
75,000
48,000
$1,091,000
36,000
200,000
50,000
50,000
130,000
1,000
10,000
130,000
37,000
32,000
20,000
5,000
10,000
5,000
56,000
19,000
22,000
16,000
24,000
3G.0C0
20,000
6,000
4,000
11,000
52,220,000
$ 4,000
$ 31,000
S 19,000
$ 44,000
$ 22,000
$ 300,000
$2,620,000
$3,590,000
Source: (46)
4-62
-------
TABLE 4-18. ESTIMATED COST OF OPERATING BAGHOUSES AT THE
NUCLA POWER PLANT
$/year
Percent
mills/kvh
Direct Costs
Operation Labor*
Maintenance Labor
Maintenance Material
Utilities
Ash Handling
Subtotal, Directs
(9,500)
2,500
8,500
31,000
11,000
$ 53,000
(3.3)
0.9
3.0
10.8
3.8
18.5
(0.05)
0.01
0.05
0.16
0.06
0.28
Indirect Costs
Depreciation - 4.92
Interest - 3.47.
Insurance - 0.1%
Taxes
Subtotal, Indirects
TOTAL
127,000
81,000
3,000
23,000
$ 234,000
$ 287,000
*Not added since no new costs were incurred.
Source: (46)
44.3
28.2
1.0
8.0
81.5
100.0
0.68
0.43
0.02
0.12
1.25
1.53
4-63
-------
TABLE 4-l». INVESTMENT COSTS Of ESP*8 OK VMIOUI DTILITT KILOS
CASE:
1
2
3
4
Boiler ilce, KV
200
200
200
700
Precipitator Type
Cold
Bot
lot
Bot
Inlet and Outlet Cae Tlcm
¦ ef a
798,000
985,000
985.000
3,450,000
°r
350
700
700
700
icfa
921.000
450,000
450,000
1,180,000
Molature, Vol, X
10
10
10
10
Inlet gr/acf
1.76
1.43
1.43
1.43
Inlet lb/hr
12,000
12,000
12,000
42,200
Outlet gr/acf
0.009
0.012
0.007
0.007
Outlet lb/hr
60
100
60
210
R£ibdv«1 efficiency, 2
99.4
99.2
99.5
99.5
£al9ileo Control Lewi,
ng/joulc
1)
22
11
13
(lb/10* Itu)
(0.03)
(0.05)
(0.03)
(0.03)
Equipment Coata
Dtvlc*
2,066,100
1.546,100
1,837,000
6,007,300
Auxiliary equipment
207,(00
190,200
196,000
609,400
Ash handling equlpo^nt
75,(00
47,500
52.500
212,700
Total
2,329,300
1.783,800
2,095,500
(.829,400
Installation Coats - Direct
Foundation and supports
173,000
151,900
166,600
500.500
Insulation
436,(00
388,700
424,700
1,372,000
Painting
5,(00
5,300
5.600
7,200
Electrical
181,600
133.300
205, WO
664,000
Other
1,231,900
949.200
1,144,200
3,574,900
Total
2,078.700
1.62A,400
1,946,400
6,119,200
Installation Coats - Indirect
Engineering
131,200
127,700
129,600
193,100
Construction fc field expanse
127,700
89,600
107,000
399,900
Construction fees
26,900
27,000
28,000
69,500
Scart-jp
11,900
11,100
12,300
36 , 300
Performance testa
25,800
25,800
25,800
56,000
Contingencies
87,800
64.600
76,000
2(7,100
Total
*13,100
345,BOO
378,700
1,021,900
Total Turvkay Coat
$4,821,100
$3,758,000
$4,420,600
513,970,500
5/kW Investment (1976)
24.11
18.79
22.10
19.96
(19 78)
27.97
21.30
25.64
23.16
Sourca: (81)
4-64
-------
TABLE 4-20. ANNUALIZED OPERATING COSTS OF ESP'S ON
VARIOUS UTILITY BOILERS
Caaa
l
2
3
4
¦ollar Siaa, HV
200
200
200
700
Precipitator Location
Cold
Bee
Cold
let
lolac and Outlat Gaa new
•ch
790,000
983,000
983,000
3,430,000
•T
330
700
700
700
Ufa
121,000
430,000
430,000
1,380,000
HoleCura
10
10
10
10
Particulate Loading
Inlet gr/aef
2.31
1.63
1.43
1.43
Inlet lb/hr
13,900
12,000
12,000
42,200
Outlet gr/ac1
0.009
0.012
0.007
0.007
Outlet lb/hr
60
100
60
210
loovtl efficiency, Z
99.6
99.2
99.3
99.3
Ealailoo Control Level
U
23
22
ng/Joule
13
22
13
13
(lb./10* leu)
(0.03)
(0.03)
(0.03)
(0.03)
Operating Coat Itea unit cost
Direct Coata
Operating Labor
Operator $10/aaa-hr
9,130
9,130
10,840
27,280
Supervisor 912/miD-hr
2,320
2,320
2,320
3,780
Total
11,630
13,360
11,630
31,060
Maintenance
Labor $i0/man-hr
10,980
11,130
11,730
38,840
lUcerlala
1,070
3,390
3,180
12,950
Total
14.030
13,340
14,330
31,790
Baplaceaeat Pirn
7,300
U. 000
9,300
37.000
Utllltlaa
Electricity 50.03/kwb
123,330
212,690
168,830
633,730
total Direct Coata
136,530
233,290
204,330
753,380
Indirect Coata
Overhead Charges
Payroll 20Z oper. lab
. 2,330
1,680
2,330
6,210
Plant $02 lab. &
¦alot.
13,160
14,350
12,990
41,430
Total
13.190
17,030
13,320
47,640
Capitalization 171 of
Qiarges loveacMnt
327,930
731,300
638,830
2,374,990
Total Indirect
Charge*
9363,930
768,330
5634,190
$2,422,630
Total Aanuailied
Cost
$699,670
>1,020,920
9838,310
$3,176,210
Kills/Itwh Oper- (1976)
etlng Cost
0.40
0. 38
0.49
0.32
(1978)
.46
.61
.47
.60
Eaala: 6,760 operaeiag houra per
yaar at 632
capacity factor
Source: (85)
4-65
-------
4.4.3 Wet Particulate Scrubber Costs
Although wet particle scrubbers have been widely used in the utility
industry, there has been no recent literature reporting detailed capital
and operating costs for these devices. However, PEDCo (see Glossary)
reported capital and operating costs for several particulate control
alternatives including a venturi scrubber (86). Pertinent parameters
used to develop the cost of the venturi are presented in Table 4-21.
The estimated capital and operating costs associated with achieving two dif-
ferent emission levels with a venturi scrubber are presented in Table 4-22.
4.4.4 Comparative Costs of Particulate Control Devices
Recent cost data are unavailable in many cases and inflation obscures
attempts to develop good cost data on the basis of escalation. However, the
relative costs of achieving a given emission level with various particulate
control devices can be assessed. Stearns-Roger developed an economic com-
parison between a baghouse and an ESP for a 500 Mw utility boiler; their
costs are presented in Table 4-23 (87). The operating costs associated with
utilizing a baghouse and various ESP' s on a 500 Mw utility boiler are can-
pared in Table 4-24 (87). PEDCo developed capital and operating costs Df
a cold-side ESP and a venturi scrubber for two emission levels and several
sizes of utility boilers; these costs are compared in Table 4-25 (45).
4.5 COMBINING CONTROL PROCESSES TO INCREASE COLLECTION EFFICIENCY
Because of the stringent emission standards that are being established,
two or more control processes can be combined in order to reduce the
emissions of particulate and gaseous pollutants so that the standards may
be met. A recent survey of 43 new or proposed boilers indicates that
nearly half of these installations plan or do use a combination of pro-
cesses for particle and SO2 control (58). In such instances, it is of
interest to project the overall collection efficiency that can be achieved.
The mathematical technique that can be used to predict the overall
efficiency attained by a sequence of processes is presented in Table 4-26
and an explanation of this technique follows. The control sequence is
assumed to be a dry cyclone separator followed by an electrostatic
4-66
-------
TABLE 4-21. VENTURI SCRUBBER DESIGN PARAMETERS
ReRulation Level,
nE/J (lb/10' Btu)
Control
Svstem
Design Parameter
43
(0.1)
22
(0.05)
Ven curi
scruhbcr
L/G ratio. 1/m'
(gal/1000 acf)
2
(15)
2
(15)
Gas velocity, m/sec
(fc/sec)
38
(125)
38
(125)
Pressure drop, nm H?0
(in. HjO)
203
(8)
762
(30)
Source • (86)
TABLE 4-22. ESTIMATED COSTS OF A PARTICLE VENTURI SCRUBBER (Mid-$19 80)
Particulate Control Alternative
Venturi Scrubbers
Coal Boiler Annual Cost
Regulation Sulfur Ash Capacity Capital Cost (mills/lcwh)
Level (%) (%) (megawatts) ($/kW) O&M Fixed
22.0 ng/j
(.05 lb/106 BTU)
3.5 14.0 25
100
500
1000
43.0 ng/j
(.1 lb/106 BTU)
3.5 14.0 25
100
500
1000
Source: (91)
178.48
128.10
72.63
68.65
1.45
1.30
0.80
0.78
7.15
5.15
3.03
2.87
112.52
99.97
58.67
57.21
1.42
1.26
0.77
0.75
4.51
4.02
2.45
2.39
4-67
-------
4
>
TABLE *-23. CAPITAL COST COMPARISON TO* MGHOOSE AMD ESP'8 Ml * 500 W Willi? KltLEI
*>
I
a*
00
Coal
Collector
Type
Halt
(lb/10• BTOJ
Mlnlmia
Efficiency
X
8CA or A/C Ratio
(ACPK/ft')
Caa
10*
flou,
ecfm
Collection
Area
(60 ' ft ')
No. Hndulea
Value factor
Capital
IneeataERt
(510* 1977)
Hot-Side
esp
0.10
0.03
0.014
99.18
99.64
99.50
368
462
683
2.68
2.68
2.68
985
1239
1830
--
—
23.2
26.3
33.0
Wyoaini
European
Cold-Side
ESP
0.10
0.05
0.01*
99.28
*9.6*
99.60
536
70*
1155
1.86
1.86
1.86
996
1309
2148
__
—
19.)
24.0
35.6
Fabric
filter*
—
1.93
1.93
1.91
1.86
1.86
1.86
964
28
20
49
1.06
1.0*
1.25
14.1
14.1
16.9
North
Dakota
Aacrlcao
Cold-Side
ESP
0.10
0.05
0.01*
99. J*
99.67
99.91
326
*10
588
2.41
2.41
2.41
785
987
1418
—
—
17.1
19.6
2*.*
Lignite
Fabric
filter
—
1.93
2.41
1332
30
1.05
17.2
Hot-Side
ESP
0.10
0.05
0.014
98.15
99.11
99.SI
263
336
515
2.41
2.43
2.43
643
824
1261
17.2
19.8
25.6
Aaerlcan
Cold-Side
ESP
0.10
0.05
0.014
98.65
99.32
99. il
*73
336
1050
1.97
2.41
1.97
928
824
2061
—
—
16.1
19.6
26.0
Alabaaa
European
Cold-Slda
ESP
0.10
0.05
0.014
98.65
99.12
99.81
420
610
1030
1.97
1.97
1.97
825
1238
2063
—
17.1
19.2
26.0
fabric
filter
—
1.93
1.97
1086
20
1.06
1*.9
Eaetera
¦lgji
Sulfur
Aaerlcan
Cold-Side
ESP
0.10
0.05
0.01*
99.*8
99.74
99.91
4*1
567
830
2.0
2.10
2.10
917
1191
1743
16.*
19.1
24.0
fabric
filter
—
1.91
2.10
1161
70
1.06
15.6
Tliree f l(uree ahova (or the fabric filter applied to Wyoalns coal are, froa top to bo(t
-------
TABLE *-24. COMPARISON OF ANNUAL OPERATION ANO MAINTENANCE COSTS POR MCIIOUSB AND RSP'S
IVR A 500 HW UTILirr BOILER
Cbal
Collector
I
ON
v©
lalailoa
Llolt
(lb/10*
Collection Syitw
Aeh-KaaoTel STitf
Collection
Aral
Operetloa
NalntcntDca
(S/yr)
Materiel Labor
Operation
Maintenance
($/yr)
Material Labor
Total Opirttloa
(ion 4 Main-
tenance
Hot-Side
ESP
*
O ^ N
-4 o O
o o o
0.985
1.2)9
1.830
20.000
20,000
20.000
25,000
31.000
43,000
25,000
31.000
45,000
60,000
60.000
60,000
30.000
37,000
35,000
40,000
37,000
35,000
190,000
216.000
380,000
Vyoaiag
Europeaa
Cold-Side
EPS
0.10
o.os
0.014
0.996
1.309
2.148
20,000
20,000
20,000
IS,000
20,000
32,000
15,000
20,000
32.000
60,000
60,000
60,000
10.000
13,000
21.000
10.000
13,000
21,000
130,000
146,000
186,000
Fabric*
Filter
—
0.964
20,000
20.000
20,000
270,000
133,000
270,000
34.000
17,000
34,000
60,000
60,000
60,000
7,700
7.700
14.000
7,700
7,700
14,000
400.000
248,000
412.000
fcrth
Dakota
Lignite
American
Cold-Side
ESP
0.10
o.os
0.014
0.783
0.987
1.418
20.000
20,000
20,000
20,000
23,000
33,000
20,000
23.000
35,000
60.000
60,000
60,000
7.900
10,000
14,000
7,900
10,000
14,000
136,000
150.000
178.000
Fabric
niter
—
1.249
20,000
330,000
44,000
60,000
10,000
10,000
493,000
Hot-Side
ESP
0.10
o.os
0.014
0.64S
0.824
1.263
20,000
20,000
20,000
16,000
21,000
32,000
16.000
21.000
32,000
60,000
60,000
60,000
19,000
25,000
38,000
19,000
25,000
38,000
130,000
172,000
220,000
•—
Aaerlcen
Cold-Side
ESP
0.10
0.05
0.014
0.928
1.238
2.063
20,000
20,000
20,000
32,000
43,000
72,000
32,000
43,000
72,000
60,000
60.000
60,000
9,000
12,000
21,000
9,000
12,000
21,000
162,000
190,000
266,000
Earopean
Cold-Side
ESF
0.10
o.os
0.014
0.82S
1.094
1.816
20,000
20,000
20,000
12,000
16,000
27,000
12,000
16,000
27,000
60,000
60,000
60,000
8,300
11,000
18,000
8.300
11,000
18.000
121,000
134,000
170,000
Fabric
FUter
—
1.021
20,000
286,000
36,000
60.000
8,200
8,200
419,000
Aaerlcan
Cold-Side
0.10
o.os
0.927
1.191
20,000
20,000
32,000
42,000
12,000
42,000
60,000
60.000
9.300
12,000
9,300
12,000
162,000
188,000
Eaetere
Ugh-
Sulfur
ESP
Fabric
FUter
0.014
1.743
1.088
20,000
20,000
61,000
305,000
61,000
38,000
60.000
60.000
17,000
8,700
17,000
8,700
230,000
440,000
• Entrlee for Ityoalng coal applied to the fabric filter repreaeot three alternatlvee — froa to to bottom, the 20*
-------
TABLE 4-25. CAPITAL COST COMPARISON OF AN ESP AND A VENTURI SCRUBBER
I'AR'I'ICUlAfK CONTKOI. Al.TtKNAllVfc
Ri'p.ulnt Ion
I.eve I
Coal
Sulfur
(*)
Anli
(X)
F.ilirlc Kilters
Roller Capital Annual CokI
Capacity Cost (ml Ils/kWh)
(¦pg.iunt t s) ($/kU) OfcM Fixed
Elect rout atIc
I'rec Ipltatom
Capital Annual Cost
Cost (¦!IIs/kWh)
($/I.W) O&M Fixed
_ Venturl Scrubbers
Capital Annual Cost
Cost _4piJL1 lo/_KW|i}_
($/kW) OAM Fixed
17.0 nr./(
3.5
14.0
25
100
500
1000
B9.90
53.1ft
28.21
24 . 76
1.81
0.91
0.47
0.41
2.68
1.59
0.84
0.74
178.48
128.10
72.61
68.65
1.45
1.30
0.80
0.78
7.15
5.15
3.03
2.87
43.0 nR/J 3.5 14.0 25 91.80 1.82 2.74 112.52 1.42 4.51
100 51.11 0.87 1.53 99.97 1.26 4.02
500 26.R5 0.45 0.80 58.67 0.77 2.45
O 1000 23.61 0.39 0.71 57.21 0.75 2.39
H l.evel exntnlned wan 13.4 ng/J.
^ Costs are for Venturis an an Integral part
of .i flue gas desulfurIzatIon system.
Source: (45)
-------
TABLE 4-26. PREDICTED OVERALL COLLECTION EFFICIENCY FOR A CYCLONE AND
ESP COMBINATION
Particle Sice Fraction Fraction of Klectrnslallc
Partlclc Slxe
DlstiJbutlout
Hlctona
Hlilpnlut
of Rrtttge,
Microns
ol Total
Ihial In
Rouge, t
Cyclone
tfflclcnry at
Midpoint. X*
Dust
Collected
In Cyclone, X
Duat f run
Cyclone In
Range
Precipitator
Ef 1 lc lenry at
Midpoint, I
Duflt
Collectcd
In ESP, t
0-2.5
1.25
12
*
11.5
4.0
50.1 x
7/.0 -
18.7
2.5-5
J.75
8
X
64.5
5.2
17.6 x
90.5 -
16.0
5- 7.5
6.25
6
X
76.7
4.6
8.8 x
94.0 »
8.1
7.5-10
8.75
4
X
84.2
1.4
1.8 x
95.0 -
1.6
10-15
12.50
8
X
89.1
7.1
5.7 x
95.5 -
S.4
15-20
17.50
7
X
92.0
6.4
1.8 x
96.0 -
1.7
20-10
25
in
X
94.1 -
9.4
1.8 x
96.5 -
1.7
10 40
15
10
¦
96.0
9.6
2.5 x
96.8 -
2.4
40-60
50
15
X
97.1
14.6
2.5 x
97.7
2.4
60-75
67.50
10
X
98.5
9.9
0.6 x
98.7 -
0.6
75-104
89.50
7
X
99.1
6.9
0.6 x
99.2
0.6
104-150
127
1
X
100.0
JL0
84.IX
85.4X
MflclciwICfl
Calculating emitted dust fro* collected: ^ ^ ^
Percent of 1.25 Micron dust emitted - 84~l""
Calculating combined efficiency:
Cyclone traction emitted ¦ 1,000 - O.HM * 0.1)9
riccl|iltalor fraction emitted " 1.000 - 0.8)4 - 0.146
Combined fraction emitted ¦ 0.159 x 0.146 ¦ 0.0232
Combined fraction collected ¦ I - 0.0232 ¦ 0.9/7
Combined percent collected " 9/.7X
-------
precipitator. Knowing the size distribution of fly ash discharged from
the boiler and the cyclone's collection efficiencies for the various
particle size ranges allows the percentage removal of particles in a given
size range to be calculated. The summation of the respective collection
efficiencies yields the total collection efficiency exhibited by the cy-
clone. Since the cyclone removes the different sized particles to varying
degrees, the fly ash exiting the cyclone exhibits a new size distribution.—
The fraction each particle size makes up of the distribution can be cal-
culated by the following expression:
% of total distribution for given particle size = ^qq ^ (4-1)
where:
A = fraction of fly ash leaving boiler (%),
B = fraction of fly ash exiting control process (%), and
C * overall collection efficiency of control process {%).
For a 1.25 |_ra particle, the fraction of the fly ash exiting the cyclone is
50.3 percent. By multiplying the fraction of each si2e range that makes
up the total fly ash exiting the cyclone by the collection efficiency
exhibited by the ESP for each size range, the fraction of dust collected
in each range is calculated. As before, summation of these collection
efficiencies yields the ESP's"overall collection efficiency. Once the
overall efficiency of each process is known, the efficiency of the combina-
tion is calculated as follows:
Cyclone fraction emitted = 1.00 - 0.841 = 0.59
Precipitator fraction emitted = 1.00 - 0.854 ¦ 0.146
Combined fraction emitted = .159 x .146 = .0232
Combined fraction collected = 1.0 - .0232 = .977
Combined percent collected - 97.7%
The overall collection efficiency that is achieved by a combination of
control processes for a specific trace element can be approximated by an
approach that is similar to the one presented in Table 4-26; however, addi-
tional data that correlate trace element concentration and particle size are
4-72
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required. These data may be expressed in units of concentration or en-
richment. Enrichment is defined as the fractional distribution for an
element in a stream relative to the fractional distribution for ash in that
stream. For example, assume 1.6 percent of the ash is emitted as fly ash.
If no enrichment (increase in concentration) occurs for the trace metal
being considered, then 1.6 percent of that metal is emitted in the fly
ash. If, however, 1.85 percent of that metal is emitted, then its sub-
sequent enrichment is about 1.85/1.6 or about 1.15. If an enrichment
factor of less than one occurs then the specie has been depleted. In
order to illustrate how the overall trace element collection efficiency —
of a treating sequence could be approximated, it is assumed that the
sequence will consist of an electrostatic precipitator followed by a
venturi scrubber. The electrostatic precipitator is assumed to have an
overall collection efficiency of 85 percent for copper. Calculation of
the venturi's collection efficiency is shown in Table 4-27 (63).
4.6 EMERGING CONTROL TECHNIQUES
The utility industry is currently investigating various ways to reduce
trace element emissions. One technique involves washing the coal with a
solvent before it is combusted; however, no information on the effectiveness
of this technique is ava'ilable (88-90). Experiments conducted with a
bench-scale, fluidized-bed combustion have shown that fluidized combustion
offers significant potential for reducing trace element emissions (91, 92).
Several processes are currently being developed to achieve further
removal of fine particles and, correspondingly, trace elements. These
processes are in various stages of development ranging from conceptual
design to full-scale operating units. Those processes that appear to be
the most promising at this time are briefly discussed below.
4.6.1 Steam-Hydro Air Cleaning System
This system has recently been developed by Lone Star Steel and utilizes
a high-speed steam drive with injected water to reoove particles. Nor-
mally, the system operates on energy produced by waste heat captured from
the process being controlled. The heat is used to generate steam in a
4-73
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TABLE 4-27. APPROXIMATION OF VENTURI SCRUBBER'S COPPER COLLECTION EF7ICIEJC7
Venturi*
Characteristics of Ash Exiting the ESP „ _
Q Concen- Removal Concen-
Particle1 Ash Fraction1 tration Efficiency tration
Size (ym) Distribution(Z) Enrichment1 A2 (X) B*
> 8.0
9.5
X
1.4
13.30
X
100
13.30
5.0-8.0
11.4
X
1.8
20.52
X
99.5
20.42
3.3-5.0
16.6
X
1.5
24.90
X
99.15
24.69
2.3-3.3
11.6
X
1.7
19.72
X
99
19.52
1.5-2.3
20.9
X
2.0
41.80
X
99
41.38
.74-1.5
17.2
X
2.4
41.28
X
96.86
39.98
.45-.74
8.6
X
2.6
22.36
X
91.5
20.46
.30-.45
2.7
X
2.7
7.29
X
78
5.69
< .30
1.6
X
9.7
15.52
X
70
10.86
I A
206.69
I B
196.57
Overall venturi collection efficiency for copper x
A
-952
Overall collection efficiency of sequence:
ESP - 1 - .85 - .15
Venturi ¦ 1 - .95 ¦ .05
Fraction emitted ¦ .15 x .05 ¦ .075
Combined fraction collected ¦ 1 - .075 ¦ .9925
Combined collection efficiency ¦ 99.25%
xAsh characteristics from (63)
Concentration A » Concentration of copper on given particle size exiting
if no further control used.
3Ty?ical venturi particle size collection efficiencies from (AO).
"Concentration B « Concentration of copper removed in each size range.
A-7 4
-------
waste heat boiler. Steam requirements are reported to be 0.002-0.01 lb/ft3
of gas, while required water rates are approximately 230 lb/1000 ft3 of
gas.
Preliminary tests indicate that 99.5 percent collection efficiency
could be obtained for a dust having a mass mean diameter of 1.5 microns at
an average loading of 1.26 grains/scf. Based on the results of preliminary
tests, the Steam-Hydro system offers excellent promise as a new system for
the control of fine particle emissions (41, 93).
4.6.2 ADTEC Wet Scrubber
The ADTEC system, developed by Aronetics, Inc., Tullahoma, Tennessee, is
a wet scrubbing system that operates on the conventional venturi collection
mechanisms of inertial impaction, but establishes the required particle-drop-
let differential velocity by utilizing waste process heat rather than exter-
nal energy. Water (at 300 psi) is heated to 150-205°C by the flue gas and
is then atomized by partial flashing and expansion through a nozzle. Dirty
gas is introduced into the two-phase mixture of steam and water; cleaning
occurs primarily by impaction. The water and collected dust are separated
from the gas, while the remaining steam exits with the flue gas.
A test unit was installed on a ferro-alloy furnace of the Chromium
Mining and Smelting Corporation (Chromasco) at Woodstock, Tennessee. Collec-
tion efficiencies of 99+ percent were reported. Mechanical energy consumed
in pumping the water to the required pressure of 275-300 psi is about 3 hp/
1000 cfm of gas while the power required in the form of heat input to the
water from the gas stream exceeds 200 hp/1000 cfm. Capital costs have been
established by Aronetics to be between those of venturi scrubbers and
fabric filters.
On the basis of currently available information, this system also
appears to offer significant improvement in the collection of fine particles
at modest energy consumption rates where a waste gas which contains a suffi-
cient amount of thermal energy to heat the water is available (41) .
4-75
-------
4.6.3 Wetted-Knit Mesh Filters
Scrubbing systems in which a vetted-knit mesh filter is utilized
have recently been developed and promoted by Heat-Systems-Ultrasonics and
by Dupont. In both systems the gas stream is first sprayed with water and
then the gas-liquid mixture is passed through a fiber bed structure having a
pore size and pore length that are sufficiently fine and long enough to
provide intimate contact of the gas stream containing the particulate
solids and mist with the scrubber liquid. In performance tests conducted
by Dupont with a laboratory-scale unit, the wetted-knit mesh filter
exhibited a collection efficiency of greater than 80 percent for a dust
having a size distribution of 50 percent <2.4 ym, 28 percent <1 ym, and
14 percent <0.5 yra. If the efficiencies reported by Dupont for their
laboratory-scale system can be substantiated by testing of pilot-scale
or demonstration-scale systems, wetted-knit mesh filters will be an addi-
tion to technology for the control of fine particulates (41).
4.6.4 Other Technologies
Other control processes that may be effective for removing fine parti-
culates include Cross-Flow Nucleation Scrubber, Pentapure Impinger, Dynactor
Wet Scrubber, Kystaire Scrubber, Dupont Vet Scrubber, granular bed filters,
fluidized beds, condensation scrubbers, foam scrubbers, charged droplet
scrubbers, electrified filters, gamma-ray precipitator, and sonic agglomera-
tors. Descriptions of these processes are presented in Evaluation of Eight
Novel Fine Particle Collection Devices (92).
4.7 UNAVAILABLE DATA
Further data are needed before a comprehensive assessment of fine
particulate and trace element emissions from coal combustion technologies
can be conducted. These data include the following:
• More information characterizing particulate and trace
element emissions from various coal using technologies
is needed.
• More information characterizing the abilities of the
various control processes being used in the utility industry
4-76
-------
to reduce trace element emissions at various dust loadings
Is needed.
• More data regarding the trace element collection efficiencies
of a baghouse applied to a conventional combustion source are
needed.
• Current cost data for different control processes are needed.
• Operating data showing the overall trace element collection
efficiency achieved by a combination of control processes
are needed.
Presently, electrostatic precipitators and baghouses exhibit the highest
trace element removal efficiencies of all the commercially proven control
processes. Optimization studies focused on increasing the efficiencies
and reliabilities of these processes should be conducted. An ESP optimiza-
tion study might consider the effect of conditioning ash with a chemical
additive on trace element collection efficiency. For baghouses, various
filter fabrics should be tested in order to find fabrics that are more
resistant to thermal and chemical degradation.
4-77
-------
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pp.434-440.
78. Reigel, S. A., and R. P. Bundy. Why the Swing to Baghouse? Power,
121(1):68-73, 1977.
79. Janoso, R. P., and J. A. Meyler. Baghouse Operating Experience with
Coal Firing. Power Eng., 80(10):62-64, 1976.
4-84
-------
80. Hobson, M. J. Review of Baghouses Systems for Boiler Plants. APCA
J. , 26(1):22-26, 1976.
81. Venditti, F. P., J. A. Armstrong, and M. Durham. Symposium on the
Transfer and Utilization of Particulate Control Technology: Volume
2. Fabric Filters and Current Trends in Control Equipment.
EPA 600/7-79-004b, Denver Research Institute, Denver, Colorado.
1979, 405pp.
82. Seale, L. M. Proceedings: Symposium on the Use of Fabric Filters for
the Control of Submicron Particulates. (April 8-10, 1974, Boston,
Massachusetts). EPA 650/2-74-043, PB 237 629, GCA, Corporation,
Bedford, Massachusetts, 1974. 306pp.
83. Yeh, J. T., C. R. McCann, J. J. Demeter, and D. Bienstock. Removal of
Toxic Trace Elements from Coal Combustion Effluent Gas. PERC/R1-76/5
Energy Research and Development Administration, Pittsburgh,
Pennsylvania, 1976. 21pp.
84. Economic Indicators. Chem. Eng., 86(1):7, 1979.
85. Shanks, H. R., J. L. Hall, and A. W. Joensen. Environmental Effects
of Burning Solid Wastes as Fuel. In: Proceedings of Fourth Joint
Conference on Sensing of Environmental Pollutants, New Orleans,
Louisiana. November 1977, pp. 739-41. American Chem. Soc.,
Washington, D.C., 1978.
86. Shanks, H. R., J. L. Hall, and A. W. Joensen. Environmental Effects
of Burning Solid Wastes as Fuel. In: Proceedings of Fourth Joint
Conference on Sensing of Environmental Pollutants, New Orleans,
Louisiana. November 1977, pp. 739-41. American Chem. Soc.,
Washington, D.C., 1978.
87. Shanks, H. R., J. L. Hall, and A. W. Joensen. Environmental Effects
of Burning Solid Wastes as Fuel. In: Proceedings of Fourth Joint
Conference on Sensing of Environmental Pollutants, New Orleans,
Louisiana. November 1977, pp. 739-41. American Chem. Soc.,
Washington, D.C., 1978.
88. Cleaning Coal by Solvent Refining. Environ. Sci. Technol,
8(6):510-511, 1974.
89. Coleman, W. M., W. M. Szabo, D. L. Wooten, H. C. Dorn, and L. T.
Taylor. Minor and Trace Metal Analysis of a Solvent-Refined Coal by
Flameless Atomic Absorption. Fuel, 56(2):195-198, 1977.
90. Ford, C. T. Coal Cleaning to Remove Trace Elements Prior to Utili-
zation. Pap. Symp. Coal. Util., 4:146-191, 1977.
4-85
-------
91. Fennelly, P. F., et al. Coal Burns Cleaner in a Fluid Bed. Environ.
Sci. Technol., 11(3):244-248, 1977.
92. Swift, W. M., G. J. Vogel, and A. F. Panek. Potential of Fluidized-
Bed Combustion for Reducing Trace-Element Emissions. CONF-730616-4
Argonne National Lab., Argonne, Illinois, 1975. 20pp.
93. Cooper, D. W., R. Wang, and D. P. Anderson. Evaluation of Eight Novel
Fine Particle Collection Devices. EPA 600/2-76-035, PB-251 621, GCA
Corp., Bedford, Massachusetts, 1976. 192pp.
4-86
-------
SECTION 5
TRACE ELEMENT EMISSIONS FROM SCCP
The law of conservation of matter requires that trace elements that
enter a combustion process must leave the process and return to the environ-
ment. Combustion processes change the matrices in which trace elements
occur. They also change the physical location of trace elements in the
environment. In addition, combustion processes may change chemical forms,
concentrations and physical states of trace elements. These changes can
be expected to influence the effects that trace elements have on the environ-
ment and on the human population.
This section reports information taken from the literature concerning
the amounts of trace elements leaving combustion processes. These trace
element emissions can be reported in several ways. The three most common
ways to report trace element emissions are: as a function of time, as a
function of volume of the effluent stream, and as a function of the heating
value of the fuel. All three ways of reporting effluents occur in this
section.
Trace elements from combustion processes are directly emitted to the
air, to the land and to surface waters. Emissions to the air may be as
suspended particles or as vapors. Emissions to the land are as solid wastes
(ashes and flue gas desulfurization sludges). Direct emissions to surface
waters come from cleaning operations, from discharge of spent cooling water,
and from flue gas desulfurization processes.
Secondary or indirect emission of trace elements to the environment
occurs when natural waters interact with solid waste. Rain water, surface
water or ground water will leach trace elements from solid waste and then
the leachate can enter the environment.
5-1
-------
The bulk of the information available in the literature concerns trace
element emissions from coal-fired utility boilers. This distribution oi:
information reflects the fact that coal combustion has a higher potential
than other combustion processes for discharge of trace elements to the
environment. The amount of coal burned, the amount of ash produced, and
the trace element concentrations in the ash combine to make coal combustion
the major potential source of trace element emissions to the environment:.
Coal, however, accounts for only about twenty seven percent of domestic
(non-transportation) fossil fuel consumption. Oil, usually less than
0.1 percent ash accounts for thirty five percent of fossil fuel comsumpliion
(natural gas is thirty-eight percent), and, therefore, cannot be neglected
as a potential source of trace metal pollutants.
Most trace elements in fuels remain in the ash after combustion. These
trace elements are more concentrated in the ash then they were in the fuel.
Coal combustion produces much more ash than does combustion of oil. Although
combustion of coal and wood produce comparable amounts of ash, significantly
more coal is used as fuel. The emphasis on utility boilers reflects the
fact that more coal is burned in utility boilers than in other combustion
facilities.
Information relating to emissions from coal-fired facilities is pre-
sented in the first five sections of this chapter. Studies of trace element
emissions to the atmosphere from coal-fired facilities are discussed first.
Atmospheric emissions which could be related to the heating value of the
coal are discussed in Section 5.1. Atmospheric emissions which could not
be related to the heating value of the coal are discussed in Section 5.2.
Trace element emissions associated with solid waste and aqueous effl.u-
ents are presented next. Solid wastes and primary aqueous effluents are
discussed in Section 5.3 and secondary aqueous effluents are discussed :.n
Section 5.4
Observed distributions of trace elements in various ash streams within
a coal combustion facility are presented in Section 5.5. This section
includes data relating to enrichment of some trace elements in various
5-2
-------
size fractions of fly ash. Data demonstrating surface predominance of some
elements on the surfaces of fly ash particles Is presented.
The next sections present available information concerning emissions
from the combustion of oil and gas, municipal refuse, and wood. Identifica-
tion of data gaps and suggestions for further work complete this chapter.
5.1 TRACE. ELEMENT EMISSIONS TO THE ATMOSPHERE FROM COAL-FIRED POWER PLANTS
IN TERMS OF HEATING VALUE OF COAL
Many studies of atmospheric emissions from coal-fired power plants
have been reported. Reports from five of these studies included the heating
value of coal and enough other information so that emissions could be calcu-
lated as weight of element released per unit heating value of the coal.
The data from these studies have been recalculated in these terms. The
results of these calculations are listed in Tables 5-1 and 5-2.
Emission values are listed for twelve sets of measurements. These
data represent measurements on ten coal-fired boilers at seven plants. The
reports that the data were taken from are Ondov et_ al. (1), Lyon (2),
Mann ail. (3), Radian (4) and Cowherd et^ al^. (5). Several analytical
techniques were employed and the reliability of the data varies from study
to study and often even for individual elements within a given study.
The units chosen for reporting trace element emissions are grams of the
element per trillion (10lz) joules of energy in the coal. The amount of
electricity which can be generated from 1012 joules will vary somewhat with
the efficiency of the plant, but typically, about 140 megawatt-hours of
electricity can be produced. The numbers in the table then represent the
hourly emission rate of a 140 MW plant operating at capacity. Multiplica-
tion of the numbers by 7 will give the approximate hourly emission of a
1000 MW plant operating at capacity.
The tables are arranged according to the type of particle control
device employed on the units studied. Electrostatic precipitators are the
most common type of unit used to control particulate emissions from coal-
fired boilers. Cold-side electrostatic precipitators are located on the
downstream side (cold side) of the air preheater. Hot-side electrostatic
precipitators are located on the upstream side of the air preheater. See
5-3
-------
TABLE 5-1 . ATMOSPHERIC EMISSIONS OF TtACZ ELEMENTS HI OH COAL-FIttD
POWER PLANTS WITH COLD-SIDE (CS) OR HOI-SIDE (HS)
ELECTROSTATIC PRECIPITATORS FOR PARTICULATE CONTROL
(GrftBS
Element
Emitted Per
10*2 Joules
in the Coal)*
Particulate Control
with Cold-Side
Electrostatic
Precloltators
Particulate Control
vlch Hot-Sid*
Electrostatic
PraclPllacori
Plant
Designation
ttait 3
Allen
Allen
CS Unit 1
Station 11
KS Unit 2
Firm* Method
PC
CYC
CTC
PC
PC
PC
Coal
Type
Western
EMtern
Eat-.ero
Wei cam
Wtstcrn
Western
First
Author
Ondcv
Lyoo
Lyon
Mann
Radian
Mann
Clement
Dace
July 1975
Jan 1972
Auc 1973
Sept 1976
Oct 1974
Sept 1976
Alumlnuc
15,GOO.
13,000.
SOD.
3200.
Ancinooy
2.15
5.
0.3
Arsenic
15-3
6.
5.
1.1
0.08
4.6
Bariuffi
807.
16.
8.
< 26.
Be ryl Hub
0-72
0.17
0.43
0.40
Bismuth
0.06
Boron
94.
frrooine
6.6
0.6
0.4
Cadmlua
0.26
0.3
0.6
0.18
< 0.2
0.77
Cai^luo
WOO.
600.
300.
5700.
Car ion
16.
1.
o.a
Ceaium
0.410
0.3
0.3
< 0.08
Chlorine
2.
3000.
Chromium
9.58
20.
8.
4 .0
6C.
13.
Cobalt
2.38
1.
0.5
1.5
Pr»pn«r
20.
2.
37.
2.8
23.
Dysprosium
1.12
< 0.08
Erbium
< 0.08
Europium
0.164
0.01
« C.08
Fluor lne
691.
280.
330.
Gadolinium
< 0.08
Galiiun
18.7
3.4
C« ruaniun
0.2
Gold
< 0.08
Mafniuo
1.37
0.05
< 0.08
Ho 1olua
< 0.08
Indium
0.108
-
Iodine
< 0.08
Iridium
< 0.08
Iron
3670.
6000.
2000.
980.
Lanthanum
8.96
1.
0.5
0.6
Lead
6.
5.
6.2
Lithium
0.2
Lutetlua
0.164
< 0.08
Magnetlun
1360.
200C.
830.
Hanganese
41.2
26.
5 .
8.7
19.
16.
Mercury
3.(gas)
0.92
1.7
0.77
Molybdenum
6.-8
3.2
« These numbers represent the hourly etiation rate of each eltaent from a plant (Continued)
with approximately 140 m capacity.
SOURCE: Ondov at il, (1); Lyon (2); Hanr. «t al¦ (3) and Ladiao (*»).
5-4
-------
TABLE 9-1. (Coat'd)
(Graft
a Eleoenc
Ealtced Per
LO12 Joulea
Id che Coal)*
Particulate Control
irtth Cold-Side
Elactroatatlc
Precipitators
Particulate Control
with Hoc-Side
Electroacacic
Precipitators
Fiast
Desinat ion
Doit 3
Alias
Allen
CS Doit 1
Station 11
BS Dn It 2
PlrlnR Method
PC
etc
CYC
rc
PC
PC
Cc *i
Type
Western
Eastern
Eaecern
Western
Western
Western
Ondov
Iron
Lvon
Hum
Badl&n
Kane
Element
Dace
Jul? 1975
Jan 1972
Aug 1973
Sept 1976
Oct 197<.
Sect 1976
Neodymluit
6.05
1.1
Nickel
2.
2.5
30.
9.8
Niobiua
0.4
Osclum
< 0.08
Palladium
« 0.08
Phosphorous
450.
P1 a t i n urn
< 0.08
Potassium
905.
600.
200.
77.
Praseodymium
0.2
Rheniuc
< 0.08
Rhodium
< 0.08
Rubidium
5.52
-
2.
0.6
Ruthenium
< 0.08
Saccari ur>
1.14
-
0.0B
< 0.08
Scar.dltfu
1.96
5.
0.3
0.4
Sp1pn1 «jm
5.82
32.
10««, 0.8
0.59
13.
7.7
SiJ v*r
Stilus
Scronc iuD
Sulfur
Tantalum
Tellurium
Terbium
Tha 11 lun>
Tho riuic
Thulluo
Tin
Titar.iiio
Tungsten
Uranlus:
Vanadium
Ycccrbl'jm
Y11 r1 un
Zinr
Z1rconino
TS?
2210.
B5.4
0.323
0.112
J.67
692.
2.78
3.29
39.7
3.503
44.B
34.6
123,000.
300.
100.
0.02
0.6
1.
30.
60.
100.
0.6
10.
50.
94.
0.28
46.
0.04
190.
170.
245 ,000.
< 0.08
0.2
< 0.03
< 0,0B
c 0.0B
<0.06
0.6
230.
< 0.08
0.32
26.
< O.OB
8.5
8.7
3-4
635.
0.79
14.
* These nunbers represent the hourly emission rate of each free a plane
with approximately 1<.D MW capacity.
•~Selenium was analyzed by two aachods. Cae chroaacograghy-Mlzrcvave emission
spectroscopy gave a value of 10 grans seleoiua per i0:* jouieB. Neutron
activation analysis gave a value of 0.6.
SOVKCES: Ondov e^ al. . (1); Lyon, (2); Mann £t.
(3) ; and Radian, (4).
5-5
-------
table 5-2. atmospheric emissions of trace elements frdm
COAL-FIRED POWER PLANTS WITH WEI SCRUBBERS OR
CYCLONES FOR PARTICULATE CONTROL
(Gia
Eleoent Emitted ?«r 10" Joulea in Coil)*
Element
Plant Designation
First Author
Particulate
Control with
Wet Scrubbers
1
Pnlt I
2 I
Firing Method
PC
PC
PC
PC
CYC
PC
Coal Type
Weatern
Was tan
Weataro
Waatem
Weateni
Eastern
Particulate
Control
with Cyclones
Vl&rv'a
Ondov*
Opdcv
Ondov
Radian : fradiaa
Date
C°"htaL
June 1975 Feb 1976 June 1975 Sent 1974 T Aug 1974 Mid 1974
Aluminum
Ant lmony
Arsenic
Barium
Beryllium
Bismuth
Boron
Brosine
Cadclum
Calcium
Cerium
Cc s ium
Chlorine
Chromiur:
Ccbalc
Copner
Dysprosium
Erbium
Europiua
Fluorine
Cadolinl-JK
Cal1lum
Ge raanlun
Cold
Hafnluc
Helnlua
Indium
Iodine
1 ndius
I ron
Lanthanum
Lead
Lithium
Lucecluit
Magnesium
Manganese
Mercury
Mo IvbdenuB
1320.
3.26
13.5
450.
2.0
0.93
63.
20.7
0.57
.055
0.012
680.
1.3B
5.24
97.9
0.98
7B2.
0.48
0.014
37.0
13.4
0.165
11.6
0.026
0.0074
5.3 2.01
0.075 0.032
0.019 0.0140
1.21,
455. 239.
0.46 0.275
.0052 0.0045
230. 112.
38. 23.0
1130.
1.7
9.2
580.
0.53
0.84
0.45
49.
3.4
0.30
a.a
o.nsi
0.012
4.3
2.07
2.0
0.050
0.014
0.82
425.
0.45
0.010
29C.
15.7
2.7
3610.
0.37
4.6
90.
0.26
0.2
146.
< 0.2
1.7
12,000.
2.8
3.7
3900.
170.
2.8
13.
< 0.2
< 0,2
< 0.2
190.
0.4
12.
1.3
< 0.2
< 0.2
< 0.2
< 0.2
< 0.2
2000.
2.6
11.
1.5
< 0.2
2000.
48.
4.8
79.
72,700.
19
120.
< 680.
3.
3.6
6600.
6.0
6.8
176,000.
27.
27.
4 300.
4 30.
30.
210.
2.1
0.8
1.5
3700.
3.
410.
140.
< 1.4
< 1.4
< 1.4
< 1.4
< 1.4
31,000.
10.
37.
14.
< 1.4
44,000.
710.
10.
340.
2.30
13.7
1600.
14,1
13.0
31,000.
916.
331.
5.7
112.
1020.
169,000.
57.
313.
27.
* These nuebers represent the hourly emiaaion tat* of each eleaent from a (Continued)
plant ulch approximately 140 jy capacity.
SOURCE: Ondov ct_ al_. (L); Radian, (4): Covhcrd «£ al. , CI).
5-6
-------
TABLE 5-2. (Cont'd)
(Grams Eleaeot Eitltctd Par 10 Joulaa Id Coal)*
Particulate
Control vith
W«c Scrubbers
Plant D»«lan«tlon
Firing Methoc
Coal Type
Elemenc
Date
P°it 1
Dale 1
PC
_££_
Unit 2 Station I
_zs_
EC
Parclculaca
Control
vlth Cvdemei
Gidov'a
Station XXI Creek
CTC
Western Western Western Western 1" Western
Ondav
Ondov
Ondov
_E£_
Eaatern
E»dian C9uherl
1975 Feb 1976 June 1975 Seat 1974 I Au« 1974 Mid 1974,
Neodymlum
Nickel
Nloblim
OanluE
Palladium
Phosphoroua
Platinum
Potassium
Praseodymium
Rhen 1 urn
Rbodluc
Rubidium
Ruthenium
Saurluot
ScanGiuib
Selenium
0.27
15.
41.
0.061
0.127
23.5
0.32
13.3
27.7
0.55
49.
0.0355
0.0552
12.9
0.055
0.09 7
21.0
J. 5
22.
2.0
< 0.2
<0.2
B30.
< 0.2
400.
0.4
< 0.2
< 0.2
11.
e 0.2
< 0.2
* 0.2
3.7
10.
319.
10.
< 1.4
< 1.4
< 1.4
22,000.
2.9
< 1.4
* 1.4
370.
« 1.4
< 1.4
« 1.4
35.
190.
< 26.
Si 1 ve r
1.5
<0.4
Sodluz
230.
170.
219.
3100.
41,000.
St rontium
18.4
9.44
20.
iai.
5100.
Sulfur
259,000.
871,000.
Tan c dliin
0,05 b
0.017
0.022
0.4
3.5
TeIlurium
0.2
7.4
< 49
Terbiuc
< 0.2
< 1.4
Thallium
1.3
22.
Th^rli;;
0.22
0.102
0.195
0.2
< 1.4
Thuliun
< 0.2
< 1.4
Tin
12.
670.
2
TltaDlum
76.
43.1
77.
170.
2000.
10,300
Tungsten
2.26
1.04
1.72
0.9
il-
Uranium
1.08
0.527
0.58
1.2
ls.
Vanadium
16.b
9. 39
19.9
200.
290.
652
Ytterbium
0.021
0.0187
0.0136
< 0.2
« 1.4
Yttrium
1.3
Zinc
8.8
5.33
4.6
120.
350.
596
Zlrcorlum
2 .46
6.6
2.6
73.
TSP
10,900.
* These numbers represent the hourly esi&fiion rate of each element from a plant
with approxlutely 140 MV capacity.
SOURCES: Ondov et al. (I): Radian, (4); Cowherd at al., (5).
5-7
-------
Section 4 of this report for a more complete definition of types of electro-
static precipitators. Table 5-1 lists emissions reported from three uni :s
with cold-side electrostatic precipitators and two units with hot-side elec-
trostatic precipitators. One of the units with cold-side precipitators was
sampled in 1972 and again in 1973. Although the plants are not identified,
striking similarities between the plant descriptions for the units with hot-
side electrostatic precipitators lead one to believe that the units sampled
are located at the same generating station. Unit One was sampled for one
study and Unit Two was sampled for the other study. Atmospheric emissions
of most elements vary widely even for the three cold-side electrostatic
precipitators. Some of this variation can be ascribed to differences in
precipitator efficiency. Other differences are probably related to differ-
ences in trace element concentrations in the coal, differences in concentra-
tions of major elements in the coal ash, different types of boilers and
possibly other variables. Failure to collect representative samples and
analytical errors also contribute to observed differences. The same factors
influence differences between emissions from hot-side electrostatic precipi-
tators and cold-side electrostatic precipitators. In addition, the different
temperature history of the collected particles influences the emission rates
of some elements. Emission rates of elements which volatilize and then con-
dense are most likely to be influenced by temperature variations.
Table 5-2 lists atmospheric emission rates as a function of heating
value of the coal for coal-fired boilers with other types of particles
control devices. The particle control devices on the units were wet scrub-
bers and cyclones (mechanical collectors). The emission rates from the
scrubbers studied generally varied less than those from other types of con-
trol devices. All plants listed with scrubbers for particle control fired
pulverized western coal.
Emissions from units using cyclones for particle control generally
were higher than emissions from units with other particle control de-
vices. This reflects the generally lower efficiencies of cyclones. Dif-
ferences in calcium, iron and other elemental emissions from the two
5-8
-------
plants with cyclone collectors reflect the different concentrations of many
elements in eastern and western coal ashes.
The studies which provided the data listed in Tables 5-1 and 5-2 are
described briefly in the following sections. Plant descriptions and key
operating parameters are given.
5.1.1 Studies of Trace Element Emissions from a Western Power Plant;
Comparison of a Venturi Wet Scrubber System with a Cold-Side
Electrostatic Precipitator
Ondov £t al. (1) reported trace element emissions to the atmosphere
for three units of the same western power plant. Particles were con-
trolled by a venturi wet scrubber on two units. Particles were controlled
with an electrostatic precipitator on the third unit. Samples of particu-
lates leaving the control device were collected from one or more of these
units during three tine periods. The first set of samples was tkaen in
June 1975, the second set was collected in July 1975, and the third set
was taken in February 1976.
Table 5-3 lists the characteristics of the units sampled. Only par-
ticulate matter was collected. Trace elements present in the flue gas in
the vapor phase were not collected. Trace elements were measured using
instrumental neutron activation analysis (INAA), atomic absorption spectro-
photometry, and X-ray fluorescence.
TABLE 5-3. CKAAACTZBISTICB OF WITS AT if&STEM FOWn PLANT STUDIED IT OMDOV. ¦> il-
Unit 1
Unit 1
Unit 3
Generating Capacity (Ml)
105
2*0
710
Coal Sit*
and Firing Hoda
Fulvatlied
Coal,
Front Fired
Fulve rixed
Coal,
Front Flrnd
Fulvarlied
Coal.
Front and tear
Fired
Particulate Control
Sytcti
Venturi
Bcrubbar
Venturi
Scrubber
Cold-Side
Electrostatic
Precipitator
Particulate Collector efficiency (2)
99.2
99.2
97
•oiler
Efficiency (J)
17
87
B8.7
Mavlsua
Continuous
Sltaa
Capacity (kg/aec)
160
203
654
Caceaa Air (t)
15
12.3
16
SOURCE: Ondov, it il. (1).
5-9
-------
5.1.2 Studies of Trace Element Pathways Through the T.A. Allen Steam Plant
The atmospheric emissions listed for the Thomas A. Allen Steam Plart in
Memphis, Tennessee, are part of the results of a series of interrelated,
interdisciplinary studies carried out on this plant. These studies were
carried out by several groups from the Oak Ridge National Laboratory. The
results of these studies have been summarized by Lyon (2). Many of the
results were previously reported in a variety of presentations, reports and
publications (6-18). Slight differences exist among these reports con-
cerning emission rates. In case of conflict, the values presented by
Lyon (2) are given.
The Thomas A. Allen Steam Plant is part of the Tennessee Valley
Authority (TVA) electrical generating system. The plant was built in IS'56
to 1959. The plant consists of three similar cyclone fired boilers. Ec.ch
unit has a generating capacity of 290 MW(e). Samples were taken around the
Number 2 Unit. Two sets of samples were taken, the first in January 1972
and the second in August 1973. Impinger solutions were used during the 1973
sampling effort to measure elements leaving the plant in the vapor phas«'.
Ihe impinger solutions were analyzed for antimony, arsenic, selenium, arid
mercury. Each set of samples represented several days of plant operation.
A new high efficiency electrostatic precipitator had been installed on the
Number 2 Unit just before the first set of samples were taken. Operating
parameters for the plant during the sampling periods are listed in Tabl«; 5-4.
Elemental flows and mass balance data are presented for 38 elements;.
Mass balances for five of these elements showed serious imbalance. Chlorine
and bromine exhibited serious negative imbalance indicating that these ele-
ments were escaping as vapors. Impinger solutions were not analyzed for
these elements. Serious positive imbalances were observed for chromium and
vanadium. Lyon speculated that corrosion of boiler tubes might be respon-
sible. Arsenic exhibited large negative imbalances for one sample set and
large positive imbalances for the other. Sampling and analytical difficul-
ties were blamed for the arsenic imbalances. The standard deviation from
balance of the remaining mass balances was 15 percent.
5-10
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TABLE 5-4. OPERATING CONDITIONS FOR THE T.A. ALLEN STEAM PLANT
January 1972 February 1973
Heating value of coal (joules/g)
24
,960
26,480
Operating level (MW)
240
280
Coal flow rate (g/min)
1.24
x 10s
1.47 x 106
Slag flow rate (g/min)
1.33
x 105
8.43 x 10k
Inlet Fly ash (g/min)
5.50
x 10*
7.39 x 101*
Outlet fly ash (g/min)
1
,900
370
Precipitation efficiency (%)
96.5
99.5
SOURCE: Lyon (2)
Instrumental neutron activation analysis was used for the measurement
of the concentration of most of the elements. Other analytical techniques
used were:
• isotope dilution spark source mass spectrometry,
¦ flameless atomic absorption,
• gas chromatography with microwave emission
spectrometric detector, and
• X-ray fluorescence.
See Chapter 8 for a full explanation of these techniques.
5.1.3 Studies of Trace Element Emissions from Coal-Fired Steam
Plants Equipped with Hot-Side and Cold-Side Electrostatic
Precipitators for Particulate Control
Mann et al. (3) reported the results of a study of trace element
emissions from two power plants using pulverized Wyoming sub-bituminous
coal. Both plants had tangentially fired boiler configurations. Although
both coals were of the same type, they differed in moisture and ash content
and in heating value. In one plant, particles were controlled by a hot-side
electrostatic precipitator and in the other plant particulates were controlled
by a cold-side electrostatic precipitator. The hot-side electrostatic pre-
cipitator operated at approximately 370°C (700DF) and the cold-side electro-
static precipitator operated at about 120°C (250°F).
5-11
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To measure emissions to the atmosphere, particles and vapors were
collected downstream from the electrostatic precipitators. The sampling
devices employed were cyclones backed up by wet electrostatic precipitators.
The collected particles and vapors were analyzed for up to 15 elements.
Emissions to the atmosphere were reported for 13 elements. These emissions
are listed as percentages of the elements entering with the coal in Table 5-5.
TABLE 5-5. PERCENTAGES OF ELEMENTS ENTERING WITH THE COAL WHICH
WERE EMITTED TO THE ATMOSPHERE FROM TWO WESTERN
COAL-FIRED POWER PLANTS
Hot-Side Station Cold-Side Station
Arsenic
10.0
0. 7
Beryllium
1.0
0.6
Cadmium
2.2
0.7
Chromium
2.4
0.8
Copper
4.3
7.1
Fluorine
16.5
33.9
Manganese
1.8
0.7
Mercury
14.3
22.3
Nickel
3.6
1.3
Selenium
16.7
0.9
Titanium
2.5
0.2
Uranium
2.3
0.4
Zinc
3.1
18.8
Ash
2.6
0.3
SOURCE: Mann et al.
(3)
5.1.4 Trace Element
Emissions
from Three Western
Coal-Fired Power Plants
Radian Corporation (4) has reported mass balances for 27 trace elements
around 3 western coal-fired power plants. Samples were taken simultan-
eously for all streams entering and leaving each unit sampled for a two-day
5-12
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sar.pling period at each plant. A unit consisted of a boiler and its
associated particle control device. Very fine particles and elements in
the vapor phase in effluent gases were collected with the aid of a wet
electrostatic precipitator. Mercury vapor was collected from the effluent
gas on a plug of gold wire.
Station I consisted of four units with a total capacity of 750 MW.
Unit No. 4 was sampled. This unit had a tangentially fired balanced draft
boiler and an electrical generating capacity of 330 MW. Three venturi
scrubbers provided particulate emission control. The boiler was fired
with Wyoming sub-bituminous coal mined near the station. Bottom ash was
sluiced to a nearby settling pond. The scrubber slurry discharge was pumped
to the same pond.
The coal contained 27.0 percent moisture, 15.0 percent ash, 31.1
percent volatile matter, 0.52 percent sulfur and 16.15 x 106 joules per
kg (6948 Btu per pound) on an as received basis. The coal was fed at the
rate of 1.28 x 10 kg per hr (2.83 x 105 lb per hr).
Elemental flows were calculated by multiplying the elemental concentra-
tion in a stream by the flow rate of the stream. The elemental flow rates
for all streams entering the unit were added up and the elemental flow rates
for all streams leaving the unit were added up. Error limits were determined
for all measurements of elemental concentrations and stream flow rates. An
error propagation analysis was carried out to determine the error in elemen-
tal flow rates entering and leaving the unit. These errors were given at the
95 percent confidence level. If the error band for the flow rate of an ele-
ment entering the unit overlapped with the error band of that element leaving
the unit the material balance was said to close.
Material balances were achieved within estimated error limits for 24 of
the 27 elements measured. The material balances did not close within the
preset error limits for cadmium, lead and mercury. The ratio of the elemen-
tal flow rate leaving the unit to element flow rate entering the unit (for
5-13
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those elements achieving material balance closure) ranged from 0.80 for
beryllium to 1.38 for zinc. The root mean square of normalized deviations
from material balance closure was 24 percent. This value included deviations
for those elements which did not achieve material balance closure.
Station II was a 350 MW unit with a tangentially fired boiler. The coal
was pulverized before firing. Pyrites were removed from the pulverized coal
at the mill. Bottom ash, economizer ash and pyrites from the pulverizing
mill were sluiced to a settling pond. Particles were controlled with hot-
side electrostatic precipitators. Ash collected in the precipitators was
trucked from the plant site.
Wyoming sub-bituminous coal was used as fuel. Coal analysis for
Station II was 29.2 percent moisture, 5.12 percent ash, 0.35 percent sulfur
and 19.27 x 106 joules per kg (8290 Btu per lb) on an as-received basis.
Coal was fed at a rate of 1.25 x 10s kg per hr (2.75 x 105 lb per hr).
Elemental flow rates were given for all streams entering and leaving the
unit. Material balances were calculated as described above for Station I.
Material balances were achieved for 23 of the 27 elements measured. Material
balances were not achieved for chlorine, mercury, selenium and uranium. The
root mean square of normalized deviations from material balance closure was
reported to be 48 percent. This value included deviations for those elements
which did not achieve material balance closure.
Station III was a 250 MW cyclone fired unit. North Dakota lignite was
the fuel. Bottom ash and economizer ash were sluiced to a nearby pond.
Particles were controlled with cyclones (mechanical collectors). The lignite
analysis was reported to be: 36.8 percent moisture, 7.84 percent ash, 0.91
percent sulfur and 14.44 x 106 joules per kg (6214 Btu per lb) on an as-
received basis. It was fired at a rate of 1.06 x 105 kg per hr (2.34 x 105
lb per hr) .
Material balances closed within error limits for 21 of the 27 elements
measured. Material balance closure within limits was not achieved for cobalt,
chlorine, mercury, molybdenum, selenium or uranium. The root mean square of
normalized deviations from material balance closure was reported to be 37
5-14
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percent. This value included deviations for those elements which did not
achieve material balance closure.
Analytical techniques used for the three-station study were:
• atomic absorption,
• X-ray fluorescence,
• ion selective electrodes,
• fluorometry,
• spectrometry, and
• spark source mass spectrometry.
The first five methods were reported to yield significantly better
material balance closure and repeatability of duplicate analyses than spark
source mass spectrometry.
5.1.5 Trace Element Emissions from TVA's Widows Creek Power Plant
Cowherd et al. (5) reported the results of a trace element study carried
out at the Widows Creek Steam Electric Power Plant. This plant is part of
the Tennessee Valley Authority's (TVA) electric generating network. Unit 5
of this plant was selected for the test program. The Widows Creek station
is five miles southwest of Bridgeport, Alabama.
Unit 5 was put into commercial operation in 1954. The unit fired
pulverized coal in a dry bottom furnace. The generating capacity of this
unit was 125 MW. Particulates were controlled with a mechanical fly ash
collector (two four-bank multiclone units were used). Bottom ash was sluiced
from the ash hopper. Samples were collected over a nine-day period in August,
1974.
Pollutant mass flow rates were given for 23 elements. Mass balances were
within ±25 percent for about half of these elements. The authors reported
large negative mass imbalances ascribed to inefficient pollutant collection
for the following elements: antimony, arsenic, fluorine, mercury, and
selenium.
5-15
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5.2 ATMOSPHERIC TRACE ELEMENT EMISSIONS FROM COAL-FIRED POWER PLANTS;
VALUES NOT BASED ON HEATING VALUE IN COAL
Several studies have been reported in addition to those given in
Section 5.1. These studies reported emissions in a variety of ways but did
not provide enought information to calculate emissions on the heating value
basis presented in Tables 5-1 and 5-2. These studies are described below.
5.2.1 Trace Element Emissions to the Atmosphere from the Valmont Power
Station, Boulder, Colorado
Kaakinen et_ al_. (19) (also 20, 21, 22) reported the partitioning of 17
elements in the Valmont Power Station. Flow rates and elemental concentra-
tions were given so absolute elemental flows and emission rates could be
calculated. The heating value of the coal was not given. An assumption
would have to be made concerning the efficiency of the unit sampled to cal-
culate emissions normalized to the heating value of the coal. Mass balances
were reported for 12 of the elements measured.
The measurements were taken at Unit Number 5 of the Valmont Power Station
belonging to Public Service Company of Colorado. This plant is near Boulder,
Colorado. The coal used was from a single mine and contained about 0.6
percent sulfur and 6 percent ash. The coal was pulverized before it was
fired. The capacity of the Unit Number 5 is 180 MW (net).
Three types of particulate collection devices were being used on this
plant when the samples were collected.
All of the flue gas from the boiler passed through a mechanical dust
collector (cyclone) . The mechanical collector removed approximately 86
percent (by weight) of the particles from the flue gases. The partially
cleaned stream was split. Approximately half of the stream passed through an
electrostatic precipitator and the other half passed through a wet scrubber.
Concentrations of 11 elements were given for eight streams in the plant.
The eight streams were: the coal entering the plant, the scrubber inlet
stream, and six streams leaving the plant. Four more elements were measured
5-16
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in some of the streams. The BET (see Glossary) surface area of the particles
from several of the streams leaving the plant was measured.
Analytical methods used were:
• atomic absorption spectrophotometry (conventional and flameless),
• wet chemistry, and
• X-ray fluorescence.
Three radioactive isotopes were measured using radiochemical analysis.
Mass balances were poor for selenium and mercury. These elements were
thought to escape as elemental vapors.
Kaakinen et^ jjl. referred to work by Bethell (23) who was said to have
reported that the calcium concentration in the coal would influence the
volatility of arsenic in the coal. In high calcium coals arsenic was said
to be largely retained as arsenate/arsenite. But, in low calcium coals the
arsenic was said to be volatilized as arsenic trioxide.
5.2.2 Trace Element Concentrations in Materials from the Chalk Point
Electric Generating Station
Gladney et_ al^ (24) have reported trace element concentrations in
materials from the Chalk Point Electric Generating Station in southeastern
Maryland. Concentrations in coal, precipitator ash and fly ash passing
through the electrostatic precipitator were reported. Fly ash particles
were collected using a University of Washington Mark III Cascade Impactor.
Elemental concentrations were reported for each of the seven collecting
stages and the back-up filter. Flow rates were not given so emissions rates
could not be calculated. Only particles were collected; no information
about trace elements in the vapor phase was reported.
The Chalk Point Electric Generating Station is operated by the Potomac
Electric Power Company. At the time the samples were taken the plant con-
sisted of two 355 MW generators each consuming 105 kg of coal per hour at
full load. The coal is ground to 50 mesh and blown from the pulverizer into
the water wall furnace. The coal is mined in West Virginia and Pennsylvania.
5-17
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The authors reported the following distribution of ash: bottom slag, 9
percent; economizer ash, 12 percent; precipitator ash, 75 percent; fly ash
to atmosphere, 4 percent. The temperature in the combustion zone was
reported to reach 1600°C. The gas at the outlet of the economizer was
reported to be 450°C. The temperature at the inlet to the electrostatic
precipitator was reported to be 130°C and the temperature at the outlet of
the electrostatic precipitator was 120°C.
Gladney et al_. reported that their observed instack elemental distribu-
tions with particle size did not match ambient particle size distributions
observed for trace elements in urban areas. They suggested that if the
emissions from other coal plants were similar to those observed at Chalk
Point, emissions from coal-fired installations do not have a major impact
on observed urban trace element concentrations.
All samples were analyzed non-destructively by instrumental neutron
and photon activation analysis. Mercury was determined using a combustion
procedure and was measured on only one set of samples.
5.2.3 Beryllium Emissions to the Atmosphere from the Chalk Point Electric
Generating Station
Gladney and Owens (25), in a study related to the one discussed in
Section 5.2.2, reported values for atmospheric emissions and mass balanc=s
for beryllium.
Samples were collected for nine days in August, 1973, from the Chalk.
Point Electric Generating Station. Suspended particles which had passed
through the electrostatic precipitator used for particulate emission control
were collected with a University of Washington Mark III Instack Cascade
Impactor.
Measurements were made on bottom slag, economizer ash, precipitator
ash and/or particles collected downstream from the electrostatic precipi-
tator. Aluminum was used as an internal reference for normalizing data.
Slight enrichments of beryllium relative to aluminum were observed for all
of the ashes collected in the plant. The particles collected downstream
5-18
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from the electrostatic precipitator showed a slight overall depletion in
beryllium although they exhibited increasing beryllium concentration with
decreasing particle size.
Beryllium concentrations were measured with a flameless atomic absorp-
tion method developed especially for handling refractory samples such as
fly ash.
The authors concluded that no more than 4 or 5 percent of the beryllium
present in the coal was leaving with the fly ash leaving the plant. The
authors noted several inconsistencies in the beryllium analyses reported
by Phillips (26).
5.2.4 Airborne Beryllium and Beryllium in Coal at the Hayden Power Plant
Near Hayden, Colorado
Phillips (26) reported the results of chemical analysis of a composite
coal sample and a composite fly ash sample from the Hayden Power Plant near
Hayden, Colorado. Based on these two samples 84 percent of the beryllium
entering the plant with the coal was calculated to be emitted to the atmo-
sphere. Spark source mass spectrometry was the analytical method used for
these analyses. On a separate occasion a sample of airborne particulate
matter was collected near the plant. An ambient beryllium concentration of
0.004 pg per cubic meter was calculated based on the analysis of the par-
ticles collected.
Gladney and Owens (25) have pointed out internal inconsistencies and
possible sources of analytical error in Phillips' report.
5.2.5 Trace Element Emissions From a Coal-Fired Power Plant in Illinois
Lee et al. (27) reported measurement of trace element emissions from
a coal-fired power plant in Illinois. No attempt was made to calculate
trace element balances around the plant.
The generating capacity of the power plant was 105 MW. Siocty tons
(54 Mg) of coal per hour were fed to the unit, Coal characteristics were
not given. The stack, gas flow rate was 7273 m3 per minute (dry basis).
5-19
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Particulate emissions were controlled by an electrostatic precipitator vith
a rated efficiency of 99.7 percent. The total particulate emissions of the
power plant were reported to be 2364 g per minute. Of the particulate emis-
sions, 284 g per minute were reported to be in the submicron size range.
Particle matter was collected using a University of Washington Marie III
Cascade Impactor. Collected materials were ashed in a low temperature asher
and dissolved in 1:1 nitric acid. The solution obtained was analyzed for
antimony, cadmium, chromium, cobalt, copper, iron, lead, manganese, nickel,
vanadium, and zinc. Analysis was by atomic absorption spectrophotometry in
a graphite furnace. Table 5-6 lists the concentrations of trace elements in
the particulate emissions to the atmosphere.
5.2.6 Total Mercury Mass Balance at a Coal-Fired Power Plant
Kalb (28) has reported the results of a series of test runs to measure
mass balances for mercury around a coal-fired power plant. The power plant
studied was built in 1949, had an output of 93 MW and fired pulverized coal.
Particles were controlled by two mechanical collectors in series and an
electrostatic precipitator. The mechanical collectors were reported to be
40 percent efficient and the electrostatic precipitator was reported to oe
91 percent efficient.
The results of 14 test runs showed that:
¦ some of the mercury was not volatilized during combustion,
• about 10 percent of the volatilized mercury was recovered by
adsorption onto suspended ash particles,
• some of the mercury was removed from the system by
adsorption onto the walls of stacks and ducts, and
¦ the major portion of the volatilized mercury was released
to the atmosphere in the vapor phase.
5.2.7 Other Studies of Trace Element Emissions from Coal-Fired Facilities
Stephens et^ ^1_. (29) analyzed samples of pulverized coal, fly ash,
bottom ash and ash pond liquid and ash pond sediments for a number of trace
elements. Analytical methods used were neutron activation analysis and
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TABLE 5-6. CONCENTRATION OF TRACE ELEMENTS IN PARTICULATE EMISSIONS TO
THE ATMOSPHERE FROM A COAL-FIRED POWER PLANT IN ILLINOIS
Elements
Concentration
(yg/m )
Mass Median
Diameter of Particles
Bearing Element
(urn)
Antimony
6.8
0.6
Cadmium
0.1
5.0
Chromium
0.7
<0.5
Iron
1340.
2.6
Lead
1.4
1.1
Manganese
0.0
Nickel
1.3
5.4
Vanadium
1.5
1.6
Zinc
0.7
4.7
Total Particulate Matter
8700.
4.7
Selenium1
6.5
4.7
Total Particulate Matter1
9600.
4.7
Selenium was analyzed on a separate sample set using neutron activation
analysis.
SOURCE: Lee et al. (27)
5-21
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atomic absorption spectrophotometry. A mass balance was attempted to
determine the emission points in the combustion process.
Rancitelli (3) calculated emissions of 12 elements from the Hanford
Steam Plant in 1971. He reported that chromium, iron, sodium and rubidium
vere conserved, but found that antimony, mercury and selenium were depleted
in ash relative to the coal. He calculated emissions based on the depletions
observed. Neutron activation analysis was the analytical method used.
Carter et^ _al. (31) reported mass balance results around a coal-fired
electric generating plant. Thermal emission, spark source and isotope dilu-
tion mass spectrometry were the analytical methods used. These results vere
reported in 1973.
Schultz (32, 33) has reported on the fate of trace elements during ;oal
pretreatment and combustion.
5.3 TRACE ELEMENT EMISSIONS VIA SOLID WASTES OR AQUEOUS EFFLUENTS FROM
COAL-FIRED FACILITIES
Trace elements enter a coal combustion facility with the coal. If they
are not emitted to the atmosphere they must leave with solid wastes or with
aqueous effluents. Since solid wastes and aqueous effluents are often com-
bined with each other, they will be considered together.
The major solid waste streams from a coal-fired facility are ashes and
wastes from throwaway type flue gas desulfurization (FGD) systems. Ashes
commonly collected at a coal-fired facility include bottom ash or slag plus
fly ash collected in the economizer, mechanical collector, electrostatic
precipitator and/or wet scrubber.
Most utilities dispose of their solid wastes by ponding or by landfill.
Ponding is a disposal method in which the waste material is wet when it
enters the pond. Impoundments or other restraints are required for mechani-
cal stability. In this chapter landfill will be defined to mean any waste
disposal operation in which the waste material has enough structural integ-
rity throughout the disposal site that impoundments or other structural
supports are unnecessary.
5-22
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Ponding Is widely used by utility companies. Often ponding is used
for temporary storage. When the pond is nearly full of solid material it
is allowed to dry and the solid waste is removed to a landfill for permanent
disposal. Ponds may contain only one type of waste or they may contain a
mixture of coal-related solid wastes.
In many cases supernatant liquor from the pond or ponds is recycled to
the power plant. Ihe recycled liquor may be used as ash sluice water or as
scrubber make-up water. In other cases the pond overflow enters the envi-
ronment via the nearest stream. Of course, partial recycle and partial dis-
charge of pond liquors is possible.
In many cases physical or chemical properties of the waste are not
compatible with immediate or permanent use in a landfill site. In these
cases ponding must be used for permanent disposal.
Many utility companies choose to dispose of some solid wastes directly
in landfills. It is not unusual for a plant to truck precipitator ash and/or
economizer ash to a landfill site and to sluice bottom ash to a pond. Flue
gas desulfurization sludges are usually ponded, at least initially.
Aqueous effluents can be divided into two classes. In the first class
the emission points are usually well defined streams. These emissions
usually result directly from the day to day operation of the facility.
These effluents include discharges such as once through cooling water and
pond overflows. These effluents usually enter surface waters.
The other class of aqueous effluent enters the environment from more
dispersed sources. This class includes surface run-off from landfill opera-
tions, run-off and leachate from ponds and landfill operations. There efflu-
ents may enter either surface waters or ground water.
Reports dealing with trace element emissions associated with solid
wastes or aqueous effluents are discussed below. This section contains
discussions of emissions associated with solid wastes and well defined
aqueous streams. The next section deals with run-off and leachates.
5-23
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5.3.1 The Impact of RCRA on Utility Solid Wastes
Hart (34) have prepared an extensive review of the impact of the
Resource Conservation and Recovery Act of 1976 on utility waste disposal
practices. Utility solid and liquid waste streams were categorized with
respect to environmental hazard potential. Comparisons were made between
proposed hazardous waste criteria and reported composition of various waste
streams. Processes which were reported to produce waste streams which could
exceed the criteria were presumed to be a candidate for regulation under the
act.
The first category identified was waste streams having the greatest:
hazard potential. These streams were considered most likely to be included
on a presumptive process list. Streams belonging to this category were:
• coal fly ash,
• coal bottom ash, and
• FGD scrubber sludge.
The second category was waste streams which are possibly hazardous..
It was considered possible that these streams might be included on a pre-
sumptive process list:
• metal cleaning wastes from boiler generator tubes,
boiler fireside, and air preheater,
• coal pile drainage,
• boiler blowdown,
• recirculating condenser cooling system wastes,
• oil fly ash, and
• ion exchange wastes.
The third category included least hazardous wastes. It was considered
unlikely that these wastes would be included on a presumptive process list.
Wastes in this category were:
• water treatment wastes and
• once through condenser cooling system wastes.
See Chapter 4 for an explanation of these waste streams.
5-24
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Hart et^ al_. reported information available from the literature. This
report is a convenient source of information from diverse sources; however,
sometimes information from several sources has been combined into a single
table and it is not possible to associate a particular piece of information
with a given source.
The constituents of coal-pile run-off as compiled by Hart et^ al_. are
listed in Table 3-7. The data in this table were obtained from three orig-
inal sources: Cox and Ruane (35), Rice and Strauss (36), and USEPA (37).
5.3.2 Review and Assessment of the Existing Data Base Regarding Flue
Gas Cleaning Wastes
Coltharp et^ jil, (38) have prepared an extensive review of information
regarding flue gas cleaning wastes. Flue gas cleaning wastes include fly
ash, flue gas desulfurization (FGD) sludge, mixtures of fly ash and sludge,
aqueous solutions associated with the solids at time of disposal and leach-
ates from the solids. The review covers information available from the open
literature and from persons working in the field through mid-1977. The
available information was critically assessed and data gaps identified.
The appendix to the Coltharp report contains a comprehensive compilation
of the public information concerning flue gas cleaning wastes available at
the time the report was prepared. It provides another convenient source (in
addition to that provided by Hart et al.) for these data. References are
given in such a way that the original sources of all data presented can be
identified.
Some of the data presented in the Coltharp report are presented with
discussions of individual projects below. Table 5-8 presents concentrations
of trace elements in liquors adhering to the sludge (sludge liquor) and in
solutions obtained when additional water was passed through the sludge
(elutriates). The data were taken from three sources as reported by Coltharp
et al.
5-25
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TABLE 5-7. CONSTITUENTS OF COAL PILE RUNOFF
Range (me/1)
Conventional Measures of Pollution
pH
2.1
-
6.6
Total Suspended Solids
22.
-
610.
Total Dissolved Solids
720.
-
26,970.
Turbidity
2.77
-
505.
Tot.il Hardness
130.
—
1,851.
Major Chemical Constituents
Ammonia
0.0
-
1.77
Nitrate
0.3
-
1.9
Phosphorus
0.2
-
1.2
Sulfate
130.
-
20,000.
Chloride
3.6
-
481.
Aluminum
66.
-
1,200.
Iron
0.06
-
4,700.
Manganese
90.
-
160.
Sodium
160.
—
1,260.
Trace Element Constituents
Arsenic
0.005
-
0.6
Beryllium
< 0.01
-
0.07
Cadmium
< 0.001
-
0.003
Chromium
0.0
-
16.
Cobalt
0.025
-
—
Copper
0.01
-
3.9
Magnesium
0.0
174.
Mercury
< 0.0002
i _
0.007
Nickel
0. 24
0.75
Selenium
< 0.001
-
0.03
Zinc
0.006
-
12.5
SOURCE: Hart _et_ al_. (34): Original sources were Cox and Ruane (35),
Rice and Strauss (36) and USEPA (37).
5-26
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TABU )-8. SUMMIT Of UJWttWT HAT I OK 3 OF T1ACX ELEMENTS SLUDGE LtqUOM AND RUJTRIATVS
Holland, and Jones Roaaoll and Rossi Bornsteln *11 Sources
Cearat
Mn(«, (¦«/!)
Mean, <¦(/!)
Range,
Eastern
(>g/i>
Coal
Median, (ig/1)
Range
Uestara Coal
(¦g/1) Median, (ag/1)
Range,
(¦*/!)
Range,
(¦s/O
AIubIoub
_
.
__
_
0.0)
to 0.)
0.0)
to
0.)
Aoiloony
0.09
to
2.9
0.2
0.46
to
1.6
1.2
0.09
to 0.22
0.16
0.09
to 2.)
0.09
to
2.9
Araenlc
0.004
to
0.)
0.009
< 0.004
to
1.8
0.02
<
0.004
to 0.2
0.009
< 0.004
to 0.)
<
0.004
to
0.)
tenrllloB
0.0006
to
0.14
0.01]
< 0.000J
to
0.03
0.014
0.0006
to 0.14
0.01)
< 0.002
to 0.14
<
0.000)
to
0.14
Boron
0.9
to
46
__ 1
41
41
8.0
8.0
8.0
to 46
0.9
to
46
Cidalui
0.002
to
0.044
0.0)2
0.004
to
0.1
0.023
0.011
to 0.044
0.0)2
0.004
to 0.11
0.002
to
0.11
Chroalua
0.003
to
0.4
0.08
0.001
to
0.3
0.02
0.024
to 0.4
0.08
0.01
to 0.)
0.001
to
0.3
Cobalt
0.1
to
0.7
--
< 0.002
to
0.1
0.33
0.1
to 0.17
0.14
0.10
to 0.7
<
0.002
to
0.7
Copper
0.002
to
0.6
0.20
0.002
to
0.4
0.013
0.002
to 0.6
0.20
< 0.002
to 0.2
<
0.002
to
0.6
Fluor loo
0.7
to
3.0
i.S
1.4
to
70
3.2
0.7
to ).0
l.S
0.7
to
70
I rem
0.02
to
8.1
i
0.02
to
0.1
0.026
0.42
to 8.1
4.)
0.02
to 8.1
0.02
to
8.1
Uad
0.001
to
0.4
0.016
0.002
to
0.33
0.12
0.0014
to 0.)7
0.016
0.01
to 0.4
0.001
to
0.33
HfOfUCN
0.007
to
2.3
< 0.7*
< 0.01
to
9.0
0.17
0.007
to 2.)
0.74
0.09
to 2.)
0.007
to
9.0
Mercury
0.0004
to
0.07
< 0.01
0.0009
to
0.07
0.001
<
0.01
to 0.07
0.01
0.0004
to 0.07
0.0004
to
0.07
Melrbdema
0.07
to
6.)
l
].]
3.3
0.91
0.91
0.91
to 6.)
0.07
to
6.)
Nickel
0.005
to
1.3
0.09
0.0)
to
0.91
0.13
0.003
to l.J
0.09
0.0)
to l.S
0.00)
to
1.3
Salettloa
0.001
to
2.2
O.Uj
0.00}
to
2.7
0.11
<
0.001
to 2.2
0.14)
< 0.001
to 2.2
<
0.001
to
2.1
Silver
0.003
to
0.6
—
—
—
—
o.oos
to 0.6
0.00)
to
0.6
Tla
3.1
to
).3
--1
—
—
—
—
).l
to l.S
).l
to
3.3
Vanadlas
0.001
to
0.67
—1
—
—
—
—
0.001
to 0.67
0.001
to
0.6?
ZlAC
0.0)
to
2.0
0.18
0.01
to
27
0.046
0.028
to 0.88
0.18
0.01
to 0.»
0.01
to
27
'liu Mtt set mllatls for cilnlitlM of s asaa.
MOVSi MM mt Joaaa (JOI loatoff mai ImiI (40)| Smstsla («1).
-------
5.3.3 Trace Element Emissions in Solid Wastes and Aqueous Effluents
from Three Western Coal-Fired Power Plants
Radian Corporation (4) has reported trace element concentrations in
coal, ashes and sluice waters from three western power plants. These plants
were described in Section 5.1.4. Trace element concentrations are listed in
Tables 5-9, 5-10, and 5-11. The flow rates for the streams listed in these
tables are given in Tables 5-12, 5-13, and 5-14. The amount of the element
emitted per unit time can be calculated by multiplying concentration of the
element in a stream by the flow rate of the stream.
5.3.A Comparison of Levels of Trace Elements Extracted from Fly Ash
and Levels Found in Effluent Waters from a Coal-Fired Plant
Dreesen et_ _al. (42) determined concentrations of 11 trace elements in
precipitator ash and in waters entering and leaving a western coal-fired
power plant. The plant was located near Fruitland, New Mexico, and by impli-
cation had both electrostatic precipitators and venturi scrubbers for pollu-
tion control. Concentrations of trace elements in waters entering and
leaving the plant are listed in Table 5-15.
A number of extraction experiments were carried out. In these experi-
ments precipitator ash was extracted with a number of acidic, neutral ar.d
alkaline extractants. The results of the extraction study are presented in
Table 5-16. It should be noted that redistilled water was one of the
extractants. The water started out at a neutral pH but the alkalinity of
the fly ash increased the pH to 11.9 at the end of the extraction.
Elements found to be most extractable in water were boron, fluorine,
molybdenum and selenium. Elements most extractable in acid were arsenic,
boron, cadmium, fluorine, molybdenum and selenium. Elements most elevated
in effluent waters were arsenic, boron, molybdenum and selenium. The authors
noted a positive correlation between readily extractable elements and elements
elevated in effluent waters.
Dreesen et al. also noted that the elements most extractable in acids
were among those reported to be concentrated on the surfaces of fly ash
particles. A second factor which the authors discussed was that elements
5-28
-------
TABLE 5*9. TRACE ELEHDJT CONCQTT&AIIONS IS COAL, ASHES, AND AQUEOUS SAMPLES ASSOCIATED VITH
A WESTEiOl COAL*FIRED POWER FL&NT (STATION I)1
Coal
(yg/g)
Boteon
Afih
(jjg/g)
Boctea
Asb
Sluice
Water
(og/1)
Scrubber
Slurry
Solids
(ug/g)
Scrubber
Slurry
Liquid
(Bg/1)
CI fear
Pood
Return
(mg/&)
AlualDUB
23,300.
103,000.
2.4
108,000.
4.8
5.0
Aaclaoay
.53
.39
.041
2.3
0.36
.024
Arsenic
.83
1.3
.0041
5.2
.0013
.0045
Btrlua
130.
670.
<.5
840.
<•5
<.5
Berylllua
.82
2.5
.0013
3.2
.0015
.0013
Boron
SI.
160.
2.5
220.
2.8
3.2
Cadalua
.18
i.O
.0038
1.8
.0068
.0054
Calcium
17,600.
86,600.
790.
113,000.
910.
790.
Chlorine
44.
140.
28.
89.
28.
28.
Chroalua
21.
67.
.12
118.
.14
.074
Cobalt
2.1
7.0
.005
8.1
.011
.0081
Copper
34.
93.
.024
155.
.049
.036
Fluorine
140.
100.
16.
820.
20.
20.
Iron
4,900.
25,100.
.30
22,500.
.74
.31
Lud
4.2
7.1
.007
49.
.023
.008
Manganese
170.
690.
.79
1,000.
.88
. 86
Magnesium
2,900.
12,000.
68.
13,600.
62.
68.
Mercury
.13
.014
<.0005
.053
.0007
<•0005
Molybdeauo
4.0
3.7
.036
10.
.015
.035
Nickel
9.0
39.
.015
38.
.015
.025
Selenlus
2.2
.70
.031
8.7
.12
.048
Tlunlus
1,100.
4,500.
<•1
4,000.
<.1
<•1
Silver
.045
.11
.0004
.23
.0005
.0003
Sulfur
7,200.
.11
770.
14,400.
865.
785.
Uranlua
1.3
13.
.0058
3.6
.0087
.010
Vanadium
51.
230.
.19
268.
.23
.16
Zinc
24.
41.
.076
190.
.089
.10
1 Values represent average of duplicate deternloatioos: Coal vis reported Co be 20.62
percent ash au a dry baslft.
SOUiHB; Radian, 7o1um II, <4).
5-29
-------
TABLE .5-10 TRACE ELEMENT CONCENTRATIONS IK COAL, SLUICE ASH , AND
AQUEOUS SAMPLES FROM A WESTERN PULVERIZED COAL-FIRED
POWER PLANT (.STATION II)'
¦ ¦¦¦¦¦- ' binitf"
Inlet Sluice Sluice2 Ash
Coal Water Ash Filtrate
(pg/g) (mg/l) (ui'i) (mg/l)
Aluminum
7,100.
< .1
109,000.
9.2
Antimony
.16
.0023
<.08
.0038
Arsenic
2.5
<.0001
1.4
<.0001
Barium
460.
<•6
5,200.
<.6
Beryllium
.29
<.002
4.1
<.002
Boron
31.
.17
240.
.49
Cadmium
<•1
<.002
<.8
<.002
Calcium
10,900.
57.
151,000.
113.
Chlorine
9.4
8.6
<1.
15.
Chromium
9.3
<.053
<.053
Cobalt
1.5
<.003
18.
<.003
Copper
31.
.012
230.
.022
Fluorine
67.
.45
19.
.70
Iron
2,100.
.12
40,600.
.01
Lead
2.3
.017
11.
.006
Manganese
24.
.034
310.
.016
Magnesium
1,500.
15.
20,600.
16.
Mercury
.14
.08
<¦010
<.0004
Molybdenum
.64
<.0002
3.5
.015
Nickel
2.1
<¦02
27.
<.02
Selenium
1.6
.0017
.35
.0038
Tltaalun
565.
<.1
9.100.
<.1
Silver
.048
<.0003
.11
<.0003
Sulfur
4,900.
14.
910.
108.
Uranium
.89
.0084
5.0
.0044
Vanadium
20.0
0.058
190
0.071
Zinc
4.1
.39
156.
.0084
1 Values represent the average of duplicate determinations.
The coal vas reported to be 7.23 percent ash on a dry basis.
1 Sluice ash Is a coiEblnation of bottom ash, economizer ash, and pyrites
frcrai the mills which pulverlre the coal
SOURCE: Radian, Voluoe III, (4) .
5-30
-------
TABLE 5—11 TRACE ELEMETT CONCENTRATIONS IN COAL, ASH,
AND AQUEOUS STREAMS FROM A WESTERN CYCLONE
TYPE COAL-FIRED POWER PLANT (STATION III)1
Element
Coal
(ug/g)
Aah
Sluice
Water
lolet
(mg/1)
Bottom
Ash
Wg>
Bottom
Aah
Sluice
Water
(¦«/l)
Economizer
Aah
(ug/g)
Economizer
Aah
Sluice Water
(mg/1)
Aluminum
7400.
.42
87900.
1.7
84BOO.
¦ 5B
Antimony
.40
.018
.8
.034
.56
.021
Arsenic
8.0
.006
20.
.0087
126.
.0012
Barium
440.
<¦5
5700.
< .5
B300.
<•5
Beryllium
.60
.0014
5.3
.0017
8.8
.003
Boron
150.
.26
520.
.25
740.
2.4
Cadmium
.20
.0003
.87
.0011
1.8
.0012
Calcium
13800.
35.
130000.
43.
120000.
46.
Chlorine
55.
12.
88.
16.
119.
17.
Chromium
13.
<.053
95.
< .053
121.
<¦053
Cobalt
.75
.0003
10.
.0041
12.
.0039
Copper
10.5
.0084
50.
.014
94.
.008
Fluorine
57.
.21
<10.
.25
65.
.21
Iron
7500.
.43
664000. -
2.1
66900.
1.4
Lead
.86
.015
< .8
.024
8.3
.025
Magneslua
3700.
26.
37100.
26.
37700.
24.
Manganese
79.
.082
720.
.055
900.
.096
Mercury
.074
<.0005
< .010
< .0005
.12
<•0005
Molybdenum
2.0
.033
18.
.016
44.
.012
Nickel
5.4
.006
23.
.0014
36.
.007
Selenium
1.3
.0012
.25
.0011
.14
.0012
Titanium
350.
<•1
3500.
< .1
3B00.
<.1
Silver
.034
<•0003
.11
< .00003
.32
<.0003
Sulfur
14400.
68.
95.
74.
1300.
77.
Uranium
1.5
.0022
3.2
.0035
11.
.0044
Vanadium
15.
<¦005
140.
< .005
110.
<.005
Zinc
7.8
.013
IB.
.013
140.
.028
J Values represent the average of duplicate determinations.
Coal was reported to be 12.40 percent aah on a dry baala.
SOURCE: Radian, Volume IT, (4)
5-31
-------
TABLE 5-12. FLOW RATES FOR STREAMS AROUND STATION I
Stream Flow Rate
Coal
1.28
X
105
kg/hr.
Bottom Ash
Sluice Water
Inlet
0.585
X
106
kg/hr.
Cooling Tower
Blowdown
1.99
X
10s
kg/hr.
Scrubber Make-up
Water
1.81
X
106
kg/hr.
Lime
2.17
X
103
kg/hr.
Bottom Ash
0.522
X
10*
kg/hr.
Bottom Ash
Sluice Water
Outlet
0.585
X
106
kg/hr
Scrubber Solids
2.27
X
10"
kg/hr.
Scrubber Liquid
1.90
X
106
kg/hr.
Economizer Ash
11.9
kg/hr.
Flue Gas
1.42
X
10
m3 /hr
Fly Ash
74 .8
X
102
kg/hr.
SOURCE: Radian, Volume I (4).
5-32
-------
TABLE 5-13. FLOW RATES FOR STREAMS AROUND STATION II
Stream Flow Rate
Coal
1.25
X
105
kg/hr.
Inlet Sluice Water
2.28
X
105
kg/hr.
Sluice Solids
2.0
X
103
kg/hr.
Sluice Liquid
2.28
X
10s
kg/hr.
Precipitator Ash
6.94
X
103
kg/hr.
Flue Gas
1.55
X
106
m3/hr.
Fly Ash
63 .5
X
102
kg/hr.
SOURCE: Radian, Volume I, (A).
5-33
-------
TABLE 5-14. FLOW RATES FOR STREAMS AROUND STATION III
Stream Flow Rate
Coal
1.06
X
105
kg/hr.
Bottom ash and
economizer ash
sluice water
inlet
1.20
X
10s
kg/hr.
Bottom ash
7.62
X
103
kg/hr.
Bottom ash
sluice water
outlet
8-07
X
10"
kg/hr.
Economizer ash
69.9
kg/hr.
Economizer ash
sluice water
outlet
3.95
X
10u
kg/hr.
Cyclone ash
2.83
X
103
kg/hr.
Flue gas
1 .16
X
10E
m3/hr
Fly ash
1.55
X
103
kg/hr.
SOURCE: Radian, Volume I, (4).
5-34
-------
TABLE 5-15. TRACE ELEMENT CONCENTRATIONS IN WATER ENTERING
AND LEAVING A WESTERN COAL-FIRED POWER PLANT
Element
Influent
Waters
Effluent
Waters
Cooling lake
intake
(ug/i)
Cooling lake
outlet,
(Ug/1)
Ash pond
ef fluent,
(yg/D
Ash pond
surface,
(yg/i)
Arsenic
2.6
7
27
33
Beryllium
<0.2
<0.2
<0.2
<0.2
Boron
<100
950
12000
11000
Cadmium
1
1
1
1
Chromium
<1
1
2
3
Copper
3
2
3
2
Fluorine
220
37001
16000
ND2
Molybdenum
<1
23
170
160
Selenium
<1
1
57
60
Vanadium
2
60
130
140
Zinc
590
350
440
580
'Data for September 1975, from the New Mexico Environmental Improvement
Agency. No data.
SOURCE: Dreesen et al. (42)
5-35
-------
TABLE 5-16 TRACE ELEMENT CONCENTRATIONS IN PRECIPITATOR ASH AND PERCENTAGE OP
TRACE ELEMENT CONTENT OF ASH EXTRACTED BY SEVERAL EXTRACTING SOLUTIONS
Amount of Each Element Extracted (.X)
Cone. In
Molarity
1.0
1.0
0.1
0.1
0.01
0.001
0.1
Precipitator
Solution
UNO,
HC1
Citric Acid
HN0)
HNOj
HN0]
HjO
NH«0H
Ash
Initial pH1
: 0.5
0.5
2.2
1.4
2.2
3.1
7.4
11.3
Element
(pg/g)
Final pH :
0.5
0.6
3.6
4.1
11.7
11.9
11.9
11.9
Arsenic
12
64
78
59
0.65
0.31
0.17
0.10
0.51
Beryllium
4.7
8.6
12
6.1
1.7
<0.09
<0.09
<0.09
<0.09
Boron
260
78
24
94
55
3.9
1.4
1.5
<0.05
Cadmium
0.29
48
32
33
35
3.8
0.28
<0.14
0.14
Chromium
34
15
14
13
1.2
0.53
0.38
0.33
0.29
Copper
58
7.3
7.9
4.6
3.3
0.11
<0.01
<0.01
<0.01
Fluorine
120'
75
63
86
83
11
8.1
7.2
8.7
Molybdenum
4.2
120
120
110
4.7
57
55
59
54
Selenium
8.0
78
35
46
5.1
11
5.9
5.1
4.5
Vanadium
98
20
28
16
0.04
0.02
<0.01
<0.01
<0.01
Zinc
160
3.1
3.1
1.8
1.2
0.27
<0.03
<0.03
0.07
'pH determined before ash was added to the extractants. 2pH determined after agitation of ash-extractant mix-
ture. 'The fluorine concentration given la the mean concentration reported by the Southwest Energy Study
(43, 44).
SOURCE: Dreesen (42)
-------
which form anionic species remain soluble in alkaline environments. They
suggested that molybdate, borate, fluoride, selenate, arsenate, chromate
and vanadate could occur as soluble forms.
The authors were not able to tell whether the elements enriched in the
effluent waters were dissolved in the acidic environment of the venturi
scrubbers and not reprecipitated or if they were extracted under more alka-
line conditions. They suggested that arsenic, boron, fluorine, molybdenum
and selenium were elements of prime interest for future studies of soluble
contaminants fro7n coal ash disposal in alkaline environments.
5.3.5 Concentrations of Trace Elements in Ash Ponds at Coal-Fired
Power Plants Operated by the Tennessee Valley Authority
Chu ^t _al. (A5) have reported trace element concentrations in ash ponds
at coal-fired power plants operated by the Tennessee Valley Authority. The
values reported are listed in Tables 5-17, 5-18, and 5-19.
Plants A, B, E, G, and I were reported to burn coal from Western
Kentucky. Plants C, F, and K burned coal frora Western Kentucky and Southern
Illinois. Plant D burned coal from Eastern Kentucky. Plants H and J burned
coal from Eastern Kentucky and Eastern Tennessee. Plant L burned coal from
western Kentucky and Northern Alabama. Plants A and C employed cyclone
firing. All other plants fired pulverized coal.
5.A SECONDARY EMISSIONS OF TRACE ELEMENTS FROM SOLID MATERIALS ASSOCIATED
WITH THE COMBUSTION OF COAL
This section addresses trace element emissions from run-off and
leachates. These emissions generally do not occur as readily identifiable
waste streams. Furthermore, emissions to the environment in leachates have
the potential for occurring long after the solid material is deposited in a
pond or landfill.
Leachates from ponds or landfills are not the only secondary aqueous
emissions which occur. Particles that are emitted to the atmosphere with
effluent gases eventually fall to earth, but the trace elements associated
with them are not mobilized to the environment unless or until they dissolve
in aqueous solution.
5-37
-------
TABLE 5-17. AVERAGE CONCENTRATIONS OF TRACE ELEMENTS IN
LIQUORS FROM ASH PONDS AT COAL-FIRED POWER PLANTS
OPERATED BY THE TENNESSEE VALLEY AUTHORITY
(all concentrations in mg/liter)
Plant A Plant A Plant B Plant B
Fly Ash Bottom Fly Ash Bottom
Element Pond Ash Pond Pond Ash Pcnd
Arsenic
0.010
0.006
0.03
0.018
Barium
0.3
0.2
0.1
0.1
Beryllium
0.01
<0.01
<0.01
<0.0].
Cadmium
0.037
0.001
0.001
0.003
Chromium
0.067
0.009
0.02
0.0L
Copper
0.31
0.065
0.02
0.041
Lead
0.06
0.02
0.01
0.02
Manganese
0.48
0.16
0.13
0.5S
Mercury
0.0003
0.0007
0.001
0.001
Nickel
1.1
<0.05
0.05
o.i:>
Selenium
0.002
0.002
0.015
0.011
Silver
<0.01
<0.01
<0.01
o. o:.
Zinc
1.51
0.09
0.06
<0.1't
pH
4 .4
7.2
8.0
9.8
TDS
7.2
167.
142.
524.
SOURCE Chu, et al. (45).
5-38
-------
TABLE 5-18. AVERAGE CONCENTRATIONS OF TRACE ELEMENTS IN LIQUORS
FROM COMBINED ASH PONDS AT COAL-FIRED POWER PLANTS
OPERATED BY THE TENNESSEE VALLEY AUTHORITY
(all concentrations in mg/liter)
Element
Plant C
Plant D
Plant E
Plant F
Plant G
Arsenic
0.013
0.03
0.005
<0.005
0.029
Barium
0.2
0.2
0.2
0.2
0.2
Beryllium
<0.01
<0.01
<0.01
<0.01
<0.01
Cadmium
0.005
0.001
0.001
0.001
<0.001
Chromium
0.005
0.004
0.019
0.043
0.012
Copper
0.03
0.01
0.08
0.02
0.03
Lead
0.02
0.01
0.014
0.01
0.01
Manganese
0.22
0.03
0.01
0.01
0.05
Mercury
0.015
0.0002
0.0002
0.038
0.0008
Nickel
<0.05
0.05
<0.05
<0.05
<0.05
Selenium
0.014
0.065
0.009
0.016
0.010
Silver
0.01
<0.01
<0.01
<0.01
<0.01
Zinc
0.12
0.03
0.05
0.04
0.03
PH
7.1
8.6
11.2
11.2
9.6
TDS
363.
151.
380.
452.
279.
SOURCE: Chu et al. (45)
5-39
-------
TABLE 5-19. CONCENTRATIONS OF TRACE ELEMENTS IN LIQUORS FROM COMBINED
ASH PONDS AT COAL-FIRED POWER PLANTS OPERATED BY THE TEN-
NESSEE VALLEY AUTHORITY (all concentrations in mg/liter)
Element
Plant H
Plant I
Plant J
Plant K
Plant L
Arsenic
Bar ium
Beryllium
Cadmium
Chromium
Copper
Lead
Manganese
Mercury
Nickel
Selenium
Silver
Zinc
pH
TDS
0.10
0.2
<0.01
<0.001
0.006
0.05
0.01
0.05
0.0006
0.05
0.013
< 0.01
0.04
8.5
268.
0.005
0.2
<0.01
<0.001
0.024
0.05
0.01
0.01
0.0002
<0.05
0.004
<0.01
0.08
11.3
270.
0.038
0.2
<0.01
0.001
0.006
0.06
0.02
0.39
0.0003
0.05
0.003
<0.01
0.05
6.3
197.
0.012
0.2
<0.01
<0.001
0.021
0.05
0.025
0.01
0.0004
0.07
0.011
<0.01
0.05
10.8
232.
0.036
0.1
<0.01
0.001
0.008
0.04
0.01
<0.01
0.0003
<0.05
0.010
<0.01
0.04
10.5
219.
SOURCE: Chu et al. (45)
5-40
-------
The solubility of trace elements in ashes is related to the chemical
form of the element in the ash. It is also related to the concentration of
the element at the surface of the ash. Several studies have indicated that
several trace elements are concentrated on the surfaces of fly ash particles.
The subject of surface predominance of trace elements is discussed at length
in Section 5.5 of this report. Some references to leaching behavior are con-
tained in that section. However, reports concerned primarily with leaching
behavior of fly ashes and related topics are discussed in the current section.
Reports from laboratory studies and field studies are included.
Mobilization of trace elements to the environment requires initial
solubility in water. Continued solubility after the leachate interacts with
natural surface water or with groundwater and soils also is required. Results
of field studies and laboratory studies concerned with the interaction of
trace elements in solution with hydrous oxides in the solid phase are out-
lined.
5.4.1 Laboratory Study of Trace Element Emissions from Coal Refuse
Pile Leachate
Wewerka e_t al^. (46) have reported the results of a study of trace
element contamination of drainage from coal and coal cleaning wastes. Their
study was aimed toward cleaning wastes generated at the mine rather than at
the point of use. But, some of their results can be adapted to drainage from
coal storage piles at the combustion site and refuse piles generated at the
combustion site.
This study of Wewerka et^ al^. was concerned only with coals from the
Illinois Basin. Coals and associated refuse from other coal producing areas
will be the subjects of further studies.
The objectives of the program were to assess the potential for environ-
mental pollution from trace and minor elements released in the drainages from
coal preparation wastes and stored coals. Suitable control measures, if
necessary, were to be identified. Trace elements were defined as all elements
except carbon, hydrogen, sulfur and oxygen. The levels and occurrences of
5-41
-------
trace elements were determined in refuse samples. Minerals in the coal
refuse were identified.
Elements present in major proportions such as iron, aluminum and siLicon
made up the major minerals identified. Minor elements occurred as constitu-
ents of minor minerals, components of residual coal, or as substituents In
the major mineral lattices. Several elements which are generally considered
to be environmentally sensitive were found in refuse in concentrations aoove
30 yg/g. Among the elements found in these concentrations were fluorine,
aluminum, manganese, iron, cobalt, nickel, copper, zinc, arsenic, and lead.
Static and dynamic leaching studies were carried out. These experiments
were needed so quantitative predictions could be made about trace element
concentrations in drainage from coal refuse dumps and coal storage piles.
The concentration of sulfur was high in the refuse materials studied. These
materials had a pronounced tendency to produce acidic leachates rapidly.
Leachates from the refuse samples studied were reported typically to hav=
pH values in the range 2 to 4.
The acidic leachates were very efficient in dissolving or degrading
many of the mineral components. When the mineral components were dissolved
or degraded, trace or minor elements were released.
Two types of trace element leachabilities were observed. Some elements
(iron, aluminum, calcium, magnesium) were released in high absolute quanti-
ties because they were abundant in the materials being leached. Other less
abundant elements (nickel, cobalt, zinc, copper) were found to be highly
leachable from the refuse. These elements were present in relatively higher
concentrations in the leachates than in the refuse materials.
Studies designed to simulate intermittent leaching showed that inter-
mittently leached dumps presented a greater pollution threat than those
wastes that were always in contact with water. If not in contact with water,
the S oxidized to SOi, which is water soluble creating a more acidic solution,
thereby activating more trace metals.
5-42
-------
Comparisons were made between the results of laboratory leaching
studies and leachates taken from refuse dumps. The high level of agreement
between the two sets of results was taken to indicate that the laboratory
studies realistically simulated refuse dump conditions.
Nine elements were identified as having the greatest potential to con-
taminante drainage or run-off from Illinois Basin coal preparation wastes.
These elements are listed in Table 5-20. The table also gives the reasons
these elements were selected as priority elements.
TABLE 5-20. TRACE ELEMENTS OF MOST ENVIRONMENTAL CONCERN IN LEACHATES
FROM HIGH-SULFUR ILLINOIS BASIN COAL REFUSE
Labile Mineral High Leachate High Inherent
Elements Association Concentration Leachability
Aluminum
X
Cadmium
X
Cobalt
X
X
Copper
X
X
Fluorine
X
Iron
X
X
X
Manganese
X
X
X
Nickel
X
X
Zinc
^r«a=a«am=3 i ¦ - - - J *.
X
X
SOURCE: Wewerka £t al_. (46)
The authors pointed out that almost any designated level of trace ele-
ments in a refuse drainage system is somewhat arbitrary from an environmental
viewpoint. The actual harm that toxic elements can cause is a function of
the accumulation in the surrounding ecosystem. Factors such as the volume
and dilution of the drainage and the ability of plants, animals and soils in
the area to concentrate specific toxic elements must be considered.
The authors noted that refuse piles from low sulfur, alkaline western
coals could be expected to exhibit leaching characteristics very different
from those observed for Illinois Basin coals.
Constituents of coal pile run-off, as reported by Hart et al., were
given previously in Table 5-7.
5-43
-------
5•A.2 Trace Element Concentrations in Leachate from Ponded Ash and Sulfar
Dioxide Scrubber Sludge
Holland al_. (47) and Carlisle et_ al. (48) have reported the resuLts
of a study regarding possible trace element contamination of groundwater
from disposal of solid wastes from coal-fired power plants. Ash and sludge
from five operating plants were mixed with water to simulate ponding. Trace
element concentrations in the resulting aqueous phase were near the analytical
detection limit. Soil leaching tests indicated that soil under a pond cauld
remove trace elements from the leachate.
Concentrations of trace elements in coal ash leachate as reported by
Holland ££ a]^. are listed in Table 5-21. Station 1 fired low sulfur western
coal. Stations 2 and 4 fired eastern coal which contained approximately 4
percent sulfur. Station 3 fired high sulfur eastern coal. Particulate
emissions were controlled with electrostatic precipitators at the first four
stations. Station 5 fired eastern coal with approximately 5 percent sulfur.
Station 5 used ash reinjection to control particulate emissions.
The range of concentrations and the median concentration of trace
elements in FGD sludge leachates, as reported by Holland and Jones (39),
were listed above in Table 5-8.
Rossoff and Rossi (40) described the chemical composition of leachate
from sulfur dioxide scrubber sludge. Values were given for two sludges.
One sludge was from a plant burning eastern coal and the other was from a
plant burning western coal. The concentrations of trace elements in these
leachates also were reported in Table 5-8 above.
Jones £t^ «il. (49) have reported the results of a coordinated laboratory
study of flue gas cleaning wastes. Flue gas cleaning wastes include coal
fly ash, sulfur dioxide scrubber sludge and mixtures of fly ash and sludge.
The chemical and physical properties of these materials were investiaged.
Trace element concentrations in leachates from selected fly ashes and ash-
sludge mixtures were reported to be below EPA drinking water standards in
most cases, however, trace element concentrations were above drinking water
5-44
-------
TABLE 5-21. EQUILIBRIUM CONCENTRATIONS OF TRACE ELEMENTS IN COAL
ASH LEACHATE
Station Number
1
2
3
4
5
Bottom Ash
(vtl)
20
20
20
SO
100
Precipitator ABh
(wtl)
BO
eo
80
50
—
PH
12.5
9.5
12.2
12.0
8.2
Element jjr/r
Antimony
.006
.018
.033
.022
.0087
Arsenic
<.002
.084
.015
.072
.006
Barium
AO
<.3
<.3
<•3
<•3
Beryllium
.003
.00064
.0007
.001
.00026
Boron
.03
16.9
.21
1.1
.048
Cadmium
<.001
.0025
<.01
<.001
.0011
Chromium
<.001
.21
.11
1.0
.014
Copper
<.005
.031
.092
.013
.015
Fluorine
2.3
1.4
2.0
17.3
1.4
Germanlun
<•01
<.01
<.01
<•01
<.01
Lead
.0068
.0027
. 024
. 00 A 3
.0063
Manganese
<•002
<¦002
<.002
<.002
<-002
Mercury
.0006
.0005
.015
.0003
.0003
Molybdenum
.047
.052
.05
.69
.010
Nickel
<•05
.015
.025
<-05
.046
Selenium
.009
<.0005
.033
.47
<.0005
Vanadium
<•1
<.1
<.1
<.2
<.1
Zinc
.038
¦025
.19
<¦005
.0175
Source: Holland
et al. (47).
5-45
-------
standards in a significant number of cases. The values reported are
summarized in Table 5-22.
5.4.3 Sorptive Behavior of Trace Metals on Fly Ash in Aqueous Systems
Theis and Wirth (50) reported the results of chemical extraction of
trace elements from the surface of fly ash particles. Ashes collected by
electrostatic precipitators from 11 coal-fired power plants were studied.
Chemical extractants used were:
• hydrofluoric acid and aqua regia (for complete dissolution),
• ammonium oxalate (to dissolve X-ray amorphous oxides of iron,
aluminum and manganese),
• hydroxylamine hydrochloride at pH = 3 (for selective
dissolution of manganese oxides), and
• aqueous solutions of sodium hydroxide or perchloric acid
(to determine extractabilities of elements in fly ash at
pH = 3, 6, 9, and 12).
Relative amounts of lime and amorphous iron oxides were reported to
define the acidic or alkaline nature of fly ash in the presence of excess
water. The natural pH of water in contact with the ashes studied varied
from about A to above 12.
Extraction studies have shown that at least seven trace metals tend to
associate with the more abundant metal oxides (Fe203 and MgO). Furthermore,
differential extractions were used to estimate the degree of surface concen-
tration (enrichment) of the seven trace elements studied.
The oxides of aluminum, iron, and manganese were presumed to be available
on the surfaces of the fly ash particles. Arsenic, chromium, copper and zinc
were found to be preferentially extracted with iron for most of the fly ashes
studied. Chromium and nickel were found to be preferentially extracted with
manganese for most of the fly ashes studied. Lead was preferentially ex-
tracted with manganese for five fly ashes and with iron for three fly ashes.
Table 5-23 lists the range of concentrations found for each of the
seven trace elements studied for eleven ashes. The mean concentration ef
each element is given. This table also lists a measure of the surface
5-46
-------
TABLE 5-22 CONCENTRATION OF POTENTIAL PROBLEM SPECIES IN SELECTED FLY ASH AND SLUDGE LEACHATES1
(all concentrations are In mg/llter)
Art 1 f lc lal
Sludge'1
Fly
Ash
Element
Ash 01
Ash 02
Ash 9 3
Ash 04
Ash 05
Ash 06
Ash 17
Ash 08
Arsenic
.02
.08*
^16
.03
.02
<•003
.01
.01
Barium
.2
1.0
.14
.9
.2
2
1
.2
Boron
.6
.08
.003
.02
^9
.01
Cadmium
<•002
<.002
<•002
.002
<•001
.003
<-002
<.001
Chlorine
1160
2820
2440
2
.05
2
.8
.2
Chromium
.02
.02
.07
.002
.02
.03
.02
Copper
.018
.02
.02
.009
.009
.02
.02
.01
Fluorine
=2
= .4
= 1.4
= .2
- .05
= .05
= .5
zl
Iron
.2
.2
.18
.2
.07
.1
1
.2
Lead
<.01
<•009
.045
.005
.003
.01
^06
.009
Hanganese
.02
<.001
.004
.003
.02
.001^
.01
.009
Selenium
<•007
<.02
<¦006
.01
.005
.01
.02
.02
Silver
<.002
<•002
<.002
<.001
<.001
.001
<•001
<.001
Sulfate
5140
2400
2400
1430
1600
1440
910
1420
Zinc
.4
.04
.06
.02
.01
.02
2
.06
TDS
9640
7750
8090
2310
2290
2450
1560
2690
PH
11.1
10.5
10.0
11.2
7
10.9
9.7
6.5
'Trace element concentrations were estimated by Spark Source Mass Spectroscopy which has an error limit
of + a fnctor of 2.
JHie composition of artificial sludge was 50 percent by weight calcium sulfite-sulfate co-preclpltate
prepared In the laboratory and 50 percent fly ash.
'Artificial sludges prepared with Ashes Nos. 1,2 and 3 were leached using a "worst case" batch
leaching teat. The other aamples were leached using column leaching test.
^Concentrations which have been underscored are equal to or exceed water quality standards.
SOURCE: Jones et al., (49)
-------
enrichment of these elements. The measure of surface enrichment is the
percentage of the element which was extracted under the conditions used.
Ranges and mean values are given for each element.
TABLE 5-23. AVERAGE CONCENTRATIONS AND SURFACE ENRICHMENT OF TRACE ELEMENTS
FOR ELEVEN FLY ASHES
Average i
Concentration
Surface
Enrichment
(ug/g
of Fly Ash)
(Percent
of Total)
Element
Range
Mean
Range
Me an
Arsenic
6-1200
157
65-100
93
Cadmiun
5-20
8.1
<2-58
25
Chromium
44-320
109
15-84
44
Copper
28-350
97
25-75
48
Lead
30-1120
157
5-40
8
Nickel
90-600
220
5-42
11
Zinc
100-3300
515
10-70
30
SOURCE: Theis and Wirth (50)
The seven elements studied were leached more efficiently with acidic
than with alkaline aqueous solutions. Arsenic and, to some extent, cadmium
were observed to exhibit increased solubility at pH 12.
The leaching techniques used in this study were said to provide a
measure of the amount of trace element available for environmental release
on a short-term basis.
The large ranges observed in fly ash composition and surface enrichment
were attributed primarily to the variable geochemical matrix in which the
trace elements occur in the coal.
Elemental concentrations were determined using atomic absorption spectro-
photometry.
A procedure was applied to distinguish between elemental mercury and
ionic mercury. Mercury was observed to occur primarily as the element in
four fly ashes and primarily in the ionic form in four fly ashes. Three fly
ashes had extremely low concentrations of mercury.
5-48
-------
The authors point out the extreme variability of trace element
concentrations and mode of occurrence in fly ashes. They caution against
using studies of only one fly ash or averages of values determined for
several fly ashes to predict effects for a particular situation.
Talbot et^ £l_. (51) have reported the results of another study concerning
adsorption reactions. They report that adsorption reactions have an impor-
tant influence over the dissolved concentrations of cadmium and phosphorous
in aqueous media in contact with coal fly ash.
5.4.4 Chemical Speciation of Heavy Metals in Power Plant Ash Pond
Leachate
Theis (52) has been concerned with properties of ash pond leachate.
More recently, Theis and Richter (53) have reported measurements of concen-
trations of seven trace elements near a power plant ash pond. The power
plant was located in an area of sand dunes adjacent to Lake Michigan, and
used high sulfur coal from Southern Illinois as fuel. Elemental concentra-
tions of arsenic, cadmium, chromium, copper, lead, nickel and zinc were
measured in soil particles and in the associated aqueous phase. The computer
model REDEQL2 was used to calculate the chemical species of the trace elements
(except arsenic) in the systems studied.
The approach taken by these authors is unique with respect to application
to effluents from combustion wastes. This approach makes it possible to
estimate the true impact of leachates upon the environment. The validity of
the approach depends heavily upon the reliability of the adsorption constants
and solubility product constants in the computer program. Good correlations
between measured and predicted metal solubilities for five of the six metals
studied lend credibility to the results.
The results of this study are site specific; however, they give one set
of interactions between leachates and the environment. Additional studies
at other sites with different coals and different soils would be required to
obtain a general understanding of these interactions. The results of this
study are outlined in the following paragraphs.
5-49
-------
Less than one percent of any of the elements exlBted In a soluble
form in the soil-water system studied. The major portion of each element
was found to be associated with the solid phase in one way or another.
The two primary modes of association with the solid phase were assumed
to be adsorption on metal oxides and precipitation as discreet phases.
The major sorbing sinks for trace elements were assumed to be the oxides of
iron, manganese and silicon.
Soil and leachate samples were taken from several points around the
pond. The geometry of the sampling points provided a means of determining
the effects of changing soil and leachate properties. Samples taken in-
cluded pond water, leachate after passing through soil but before mixing
with natural groundwater and leachate after mixing with groundwater.
The computer model was capable of calculating the relative amounts o;:
various chemical species present in a chemical system. Thermodynamic
equilibrium was assumed. The input data required were total concentrations
of trace elements and sorbing metal oxides. In addition, the model required
input of the chemical composition of the leachate.
The model calculations indicated that free aquo and sulfato complexes
were the dominant soluble species in the pond liquor. As the leachate
entered the soil environment several chemical reactions occured. Zinc,
cadmium and nickel were sorbed from the leachate onto iron oxide and to some
extent onto manganese oxide. This sorption was indicated by model cal-
culations before and after the leachate encountered natural groundwater.
The computer model indicated that the solubilities of chromium, coppar
and lead were controlled by precipitation of sparingly soluble species.
Mixture of the leachate with natural groundwater did not influence the
solid phase for chromium and copper. Soluble chromium species were in
equilibrium with chromium hydroxide [Cr(OHs)]. Soluble copper species
were in equilibrium with basic copper carbonate [Cu2(0H)2C03].
The carbonate in natural ground water changed the form in which lead
was predicted to precipitate. In the pond leachate soluble lead species
were in equilibrium with lead hydroxide [Pb(OH)z]. In pond leachate mixed
5-50
-------
with natural groundwater soluble lead species were in equilibrium with lead
carbonate (PbCC>3) .
In the study by Theis and Richter, the partitioning of the elements
studies between solid and liquid phases was most influenced by pH, p(FeOOH),
p(MnOx) and p(SO^). In general, higher pH was predicted to result in greater
adsorption and precipitation. Chromium was an exception to this generaliza-
tion. Chromium solubility was predicted to increase at pH values above 7.5
because soluble hydroxo complexes such as Cr(OH)iT form. Changes in pH also
influenced predictions about which solid phase controlled solubility for
lead and copper.
The amount of available surface area of iron oxide or manganese oxide
was predicted to influence the amount of trace elements in the liquid phase.
Sulfate concentrations in the leachates studied were not shown to
influence solubilities; however, the model predicted that sulfate concentra-
tions above about 0.01 molar (1000 mg/£) could be expected to increase the
solubilities of all the trace elements studied except chromium.
5.4.5 Effect of Complexing Ligands on Trace Metal Uptake by Hydrous Oxides
Davis and Leckie (54) have reported the results of a laboratory study
concerning the sorptive behavior of trace elements. In this study, silver
and copper ions in solution were sorbed onto amorphous iron oxide in suspen-
sion. Sorption studies were carried out at several values of pH and with
and without complexing ligands present. Inorganic and organic ligands were
used.
The authors studied the adsorption behavior of complexing ligands.
This.behavior must be considered in determining the overall sorption of trace
elements on hydrous oxides. In some cases metal sorption was increased in
the presence of ligands because the ligands were sorbed on the surface of
the oxide. Other ligands were not sorbed but remained in solution and com-
peted with the hydrous oxide surface for coordination of metal ions.
The authors suggested that the distribution of trace elements in natural
aqueous systems may not be controlled by simple sorption on hydrous metal
5-51
-------
oxides. They suggested that trace elements may be bound on the surfaces of
colloidal particles coated with humic compounds.
5.5 VARIABLE DISTRIBUTION OF TRACE ELEMENTS BETWEEN BOTTOM ASH AND FLY
ASH AND AMONG VARIOUS SIZE FRACTIONS IN FLY ASH
A number of studies have reported enrichment of certain trace elements
in precipitator ash relative to bottom ash. Several studies have reported
variable concentrations of a number of elements in various size fractions of
precipitator ash or fly ash. Some elements have been reported to concentrate
in the finest particulates. Other elements have been reported to exhibit
concentration maxima or minima as a function of particle size.
The most popular explanation of these phenomena involves volatilization,
followed by condensation of the enriched elements on the fine particles.
Most authors suggest that the elements which volatilize are those which have
elemental boiling points below or near the maximum temperature in the com-
bustion zone (1500-1600°C). Suggestions have been put forth that elements
may have access to the vapor phase in various compounds (oxides or carbonyls).
Other authors have suggested that elements may have access to the vapor phase
because they are associated with organic matter in the coal, or because they
are associated with the sulfur bearing minerals in the coal. Some studies
have concentrated on demonstrating surface predominance of certain elements.
Some elements are reported to exhibit enrichment in most studies on this
subject. Other elements are reported to exhibit one type of behavior by one
study and another type by another study. Thus, it appears that a number of
variables influence enrichment behavior. The results of several of the
studies in this area are summarized briefly in the following sections.
5.5.1 Enrichment of Trace Elements as a Function of Particle Size in
Aerosols Leaving an Electrostatic Precipitator and a Wet Scrubber
Ondov £t al. (1) reported enrichment of some elements with particles
emitted from wet scrubbers relative to particles emitted from an electrostatic
precipitator at the same power plant. (This plant was described in Section
5.1.1 of this report). Elements reported to be enriched in this way included:
antimony, arsenic, bromine, chromium, selenium, uranium, and vanadium.
5-52
-------
The scrubber aerosols were reported to contain a greater proportion of their
mass in particles of respirable sizes. The authors concluded that wet scrub-
bers were less effective in reducing the potential inhalation hazard from
particulate emissions than were electrostatic precipitators of comparable
efficiencies.
Mass median aerodynamic diameters of particles associated with several
elements leaving a scrubber and an electrostatic precipitator are given in
Table 5-24.
5.5.2 Characterization of Trace Element Emissions from Coal-Fired Power
Plants
Ondov et al. (55) have reported enrichment factors for elements in
aerosols from five coal-fired plants. They had measured elemental concen-
trations in particles from two of the plants. The enrichment factors were
calculated from their measurements and from reports of others. The
enrichment factors are presented in Table 5-25.
These same authors [Ondov _et _al. (56)] have reported the results of
an earlier study of trace element distribution in particles sized with an
inertial cascade iropactor. These authors also have collaborated with others
[Ondov ^t j|l^ (57)] to report time-phased measurements of elemental concen-
trations in the plume and in the stack of a western coal-fired power plant.
5.5.3 Trace Element Partitioning in the T.A. Allen Steam Plant
The T.A. Allen Steam Plant was described in Section 5.1.2 of this report.
Lyon (2) reported partitioning of elements between the gas phase, fly ash
leaving the electrostatic precipitator, precipitator ash, and bottom slag.
Three types of partitioning behavior were observed. The various elements
were assigned to classes based on their partitioning behavior. Enrichment
factors for this plant were presented in Table 5-25.
Class III elements were those that remained essentially completely in
the. gas phase. Bromine, chlorine and mercury were reported to belong to this
class.
5-53
-------
TABLE 5-24
MASS MEDIAN AERODYNAMIC DIAMETERS (MMAD)
OF ELEMENTS IN AEROSOLS EMITTED FROM TWO
COAL-FIRED ELECTRICAL GENERATING UNITS
ESP unit, July 1975 Scrubber units. Feb. 1976
Elements MMAD1 (vim) Elements MMAD (ym)
Cr,
Cs,
Rb,
Zr
10.7-12.3
Co,
Cr,
Ni
7.1-12
Fe,
K,
Mg,
Na, Zn
3.0-4.0
Al,
Br,
Ce,
Co, Dy
9.1-10.0
Al,
Br,
Ce,
Dy, Eu
1.4-2.1
Eu,
Fe,
Hf,
K, La
Hf,
Lu,
Sc,
Sm, Th, La
Lu,
Mg,
Nd,
Sc, Sm,
Ta,
Tb,
Th,
Ti
Ca,
Ga,
In,
Mo
1.69-0.81
Ca |
Mn,
Na,
Se
7.9-8.6
As,
Ba,
Ga,
In
Mo,
Sb,
u,
V, W, Zn
4.4-6.3
As,
Ba,
Sb,
Se, U, V, W,
0.49-0.59
*Range of median values of MMADs from distributions of up to 6 impactor samples.
SOURCE: Ondov, et al. (1)
5-54
-------
TABLE 5-25 ENRICHMENT FACTORS FOR ELEMENTS IN AEROSOLS
EMITTED FROM SEVERAL COAL-FIRED POWER PLANTS
Ondov
Ondov
Plant A
Plant B
Lyon1
Gladney2
Kaakinen 3
Aluminum
0.86
0.75
0.44
0.83
0.94
Antimony
7.0
5.3
6.7
4.0
—
Arsenic
6.6
7.9
6
6.3
—
Barium
2.5
2.7
0.7
0,92
—
Beryllium
—
0.6
—
0.64"
—
Bromine
0.2
0.1
—
0.17
—
Cadmium
—
6.0
—
—
—
Calcium
0.76
0.89
—
0.92
—
Chromium
2.5
2.6
3.0
1.1
—
Cobalt
2.3
1.7
1.4
1.0
—
Gallium
4.3
3.0
—
1.2
—
Indium
5.5
3.7
—
—
—
Iron
1.1
0.90
0.84
0.83
1.0
Lead
—
3.8
8.1
3.7
3.1
Magnesium
1.1
0.8
0.54
—
—
Manganese
0.68
1.1
0.78
—
—
Molybdenum
1.8
3.5
—
—
3.0
Potassium
1.0
0.7
0.95
0.83
—
Scandium
1.0
1.0
1.0
1.0
—
Selenium
3.0
5.3
5.5
5.7
1.7
Sodium
1.0
1.1
0.99
—
—
Thorium
0.95
0.90
0.76
—
—
Tungsten
—
4.9
—
—
—
Uranium
3.3
2.5
—
—
—
Vanadium
2.0
2.5
2.5
0.75
—
Zinc
4.3
4.3
7.8
1.5
2.5
]Based on data
of Klein et^
al. (6).
2Unless indicated, values are based on
data of Gladney
et ^1. (24)
and
Gordon et al.
• (58).
3Derived from data of Kaakinen et ad. (19) for the ESP-equipped unit.
Data normalized to Fe. The value for Pb was based on 210Pb.
''Based on value from Gladney and Owens (25) normalized to Sc.
SOURCE: Ondov et al. (55)
5-55
-------
Eight elements were reported to be in Class II. These elements are
poorly incorporated into slag and exhibited successive enrichment in inlet
fly ash and outlet fly ash. The elements belonging to this class were:
antimony gallium
arsenic lead
cadmium selenium
copper zinc.
Twenty-five elements were reported to belong to Class I. These elements
were readily incorporated into the slag and showed no definite tendency to
concentrate in the smaller particles. They were:
aluminum
cobalt
manganese
sodium
barium
europium
potassium
strontium
calcium
hafmium
niobium
tantalum
cerium
iron
scandium
thorium
cesium
lanthanum
silicon
titanium
chromium
magnesium
samarium
uranium
vanadium.
Two elements, nickel and molybdenum, did not fit the classification
scheme outlined above. Lyons stated that molybdenum probably should be
included in Class II and nickel probably should be assigned to Class I.
5.5.A Trace Element Partitioning in Atmospheric Emissions from Plants
Using Hot-Side and Cold-Side Electrostatic Precipitators
Two western coal-fired power plants were described in Section 5.1. .1
of this report. One plant used a hot-side electrostatic precipitator for
particulate control. The other plant used a cold-side electrostatic pre-
cipitator for particulate control. Mann £t_ al_. (3) reported that the alms
of the study were to:
• quantify trace element enrichment in fly ash compared
to raw coal,
• determine trace element enrichment as a function of
particle size,
• investigate the affinity of elements for inorganic or
organic fractions of coal, and
5-56
-------
• investigate particulate collection efficiency and trace
element enrichment of emitted fly ash of hot-side and
cold-side electrostatic precipitation control devices.
Trace elements in coals may be associated vith the inorganic (mineral)
portion of the coal or with the organic portion of the coal. Coal from each
of the plants studied was separated into four density fractions (<1.35, >1.35;
and <1.45, >1.45) using a sink-float technique. Each of the fractions was
analyzed for 15 trace elements. The organic-inorganic association of each
element was calculated.
Correlation of enrichment of certain trace elements with decreasing
particle size in the fly ash was investigated. Good correlation of increas-
ing enrichment with decreasing particle size was found for four elements
(arsenic, copper, nickel, zinc) for both plants.
Three additional elements exhibited this correlation only at the cold-
side station: cadmium, chromium, and manganese. Selenium also exhibited a
good correlation of enrichment with decreasing particle size but only at the
hot-side station.
Enrichment of volatile trace elements in the fly ash leaving the control
devices was said to depend on two factors. These factors were:
• particulate loading at the point of condensation, and
• degree of element volatilization.
Particulate loading at the point of condensation was said to determine
the available surface upon which condensation could occur. A high particulate
loading was reported to lead to lower enrichment than a low particulate loading.
The surface area available for condensation would be greater with the higher
loading. The location of condensation with the process will vary from element
to element and will depend on the temperature profile of the gas stream.
The higher enrichment of arsenic and selenium in particles leaving the
hot-side electrostatic precipitator was attributed to condensation of these
elements in the air preheater. The particulate loading in the air preheater
would be much lower in a plant with a hot-side electrostatic precipitator
than in a plant with a cold-side electrostatic precipitator.
5-57
-------
The degree of elemental volatilization was reported to depend on th<;
characteristics of the element and its association in the coal.
An element such as mercury with a low boiling point is volatilized at
fairly low temperatures. Other elements such as iron or nickel are suscep-
tible to forming volatile metal carbonyls in gas streams rich in carbon
monoxide. Arsenic, cadmium, chromium, lead, nickel, selenium and zinc
exhibit boiling points either as the element or as a compound which would
result in partial volatilization in the boiler.
Kuhn and Shimp (59) have reported that the association of an elemen:
with the organic fraction of coal influences the volatility of that element
during pyrolysis or combustion. Several elements were observed by Mann lit al.
to be preferentially associated with the organic phase in the coal. These
elements also exhibited higher enrichment in the fly ash from the station
with the cold-side electrostatic precipitator. Elements exhibiting this
behavior were:
beryllium fluorine
cadmium mercury
chromium uranium
copper zinc.
Mann et aJL. pointed out that although a relationship of enrichment with
organic phase association was found, a larger data base was needed to estab-
blish a valid correlation.
5.5.5 Trace Element Enrichment in Vapors and Particles Emitted to the
Atmosphere from Three Western Power Plants
Three western coal-fired power plants were described in Section 5.1.A of
this report. Radian Corporation (4) reported that 18 elements were concen-
trated in the flue gas stream and depleted in the bottom ash stream of Station
I. The flue gas stream included entrained particles. Elements which exhibited
this behavior were:
5-58
-------
antimony cobalt nickel
arsenic copper selenium
boron fluorine silver
cadmium lead sulfur
chlorine mercury vanadium
chromium molybdenum zinc.
Eight elements were distributed in proportion to total ash flows in
Station I with no significant concentration or depletion. These elements
are listed below:
aluminum iron
barium magnesium
beryllium manganese
calcium titanium.
Uranium was concentrated in the bottom ash and depleted in the precipi-
tator ash of Station I.
Thirteen elements were observed to be enriched in the flue gas (and
entrained particles) of Station II. These elements were:
antimony chromium nickel
boron fluorine selenium
cadmium lead sulfur
chlorine mercury zinc,
molybdenum
Five elements were found to be enriched in the precipitator ash stream
of Station II. These elements were:
arsenic
cobalt
copper
silver
uranium.
5-59
-------
Kine elements were found to be uniformly distributed in the ash struam
of Station II. These elements were:
aluminum magnesium
barium manganese
beryllium titanium
calcium vanadium,
iron
Fifteen elements were found to be enriched in the flue gas stream of
Station III (including entrained particles).
antimony cobalt molybdenum
boron copper nickel
cadmium fluorine selenium
chlorine lead sulfur
chromium mercury zinc.
Three elements, arsenic, silver, and uranium, were enriched in the
cyclone plus economizer ash for Station III.
Nine elements were found to be distributed in proportion to the amount of
ash present in Station III. These elements were:
aluminum calcium manganese
barium iron titanium
beryllium magnesium vanadium.
In addition to the results presented above, enrichments of some elements
in fly ashes as determined by spark source mass spectrometry (SSMS) were
reported for all three stations. This report contains quantitative informa-
tion concerning degree of enrichment of each element for each station studied.
5.5.6 Trace Element Partitioning in Effluent Particles from the Widows
Creek Power Plant
The Widows Creek Power Plant was described in Section 5.1.4 of thi:i
report. Cowherd et al. (5) reported that chromium and lead were enriched in
outlet fly ash compared to coal ash.
5-60
-------
Measurements of concentrations of 15 elements in samples collected in
a Brink particle size train were presented. The authors reported that the
values were subject to error since large blanks had to be subtracted from
the reported values. The reported values indicate successive enrichment in
smaller particles for many of the elements measured. Other elements exhibited
apparent maximum concentrations at intermediate particle sizes. Elements
exhibiting successive enrichment were:
beryllium thallium
cadmium vanadium
copper calcium,
manganese
The following elements had a maximum concentration at 0.56 to 0.87 ym
equivalent diameter:
chromium
cobalt
lead
tin
zinc.
Nickel exhibited a maximum concentration at 0.87 to 1.51 ym equivalent
diameter and iron a maximum concentration at 1.6 to 2.35 ym.
5.5.7 Enrichment of Trace Elements in Particulate Emissions from the
Chalk Point Electric Generating Station
The Chalk Point Electric Generating Station was described in Section
5.2.2 of this report. Gladney e£ al^. (24) reported enrichment factors rela-
tive to Chalk Point coal for the precipitator ash, and for ash collected from
the effluent gases.
Enrichment factors plotted as a function of particle size exhibited
three types of behavior. One group of trace elements (antimony, arsenic, and
lead) showed a definite increase in enrichment factor on small particles.
Another group of trace elements (bromine, iodine, mercury and selenium)
were observed to exhibit enriched concentrations in the smallest particles,
5-61
-------
have a minimum in enrichment in particles around 1 p in diameter and to
exhibit another enrichment factor maximum in large particles. No explan«.tion
was offered for this bimodal distribution.
Most elements measured exhibited little enrichment factor dependence: as
a function of particle size. Elements in this group were:
chromium
gallium
nickel
sodium
zinc.
Other elements which exhibited little enrichment factor structure, or whose
distributions were not shown were:
barium rubidium
calcium scandium
cobalt strontium
hafnium tantalum
manganese titanium
magnesium thorium
potassium vanadium, and
all rare earths zirconium,
except cesium
Iron and cesium were reported to be depleted in small particles and
enriched in large particles. The authors suggested that the iron distribution
might be explained by noting that the iron in the coal occurs primarily as
pyrites. They suggested further that pyrites might be expected to behave
differently from aluminosilicates during combustion. No explanation was
offered for the observed behavior of cesium.
5.5.8 Enrichment of Trace Elements in Particulate Matter Associated
with the Valmont Power Plant
The Valmont Power Plant was described in Section 5.2.1 of this report.
Kaakinen et al. (19) found six elements were enriched in the particles leaving
5-62
-------
with the effluent gases from the precipitator outlet and scrubber outlet.
These elements were:
antimony lead
arsenic molybdenum
copper zinc.
These elements were referred to as "Group B." The authors noted that
all oxides of Group B elements, except copper, volatilize completely at
temperatures below 1500°C. The boiling point of CU2O is 1800°C. These
elements are classified geochemically with sulfur bearing minerals in the
earth's crust (chalcophile).
Elements found to show no pronounced enrichment were:
iron strontium
niobium yttrium,
rubidium
These elements were referred to as "Group A," These elements (except
rubidium) have oxide boiling points greater than 2400eC. The author hypothe-
sized that rubidium was associated with the aluminosilicate portion of the
ash and did not volatilize. Group A elements are classified geochemically
as lithophile.
Zirconium was depleted in the particles leaving with the flue gases.
The authors reported that zirconium often occurs in coal as zircon which has
a melting point of 2550°C. They suggested that zircon would not melt in the
furnace to form glassy spheres and that the mineral would occur in relatively
large particles and therefore would be collected by the mechanical collectors
more efficiently than the bulk of the fly ash.
5.5.9 Enrichment of Trace Elements on the Surface of Particulates
Emitted to the Atmosphere from Coal-Fired Power Plants
Natusch and co-workers have carried out a series of experimental studies
concerned with enrichment of trace elements in 6mall particles. Two reports
of these studies are discussed in this section and two others are discussed
in the following section.
5-63
-------
Natusch et_ a_l. (60) reported that a number of potentially toxic trace
elements were concentrated in the smallest particles emitted from coal-fired
power plants. The elements they found to be enriched in small particles
were: arsenic, antimony, cadmium, lead, selenium, and thallium. They sug-
gested that these elements or their compounds were volatilized during com-
bustion. They suggested further that as the effluent gases cooled, the
volatilized elements preferentially adsorbed or condensed onto small particles.
They pointed out that small particles pass through conventional control Equip-
ment more readily than larger particles.
Precipitator ash and airborne ash which passed through the precipitation
system was collected from eight power plants. Precipitator ash was divided
into several size fractions. Fractionations were carried out mechanically by
sieving and aerodynamically using a Roller particle size analyzer. Airborne
fly ash leaving the plant was collected and sized in-situ using an Andersen
cascade impactor. Data were reported for only one plant.
Davison et al. (61) presented additional data and an extended interpre-
tation of the data which had been presented by Natusch ^t al^. (60). The fly
ashes studied were from a coal-fired power plant burning coal from southern
Indiana. Cyclonic precipitators were used to control particulate emissions.
The authors presented no information concerning plant characteristics or
efficiency of the control system. No gas flow rates or concentrations of
particles in the effluent gases were given so no emissions can be calculated.
No material balances were attempted.
Davison et^ al. stated that the trace element content of the ash from the
plant studied had been shown to be representative of that in eight U.S. power
plants using a variety of coal types.
A variety of analytical techniques were used to measure the concentrations
of 25 elements in the fly ashes. The analytical methods used were: spark
source mass spectrometry, optical emission spectrography, atomic absorption
spectroscopy, and X-ray fluorescence spectroscopy. Data were reported for
the method considered most reliable for the element in question.
5-64
-------
The following 10 elements were reported to show marked increases in
concentration with decreasing particle size:
antimony nickel
arsenic selenium
cadmium sulfur
chromium thallium
lead zinc.
These elements exhibited concentration increases well above experimental
error. The concentration increases were confirmed by at least two analytical
techniques. The increases were consistently observed in a range of samples
and were present in the airborne fly ash collected from the ducting.
Eight elements showed limited concentration trends. Concentration
trends were found only for the ash collected in the precipitator, or they
exhibited non-uniform concentration dependence on particle size. These
elements were:
aluminum magnesium
beryllium manganese
carbon silicon
iron vanadium.
The remaining seven elements showed no concentration trends. They were:
bismuth potassium
calcium tin
cobalt titanium,
copper
The authors presented a model for concentration dependence which involved
vaporization of the element or one of its compounds in the combustion zone.
Vaporization was followed by condensation or adsorption onto entrained parti-
cles. They rejected the hypothesis that the ashing characteristics of pyritic
inclusions gave rise to predominantly small particles. They pointed out that
at 25°C as much as 80 yg/m of selenium (as selenium dioxide) and 70 pg/m of
arsenic (as arsenic trioxide) could exist in the vapor form.
5-65
-------
5.5.10 Enrichment of Trace Elements In Coal Fly Ashes Fractionated
According to Size, Density and Ferromagnetism; Surface
Predominance of Some Trace Elements
Natusch et_ al. (62) separated coal fly ashes on the basis of particle
size, particle density and ferromagnetic character. Thirty-two fractions
were obtained. Trace element concentrations were measured in each of these
fractions.
Common factor analysis and cluster analysis were used to interpret the
data. The authors interpreted the correlations identified in terms of p.irticle
size, matrix composition of the particles, and the nature of the chemical
elements themselves. They suggested:
a The distribution of elements not volatilized during the
combustion process depends on the chemical species in
which the element exists and the composition of the fly
ash matrix;
• The distribution of elements volatilized in the combustion
process depends on the composition of the fly ash particle
on which the element deposits and the surface area of
those particles;
a The distribution behavior of elements partially volatilized
is intermediate between that exhibited by the two classes
above.
The environmental significance of the above interpretation was said to
be three-fold.
• Many potentially toxic elements are preferentially
associated with aerodynamically small particles (<1 ^m).
These particles are preferentially emitted from power plants,
have long atmospheric residence times and can deposit in
the innermost region of the lung.
• Surface concentration of potassium and sodium on small
particles can be expected to lower the electrical resis-
tivity of these particles. This lowered resistivity will
make these particles easier to collect in electrostatic
precipitators.
• The complex dependence of elemental distributions upon
particle matrix composition and particle size suggests
that distributions may be very sensitive to coal type
and combustion conditions. Translation of distribution
information from one fly ash to another should be
approached with caution.
5-66
-------
Direct evidence of surface predominance was sought by ion microprobe
mass spectrometry, Auger microprobe spectroscopy and electron microprobe
X-ray spectrometry. Table 5-26 gives the results of the direct determination
of surface enrichment of elements on fly ash particles.
Natusch £t_ al. (62) also presented preliminary results of extraction
experiments.
Linton et al. (63) presented additional depth profiles obtained by
using the ion microprobe. They presented profiles for leached and unleached
fly ash samples. Lead and thallium exhibited the highest relative surface
concentrations of the elements leached. Water and dimethylsulfoxide (DMSO)
were used as leaching agents.
The results of the leaching experiments are listed in Table 5-27. More
than five percent of the iron, lithium, manganese, potassium, sulfur, and
thallium present in the ash was dissolved in water under the conditions
used. The authors identified four groups of elements based on teachability,
the extent of surface predominance, and the effect of leaching on the extent
of surface predominance. These groups are summarized in Table 5-28.
5.5.11 Trace Element Concentrations as a Function of Particle
Size for Precipitator Ash
Campbell _et^ (64) have reported major, minor and trace element
concentrations as a function of particle sizes in precipitator ash. The
ash studied was collected in the electrostatic precipitator of a western
coal-fired steam plant. No description of the plant was provided. This
ash was separated into 9 size fractions ranging from 0.5 to 50 ym (mass
median diameter). Separation was effected using a Bahco Microparticle
Classifier and an air elutriation apparatus. This procedure was reported
to produce individual size fractions strongly centered about the mass median
diameter.
The size fractions were analyzed for 32 elements. Two or three analyti-
cal techniques were used for 18 of these elements. Intercomparison of
analytical techniques yielded good results in most cases. In some cases
5-67
-------
TABLE 5-26 SURFACE PREDOMINANCE OF ELEMENTS IN FLY ASH PARTICLES
Ratio of signal intensity
Bulk Concentration1 at surface to signal intensity
Element (Ug/g) at 500 A° Depth Technique2
Aluminum
>>
15,500
1.1
1.
2,
3
Beryllium
32
6.0
1
Carbon
-
3.5
1,
2
Calcium
>
28,600
1.63
1.
2,
3
Chromium
380
3.3
1,
3
Iron
92,400
0.7
1,
2,
3
Lead
620
11.0
1,
3
Lithium
200
3.8
1
Magnesium
12,300
0.9
1
Manganese
310
6.4
1
Phosphorous
600
3.8
1,
3
Potassium
38,800
7.6
1,
2,
3
Silicon
110,000
1.1
1,
2,
3
Sodium
>
19,700
15.2
1,
2,
3
Sulfur
7,100
7.7
1.
2,
3
Titanium
4,740
0.9
1
Thallium
28
10.0
1
Vanadium
380
2.0
1
Zinc
1,250
7.2
1,
3
determined by spark source mass spectrometry.
technique (1) was secondary ion mass spectrometry. Technique (2) was auger electron
spectrometry. Technique (3) was electron induced x-ray spectrometry.
3Samples derived from only some sources exhibited surface predominance.
SOURCE: Natusch et al.(62).
-------
TABLE 5-27 LEACHING OF FLY ASH
Concentration
(ppm by wt) Amount
in unleached % Leached (wt%)
Element particles DMSO H2O
Calcium
>12000*
<1.3
<5.8
Chromium
380
2.4
4.5
Iron
92000
0.7
5.8
Lead
620
3. A
0.4
Lithium
200
17
14
Magnesium
12000
0.6
2.7
Manganese
310
7.1
35
Potassium
39000
0.2
6.0
Silicon
120000
0.1
0.3
Sodium
>53001
<5.2
Sulfur
7100
27
36
Tha11ium
30
25
11
Titanium
4700
1.5
0.5
Vanad ium
380
1.5
3.9
1Could not be quantified. Interferences were present, or analytical lines
were too intense to fall within the working range for the internal standards.
SOURCE: Linton et al. (63).
5-69
-------
TABLE 5-28 SUMMARY OF ANALYTICAL RESULTS - SURFACE CHARACTERIZATION OF FLY ASH PARTICLES
Effect of leaching on
Significant Surface concentration in the
Group Elements Peak Observed? immediate surface region Leachibility
aluminum
silicon
titanium
no
insignificant
low
iron
lithium
potassium
sodium
sulfur
yes
insignificant
moderate to
high
chromium
lead
manganese
thallium
vanadium
yes
depletions observed'
following leaching
moderate to
high
calcium
magnesium
no
generally not sig-
nificant
moderate
Source Linton et al., (63).
-------
two analytical techniques gave different values for concentrations but
yielded the same type of concentration vs_ particle size curve. Trace element
concentrations in the coal were not given.
The authors identified several groups of elements. In one group the
concentration of the element was observed to increase as particle size
decreased. The following elements belonged to this group:
arsenic
gallium
lead
magnesium
titanium.
Calcium and strontium belonged to a group that exhibited a concentration
maximum in particles of about 5 pm diameter.
The concentration of silicon was observed to increase as particle size
increased.
Iron exhibited a concentration minimum in particles of about 15 pm
diameter.
The rare earth elements exhibited a concentration maximum at 5 um and
another small one at about 15 pm.
Coinposition-particle size relationships were measured for other elements
but these elements were not assigned to groups by the authors.
5.5.12 Trace Element Emissions from a Coal-Fired Home Heating System
and a University Heating System
Block and Dams (65) have reported concentrations of trace elements in
ashes from a boiler providing heat for the University of Gent and from a
coal-fired home furnace. Elemental concentrations were determined on fly
ash fractions collected on Teflon or polyethylene impaction surfaces in an
Andersen cascade impactor. The capacity of the home furnace was 14 kg coal
per 2k hours and the capacity of the university heating facility was 1U metric
tons of coal per 24 hours for each boiler. Anthracite-type coal from Belgian
mines was used in both facilities. The coal was crushed to 12 to 24 mm diameter
chunks.
5-71
-------
Elemental concentrations V£ particle size curves were presented for
several elements. Elements were placed into three groups according to their
elemental mass-size functions. Most of the mass of elements in Group II
were emitted in particles with a diameter of less than 1 ym. The mass nedian
diameters for these elements were reported to vary from 0.4 to 1 Um.
The elements in this group were chalcophiles:
antimony mercury
arsenic selenium
copper zinc,
indium
and halogens:
bromine
chlorine
iodine.
The authors assumed that these elements were associated with the organic
fraction. These elements were reported to be in higher concentrations in
coal relative to crustal rock. The concentrations of these elements were
very high in small particles. The concentrations of the chalcophiles also
were high in particles of 10 ym diameter emitted from the home heating system.
The concentrations of the halogens also were high in large particles emitted
from both systems. The concentration minima for halogens occurred at about
3 or 4 ym for fly ash from the home heating system and at about 1 ym for fly
ash from the university heating system.
No clear preference for larger or small particles could be established
for elements from Group III. Elements which were assigned to this group
included:
cadmium nickel
cesium potassium
gallium sodium
gold tungsten
manganese vanadium,
molybdenum
5-72
-------
Mass median diameters for elements from Group III were reported to vary from
0.8 to 6.2 ym. Concentrations v£ particle size curves for fly ash from the
university heating facility showed pronounced concentration minima for man-
ganese, potassium, sodium and vanadium. The minima were in the 0.6 to 1 ytn
range.
Elements assigned to Group I were lithophile elements presumed to be
associated with the rocky portions of the coal. These elements were:
aluminum iron
barium magnesium
calcium rare earth elements
chromium scandium
cobalt thorium.
hafnium
These elements were said to be preferentially associated with the large
particles in fly ash. The mass median diameters for these elements were said
to vary from 6.3 to 10 ym. Concentrations of these elements were lowest in
small particles and highest in large particles. Aluminum, cesium, cobalt,
iron and magnesium appeared to have a minimum concentration at about 0.4 ym
in fly ash from the home heating system. Aluminum, cesium, cobalt and
magnesium appeared to have a minimum concentration in particles of 0.4 to 0.6
ym diameter in the fly ash from the university heating facility.
5.6 EMISSIONS FROM COMBUSTION OF OIL AND GAS
No information was identified relating to trace element concentrations
in natural gas. And no data were found for trace element emissions resulting
from combustion of natural gas.
Data concerning trace element emissions from combustion of oil in
stationary sources was meager compared to data on emissions from combustion
of coal. Reports containing relevant data are summarized below.
5-73
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5.6.1 Environmental Assessment of Oil-Firing in a Controlled Industrial
Boiler
Leavitt et_ _al. (66) have reported emissions from a 10 MW equivalent:
boiler. The boiler was capable of burning oil or coal or both simultaneously.
The boiler was equipped with a pilot-scale, double-alkali flue gas desulfuriza-
tion (FGD) unit designed to treat about 30 percent of the total flue gas;.
Tests were run using coal as the fuel and using oil as the fuel. The FC'-D
unit actually processed an average of 25 percent of the flue gas during the
oil-fired tests.
The authors reported that the overall particle removal efficiency cf
the scrubber was approximately 75 percent for particles generated when cil
was the fuel.
Concentrations of 22 trace elements were measured. The concentrations
of 11 of these elements exceeded their minimum acute toxicity effluent (MATE)
values at the scrubber inlet. The concentrations of 5 of the elements
exceeded their MATE values at the scrubber outlet. These 5 elements were:
arsenic, cadmium, chromium, nickel and vanadium. Arsenic, cadmium, nickel
and vanadium were removed from the gas stream with lower efficiencies than
the overall average removal efficiency.
Beryllium emissions were reported to be 0.001 mg/m3 after scrubbing.
This corresponds to half the MATE value for this element. At this concentra-
tion, the National Standard for Hazardous Air Pollutants limitation of 10
grams of beryllium per day would be exceeded by boilers of 100 MW or greater
capacity.
Mass balances were attempted for 19 trace elements. Mass balance closure
was between 50 and 136 percent for 10 of these trace elements. The balances
for the remaining elements failed to close within these limits. The authors
attributed poor balance closure to the extremely low concentrations of trace
elements present and/or contamination of the scrubber recycle solution with
materials from the coal-firing tests.
5-74
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The scrubber cake produced when oil was the fuel contained about 1
percent oil fly ash. The concentrations of all trace elements measured in
the scrubber cake except antimony, boron, molybdenum and zinc were above
health based MATE values. The concentrations of all trace elements measured
in the scrubber cake were above ecology based MATE values. The authors said
that specially designed landfills would be required for disposal of scrubber
cake. They based this conclusion on the possibility of trace elements leach-
ing from the cake. No leachate data were presented.
Table 5-29 gives trace element concentrations in the fuel oil. Table
5-30 gives trace element emissions in the flue gas before and after the
scrubber. Table 5-31 lists the trace element concentrations in the scrubber
cake. Trace element emissions in the combined aqueous effluent from the
boiler were reported to fall within acceptable limits.
5.6.2 Influence of Heavy Fuel Oil Composition and Boiler Combustion
Conditions on Particulate Emissions
Goldstein and Siegmund (70) reported particulate emissions from conven-
tional high sulfur residual fuel oil derived from Venezuelan crude. They
also reported particulate emissions from medium sulfur and low sulfur fuel
oil. The composition of the particle matter from the high sulfur fuel oil
was reported. The composition of the high sulfur fuel oil is given in Table
5-32. Table 5-33 gives the composition of particles collected from a small
package boiler burning high sulfur fuel oil.
The authors attributed the failure of carbon and ash values to add up to
100 percent to the decomposition of carbonates, nitrates and less stable
sulfates.
5.6.3 Other Studies of Emissions from Oil-Fired Facilities
Bennett and Knapp (71) reported trace element concentrations of particles
collected from three oil-fired power plants. Two of the plants burned high
sulfur (2.5 percent) fuel oil and one burned low sulfur (1.4 percent) fuel
oil. The major components of the particles were reported to be sulfur,
vanadium and nickel.
5-75
-------
TABLE 5-29 CONCENTRATION OF MAJOR TRACE ELEMENTS IN OIL
ConeentratIon In Typical
Element Fuel 011(yg/g) Range Reftrace
Aluminum
3.5
No Data
Antinony
0.03J
0.002-0.B
6
Arsenic
2.0*
0.0006.1.1
6
Beryllium
<0.05'
No Data
Boron
<0.15
No Data
Cadmium
<3.5
No Data
Calcium
5.50
No Data
Chromium
2.2
0.002-0.02
6
Cobalt
<1.25
No Data
Copper
1.40
No Data
Iron
12.3
0.003-14
6,7
Lead
2.61
No Data
Magnesium
<0.4
No Data
Manganese
0.4*
0.001-6
6
Mercury
0.09s
0.02-30
Molybdenum
2.9J
<0.1-1.5
6
Nickel
16.0
14-68
8
Selenium
0.72
0.03-1
Strontium
0.23
No Data
Vanadium
36.5
15-590
8
Zinc
3.0
No Data
Zirconium
<0.05
No Data
'Except for V and Nl, these ranges are for U.S. and foreign crude oils,
Ranges of V and N1 concentrations are for fuel oils.
2Values were calculated from concentrations at the scrubber inlet when
Inductively coupled plasma optical emission spectroscopy (ICPOES)
analysis provided upper limit data only
'Arsenic concentration calculated from concentration at the scrubber
Inlet because ICPOES value appeared to be unreasonably hlgb
"Performed by spark source mass spectrometry on a feed oil sample from
another teat.
'Performed by cold vapor analysis on a faed oil sample from another tast.
6 Kagee _et_al. (67) 7. Uoodle & Chandler (68) 8. Bennett and Knapp (69)
SOURCE; Leavitt et_al. (66)
5-76
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TABLE 5-30 EMISSION FACTORS AND MASS EMISSION RATES OF
TRACE ELEMENTS DURING OIL-FIRING TEST
Emission Factor Emission Race,
hr/J
R/h
r
Removal
Element
Scrubber
Inlet
Scrubber
Outlet
Scrubber
Inlet
Scrubber
Outlet
Efficiency
Z
Enrlchme:
Factor
,41 nirilnim
1.9
0.15
220
18
92
1.0
Antimony
0.02
0.0019
2.5
0.23
91
1.15
Arsenic
0.049
0.0094
5.9
1.1
81
2.37
Beryllium1
<0.0003
0.0003
<0.04
0.04
Unknown
>11.9
Boron
0.17
0.012
21
1.5
93
0.87
Cadmium
0.091
0.021
11
2.5
77
2.80
Calcium
0.13
0.022
16
2.7
83
2.03
Chromium
0.055
0.0057
6.7
0.69
90
1.26
Cobalt
0.033
0.0038
3.9
0.46
89
1.43
Copper
0.18
0.002
21
0.27
99
0.15
Iron
1.6
0.088
190
11
95
0.69
Lead
0.065
0.0041
7.9
0.50
94
0.77
Magnesium
0.10
0.0094
12
1.1
91
1.15
Manganese
0.010
0.0013
1.2
0.15
87
1.58
Mercury2
0.0006
0.0001
0.05
0.006
87
1.48
Molybdenum
0.072
0.0079
8.7
0.95
89
1.35
Nickel
0.36
0.063
43
7.7
83
2.16
Selenium
0.016
0.002
2.0
0.23
87
1.43
Strontium
0.014
0.0003
1.7
0.03B
98
0.28
Vanadium
0.88
0.26
110
31
71
3.61
Zinc
0.20
0.02
24
2.5
90
1.27
Zirconium
0.0049
0.0003
0.59
0.038
94
0.79
Total
6.0
0.78
710
96
87
'Beryllium was determined by spark source mass spectrometry. The other elements
except mercury, were determined by Inductively coupled plasma optical emission
spectroscopy.
'Mercury vas determined by cold vapor analysis of SASS train samples taken
during another test.
SOURCE: Leavltt, et al. (66)
5-77
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TABLE 5-31 INORGANIC CONTENT OF SCRUBBER CAKE FROM
OIL FIRING (DRY BASIS)
Concentration MATE1 Value, Ug/g Degree of Hazard
Element Ug/g Health Ecology Health Ecology
Aluminum
1,684
160
2.0
11
842
Ant imony
3 2
15
0.4
0.2
7.5
Arsenic
15 2
0.5
0.1
30
150
Boron
40
93
50
0.4
0.8
Cadmium
1 2
0.1
0.002
10
500
Calcium
200,000
480
32
417
6,250
Chromium
15
0.5
0.5
30
30
Cobalt
19 2
1.5
0.5
13
38
Copper
16
10
0.1
2
160
Iron
2,164
3.0
0.5
721
4,328
Lead
6 2
0.5
0.1
12
60
Magnesium
3,799
180
174
21
22.
Manganese
6
0.5
0.2
32
80
Molybdenum
14 2
150
14
0.1
1
Nickel
132
0.45
0.02
293
6,600
Selenium
9 2
0.10
0.05
90
180
Strontium
239
92
—
2.6
—
Vanadium
203
5.0
0.3
41
677
Zinc
36
50
0.2
0.7
180
Zirconium
37
15
—
2.5
—
Total
208,450
JMATE is an abbreviation for Minimum Acute Toxicity Effluent.
Concentrations obtained from spark source mass spectrometry were used
when inductively coupled plasma optical emission spectroscopy provided
upper limit data only.
SOURCE: Leavitt et al. (68)
5-78
-------
TABLE 5-32. REPRESENTATIVE COMPOSITION OF CONVENTIONAL HIGH SULFUR RESIDUAL
OIL DERIVED FROM VENEZUELAN CRUDE
Parameter
Value
Sulfur
Carbon
Hydrogen
Nitrogen
API gravity
Viscosity
Carbon
Hexane insoluble
Ash
Trace Metals
Vanadium
Nickel
Sodium
Iron
2.2%
66.25%
11.03%
0.41%
17.3
3138. SSU @ 38°C (100°F)
'12.51%
10.33%
0.08%
350 yg/g
41 yg/g
25 yg/g
13 yg/g
SOURCE: Goldstein and Siegmund (70)
TABLE 5-33. PARTIAL COMPOSITION OF PARTICLES EMITTED FROM OIL-FIRED FUR-
NACE BURNING HIGH SULFUR RESIDUAL FUEL OIL DERIVED FROM
VENEZUELAN CRUDE
Size
Fraction (ym)
COMPOSITION
Carbon .
(% in
particulate)
Inorganic Ash
(% in
particulate)
V205 Naz0
(as % of (as % of
Inorganic Ash) Inorganic Ash)
>10
1-10
< 1
79.4
70.7
30.1
10.1
18.1
57.1
41.6
63.7
58.2
1.7
1.8
3.4
SOURCE: Goldstein & Siegmund (70)
5-79
-------
Kukin (72) discussed addition of metal-containing additives to make
boilers cleaner, cut corrosion, and reduce stack emissions of hydrocarbons
and sulfur trioxide. Significant fuel additives were reported to contain
magnesium oxide (with or without small amounts of aluminum oxide or hydrate),
manganese, and magnesium oxide with manganese. Presumably the use of addi-
tives containing manganese would increase manganese emissions to the atn.os-
phere.
Suprenant et al. (73) have reported the results of a preliminary
emissions assessment of the air, water and solid wante pollutants produced
by conventional stationary combustion systems. This report summarizes
system characteristics. It also summarizes pollutant emissions from unit
operations for 56 source classifications. Trace element emissons are
covered.
5.7 TRACE ELEMENT EMISSIONS FROM INCINERATION OF SOLID WASTE MATERIALS
Several reports have described emissions from systems that inciner£.te
solid wastes. Wastes which have been incinerated include municipal refi.se,
sewage sludge and trash. Atmospheric emissions of particles have been
described. In addition, characteristics of collected ash and of waste water
streams have been reported. The reports identified in the literature
search are described briefly below.
5.7.1 Trace Element Emissions from Municipal Incinerators
Greenberg et al. (74, 75) have reported concentrations of trace
elements in particles emitted from three municipal incinerators. Two
of the incinerators served largely residential areas around Washington, D.C.
The other incinerator served a mixed industrial, commercial, residential
area in Eash Chicago and Hammond, Indiana.
The Alexandria incinerator near Washington, D.C. had two furnace
trains, each capable of incinerating 140 metric tons of refuse daily.
Effluent gases were passed through a water spray baffle to remove some
of the fly ash. The temperature of the gases leaving the stack was 2603C.
Total particulate emissions from this incinerator were approximately 2.3 kg
of suspended particles per metric ton of refuse burned.
5-80
-------
The Solid Waste Reduction Center #1 (SWRC) (also near Washington, D.C.)
contained six furnace trains. Each train was capable of incinerating 230
metric tons daily. Particles were controlled by mechanical separators and
electrostatic precipitators. Total particulate emissions from this facility
were 0.46 kg per metric ton of refuse burned.
The Nicosia Municipal Incinerator in East Chicago Indiana had two
furnace trains. Each train was designed to incinerate 204 metric tons of
refuse daily. Particulate emissions were controlled by a spray chamber
followed by a three-stage, horizontal, plate-type scrubbing tower. The
average total particulate emissions were about 4 kg per metric ton of refuse
consumed.
The concentrations of 28 elements in the particulate emissions from the
three facilities are listed in Table 5-34. The compositions of the suspended
particles downstream from the particle control device were not the same as
the compositions of the collected particles. Two extreme examples are cited
below. The average concentration of lead in the collected particles from
the Alexandria facility was 0.40 percent. The suspended particles from this
facility were reported to contain 9.7 percent lead. The average chlorine
concentration in collected particles from the SWRC //I was 0.13 percent. The
suspended particles from this facility averaged 14 percent chlorine.
Enrichment of several elements on small particles was observed. Elements
which exhibited this enrichment pattern were:
antimony
indium
arsenic
lead
bromine
silver
cadmium
sodium
cesium
tin
chlorine
tungsten
copper
zinc
These elements were reported typically to have more than 75 percent of
their masses in particles with diameters less than 2 ym.
5-81
-------
TABLE S-J4 ORDER OF MACNITUDE COMPOSITIONS OF PARTICLES EKITTED FUM THREE MUNICIPAL XMCINE&ATION
Concentration (wg/g)
Alexandria SWRC #1 Nicosia
1.
Aluminum
16.000
+
GO
O
O
c
21,000
+
10,000
: 5,000.'
2.
Antimory
2,400
+
2 ,400
2,400.
+
1. 100
1,600.
+
800
3.
Arsenic
210.
+
100
310.
+
160
200.
+
90
4.
Barium
690.
+
5 70
990.
+
410
220.
+
130
5.
Bromine
2,600.
*
1,400
920.
+
520
880.
+
390
6.
CtdmiuzD
1, 100.
400
1,900
+
700
1,500.
+
400
7.
Calcium
23,000.
+
11,000
11,000.
3,000
e.
Cesium
3.
1
+
1.7
5.5
+
2.2
8.5
+
3.3
9.
Chlorine
200,000
50,000
140,000.
+
30,000
2 70,000
+
30,000
ID.
Chromium
490.
+
350
870.
+
370
105.
+
17
11.
Cobalt
12.
+
7
5.4
+
2.5
2.3
+
0.5
12
Copper
2000.
+
1,200
1500.
+
5 00
1700.
+
300
13.
Gold
0.
71
+
0. 77
0.70+
0.06
0.43+
0.18
14.
Indium
6.
5
i
5.4
3.6
+
0.7
6.5
+
0.7
15.
Iron
9000.
+
3,000
7100.
+
1,400
3300.
+
1,500
16.
Lanthanum
3.
8
+
2.6
4.
6+
1. 1
2.9
+
1.6
17.
Lead
97,000.
+
26,000
77,000.
+
11,000
69. 0.
+
10,000
18.
Magnesium
6,800
+
2,500
3,600
+
700
28,000
+
8,000
19.
Hanganese
1,500
+
1,400
410
+
110
2 70
+
80
20.
Nickel
200
+
80
170
+
70
79
+
29
21.
Samarium
:o.
82
0.62+
0.15
0.40+
0.20
22.
Selenium
23.
+
21
39
+
29
49
+
37
23.
Silver
390.
+
360
1000
+
800
110
+
80
24.
Sodium
98 000.
+
26.000
65,000
+
13,000
62.000
+
13.000
25.
Thorium
1.
8
t
1.4
:3'
0. 37+
0.28
26.
Tin
10,700.
+
1,500
10,800
+
1, 100
12,900
+
1,600
27.
Titanium
2,900
i
1,400
3,600
+
2,000
rsoo1
28.
Tungsten
17
+
11
22
+
8
:b«
29.
Zinc
120,000
+
60.000
130,000
+
50.000
110,000 ;
f
30,000
'Uncertanties are standard deviations
'Only approximate concentration! could be reported
because blank values vert high.
SOURCE: Greenberg et al. (74).
5-82
-------
Elements reported to have predominantly large particle distribution
were:
aluminum,
calcium,
lanthanum,
scandium, and
titanium.
Some elements were observed to have mixed size distributions. These
elements were:
chromium
cobalt,
iron,
manganese,
selenium, and
vanadaium.
The enrichment mechanisms were said to be complex.
The authors estimated the contributions of incinerators to trace
elements in urban aerosols. They concluded that emissions from incinerators
were major sources of airborne antimony, cadmium, and zinc. They also sug-
gested that incinerators might be major sources of airborne indium, silver
and tin in many areas.
The authors did not measure mercury emissions. They noted that others
(76) had indicated that incinerators are large sources of vapor phase mercury
emissions.
5.7.2 Metals in Municipal Solids Waste and Aqueous and Solid
Effluents from Municipal Incinerators
A group at the Bureau of Mines in College Park, Maryland, has been
investigating metals in municipal waste and effluents from municipal incin-
erators. Law et_ al. (77, 78, 79) and Haynes et al. (80) have reported trace
element concentrations in the combustible fraction of municipal waste:
5-83
-------
In addition to the reports cited above, Law (81) has reported
concentrations of 26 dissolved metals in aqueous effluents from three
municipal incinerators. The concentration trends as a function of time
were studied in the recycled spray chamber waters and recycled quench wacers
of one incinerator. The spray chamber was designed to remove fly ash. 'The
quench waters were applied to bottom ash.
None of the metal concentrations in the effluents exceed local sewe::
regulations. Concentrations of zinc in recycled spray chamber waters reached
levels possibly detrimental to biological wastewater treatment. Concentra-
tions of several metals in the effluents exceed drinking water standards,
Several metals were observed to be enriched in the effluents relative to
city water. The pH of the effluent streams was observed to decrease as "he
operating temperature of the incinerator increased.
Law (82) also reported concentrations of several elements in solids
filtered from municipal incinerator effluents. Chlorine, copper, silver and
titanium were reported to be present in concentrations comparable to thor.e
found in low grade ores.
Several elements in these filtered solids were found in concentrations
to be one to three orders of magnitude above average crustal abundances.
These elements were:
antimony lead
arsenic mercury
cadmium silver
chromium tin
copper zinc.
Ash collected in particle collection devices was reported to be at least an
order of magnitude higher than coal fly ash in the following elements:
antimony nickel
cadmium silver
lead zinc.
5-84
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The elemental concentrations of ash from particle collection devices
and bottom ash were reported to be similar. Elemental concentrations in the
ashes remained constant, within experimental error, over a period of time
and for different geographical locations.
5.7.3 Trace Element Fmissions from Municipal Incinerator Near
Langley Station, Virginia
Singh (83) determined the elemental composition of aerosol particles
from a municipal incinerator. The particles were aerodynamically separated
into eight size fractions. The nominal aerodynamic diameters ranged from
0.43 pm to 20 ym. Elemental analysis was carried out using a charged par-
ticle inducted X-ray emission technique. Elemental concentrations were
calculated as concentrations in the aerosol. Sensitivities were reported
to be in the ng/m3 range for most elements with atomic number 11 and above.
The size distribution of the collected particles was determined to be
biomodal. One mode was centered at 0.54 pm and the other mode was centered
at 5.6 pm. Potassium and sulfur were reported to show a strong tendency
to concentrate on aerosol surfaces. Manganese and nickel were reported to
show a weaker trend for surface preference. Other elements were reported
to show no trend for surface preference.
5.7.4 Seleniun in Smoke from Open Trash Burning
Shendrikar and West (84) reported the analysis of smoke from open trash
burning for selenium content. Selenium was reported to be in the oxide form
and was trapped by impingement in distilled water. The methylene blue cata-
lytic method was used to measure selenium concentrations in the impinger sol-
utions. Selenium content of the smoke was related to the selenium content
of the trash. Concentrations of selenium dioxide as high as 273 yg/m3
were reported when dry wood chips were burned.
5.7.5 Other Reports of Emissions from Refuse Incineration
Rigo et^ al. (85) Drepared a summary of engineering data and criteria
from feasibility studies covering the preparation and use of refuse as fuel.
They mention that if plated metals are fed into the sterilizer, high concen-
trations of antimony, cadmium, lead, tin and zinc can be emitted as a submicron
5-85
-------
aerosol. They recommended that efficient particle collection devices such as
electrostatic precipitators, scrubbers, or baghouses be used on facilities
burning refuse.
Shannon and Schrag (86) have reported uncontrolled particulate emissions
of 0.94 to 9.4 grams per million joules for modern heat recovery incinerators.
Emitted particles were reported to have significant concentrations of trace
or heavy metals.
Niessen (87) reported a particulate emission factor of 12 kg per metric
ton of refuse. This factor was based on the average of particulate emissions
from 50 incinerators.
A feature article in Environmental Science and Technology in 1971 (68)
stated that incineration and recycling of ferrous scrap was the major source
of atmospheric emissions of cadmium in 1968.
H.F. Sidney (89) has reported that most potentially hazardous metals are
not found in significant amounts in emissions from well controlled incinerators.
Hall (90) lists incineration of refuse as a source of lead in the
atmosphere.
Devitt (91) stated that particulate emissions are the most apparent
problem when wastes are used as fuels. He also stated that calcium, copper,
iron, lead and zinc emissions were increased over coal when refuse fuel and
coal were co-fired.
Gross et al. (92) reported metal emissions from the burning of a mix-
ture of sewage and sludge. Cadmium had the lowest emission rate (3 g/hr) of
the metals measured, while lead had the highest (680 g/hr). Emission rates
for several other trace metals were between these extremes. When the ratio
of refuse to sludge was changed, cadmium again had the lowest emission rate
(3 g/hr) but zinc had the highest (966 g/hr).
Cho and Chambers (93) reviewed the use of solid waste as a supplementary
fuel in power plants. They reported that in one test emissions of hydrogen
chloride and mercury vapor were not significantly affected by the combined
5-86
-------
firing of refuse and coal. In another test, firing of 5-20 percent refuse
with Orient 6 coal increased chloride emissions by about 30 percent.
J.W. Jackson (94) has reported the results of a bioenvironmental
study of emissions from refuse derived fuel.
5.8 TRACE ELEMENT EMISSIONS FROM WOOD BURNING FACILITIES
Very little information was found in the literature describing emissions
from wood burning facilities. Hall _et ^1. (95) gave the composition of wood
ash as reported by Brown (96). These values were listed in Table 5-35. Hall
also reported that the emission factor (97) for particles from wood waste
burning boilers was 90.3 kg per million joules (0.210 lbs per million). This
factor was used to calculate elemental emissions based on heating value of
the hogged fuel. The results of the calculations also are given in Table 5-34.
The information given in this table should be taken only as an order-
of-magnitude estimate of emissions. The emission factor is an average value.
No information is given as to what controls, if any, this level of emissions
corresponds to. The assumption was made that the composition of the parti-
cles emitted would be the same as the ash. This assumption is not valid for
coal-fired facilities and may well not be valid for wood fired facilities.
In addition, the concentrations in this instance were determined by a
spectrographs analysis usually considered to give only order-of-magnitude
accuracy.
5.9 NEEDS FOR FURTHER STUDY CONCERNING TRACE ELEMENT EMISSIONS FROM SCCP
Many measurements have been made of trace element emissions from SCCP's.
These measurements have usually been made at a specific site under a
specific set of conditions. These data are useful for indicating ranges
of trace element emissions. But no empirical or theoretical framework
exists for predicting trace element emissions from a given facility with a
high degree of confidence.
It is convenient to discuss needs for further study in the same order
that was used for compilation of emission data earlier in this section.
Atmospheric emissions from coal-fired facilities will be discussed first.
5-87
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TABLE 5-35. COMPOSITION OF HOGGED FUEL (WOOD AND BARK) ASH AND CALCUUMED
ATMOSPHERIC EMISSIONS FROM HOGGED FUEL BOILERS
Calculated
Atmospheric
Emissions
Based on Heading
Concentration Value
Element
(ur/r)
(g/1012 joules
Aluminum
3.6
325,000.
Barium
0.010
900.
Boron
0.003
300.
Calcium
2.9
260,000.
Chromium
<0.001
<90.
Copper
<0.001
<90.
Lead
0.003
300.
Magnesium
0.8
70,000.
Manganese
0.016
1,400.
Mercury
nil
nil
Nickel
<0.001
<90.
Potassium
. 0.3
27,000.
Silicon
19.6
1,770,000.
Sodium
2.1
190,000.
Strontium
0.002
200.
Titanium
0.1
9,000.
Vanadium
<0.001
<90.
Zirconium
0.006
500.
1 Based on 90,300 grams of total particulate emissions per 1012 joules
heating value in fuel.
SOURCE: Hall e_t al_. (95). Data orginially from Brown (96) and USEPA (97).
5-88
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Next, emissions from coal-fired facilities to land and water will be
considered. Finally, emissions from facilities burning fuels other than
coal will be presented.
5.9.1 Needs for Further Study Concerning Trace Element Emissions
to the Atmosphere from Coal-Fired Facilities
Much of the data concerning atmospheric emissions from coal-fired
facilities have been compiled [Ray and Parker (98); Ragaini and Ondov (99)]
and recompiled [Torrey (100)]. Too few efforts have been made to analyze
and interpret the data.
As a part of the current program, atmospheric emission data from several
studies were collected and normalized to the heating value of coal. The
values calculated were presented in Tables 5-1 and 5-2. A cursory examina-
tion of these data reveals that atmospheric emissions of trace elements vary
over a wide range. These data indicate that poor particulate control permits
release of many trace elements to the atmosphere. Conversely, good overall
particulate control will reduce atmospheric emissions of most trace elements
froTr these facilities, but the degree of control for each element is not
easy to define.
To develop a predictive capability for atmospheric emissions from these
sources a two-step approach will be required. First, currently available
data need to be analyzed and interpreted. This analysis and interpretation
of programs should be planned to fill the gaps.
Subjects that should be examined when available atmospheric emission
data are scrutinized are listed below.
• Concentrations of trace elements in coal and expected range of
concentrations for coal from a given source need to be estab-
lished as a function of time (i.e. , as different parts of the
sean: are mined or delivered) .
• Effects of the concentrations of major inorganic species in
coal ash upon trace element composition of ash need to be
identified.
• Effects of association of trace elements in the coal (i.e.,
inorganic vs^ organic and chalcophile vs lithophile associa-
tions) upon trace element partitioning in the ashes need to
be studied.
5-89
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• Reliability of sampling techniques and methods of chemical
analysis need to be determined.
• Effects of boiler configuration on trace element partitioning
need to be studied.
• The effects of temperature profiles in boiler and particle
collection devices upon trace element partitioning in the
ash need to be determined.
• Effects of overall efficiency of particle collection devices
on trace element emissions to the atmosphere need to be
measured.
• Effect of particle collection efficiency v£ particle size
curve on emission of certain trace elements needs to be
established.
• Elements which may escape in the vapor phase need to be
identified.
• Factors which lead to enrichment of certain elements in very
small particles and/or on the surface of fly ash particles
need to be evaluated.
5.9.2 Needs for Further Study Concerning Trace Element Discharge to
Land and Water from Coal-Fired Facilities
Data regarding transfer of trace elements to land and water have been
examined more thoroughly than data for atmospheric emissions. Hart et el.
(3A) and Coltharp ^t <^1. (38) have prepared compilations of existing data
and have identified data gaps and research needs. The major needs identified
by these studies relating to trace element emissions are summarized belcw.
• A broader data base on the origin, chemistry and ultimate
pathways of trace elements in waste streams needs to be
developed.
• Ash characteristics relating to field disposal characteristics
(especially leachability) need to be correlated with boiler
type and coal characteristics.
• Characteristics of scrubber sludge (relating to fixation
reactions, leachability, and physical properties) need to be
correlated with scrubber type and operation.
• Studies are needed that can be used to develop correlations
between laboratory leaching data and field leaching data.
• To determine the effects of leachate on groundwater, studies
need to be made to correlate laboratory permeability measure-
ments and laboratory measurements of leachate composition
with field data on these parameters. Studies of interaction
of leachate with soils are needed.
5-90
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• Liner permeabilities need to be studied under field
conditions.
• The variability of trace element contents of ashes and
sludges needs to be established as a function of time.
• Leachability of ashes and sludges under different disposal
schemes needs to be studied.
• Disposal sites currently in operation need to be character-
ized with respect to trace element emissions.
• Analytical methods and sampling techniques need to be
evaluated.
• Effects of process changes on ash and sludge characteristics
need to be studied.
• The potential for recovery of valuable materials present in
trace amounts in ashes needs to be reevaluated.
• Disposal procedures that would allow future recovery of
valuable trace elements should be developed.
5.9.3 Needs for Further Study Concerning Trace Element Emissions from
Combustion of Oil, Municipal Refuse, and Wood
Information on trace element emissions from oil-fired combustion
processes is scant. The chemical composition of particulate emissions as a
function of trace element concentrations in oil needs to be more firmly
established.
The apparent uniformity of atmospheric emissions from municipal refuse
incinerators needs to be confirmed. The leachability of municipal refuse
ash needs to be studied further.
Characteristics of wood ash need to be more firmly established.
5-91
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88. Metals Focus Shifts to Cadmium. Environ. Sci. Technol.,
5(9):754-755 , 1971.
89. Howard, F. S. Statement: Hazardous Waste Management. Presented at
the EPA Hazardous Waste Management Meeting, 1975. 24pp.
90. Hall, S. K. Pollution and Poisoning. Environ. Sci. Technol.,
6(1):3 3-35, 1972.
91. Devitt, T. W., C. J. Sawyer, and F. D. Hall. State-of-the-Art Assess-
ment of Air Pollution Control Technologies for Various Waste-as-Fuel
Processes. In: Energy and the Environment, Proceedings of the Fifth
National Conference, Cincinnati, Ohio, 1977, D. G. Nichols, et al.,
eds. AIChE, Dayton, Ohio, 1978. pp.167-173.
92. Cross, F. L. Jr., R. J. Drago, and H. E. Francis. Metal and Par-
ticulate Emissions from Incinerators Burning Sewage Sludge and Mixed
Refuse. In: Proceedings of the National Incinerator Conference,
Cincinnati, Ohio, 1970. American Society of Mechanical Engineers,
New York, New York, 1970. pp.62-64.
93. Cho, P. and J. H. Chambers. Municipal Refuse: An Alternate Energy
Resource in Power Plants. In: Energy and the Environment, National
Conference Proceedings, Cincinnati, Ohio, 1976. pp. 204-211.
94. Jackson, J. W. A Bioenvironmental Study of Emissions from Refuse
Derived Fuel. AD/A-024661, Environmental Health Lab., McClennan Air
Force Base, California, 1976. 113pp.
95. Hall, E. H., C. M. Allen, D. A. Ball, J. E. Burch, H. N. Conkle, W.
T. Lawhon, T. J. Thomas, and G. R. Smithson, Jr. Comparison of Fossil
and Wood Fuels, Final Report. EPA 600/2-76-056, PB 251 622,
Battelle-Columbus Laboratory, Columbus, Ohio, 1976.
96. Brown, 0. D. Energy Generation from Wood Wastes. Presented at the
International District Heating Association Meeting, French Lick,
Indiana, 1973.
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97. Wood Waste Combustion in Boilers. In: Compilation of Air Pollution
Emission Factors, 2nd Ed. U.S. EPA, Research Triangle Park, North
Carolina, 1973. pp.1.6-2.
98. Ray, S. S., and F. G. Parker. Characterization of Ash from Coal-Fired
Power Plants. PB-265 374, EPA 600/7-77-010, Tennessee Valley Author-
ity, Chattanooga, Tennessee, 1977. 142pp.
99. Ragaini, R. C., and J. M. Ondov. Trace Contaminants from Coal-Fired
Power Plants. C0NF-750963-2, UCRL-76794, University of California,
Livermore, California, 1975. 18pp.
100. Torrey, S., ed. Trace Contaminants from Coal. Noyes Data Corp.,
Park Ridge, New Jersey, 1978.
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SECTION 6
ENVIRONMENTAL AND HEALTH EFFECTS
Trace metal enilssions from stationary conventional combustion processes
(SCCP's) are cause for growing interest and concern because of their en-
vironmental and health effects. The current shift in principal feedstocks
for electrical utility generation from natural gas and fuel oil to coal
has stimulated the current interest in trace metal emissions. Many of the
trace metals present in the effluent streams from a typical coal-fired plant
are toxic. Another important factor in assessing the potential for adverse
impacts from these emissions is the low ambient level of these elements in
the atmosphere and natural waters (see Section 2). To date most of the re-
gulatory emphasis concerning coal utilization has centered on S0x, N0X, and
fly ash in general. Effective control measures are well known for these
criteria pollutant classes, but recently the limitations of these systems for
control of trace metal emissions, particularly atmospheric emissions, have
been noted.
Trace metals are present in fuel oils as well as all coal types, but
their relative concentrations in coal are of the greatest concern. Many of
the trace elements in coal are required micronutrients for vegetation which
accounts for their presence. The concentrations of trace metals in coals
varies over a wide range, but almost all of the naturally occuring trace
elements are present in coal. These trace elements are released to the
environment during coal preparation as well as combustion in potentially
toxic amounts (1). Combustion of coal results in a general enrichment of
trace metals in the residual ash. Of the ten trace elements most enriched
in coal ash, nine are potentially hazardous to humans or animals: antimony,
arsenic, beryllium, cadmium, lead, molybdenum, selenium, sulfur, and uranium
(2).
6-1
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It is the emission of these and other toxic trace metals, particularly
in the atmosphere, that is of greatest concern. Numerous studies have
concluded that a high degree of correlation exists between community air
pollution and mortality or morbidity attributable to pulmonary disease (!)) •
Total trace metal emissions from coal-fired electrical generation facili-
ties constitute a sizeable percentage of total trace metal contributions
from anthropogenic sources. Projected increases in total emissions due 1:0
increased coal use in the future may result in significant elevations in
trace metal concentrations in the atmosphere. These increases will un-
doubtedly be paralleled by increased incidence of chronic diseases related
to long-tern trace metal exposure (A). Several recent studies have com-
pared the occupational and public health effects of generating electricity
from coal, uranium and oil. Dosage calculations based on airborne emissions
concluded that uranium offers less of a health hazard as a fuel than coal
(5,6) (See Section 7). These analyses are based on emission rates from plants
with conventional control units in place. Advances in control technology
for trace metal emissions can be expected to reduce the occupational and
public-health risks from coal use.
6.1 ELEMENTS OF SPECIFIC CONCERN
Several elements have received individual attention in the literature
with regard to the environmental and health aspects of their emission from
coal-fired plants. Another class of elements deserve special attention
because of their known carcinogenic, teratogenic, and oncogenic effects.
Fluorine
Even though fluorine is not a trace metal, its emission from coal-fired
plants is of special concern. Other major sources of fluorine pollution
are the production of phosphate chemicals and fertilizers and several metal-
lurgical manufacturing processes. The majority of the problems related to
fluoride emission to the atmosphere involve deleterious effects on vegetation
and animals that have ingested contaminated vegetation (7). Direct inhala-
tion of fluorine gas or fluorine-contaminated fly ash particles by animals
is less significant than uptake through contaminated forage and soil (8).
6-2
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A summary of information concerning ecological and health effects of fluorine
is presented in Section 6.6.
Mercury
The most important anthropogenic sources of environmental mercury in
the U.S. are chloralkali plants, seed-dressing agents, smelting operations,
and fossil fuel combustion. Natural sources are geothenual processes and
the land mass itself (9). At 1970 rates of coal consumption, between 275
and 1800 tons of mercury were being released to the atmosphere annually in
the U.S. This estimate is based on its average concentration in coal, be-
tween 0.5 and 3.3 ppm. Mercury is emitted primarily as a gas from coal
combustion. It is a highly toxic element which is concentrated in many
food chain processes, particularly in the aquatic environment. Inorganic
mercury is converted by microorganisms to methyl mercury which is much
more readily adsorbed, and more slowly excreted .than elemental mercury.
Numerous studies (10, 11, 12) have reported a relationship between
increased mercury contamination and an increase in the occurrence of mer-
cury poisoning in wildlife and human populations. It is a known carcinogen,
teratogen and oncogen which can induce harmful effects at very low levels.
Because it is emitted primarily as a gas, current control methods designed
to reduce particulate emissions are not effective. This fact and the known
toxic and bioaccumulation effects have earmarked mercury as a trace metal
of particular concern.
Selenium
Selenium is a semimetallic element with known environmental and health
effects. A few studies have focused on the potential hazards associated
with its increasing concentration in the ambient environments. Andren et al.
(13) calculated that 1.5 to 2.5 times as much selenium is mobilized through
coal burning as by natural weathering. The majority of the selenium re-
leased from a coal-fired plant to the atmosphere exists in the vapor phase
or attached to particles which are not removed by electrostatic precipitators;
however, the bulk of the selenium entering a plant leaves as part of the
solid waste. Stahl (14) reviewed the literature concerning selenium and its
6-3
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compounds as air pollutants. Atmospheric selenium is known to cause
irritation of the eyes, nose, throat and respiratory tract of humans, and,
under conditions of prolonged exposure, gastrointestinal disorders. It Ls
also a known carcinogen and increased atmospheric concentrations will increase
the total body burden of this toxic element.
Carcinogenic, Oncogenic, and Teratogenic Elements
Carcinogenic agents may be defined as those that are capable of pro-
ducing cancer in a tissue upon exposure. Many of the trace metals emitted
from coal-fired plants — arsenic, beryllium, cadmium, chromium, cobalt,
mercury, and nickel are known carcinogens. All of these elements and lead
are oncogenic (tumor-producing) as well. Except for arsenic, dosage-response
data for the carcinogens listed above can be found in the health effects
summaries presented in Section 6.6. Teratogenic may be defined as inducing
structural and/or functional deviation in an embryo during its development,
resulting in congenital birth defects. Barium, cadmium, lead, lithium, mercury,
and selenium are all considered teratogenic. Dosage-response information
for each of these known teratogenic elements can be found in the health effects
category in Section 6.6.
Carcinogens, as a class of pollutants, must be considered somewhat
differently than other toxic elements. Most other toxic elements have a
threshold limit value (TLV) which is associated with the minimum exposure
(as body burden) level of the pollutant at which health effects attributed to
that specific pollutant may be expected to occur. Exposure or intake of
specific pollutants in amounts below the TLV may cause health effects due
to unknown synergisms with other pollutants present, but the health effects
that occur cannot, at our present level of understanding, be related
directly to one specific pollutant.
Carcinogens, on the other hand, do not have a TLV associated with their
potential for health effects. Current theory on carcinogenic responses
holds that any increase in the exposure or intake levels of a particular
carcinogen may be expected to increase the occurrence of cancer in an
affected population of sufficient size. The dosage response information
6-4
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presented for carcinogens in Section 6.6 suggests minimum acute response
levels of these carcinogens (i.e., occurrence of cancer in a relatively
high percentage of organisms under laboratory test conditions), but this
does not imply that carcinogen levels below this amount will not result in
some increased incidence of cancer.
Chronic exposure to low level carcinogen concentrations and the poten-
tial for synergisms at low levels between these carcinogens is a point of
concern for many public health officials. At least a few of the trace ele-
ments that are known carcinogens may be emitted at relatively high concen-
trations from coal-fired plants equipped with present day control technolo-
gies. Under worst-case conditions, the ambient concentration of these
elements may be significantly elevated by SCCP's.
6.2 ENVIRONMENTAL TRANSPORT MECHANISMS
The principal environmental transport mechanisms are summarized in
Table 6-1. Material transfer of trace metals between ecological compart-
ments is difficult to impossible to quantify. The exact nature of the trans-
fer process will be dependent on a multitude of factors. The specific chemi-
cal form of a pollutant, cycling processes, biological uptake and transfer
rates, bioaccumulation effects, and type of parent soil or sediment material
where trace elements are deposited will be the principal determinant of
pollutant transfer in the environment once these chemical agents are re-
leased from a plant. All of these factors are site specific, making general-
izations about the overall process difficult. Nevertheless, a few generali-
zations can be made before examining specific results in the literature.
Source to Sink Routes
Mass balance studies on coal-fired plants equipped with an ESP or equi-
valent efficiency particle control units indicate that approximately one
percent of the total ash fraction of the plant is emitted from the stack.
Typically the remaining 99 percent forms the bottom ash and precipitation
ash fractions. These fractions are often combined and trucked or slurried
to an ash pond disposal site. An estimate of annual coal consumption
6-5
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TABLE 6-1. MAJOR TRACE METAL PATHWAYS AND TRANSPORT MECHANISMS
Atmosphere To;
1. Man - Inhalation
2. Animals - Inhalation
3. Plants - direct absorption
4. Soli - deposition
5. Surface water - deposition
Soil To:
1. Man - Inhalation of dust; Ingestion
2. Animals - inhalation of dust; ingestion
3. Plants — root uptake
4.< Surface water - deposition of dust; erosion by surface runoff
5. Groundwater - leaching from surface soils
Surface Water To:
1. Man - Ingestion
2. Animals - ingestion; absorption
3. Plants - root uptake; absorption
4. Snil - Infiltration
5. Groundwater - Infiltration
Groundwater To:
1. Man - Ingestion
2. Animals - ingestion (stock watering)
3. Plants - root uptake, absorption (irrigation)
4. Surface water - spring and seep discharge
5. Soil - upward and lateral migration
Plants To:
1. Man - ingestion
2. Animals - ingestion
3- Soil - decay and demlnerallzation
4. Surface water - decay and demlnerallzation
Anloals To:
1. Man - ingestion
2. Soil - excretion; decay; demlnerallzation
3. Surface water - excretion; decay; demlnerallzation
Man To:
1. Soil - excretion
2. Surface water - excretion
6-6
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for a 500 MW boiler is 1.88 x 106 tons/years +10% (15). Assuming a typical
ash fraction of 15 percent of the total coal mass, then approximately 2.80
x 106 tons/year +10% of materials will end up as precipitator ash or bottom
ash, and 2.82 x 106 tons/year +10% will be emitted as gaseous or particulate
effluent.
Trace element partitioning is different from the total mass partitioning
discussed above with a larger fraction of the total trace element content
of the coal being emitted from the stack (see Section 5). The remaining
trace element fractions are contained in the bottom ash and precipitator
ash. The major source of trace metal pollutants that effect terrestrial and
aquatic organisms is stack emissions; however, the potential does exist for
pollutant transfers from ash or scrubber sludge pond leachates entering
either the ground water or surface-water systems. Cooling pond water, which
is associated with many typical coal-fired plant systems, is another potential
source of contamination to surface and ground water. It is also the primary
aquatic environment where significant pollutant contamination and possible
ecological effects can be expected to occur.
Solid Waste Emissions
The solid waste fraction contains the bulk of the trace metals from
coal use. This waste stream is generally transported by mechanical means
to a disposal pond site. Transport of trace metals from the disposal pond
via leaching to other ecological compartments in the environment is deter-
mined by several factors:
¦ the type and thickness of any clay or plastic liner
that might be used,
• the permeability, cation exchange capacity, or porosity,
of the substrate; in general the mobilization-attenuation
characteristics of the soil for the specific elements
under consideration,
• soil and pond liquor pH,
• substrate trace element concentration, and
• the proximity of the disposal pond site to the ground
water table and/or surface water.
6-7
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The degree of movement of trace element pollutants from an ash pond
disposal site will be a function of the site-specific factors listed abovs.
Generally, the solid waste disposal site will be an effective sink for most
of the total trace metal mass entering the plant. Movement away from this
sink will be relatively small in most cases.
Atmospheric Emissions
The gaseous and particulate waste stream emitted from a coal-fired plant
to the atmosphere has the greatest potential for significant ecological
and health effects as it moves through the environment away from the emissions
source. When the effluent leaves the stack, the buoyant plume travels
downwind spreading vertically and horizontally decreasing in trace element
concentration by dilution with increasing distance from the plant. As the
plume encounters the ground, some particles are deposited directly on the
surface while others are reflected or "bounced" back into the atmosphere.
The rate of deposition and the surface concentration are the principal
factors that determine the degree and nature of impact that the atmospheric
trace metal concentrations will have on a particular ecological compartment.
Transport and deposition models are used to estimate surface concentraticn
and deposition velocities. Site-specific factors necessary for these models
include emission rate, wind data, precipitation data, meteorological statility
class, type of terrain, temperature, and stack height.
It is these atmospheric trace metal emissions that constitute the
greatest potential threat to man and his environment. Purves (16) has
reported that concentrations of certain trace metals in Antarctica and
Greenland are increasing due to global transport processes. General atmospheric
circulation patterns from the industrialized temperate regions to the equator
and then to the poles via the upper atmosphere can distribute regional
pollutants globally. Since fine particles can behave analogously to a gas,
the residence time in the atmosphere and potential zone of impact from even
a single point source can be quite large. These effects are felt as
added increments to ecosystems, which may vary considerably in background
pollutant levels, whether natural or otherwise.
6-8
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The above considerations reflect the difficulty in estimating prob-
able sinks, as well as quantifying transfers between ecological compart-
ments for atmospheric trace element emissions. Studies to date have shown
only slight correlation at best of source emissions with measurable changes
in atmospheric, soil, and biotic trace metal concentration even when examin-
ing effects of emissions relatively close to the source. Clearly, esti-
mates of the specific effects of trace element emissions become very diffi-
cult, if not impossible at large distances. In any case, some general as-
sumptions concerning the pathways of these pollutants through ecological
compartments is possible.
• Surface deposition of trace elements on soils will be the
major primary sink for most trace elements being emitted.
• The affected zone within the soil will be small, probably
less than 5 cm deep in most cases.
• Some trace elements may be inhaled or absorbed directly
by plants, animals, or man but most trace elements will
enter the food chain after uptake by plants or ingestion
of contaminated water or soil.
• Trace elements entering into a food chain may be concentra-
ted and eventually removed from a given area by mobile
organisms higher in the food chain, but most trace elements
will be cycled rather than transported after deposition.
• Trace elements deposited on surface waters will probably
be of less significance than those transported by erosional
factors, whether they originate from natural or anthropo-
genic sources.
• The ultimate sinks for emitted trace elements will be
determined by factors such as terrain, meteorological
conditions, substrate characteristics, and proximity
to surface water.
• Trace elements entering an aquatic environment will
probably be cycled by organisms to a certain extent,
eventually accumulating in bottom sediments.
6-9
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• Removal of trace elements entering aquatic systems will
be primarily by predation from animals or resource utili-
zation such as fishing by man.
• The principal pathways of trace elements to man will be
inhalation and ingestion of contaminated organisms.
6.2.1 Aquatic Pathways
Principal sources of trace metals from coal-fired plants include
aerial deposition of stack effluent, coal pile runoff and plant washdown
into cooling ponds, ash disposal pond leachate and overflow to surface and
ground water systems and discharges from cooling ponds to surface water.
Wood et al. (17) studied the environmental effects of coal ash landfill on
trace metal concentrations in surface water, groundwater and aquatic biota
near the site. Results showed elevated concentrations of As, Cr, Fe, Mn,
and. K. The movement of coal ash leachate through relatively impervious clay
silt, and shale was fairly restricted. This factor, together with a minimal
ground water flow in the area resulted in minimal contamination of adjacent
surface and subsurface waters.
Guthrie and Cherry (18) studied the aquatic ecosystem associated with a
coal ash basin drainage system to determine abiotic and biotic characteris-
tics and mechanisms of trace metal removal. Results of this study indicate
that sedimentation of suspended solids containing trace metals from the
ash basin was the major removal mechanism. Less than 1% of the total mass
of trace elements accounted for in their sampling was present in the water
column. Approximately 85% of the trace elements were in the benthos samples
(sediment and benthic organisms). Br, Ca, CI, Cd, Na, Sb, Se, and Zn
were more concentrated in the biotic forms than they were in the benthos
samples.
Dressen et al_. (19) compared trace elements extracted from electro-
static precipitator ash using nitric acid, hydrochloric acid, citric acid,
distilled water, and ammonium hydroxide as extractants. Effluent waters
at this plant were sampled to assess the elevation of trace element con-
centrations compared with intake waters. The results indicated a positive
6-10
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correlation between those elements most extractable by water (B, Fe, Mo, and
Se) or acid (As, B, Cd, F, Mo, Nd, Se) and those elements most elevated
in effluent waters (As, B, F, Mo, and Se). It was concluded that water in
contact with the ash In the disposal pond was most contaminated by the five
elements listed.
Alberts et (20) studied the relative availability of certain trace
metals from fly ash under simulated leaching conditions and compare these
results with trace element releases from Lake Michigan sediment. Lake
Michigan surface waters have a relatively high concentration of fly ash
particles which have an estimated residence time in the water column of one
year before sedimentation. Chemical conditions present in the sediment
apparently promoted release of Mn, Pb, and Zn, but not Fe, compared to the
fly ash leaching results.
Roffman et^ a]^. (21) report slight elevations in trace element concen-
tration in aquatic organisms present in a lake which is affected by the
Four Corners plant, but no consistant trends were noted. Concentrations of
trace elements present in aquatic plants, net plankton, and fish varied
greatly. They also reported that the quality of seepage water from the ash
pond and cooling lake was determined more by the mineral composition of the
parent soil material than the presence of trace metals in the water or ash
pond effluent which originated from plant operations.
A major interdisciplinary study conducted out of the University of
Wisconsin at Madison (22) on the ecological effects of coal-fired steam-
electric generating stations investigated the effects of trace element
emissions on the aquatic system associated with the plant. Results to date
indicate that aluminum and barium floe released from the ash basin may
be contaminating benthic communities downstream.
Anderson and Smith (23) investigated the dynamics of mercury at a
coal-fired plant — cooling lake complex and found some elevation of mercury
in lake sediments, but mercury concentrations in fish were unusually low.
Thus, slight increases of certain trace elements such as arsenic and fluorine
(19), calcium, magnesium, and sodium (21), and copper and chlorine (22)
6-11
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have been shown. These changes in trace element concentrations may be due
to evaporative losses in the cooling lake which can concentrate dissolved
constituents by a factor of 2.5 (19), or the addition of chemical agents such
as chlorine used to prevent biofouling in condenser tubes (22, 21).
A very detailed modeling study by Wagenet e£ al. (24) attempted to
simulate heavy metal transport to a lake from a hypothetical coal-fired
plant in a semi-arid climactic region. Transport of Zn, Pb, Cr, Cd, and
Hg to the lake over a 25 year period was modeled interfacing submodels
describing atmospheric diffusion, soil erosion, precipitation, and soil
chemistry. The results indicate that after 25 years, Hg-loading to the lake
is predominately due to aerosol fallout on surrounding soils while a signifi-
cant fraction, but less than the majority, of the Cd-loading to the lake is
due to plant emissions. Pb, Cr, and Zn loading rates were primarily deter-
mined by their idigenous levels in the soil and not significantly affected
by plant emissions. The major transport mode to the lake was soil erosion
rather than atmospheric fallout. The results of this study are site-specific
and would be different with different soil types and climactic conditions.
Other studies have suggested that trace metal concentration increases due
to atmospheric fallout from SCCP emissions are extremely small (21, 25).
6.2.2 Atinospheric Pathways
Atmospheric trace metal emissions have generally been considered the
most important effluent when evaluating the environmental and health effects
of coal-fired plants. This is mainly because the affected area is quite
large; however, the extremely small concentrations of these trace elements
after dilution in the atmosphere has inhibited field monitoring of their
transport and deposition. Modeling is now often relied upon instead of empi-
rical results. Only a few studies have documented elevations in trace metal
concentration due to a particular plant's operation. Klein and Russel (26)
investigated the degree of heavy metal deposition around a coal-fired
plant and correlated the measured concentrations with wind patterns. Soil
enrichment patterns for Cd, Co, Cr, Cu, Fe, Ni, Tri, and Zn corresponded to
prevailing wind direction. The concentration of Hg, emitted predominantly
6-12
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in a gaseous state, was only slightly enriched in the soil downwind from
the plant.
Raridon (25) compared measured and estimated air concentrations of
Cr, Cu, Mn, Mi, and Pb. The values were close for Cr, Cu, Mn, but not Pb.
Measured values for Pb were high, probably due to heavy traffic on a nearby
road. Cadmium concentration in a nearby watershed was also correlated with
predicted values obtained from a hydrologic model. The model used estimated
air concentration and deposition as inputs. Roffman et al. (21) studied
the potential impacts of the Four Corners Generation Power Plant. They were
unable to account for any measureable effect that stack trace element emis-
sions had on air concentrations around the plant. Numerous ecological studies
have shown that trace metal deposition has resulted in measureable change in
the concentration of some trace metals in plants and animals downwind from
a plant. The results of these studies are presented in Section 6.3.
6.2.3 Terrestrial Pathways
After deposition, trace metal transport is a function of numerous
factors. Trace element availability in a given soil is dependent upon the
solubility of the elements in that soil solution, which in turn is controlled
in part by the cation exchange capacity of the soil. The cation exchange
capacity is determined by soil texture, organic matter content, the amount
and kind of clay present, and the amount of surface area of the soil colloids
(27). Heavier soils generally have higher exchange capacities than light
sandy soils low in organic matter. Cations are usually less available in
heavy soils. Certain trace elements such as beryllium (28) and copper (29,
30) are held more strongly than most cations by the cation exchange complex,
and therefore are less mobile in the soil solution. Cations are generally
bound more tightly in neutral or slightly alkaline soils. In acid soils
they become more mobile due to increased solubility and their replacement
on the cation exchange sites by hydrogen (27). In acid soil the more mobile,
lower-valance forms of trace elements predominate over the less mobile,
high-valence forms. Therefore, soils with a pH exceeding 6.5 may pose less
potential cation toxicity problems (31).
6-13
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In general, much of the trace element deposition, particularly the catio-
nic forms, is retained in the surface layers of the soil and is not readily
leached to lower horizons, except in very acid or sandy soils. Trace anions
are usually more leachable than cations (32). Retention of trace elements in
the surface soil layers protects ground water from contamination. Neverthe-
less, surface runoff, erosion, and wind blown dust may still contaminate
aquatic systems (32).
Wagenet et^ £il^ (24) used a 6oil chemistry model that indicated aerosol
deposited and indigenous heavy metals will persist in the soil surface layer
with little downward movement. Soil erosion was estimated to be the major
transport process for deposited trace metals. After a 25 year period, madel
results predicted that approximately 15% of the total heavy metals fallout
is transported to a lake. The lake is considered the final environmental sink
according to this study.
Elevated concentrations of trace metals in soils, plants, and animals
due to coal-fired power plant emissions have been documented in several
studies. Anderson and Smith (23) reported elevated Hg concentrations in
soils downwind from a power plant in central Illinois. Raridon (25) and
Klein and Russel (26) also reported elevated soil and plant trace metal con-
centrations due to coal-fired plant emissions.
6.3 ECOLOGICAL EFFECTS
6.3.1 Known Response of Aquatic Ecosystems
Many cases documenting responses of aquatic ecosystems to trace metal
emissions are present in the literature. A summary of certain specific
references in this regard follows. Section 6.6 provides a quick summary
of the known ecological and health effects. It should be consulted when
questions concerning a specific element arise.
6-14
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Guthrie and Cherry (18) investigated trace metal effects on components
of an aquatic ecosystem present in a coal ash basin drainage system. Br,
Ca, CI, Cd, Na, Sb, Se, and Zn were more concentrated in water column biota
than in the benthic samples. Since the bottom sediments were determined to
contain the majority by mass of the trace elements in question, the selec-
tive concentration and cycling of the elements listed above was suggested.
The light metals were concentrated more in animals than plants (Figure 6-1).
SOT HER PLANTS
rPCRT£D£R|A^
" H*DR0D£J>;Oa,
fOTHER
PtANTl—y
.Cattail
CATTAIL
vATORIA
DUCKWEED
TADPOLES
MIDGES
MIDGES
HEAVY LIGHT NITROGEN ACTIVE HALOGENS
METALS METALS FAMILY METALS
ELEMENTS CONCENTRATED
Figure 6-1. Relative accumulation of the most plentiful
elements in the most abundant representatives
of the food chain in all sampling sites. (1,
includes bacteria and cypress; 2, includes
clam and shrimp.)
SOURCE: (18)
Mosquito fish and crayfish were the dominant organisms with regard to Ca,
Na, and K concentration. The benthic dwelling midges concentrated the lar-
gest number of trace elements (Co, Br, Cu, Fe, Sb, Hg, As) followed by tad-
poles (Zn, Al, Mn, CI). The active metals (Figure 6-1) Ca, Na, K, and halo-
gens Br, CI, and CI were most concentrated by organisms in the drainage sys-
tem. These elements, particularly the active metals group, will be rapidly
6-15
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and actively cycled in the food web of this system. In general, the
concentration ability was generally lower in the plants and bacteria than
animals as night be expected. Aquatic community diversity and stability
increased with increasing distance from the ash basin suggesting a depressing
effect on these ecosystem parameters perhaps due to trace element contamination.
Results of a five-day toxicity test indicated that organisms within the
drainage system were able to survive at any point within the system. Organ-
isms not indigenous to this system showed a variable resistance to the
drainage system environment. Non-indigenous channel catfish and largemouth
bass were most resistant to the toxicity tests. Non-indigenous shrimp,
darters and salamanders were least resistant with shrimp being the most
sensitive. These results indicate that, for this case at least, either
indigenous populations are selectively resistant to the trace element
environnent, or indigenous species acquire some form of resistance after
birth.
Other studies have indicated a depression in some component of aquatic
ecosystems which are directly affected by trace element contaminants frort
coal-fired plant effluents (22). Spigarelli et al. (33) are studying the:
effects and interactions of fossil fuel pollutants on Lake Michigan zoo-
plankton. Planktonic crustaceans, according to the authors, appear to bt:
more sensitive to certain pollutants than either phytoplankton or fish, ;md
thus may be critical in determining aquatic ecosystem responses. The long-
term effects of elevated Cd concentrations in Lake Michigan were investigated
using laboratory populations of Daphnia galeata mendotae. Results indicate
significantly increased prenatal mortality at all levels down to 1 ppb Ccl
and significant effects on average population numbers and biomass down to
U ppb.
Helmke (34) has shown that concentrations of Cr, Ba, and Sb are
increasing in aquatic insects taken from a fly-ash pond drainage system
since a relatively new power plant started operations. Samples from pre-
operational years and from sites not affected by the ash pond were examined
to demonstrate present trends. Roffman £t^ al^. (21) found considerable
variation in trace element concentrations of aquatic organisms present in a
6—16
-------
coal-fired plant cooling lake. Trace element concentrations in aquatic plants,
net plankton and fish samples varied greatly, but some food web concentration
effects were noted.
6.3.2 Known Responses of Terrestrial Ecosystems
The body of literature reviewed for this subsection can be divided into
those investigations that could account for changes in trace element concen-
tration of terrestrial biotic components, and those that could not. Factors
that could account for these differing results include study and detection
methods, age of plant operations, specific elements under investigation,
representative species sampled, and control technologies involved in emis-
sion systems. As such, the following results which may seem contradictory
at times should not be surprising. Since no method of evaluating impacts
has been standardized, variable results from independent investigations can
be expected at this point. This demonstrates the need for more basic data
to begin to resolve apparent discrepancies. Before reviewing the litera-
ture concerning specific impacts on terrestrial ecosystems, a short treatment
of trace metal effects on vegetation is presented.
Trace element emissions may directly affect the aerial portions of
plants in a number of ways. The vapor form of some elements, such as mercury,
can be absorbed by the aerial plant parts (35, 36, 37, 38). Particles
deposited and retained on leaf surfaces can clog stomata, decrease photo-
synthesis, or interfere with other leaf functions (39). Toxic concentrations
of trace metals such as lead and arsenic, which are normally translated from
the roots to the tops of plants, nay be ingested by livestock or other
herbivores feeding on surface contaminated plants (40). Particles originally
deposited on plant surfaces may reach the soil through leaf litter or be
incorporated into the soil by washing of plant surfaces by rainfall (41).
Plants possess the ability to concentrate essential mineral elements
from rather dilute soil solutions. When soil concentrations of essential
microelements such as zinc, manganese, cobalt, copper, and molybdenum are
increased, plants may continue to accumulate these elements to toxic levels.
Unessential elements such as cadmium or nickel may also be accumulated in
6-17
-------
the plant parts. Factors such as age, plant growth stage, or water stress
and plant rooting characteristics may affect uptake of trace elements.
Little and Martin (41) found most of the acetic-acid soluble lead, cadmium,
and zinc in the upper 3 cm of heavily polluted soils near a large lead/z:.nc
smelting complex. In these soils, plants with shallow spreading roots are
probably exposed to more toxic concentrations than deeper rooting species.
Furr et^ al. (42) grew various vegetables, grain and forage crops in fly ash-
amended soil. Their results indicated that concentrations of As, B, Mg, and
Se were greater in crops grown on fly ash-amended soil than control crops
grown on soil not amended with fly ash. Table 6-2 presents the probably
available form, average composition range, and suggested tolerance level:;
of certain heavy metals for selected agronomic crops.
Strojan and Turner (43) investigated the effects of trace element
emissions on soils and plants near the Mohave Generating Station. Concen-
trations of Cu, Ni, Pb, S, and Zn were significantly higher in surface soils
than in subsurface soils (10-20 cm). Sulfur concentrations in Ambrosia
dumosa leaves and Cu concentrations in Larrea tridentata leaves decreased
with increasing distance from the plant. Helmke (34) found that from 5 :o
32 percent of the total amount of aerosolic dust on oak leaves near a co.il-
fired plant was fly ash. Isolated samples of leaves showed damage
associated with particles of fly ash.
Horton et (44) measured trace element concentrations in soils .md
vegetation near a plant which had been in operation over 20 years. Significant
effects of stack releases upon concentrations of Ba, Be, Cu, Hg, Mn, Sr, and
Se in soil, Be, Co, Mo, Sr, and V in vegetation, and Co and Mn in ground-
water were noted.
Mosses and lichens have been proposed as good indicators of trace netal
pollution by a number of sources (46) because they tend to derive most
of their inorganic constituents from the atmosphere. A study conducted
around the Allen Steam Plant did not show excessive Hg or other heavy metal
concentrations in mosses collected near that plant. The conclusion of this
report was that the Allen Steam Plant had no detectable effects on trace
6-18
-------
TABLE 6-2. PROBABLE AVAILABLE FORM, THE AVERAGE COMPOSITION RANGE FOR SELEC-
TED AGRONOMIC CROPS, AND SUGGESTED TOLERANCE LEVELS OF HEAVY
METALS IN AGRONOMIC CROPS WHEN USED FOR MONITORING PURPOSES*
Probable
Available
Form
Common Average
Composition
Range*
EES
Suggested
Tolerance
Level
E£5
Barium
Cadmium
Cobalt
Copper
Iron
Manganese
Mercury
Lithium
Nickel
Lead
Stront ium
Zinc
Ba
<
Co
Cu-"
Fe4"4"
Miit*
Hg+
Nl++
Pb
Sr"^
Zn++
Cations
10-100
0.5-0.20
0.01-0.30
3-40
20-300
15-150
0.001-0.01
0.2-1.0
0.1-1.0
0.1-5.0
10-30
15-150
200
3
5
150
750
300
0.04
5
3
10
50
300
Anions
Arsenic AsOtT 0.01-1.0 2
Boron HBO3- 7-75 150
Chromium CrOtT 0.1-0.5 2
Fluorine F~ 1-5 10
Iodine I~ 0.1-0,5 1
Molybdenum MoOi»™ 0.2-1.0 3
Selenium SeOi»= 0.05-2.0 3
Vanadium V0a~ 0.1-1.0 2
* Average values for corn, soybeans, alfalfa, red clover, wheat, oats,
barley, and grasses grown under normal soil conditions. Greenhouse,
both soil and solution, values are omitted.
Values are for corn leaves at or opposite and below ear leaf at tassel
stage; soybeans, the youngest mature leaves and petioles on the plant
after first pod formation; legumes, upper stem cuttings in early flower
stage; cereals, the whole plants at boot stage; and grasses, whole plants
at early hay cutting stage.
SOURCE: (45)
6-19
-------
element concentrations in the vicinity. In a separate study investigating
trace element measurements around the Allen Steam Plant, Auerbach (47) has
found no appreciable part of soil trace element concentration which could
be attributed to the steam plant.
Roffman ££ al. (21) investigated trace element concentrations near the
Four Corners Plant. They examined soils, vegetation, and domestic and wild
animals for elevated trace element concentrations due to power plant
emissions. No significant effects were found.
6.3.3 Bioaccumulation Effects
Bioaccumulation by organisms may be defined as the accumulation of
higher concentrations of chemical substances than naturally occur in their
environment. Plants may selectively concentrate certain trace elements
necessary for normal metabolism via active ion uptake, an energy requiring
process. Likewise, they may exclude certain ions by actively maintaining
an internally negative ionic gradient. These processes are known to occur
but are not completely understood. Bioaccumulation information can be
found in the ecological effects summaries for individual elements in Section
6.6. Bioaccumulation information specific to edible aquatic organisms is
presented in a consolidated fashion in the following subsection.
Bioaccumulation Potential in Aquatic Organisms
Aquatic organisms are the major organismal group where bioaccumulation
effects are widespread and quite significant in some cases. The primary
reason for large concentration factors in some organisms is the effects of
foodchain magnification. For example, arsenic is a known cumulative poison
in many organisms. This means simply that these organisms, man for example,
can neither effectively excrete nor metabolize arsenic taken into the body.
Because of this, residual levels may build up if cumulative trace elements
are ingested routinely in the form of contaminated food, water, or air.
Trace element concentrations in seawater, freshwater, and edible
aquatic plants, invertebrates, and fish, as well as the concentration fac-
6-20
-------
tors associated with these organisms are presented in Table 6-3 and 6-4.
The concentration factors were derived as representative values for the main
classes of edible aquatic organisms (as the edible parts of these organisms,
i.e., muscle and soft parts of fish and invertebrates). As such, they can
be used for estimating dose to man and other organisms. These values were
derived from a wide range of organisms and ecosystems, and only an order of
magnitude accuracy for specific cases is suggested. The values presented for
concentrations in marine organisms and seawater are representative of estuarine
or continental shelf waters only. Since these waters are often high in sus-
pended solids, the reported concentrations are higher than for the open
ocean. Finally, the reader should be aware that these concentration factors
are based on the uptake of tracer radionuclides by aquatic organisms in labora-
tory studies, which may not be representative of normal feeding conditions.
Again, only an order of magnitude reliability of these values is suggested
(48).
6.4 HUMAN HEALTH EFFECTS
Growing concern over the expected rise in trace metal concentration
due to increased fossil fuel combustion and its effects on human health
is evident in the number of articles devoted to this subject in the recent
literature. Current research efforts have not yet determined what the exact
effects of chronic, low level trace metal pollution in the atmosphere will
be. Most epidemiologic and laboratory studies to date have been concerned
with occupational exposure levels found only in industry, and acute respon-
ses to trace metal pollutants. Because the concentrations of the trace
metals in question are much higher in these cases than what is expected in
the environment, extrapolation of acute responses to public health concerns
is probably not valid . The effects of synergisms with other trace metals
present in the environment is not accounted for in most laboratory or
occupational health studies. Also, many elements in question do not have
TLV's (Threshold Limit Values) associated with their toxic effects as is the
case of carcinogens mentioned in Subsection 6.1.
6-21
-------
TABLE 6-3. TRACE ELEMENT CONCEHTRATIONS IN FRESH WATER AHD FRESH HATER ORGANISMS
Element
(ppm)
Concent rat ion
In
Frerthwater
(pptn)
Concentration In
Frenhvnter Planta
ConcentrntIon
Factor
(ppm)
Concentration In
Frcflhw.itrr
Invertebrates
Concent rat Ion
Factor
(ppm)
Concentration In
Frcahwater F<9h
Concentrati
Far tor
LI tli lum
5. OOF.-3
1.50F.-2
3. OOF.O
2.OOR-l
4.OOEl
2.50E-3
5.00E-1
Rrrvlllum
5.00E-4
1.00E-2
2.00K1
5. OOF.-3
1.OOEl
1 .OOF.-3
2.OOEO
Fluorine
l.OOE-l
2.00F.-1
2. OOF.O
1.00F1
1.00E7
1.OOEO
1.OOEl
Sodium
1.00E1
1.00E3
5.00E2*
1 .70F.2
2.00E2*
2.00F.2
1.00E2*
Hagneplum
1.00E1
1 .OOF. 3
1.00F.2
I.OOF 3
1 .00F.2
5.00F2
5.U0K1
SI He on
U.OOEO
*>. OOF.2
I.25E2
1.OOE2
2.MJF1
1.00F.1
2.50E0
Phn.nphorous
2.00E-2
2.00E2
5.00F5*
2.00F.3
2. OOF'.*
2.00E3
1.00F5*
Chlorine
1.00E1
S. 00F.2
5.WEI
I. OOF.2
1 .OOF.2
5.00E2
5.OOEl
Calcium
1.50P.1
2. OOF. 3
1.33F2
5. OOF. 3
3.33F.2
f».OOE2
4.OOEl
Chrotnl nm
5.00E-3
2.00E-1
4.OOEl*
l.OUE-l
2. OOF. 3*
2.00E-1
2.00E2*
Hiingnnese
1.00E-2
1 .OOF.2
l.OOE'i*
4.00F.7
9.00F4*
1. OOF.O
4.00E2*
T ron
l.OOE-l
1.00E2
I. OOF. 3
3.20E2
3.20E3
1.00D1
1.00E2
Cobalt
5.00E-4
l.OOE-l
2.00F2
l.OOE-l
2. OOF.2
1.00E-2
5.OOEl*
Nlrkcl
1.00E-2
S.OOE-l
V00E1
I. OOF.O
1.OOE2
l.OOEO
1.00P.2
Copper
1.00E-2
1.00E1
2.00E3*
1. OOF. 1
4. OOF.2*
2.OOEO
5.00F.1*
7.1nc
1.00E-2
1.OOE1
2.00E4*
I.OOE2
1.00F.4*
1.OOEl
2. OOF. 3*
Arsenic
3.00E-3
5.OOEO
3. OOF. 3*
1.00E0
ft .OOEl*
1.OOEO
1.00E2*
Selenium
3.00E-3
3. OOF.O
1 .OOF. 3
5.00E-1
1.6/F2
5.00E-1
l.f»7P.2
Silver
1.30E-4
2.60E-2
2.00E2
l.OOE-l
7.69F.2
3.00E-A
2.31EO
Carfmlum
5. OOF.
5.00F.-1
1.00F.3
1 .OOF.O
2.00E3
l.OOE-l
2.00E2
Barium
5.00E-2
2.50E1
5.00E2
I'.OOEl
2.00F.7
2.00E-1
A.OOEO
Mercury
1.00E-*
1. OOF.-l
1. OOF. 3
1.OOEl
J.OOE5
1.00F--1
1.00E3
Lead
5.00E-3
1. OOF.O
2.00E2
b.OOF-I
1.00E2
1.50F.0
1.00F.2*
•Concentration Factors are measured, rather than derived vatum.
Sourca (48).
-------
TABLE 6-4. TRACK ELEMENT CONCENTRATIONS IN SEA WATER AND MARINE ORGANISMS
Element
(ppm)
Concent rat ion
in
Soavater
(ppm)
Concentration In
Marine Plants
Concent rat ion
Factor
(ppm)
ConccntratIon In
M,ir 1 ne
lovertrhr.ifpfl
CoucentratIon
Facfor
(ppn)
Concentration In
Marine Fishes
Concent rat 1
Factor
Lithium
2.00F-1
6.00E-)
3.00F.0
1 .OOF.-1
¦j.UOF-l
l.OOE-l
5. OOF.-1
Berylllum
5.00F-6
5.OOF-3
1.00E3
I .OOF,-3
7.OOF?
1 .OOF.-3
2. OOF.O
Fluorine
1.40F0
2. OOF.O
1 . U 3F.0
r>. OOF.O
3.57F.O
5.00E0
I. OOF.l
Sodium
1.05W
1.00F4
9.52E-1
7. OOF. 3
1.90E-1
7.00F.2
I .00F.2*
Magnesium
I.30E3
1.00F3
7.fi9F.-l
1.00F3
7.69E-1
1 .OOF. 3
5. OOF.l
Si 1 icon
3.00F0
2.00F2
6.57KI
1.00F.2
3.13EI
3.00EI
2.50F.0
Phnqphorous
7.00E-2
2.00E2
3.OOF 3*
2. OOF. 3
3.00E4*
2 .oor.3
l.OOEO*
ChlorIne
7.90E4
6.OOF3
7.59E-2
1 .50F.3
I.90F-2
1.00F.3
5.00EI
Calc turn
U.00E2
2.00E3
5.00F0
5.UOE3
1.25E1
2.00E2
U. OOF.l
Chromium
5.00E-5
1.00F.-1
2.OOF3
1.00F-1
2. OOF.3
2.00E-2
2.00E2*
Manganese
1 .OOF.-l
2.00EI
5.50E3*
1 .OOF.l
4.00E2*
6.00E-1
4.00E2*
I ron
1.00E-2
5.00F.2
7.30E2*
2.00F.2
2.00F.4
3.00E1
1.00F.2
Cobalt
1. OOF.-4
1.00E-1
1.00F3
l.OOE-l
1.0UE3
l.OOR-2
5.00F1*
Nickel
2.00E-3
5. OOF.-l
2.50F.2
5. OOF.-l
2.50E2
2.00E-1
I.OOE2
Copper
3.00E-3
3.00EO
1.00E3
5.00EO
1.67F3
2.00E0
5.00EI*
Zinc
1.OOF.-2
1. OOF. 1
I.OOF3
1.00E3
5.00E4*
2.00E1
2.00E3*
Amen lc
3.00E-3
5.OOFO
1.67E3
l.OOEO
3. 33F.2
l.OOEO
1.OOE2*
Selenium
1.00K-4
l.OOE-l
I. OOF, 3
1 .OOF.-l
1.00E3
4. OOF.-l
1.67E2
SIlver
3.00E-4
6.OOF-7
2.00F2
l. OOF.O
3.33F.3
l.OOEO
2.31EO
Cadmium
I.OOE-4
l.OOF.-l
1.00E3
2 . *>OFI
2.50F.5
3.00E-1
2.00F.2
Barium
1.00E-2
5.00F.0
5.00F2
1.OOFO
1.00E2
l.OOE-l
4.00EO
Mercury
3.OOF.-5
3.00E-2
1.00E3
1 .OOEU
3.33E4
5.00E-2
1.00E3
Lead
I.OOF-3
1.00E0
5.00E3*
l.OOKO
1.00E3
3.00E-1
I.OOE2*
•Concentration factors are meaaured rather than derived valuen.
Source (48)
-------
6.4.1 Effects of Trace Metals Exposure
Weisburger (49) of the National Cancer Institute in Maryland has
estimated that 50 to 90 percent of human cancers are caused by carcinogens
in the environment. Hamilton and Manne (50) estimated that total production of
electric power in the U.S. in 1975 was associated with between 2,000 and
19,000 deaths and 29,000 to 48,000 disabilities. This is roughly between
0.2 and 2 percent of the total deaths in the U.S. for ages 1-74 during this
time period. The percent of deaths attributable to trace metal emission!;
alone was not calculated. Jacobs (3) reviewed literature covering the past
50 years with regard to air pollution and its relationship to pulmonary dis-
ease. Besides concluding that a high correlation exists between community
air pollution and pulmonary disease, he noted that air pollution affects
those most who are least able to stand stress; those over 65 years of agu,
under 1 year of aget and the sick. Specific air pollution episodes and
related mortality increases are discussed.
Chronic air pollution has been studied with regard to occupational
health effects. A review of the literature present in this area is beyond
the scope of this report, but occupational exposure to coal dust is of
obvious interest. Carlberg .al. (51) surveyed British, German, and U.S.
data concerning concentrations of trace metals present in bituminous coal
miner's lung tissue. Be, Mg, Ti, Va, Cr, Mn, Fe, Ni, Cu, Zn, and Pb concen-
trations were higher in miners' lung tissue than values reported for non-
miners' lungs. Another study of chronic air pollution in an industrial ;irea
in Japan (52) indicated a correlation between a smog episode and increased
mortality during the period. Particles containing As, F, Pb, Ca, S, V
and other pollutants were the probable cause of the increased mortality.
Smog in this region most often occurs in the winter, and results of this
study showed that school children had lower peak bronchial flow rates in
the winter in polluted areas.
6-24
-------
Gasper and Dauzvardia (53) performed an assessment of trace element
body burdens that would result from projected coal utilization in the
Illinois River Basin. The elements examined were As, Be, Cd, Cr, Cu, Fe, Pb,
Mn, Hg, Ni, Se, V, and Zn. Regional atmospheric concentrations of trace
elements resulting from hypothetical year 2020 levels of coal consumption
were calculated from estimates of total particulate matter. The assumption
was made that trace elements would be present on the particles in concentra-
tions equivalent to: (1) their concentrations in coal, and (2) relative
rates of emission. The results concluded that new emissions may lead to a
doubling of present trace element body burdens in the area.
Hildebrand (54) is currently conducting research to monitor cellular
metabolism and fate of fossil fuel-related pollutants to determine
effects of these agents on regulation of gene structure and activity.
Results to date include an accumulation of cadmium (to levels 1000-fold
greater than in growth media) in mammalian cells cultured in levels of CdCl2
well below toxic levels. Sixty-five to seventy-five percent of the Cd was
localized in chromation. Other biochemical studies have documented the
teratogenic properties associated with Cd, Se, and Hg, mutagenic properties
associated with Pb and Hg, and carcinogenic properties of Be and Se (55).
The food and Drug Administration's Market Basket Survey (56) indicates
that total Hg, Pb, and Cd dietary intake are about 7, 14, and 75 percent,
respectively, of the WH0/FA0 recommended tolerable limits. Elevation of these
trace metals in the water, atmosphere, and foodstuffs is thus a matter of
concern. Torrey (57) cites evidence that exogenous trace elements are more
soluble than endogenous trace elements in soils, and thus more likely to
enter the food chain and ultimately affect man.
Shakeman (58) reports that environmental Cd may be important in the
development of hypertension. Hickey et^ al. (59) have correlated atmospheric
Cd and V concentrations with the incidence of mortality due to diseases of
the heart. Finally, synergisms that are associated with SO2 concentrations
and trace metal contaminated particles have been noted (60, 61, 62, 63,
64). These synergisms have resulted in a general increase in the degree of
mortality and morbidity for a given air pollution episode.
6-25
-------
Acute responses due to trace metal exposure have been noted for a few
fly ash extraction laboratory studies. Chrisp et al. (65) evaluated the
mutagenicity of soluble components of respirable fly ash taken downstream
from ESP units at a coal-fired plant. Mutagenic responses of the bacterium
Salmonella typhimurium were observed. The results were consistent with the
hypothesis that both organic and inorganic trace element mutagens are present
in coal fly ash. A similar study (66) determined that fly ash caused changes
in DNA of Salmonella typhimurium. Chemical analysis of fly ash extract
detected the presence of 11 metals including Cd, Se, Pb and Be.
6.4.2 Particle Size and Effects
Particle size distribution data for fly ash taken from two coal-fired
plants equipped with ESP units is given in Table 6-5. Examination of these
data indicates a sizeable percentage (62.5% and 67.8%) of the fly ash emitted
from these plants is in the 3.3lim or smaller size range. This size range of
particles has the greatest potential for significant inhalation health effects.
TABLE 6-5. PARTICLE SIZE DISTRIBUTION IN FLY ASH
1111 • - -=*— —-=¦ - - • ¦ J ¦ ¦ ¦ ¦———- ¦ I ... ¦ - ... ———~
Approximate Site A1 Site B2
Size Range, Ash Fraction (%) Ash Fraction (%)
>8
9.5
15.3
5-8
11.4
6.8
3.3-5.0
16.6
10.1
2.3-3.3
11.6
10.4
1.5-2.3
20.9
16.6
.75-1.50
17.2
21.8
.45-.75
8.6
13.2
.30-.45
2.7
2.5
<.30 + vapors
1.6
3.3
100.0
100.0
*A 350 MW boiler equipped with a hot-sided ESP. Source: 67
2A 350 MW boiler equipped with a cold-side ESP.
6-26
-------
Trace Metal Concentration with Particle Size
Studies have shown that certain trace elements present in fly ash
particles emitted from coal-fired plants exhibit a dependence of element
concentration on particle size. Davison _et_ al_. (68) determined Pb, Cd, Se,
Ar, Ni, Cr, and Zn all show a pronounced increase in concentration with
decreasing particle size. Fe, Mn, Si, Mg, and Be show a limited increase
in concentration with decreasing particle size. Cu, Co, and Ca show no
concentration trends with particle size. Kaakinen e£ al^. (69) measured
the amount of 17 elements in inlets and outlets of a coal-fired plant. Con-
centration of Cu, Zn, As, Sb, Pb, Po, and Se are generally lowest in bottom
ash and increase progressively in fly ashes collected downstream toward
the stack. Sections 3, A, and 5 presented various aspects of the dependence
of trace metal concentration with particle size. Although only a small fraction
of the total fly ash produced has particle diameters <1 pu, the fraction
emitted presents a greater potential health hazard per unit weight than that
retained. Existing particle control devices are least effective for
removing the most toxic particles based on these data. The predominance of
certain toxic elements in small particles is also significant in determining
the degree of enrichment of these elements in an urban aerosol, since these
small particles have the longest atmospheric residence time. Gladney et al.
(70) have shown enrichment factors of greater than ten times natural crustal
abundance for Cr, Ni, Cu, Zn, As, Cd, Pb, Se, and CI in the Boston aerosol
and have established correlations with enrichment patterns in coal fly ash,
municipal incinerator fly ash and residual fuel oil.
Dependence of Deposition and Retention Rates in the Lung on Particle Size
The difficulty of the control problems for hazardous air pollutants is
compounded because the degree of toxicity is not simply proportional to the
mass emissions. Very small amounts of small particulate material can have
severe effects on human health, not only because small diameter particles
are more potent, but because they are more easily respirable and more readily
retained in the lungs.
6-27
-------
Figures 6-2 and 6-3 demonstrate this point. Figure 6-2 shows a substan-
tial increase in the fraction of particles deposited in the pulmonary and
tracheobronchial systems with decreasing particle size. The retention of
particulate matter in the lung also increases dramatically at particle dia-
meters less than 3 ym (Figure 6-3). The peak retention rate is at approxi-
mately 1 ym at which point over 75 percent of the particles deposited ars
retained. More than half of all particles in the range of 0.5 to 2.0 ym will
be retained while only a small amount of those particles less than 0.25 Jm or
more than 3 ym are retained. Comparison of these data with the particle size
data for emitted fly ash particles presented earlier (Table 6-5) indicates
that a significant fraction (almost 50 percent) of the particles emitted will
have a 50 percent or greater retention rate in the lungs.
Other studies have suggested that the penetrating ability of small
particles, which is primarily due to geometric size considerations, is aLso
dependent on lung tidal volume (72). Deposition in a particular pulmonary
compartment may not be easily predicted according to particle size alone.
Fennelly (73) reports that irritation due to particle deposition can lead to
impairment of oxygen transfer and effect a reduction in lung tidal volume.
Conversely, another study(74) based on empirical evidence suggests that
deposition in the lung may be higher than expected for larger particles.
The smallest particles deposited in the pulmonary region are of the
most concern toxicologically for two reasons. These particles have been
shown to be enriched in many toxic trace elements, some of which are known
carcinogens. Secondly, the efficiency of extraction of toxic species from
particles deposited in the pulmonary region is high (60 to 80 percent) (68)
due to their long residence times and their larger surface area. The extrac-
tion efficiency for larger particles deposited in the tracheobronchial and
nasopharyngeal regions is low (5 to 15 percent). Particles deposited in
these regions have short residence times due to their removal by cilial
action to the pharynx where they are either swallowed or expelled. Conse-
quently, toxic species that predominate in the submicron-sized particles
will have their entry into the bloodstream enhanced over those species that
predominate in larger particles (68). Also, smaller particles cause greater
6-28
-------
j 11jiff i i 111n11 i i i)i*n
NASOPHARYNGEAL
PULMONARY
TRACHEO-
BRONCHIAL
LbbJLhJLJLAbJUKlI
10 10_i 10" 10'
MASS MEDIAN DIAMETER, MICRON
Figure 6-2. Fraction of particles deposited in
the three respiratory trace compart-
ments as a function of particle
diameter.
SOURCE: (71)
6-29
-------
RETENTION (*}
80
0.5 1.0
2.0 3.0 4.0
PARTICLE SIZE (pm)
Figure 6-3. Retention of particulate matter in lung re-
lation to particle size.
SOURCE: (71)
6-30
02-4059-1
-------
irritation (75). Other studies (76) support these findings by demonstrat-
ing that the number of free macrophages present in the lung increases when
smaller particle sizes are present.
The consequences of short- and long-term increases in toxic trace
element body burdens can be quite severe. Investigators at U.C. Davis have
reported that, based on the Ames Test, a cyclohexane extract of the finest
fly ash particles from a coal-fired plant was mutagenic. Further, mutagenic
activity increased with decreasing particle size (77). Among the specific
consequences of long term, low level exposure to highly toxic trace elements
are increased incidences of disease and reduced life spans in the affected
human population (71).
6.4.3 Safe Anbient Trace Metal Concentrations
Most research pertaining to safe ambient trace metal concentrations is
taken from an occupational health perspective. Toxicity studies based on
threshold limit values have been suggested as a possible method of assessing
trace metal hazard levels in the environment. Threshold limit value (TLV)
is the time-weighted concentration of a substance that a healthy worker can
be exposed to for a 7 or 8 hour workday and a 40 hour work week without known
deleterious effects, One author (78) has suggested that TLV values be used
in order to estimate permissible concentrations in the environment at large
for specific elements. Using this approach, elements in question are first
assigned some toxicity potential rating, and the TLV for a particular element
(or one of equivalent toxicity if no TLV for that element has been proposed)
is divided by some arbitrary safety factor to arrive at an estimated safe
concentration in the environment.
Several problems are apparent in this approach. Occupational toxicology
studies do not include the potential for contamination of food and water as
well as the atmosphere in their scope. Bioaccumulation and/or other concen-
tration effects may be very significant when the cumulative effects of
increased reliance on coal combustion are felt in the future.
The potential for significant synergisms is also not accounted for in
an approach based on TLV data for individual elements alone. Fine particles
6-31
-------
contain a full spectrum of trace metals on their surface when emitted
from a coal-fired plant. These trace metals have a potential for interactive
reactions which could result in more serious health effects than when indi-
vidual element concentrations are considered alone.
In spite of the limitations inherent in any attempt to assign a value
to safe concentration levels in the environment, data on Estimated Permissible
Concentrations (EPC) is presented in Table 6-6. This information was extrac-
ted from The Multimedia Environmental Goals for Environmental Assessment (79).
These values are based on toxicity data from a number of sources: TLVs, IIIOSH
recommendations, and/or lethal dose to some animal. The reader should not
interpret this information as an established standard, but rather as the best
estimate available for acceptable ambient level concentration of certain
trace elements in the environment; see Section 9.
The best hope for obtaining reliable estimates of safe ambient trace
metal concentrations (including contributions from anthropogenic sources;
would seem to be a multi-pollutant and multilocality interdisciplinary epi-
demiological study. Noyman (BO) has suggested an apporach such as this,
since extrapolation from present findings is difficult and unvalidated.
6.4.4 Dosage-Response Relationships
Very little data on human health dosage-response characteristics are
available. Most attempts to date to quantify the health impacts of trace
metal emissions from a specific source have estimated total body burden
increases to assess the effects. Generally speaking, increased combusticn
of fossil fuel is expected to increase the respiratory and dietary exposi.re
of trace elements in the population (81).
One study (53) investigated projected increases in trace element boc.y
burdens due to coal utilization in the Illinois River Basin in the future.
Principal routes of exposure were assumed to be absorption within the res-
piratory tract through inhalation and absorption in the gastrointestinal
tract through ingestion of contaminated food and water. Standard Reference
Man. (International Conference on Radiation Protection) was used to estimate
body burden increases: 20 m3 air inhaled per day, 2 £ water ingested per
6-32
-------
TABLE 6-6. TOXICITY-BASED ESTIMATED PERMISSIBLE CONCENTRATIONS
Air
Mg/m3
Water VJg/2.
Land pg/g *
Compound
Health
Ecology
Health
Ecology
Health
Ecology
Ag
0.024
0.10
0.01
A1
12.6
73
0.15
0.40
As
0.005
0.10
0.02
B
7.4
43
0.09
10.00
Ba
1.0
2.00
1.00
Be
0.8
4
0.008
0.02
Cd
0.12
0.02
0.0004
Co
0.12
0.7
0.000
0.1
Cr
0.12
0.1
0.1
Cu
0.5
2.0
0.2
Ge
1.3
8.0
0.016
Hg
0.1
1.0
0.004
0.1
Li
0.05
0.3
0.0006
0.15
Mg
14.0
83.0
43,300
0.2
87.0
Mn
12.0
0.1
0.04
Ni
0.24
1.4
0.003
0.004
P
0.24
1.4
0.003
0.0002
Pb
0.36
0.1
0.02
Se
0.5
0.02
0.01
Sr
3.5
27.0
0.05
Ti
14
83
4,100
0.17
8.0
V
1.2
0.1
7
0.014
0.15
Zn
9.5
10.0
0.04
Source: (79)
-------
day, and a 70 kg body weight. Results of this study indicated that except
for Hg and V, dietary contribution to the total body burden level for th«
elements in question never falls below 66 percent and averages 87 percent.
They predicted a doubling of trace element body burdens and assumed that the
human health effects would be related to body burden levels.
Dosage-response information for acute levels of exposure are presented
in the individual health and environmental summaries for specific elements
in Section 6.6. These data are primarily from laboratory studies (LD 50,
LC 50, etc.) on test animals and may only be of limited usefulness for
assessing large-scale human health and environmental effects.
6.5 RESEARCH NEEDS
Many data and information gaps have been identified in this section.
Specific research needs are discussed briefly.
A general need exists to increase the extent of baseline monitoring
around SCCP's. Evaluation of impacts to the environment requires a more
thorough understanding of baseline conditions than is currently present.
Research in this area should also attempt to elucidate environmental trans-
port processes, and determine some basic understanding on how and where
cycling of anthropogenic trace metals occurs. Field data are needed on
biological uptake and bioaccumulation processes.
Epidemiological studies of chronic, low level exposure to trace meti.ls
are needed. Emphasis should.be placed on possible synergistic responses with
other trace metals, and non-trace metal pollutants present as well. In order
to accomplish this in a meaningful fashion, more information about the speci-
fic physiochemical forms of emitted trace metals is needed. With this infor-
mation realistic biochemical studies can begin to determine specific health
effects of these pollutants at a cellular level.
Finally, more research is needed on effective control methods to linit
trace metal emissions at the source. Most of the problems center around very
fine particulate emissions which are highly enriched in toxic trace metal.s,
but some gaseous emissions (i.e., Hg and Se) are of concern as well. A dis-
cussion of this subject material is presented in Section 4.
6-34
-------
6.6 SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS LITERATURE
Table 6-7 summarizes existing ecological and health information for
a number of trace elements. The information presented was extracted from
two government publications; HASL-320 by Merrill Heit of the Health and
Safety Laboratory of the U.S. EPA, New York (82), and Multimedia Environ-
mental Goals for Environmental Assessment, Vol. II by Cleland and Kingsbury
of Research Triangle Institute, RTP, North Carolina (70). Original refer-
ences are included for completeness. This subsection is intended to pro-
vide the reader with a quick, general summary of known ecological and health
effects information in order to augment the specific studies referenced
earlier in this section.
6-35
-------
TABLE 6-7. SUMMARY OF ECOLOCICAL AND HEALTH EFFECTS
General Informat ton
Human Henlth Effects
Ecological Health Effect*
Aluminum
(Al)
On
I
U
On
Ant tmony
(Sb)
The relAtlve order of toxicity.
Imtraperttoneally, of Antimony
compounds beginning with the moat
toxic 1«»; metallic Antimony,
Antimony trlaulflde, Antimony
pentasulfIde, antImony
trloxlde, And antimony pentoxlde (88).
Although aluminum la not a highly toxic
element, large quantities may produce
deleterious effects, such as pulmonary
fibrosis from Inhalation of slumlnum
powder (83) . nnly massive oral rinses of
Aluminum are reported to be toxic to
mammala (86).
A level of 4,000 mg/kg In diet caused
phosphorus toxicity; a concentration of
0.07 mg/1 aluminum nitrate, as Al, It
toxic to stickleback (Casterosteua
sculeatua). Aluminum la reported to be
concentrated 10,000 times In Hah muscle*
and 15,000 times In henthlc algae.
Aluminum compounds may adversely affect
henthlc organisms (e.g., clams, crabs,
oysters, lobsters) C5). Hlnh concentrations
of aluminum In aolla with low pH causes
restricted root growth In plants (86). Growth
reductions In wheat and orange seedlings
were reported In nutrient solutions with
0.1 mg/l of slumlnum (85). Aluminum Is
toxic to plants In scld soils; however, at
pH values between 5.5 and 8.0 soils preci-
pitate soluble slumlnum so as to eliminate
Its toxicity (87).
Effects of Intoxication may Include skin
Irritation, InflammntIon of mucoua membranes
and ncrvoua ayatem and gaatolntestinol
effects. Chronic poisoning may result
from Inhalation of antimony or Ita compounds.
The lowest toxic concentration reported
for human Is 6,700 Mg/m for 20 weeks.
Antimony la slowly absorbed from the gastro-
intestinal tract In man. Trlvalent forms of
antimony concentrate In the red blood cells
and the liver, and are slowly excreted,
primarily In the feces. Pentavalent forms
of .mt Imony accumulate mainly In the blood
Little is known of the ecological effects
of antimony. However, antimony may be
concentrated by some msrlne organisms to
levels shove thst present In seawater (89).
LD90 (oral, rat): 100 mg/kg for antimony.
Toxicity to aquatic life: The 96 hr
for fathead minnow Is 80 ppm (sntImony
trioxtde). This Is equivalent to 67 ppm
at SR. Antimony csn be concentrated by
varloua marine forms to over 300 tlmea the
amount present In aeawater (85). Concentra-
tions as low as 1 mg/ , ss Sb, have pro-
duced effects In fish (90).
-------
TABLE 6-7.
Clement. General Information
Antlraony
conld.
Arsenic Compounds nay he absorbed by Inhal-
(As) at Ion, Ingestion, .ind through the
skin. Excretion 1r slow: 10 days
for acute Absorption > 1 year for
prolonged exposure (91). Cumulative
poison (88).
SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS
Human Health Effects Ecological Henlth Effects
plnsma, liver ^nd spleen, .ind are pri-
marily released through the urine. It
appears that antimony will not accumulate
In man over long time periods. If heavy
exponure does occur, symptoms similar
to thone of arsenic poisoning may result (04).
Chronic effects of antimony uptake In man
are unknown. Some Investigators have
suggested a relationship between antimony
and pulmonary carcinogenesis baaed on
a ponalble antimony containing abnormal
enzyme system (8'»).
An (Arsenic): The toxicity of arsenic
to humans depends upon Its chemical
form. Organic arsenic compounds are consider
ahly more toxic than the Inorganic forma
which occur In living tissues or are
used on feed additives. Differences
In toxicities of various forma are clearly
related to their rates of excretion, the
least toxic being tlip moat rapidly elimi-
nated (92). Arsenic has heen shown to
accumulate In the body faster than It is
excreted. It can build to toxic pro-
port lona from small amountn absorbed
from periodic exposure or dietary con-
tamination (93). Arsenate is nxcreted rap-
idly from tl»e kidneys and prnhablv does not
accumulate In humans. Arsenltea accumulate
In the liver, muscle, hale, nails and
skin. Tntakc-of arsenic hy man has hecn
Arsenic Is ubiquitous In the environ-
ment, occurring In various forms*
Trlvalent arsenic compounds (arsenlte)
are. In general, more toxic than pentavalent
compounds (arsenate). In nature, the arsenate
compounds are more prevalent than the arsenlte
compounds. Arsenic may also be methylnted
by microorganisms.
Arsenic occurs primarily In the pentavalent
form In the soli (95). The formation
of arsenic compounds (s affected by acidity
and the Fc, Al, Ca, P and humus content
of the soil. Soils with high reactive
aluminum levels have been found to be
less phytotoxlc even after heavy applica-
tions of arsenic (96). Arsenic toxi-
city has been observed In plants growing
on soils treated with arsenical pesticides,
herbicides and defoliants.
-------
m
TABLE 6-7.
Flenient. General Infortnntlon
Amen Ic
(contd.)
T
CO
00
SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS
Hunnn Health Effects
Ecological Health Effects
Impllcnted In okln and respiratory cancer
(86). Most arsenic Is Ingested by human* In
fish, meat and poultry (56X), dairy products
(23Z), grain and cereal (16Z), and potatoes
(61) (94).
Arsenic poisoning has caused dermatitis,
pharyngitis, conjunctivitis, and perforation
of the nasal septum (88). (lntrnmin-
cular, rat): 25 mg/kg.
Theoe plants were found to contain relatively
low level* of arsenic probably due to
Its action as a metabolic Inhibitor (97).
When present In noils, toxic amount* of
arsenic arrest the germination of seeds
and reduce the viability of seedlings. In
addition, the rate of nitrification In
the presence of nrnenlc In soils Is de-
creased (96).
Arsenic Is a cumulative poison with long
term chronic effects on both aquatic
organisms and on mamallan species. There
In some evidence that aracnlr Is concentrated
In aquatic food chains, often reaching
concentrations In exceas of proponed
EPA standards (98).
There Is little Information on the
accumulation of araenlc In freshwater organ-
ises. Some species of freshwater fish,
have been reported to concentrate arsenic
by a factor of 20 to 130 above the concen-
tration In water (99). The freshwater
Invertebrates Daphnla sp and crayflahea have
also been reported to concentrate arsenic (100).
Arsenic In accwulated by many marine
fauna. Marine algae have alno been
reported to concentrate arnenlc (97). Arsenic
also tendn to be accumulated by oyaters and
other marine shellfish where concentratlona
of up to lOOug/g have been reported (101).
-------
Element.
General Inform/it Ion
TABLE 6-7. SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS
Hum-in Health Effects
Ecological Health Effects
Arsenic
(contd.)
Barium
(Ba)
Barium le readily excreted and Is pro-
bably noncumulatIve (102).
a*
I
U>
VO
Of the barium which Is ingested, only a
small Amount In retolned In mammals (or
periods greater than 24 hours. Very low
concentrations have been found in the nam-
null inn kidney, nptccn, skeletal muBcle,
he BaO and BaCO)
Toxicity to sensitive plants varies from
110-340 kg/ha for sandy to clayey soils (85).
Concentration of 0.5 mg/t In nutrient
solutions is toxic to pineapple and orange
seedlings and reduces tomato yield 80Z (102),
Concentrations of 1.1-2.2 rag/l are toxic
to pike perch (Stltostedlon vltreua) (85),
Barium Is relatively conaton In nature and
occurs In plant and animal tissues (84).
Plonts have been shown to accumulate barium
from noil (84).
All water and acid soluble barium com-
pounds are reported to be poisonous.
However, the sulfate and carbonate present
In seawater precipitate barium and thus
tend to mitigate Its effects on marine
life (87).
Some concentration factora from seawoter
for barium have been reported an 17,000
for phytoplankton, 900 for zooplankton,
and 8 for fish muscle (87,101). An accumula-
tion of radioactive barium In the Internal
organs, gllla and scales of fish from the
northwest Pacific has also been reported (87,106).
LCsi for snail Planorbls glabratus Is re-
ported aa 11 ppm, time unspecified, for
toxic effects (85). 500 ppa barium nitrate (an
Ba) Is toxic to Stickleback (87). Ba can he
concentrated In goldfish by a factor of
150 (85).
-------
TABLE 6-7. SUMMARY OF ECOLOGICAL AH!) HEALTH EFFECTS
Element.
Cenernl Informat Ion
Human Health Effects
F.cologlcol Health Effects
Barium
(rontd)
Beryl 1lum
(Be)
On
I
O
have caused respiratory Injury In man
l.f>L0(oral rat): 335 mg/kg as BoClj
(or 220 «g/kg as Ba). Teratogenic effects:
20 »g of BaCl} Injected tntu chick yolks
produced curled toes In About 50 percent
of survivors (105). TD| ^ ¦ 87R mg/kg, as Ba.
Toxic through all routes of sbsorption. Chronic exposure to soluble as well as
Major hazard to health Is through lnsotubte compounds as particulates In
Inhalation. Particle size of beryllltim air results In berylliosis, a severe lung
dust critical factor In causing disease. Lowest reported toxic concentra-
berylllosls (107). tlons for humans Is .1 mg/m1 (108). LDj«
(oral, rat) equivalent to 9.7 mg/kg for
Be. Minimum dosage producing carcinogenic
response is equivalent to absorption by
Inhalation of 0.4 ug/kg (11)8,109).
Beryllium Is not well absorbed when given
to humans by any route. After Inhalation,
beryllltim is retained In the lungs and Is
mobilized slowly. The beryllium which Is
absorbed by the body Is mostly excreted In
the urine (84). In humans, beryllium han
been 9liown to produce many effects depen-
ding upon the dose and duration of expo-
sure. The ooet extensive changes usually
occur in the lungs (84). At present, it
la not clear If exposure to beryllium
compounds Is sssociated with nn increase
in the incidence of carcinomas In humans
(110). The salts of beryllium are not
highly toxic for intake hy Ingestion
since laboratory rats survived for
two years on s diet containing beryl-
lium at a concentration of IS mg/kg
body weight daily (87).
The addition of beryllium to soil has been
shown to have some effects on plant growth.
For example, some varieties of citrus fruit
seedlings show toxic effects at concentra-
tions uf 2.5 to 5 Ug/1 beryllium (111). In
addition, beryllium has been uhown to Inhi-
bit photosynthesis and growth in some crop
plants (112—1IA). However, it is unknown
If the same effect occurs in marine flora
where Is has been reported to be concentrated
by a factor of 1,000 (8^,115).
Toxic concentration for fathead minnow, 96 hr.
LC*o, is 0.15 tng/1 as BeCl? In soft water (85)
Can be concentrated 1,000 times In marine
organisms (102). Growth of bush beans reduced
by 0.5 mg/fc In nutrient solution (85).
-------
Element.
General Information
TABLE 6-7. SUHHART OF ECOLOGICAL AND HEALTH EFFECTS
Human Health Effects
Ecological Health Effects
Bismuth
Bismuth Is considered an one of
the les9 toxic of the hrnvy metals.
Boron
(B)
Boron la not a highly toxic element.
It causes kidney and liver d.imagc only
when ingested In large doacs (116). It
behaves similarly to lead In the body (83).
In humans, practically nil of the boron
In absorbed from food and excreted via
the kidneys. It has been reported that
concentrations as high as 30 mg/1 of water
arc not harmful to man (117).
It does not accumulate sign 1fleantly in
body tissues (85). Serious effects to
humnnn are not reported for reasonable
expoaures.
Little Is known of the effects of bismuth
on cither terrestrial or aquatic systems.
Concentrations of 0.04 to 0.3 mg/l have
been reported for mnrine animals, Indicating
concentration factors up to 10,000 (87,115).
Bismuth has a fairly low level of toxicity
to mammals. It causes kidney nnd liver
damage only when ingested in large doses (116).
LD*o for dlhydroxypropoxy bismuth (In-
travenous, rat): 13 mg/kg; molecular
wt, dlhydroxypropoxy hlamuth: 302. (as RI):
209/302 x 1J ¦ mg/kg (baaed on LD^o
for dlhydroxypropoxy bismuth).
Boron occurs regularly in natural water
supplies and in plant and animal tissues.
It Is an essential nutrient to plants,
but not to animals. While essential for
growth at higher concentrations, boron is
very toxic to many terrestrial plants and
produces adverse effects at concentrations
exceeding 1.0 ag/1 of water (87). Available
data on toxicity of born to aquatic or-
ganisms are mostly from freshwater. Since
the toxicity of boron is slightly lower
In hard water than in distilled water, it
Is anticipated that boric acid and borates
would be less toxic to marine aquatic life
than to freshwater organisms (87). The ef-
fects of boron on marine vegetation sre
unknown (87) .
-------
TABLE 6-7. SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS
F.lement.
General lnformntlon
Human Health Effects
Ecological Health Effects
Roron
(contd)
Boron hAs a low order of toxicity to live-
stock with no evidence of accumulation In
mamma1 Inn tissues (87). However, In lambs,
gastrolntestlnal and pulmonary disorders
have been reported as a result of grazing
on vegetation growing In areas of high
boron soil content (84) • Thr ingestion of 16
to 20 grams of boric acid per doy for
40 days produced no ill effects In dairy cows
-------
TABLE 6-7.
General Information
A dangerous, highly toxic, cumulative
poison.
Does not occur In organic compounds
as does Hg or Pb.
Zinc and copper Increase toxoclty.
SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS
Human Health Effects
Ecological Health Effects
Cadmium Is stated to be an extremely dan-
gerous cumulative toxicant coualng Insi-
dious, progressive chronic poisoning In
mammals, fl9h and probably other animals,
because the metal Is excreted at a very
low rate (87). In mammals, approximately
6 to 10Z of the Ingested cadmium 18
absorbed and transported through the body
by red blood cells. Cadmium collects In
the kidney, liver, pancreas and blood
vessels. Some cadmium la absorbed from
the lungs following Inhalation. The amount
of cadmium uptake from material In
the lungs dependa on the concentrotlon, -
particle size, solubility of the particu-
late matter and physiological considera-
tions. However, under normal conditions.
Inhalation does not contribute significantly
to Intake. Host cadmium salts have a short
retention time In the lungs (64,110).
The kidney has been the Initial target
organ of retained cadmium. Some symptoms
of cadmium poisoning can be prevented by
the presence of zinc, selenium cobalt,
estrogens and cysteine (64). Host cadmium
enters the human diet from grains and
cereals(21Z), fruits 18X), potatoes (18Z)
beverages (11Z), dairy products (8Z),
and meat, fish and poultry (SZ) (94).
Cadmium may enter the body via the gastroin-
testinal tract from Ingentlon of flah
from polluted vatera. Vhen Ingested at
very high concentrations. It may cause
Cadmium la stated to be "an extremely
dangerous cumulative toxicant causing
lnaldlous, progressive chronic poisoning
In mansnala, fish and probably other anlmala,
because the metal lb excreted at a very low
rate" (87).
Cadmium la always found In association
with zinc In the earth's crust (123). Cad-
mium does not degrade In the environment
but rather accuinulatea In soils and sedi-
ments where la may enter various food chains (110).
Vhen present In noils cadmium is apparently
readily taken up by a great number of plant
species especially the grasses and grains
(e.g., wheat, corn, rice, oatn and millet (124,125)*
Cadmium Is also found In peas, beeta,
lettuce and radishes. The concentration
of cadmium reported to be present In an
average background soil Is 0.55 Ug/g Cd
and the plants growing In this soli had
an average of 0.35 Ug/g Cd (26).
Yields of some crop plsnts may be reduced
up to 25Z by the addition of cadmium to
nutrient aolutlons at concentrations greater
than 100 Ug/1 (87). The mechanisms by which
cadmium la taken up by plants la still
largely unknown (126). In addition, there Is
a lack of Information on the behavior of
cadmium In terreatrlal ecosystems and Is
transport through food chains.
In freshwater systems, floatlng aquat1c plants
have been found to accumulate cadmium from
-------
F.lement.
General Information
TABLE 6-7. SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS.
Human Health F.ffectn
Ecological Health Effects
Cadmium
(contd.)
Ital Ital (ourh ouch) disease as reported
In Toynma Buy, Japan (119). Cndmlum,
as has been reported for mercury, may
form organic compounds in aquatic systems
which may he highly toxic or lead to
mutagenic or teratogenic effects when
Indented (87).
Inhalation or Ingestion produces acute and
chronic effects.
Inhalation of 0.01-0.27 mg/m' resulted
In pulmonary and renal effects for exposed
workera (88) .
Ingestion of 13-15 ppm has been toxic to
children (106).
Maximum normal body burden 20-30 mg. (120).
Minimum detectable health effects have heen
theoretically associated with long-term
(25-30 years) exposure to air concentra-
tions of 2.5 mg/m1 (121).
I.D™ (oral rat) equivalent to ft. 3 tog
as Cd.
Occupational exposure reported to Increase
cancer risk (122).
Oncogenic response minimum In an animal
Is 1 mg/kg, on Cd.
Teratogenic response minimum In an animal
Is 1 mg/kg, as Cd.
concentrations as low as 0.01 iig/g.
Although this results In Inhibited growth,
the concentrations of the metal which
accumulated In the leaves and fronds was
up to 82 ug/g or a concentration factor
of 8200 (127).
Little data la available on the cadmium
content of marine and freshwater fish,
but it doea concentrate In the liver (128,129).
Of these few aquatic organisms studied for
cadmium uptake, mollusks received most of
the attention (130,131). The mollusks accuinulat
their cadmium In calcareous tissues and
In the viscera. Concentration factors
of 1,000 for cadmium have been reported
In fish muscle, as have a concentration
factors of 3,000 In marine planta and up
to 30,000 In some marine animals (87).
Cadmium fa also known to have marked acute
and chronic effects on aquatic organisms.
The eggs and larvae of fish are apparently
more sensitive than adult fish to
poisoning by cadmium, while crustaceana
appear to be more sensitive than fish
cggB and larvae (123). Cadmium la particularly
toxic to gill-bearing marine and fresh-
water crustaceans and may Induce ultra-
structural changes In the gills (132).
In mamnals, approximately 6 to 10X of the
Ingested cadmium is absorbed and transported
through the body by red blood cells.
Cadmium collects In the kidney, liver,
pancreas and blood vessels. Some cadmium
is absorbed from the lungs following Inha-
latlor.
-------
TABLE 6-7. SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS.
Element.
Ceneral Information
Human Health Effects
Ecological Health Effect*
Cadmium
(rnntd.)
On
I
Ui
Chromium
(cr)
All chromium compounds considered
poisonous.
Chromium Is only biologically Important
in the trl- and hex.ivalent states. In
iuidiuIb, there la a conversion of hexavalent
to trlvalentchromium. Trlvalent chromium
la postulated to be nn eanentlal element
to mammals (04). Even in lta moat soluble
forms, chromium la not absorbed by maranala
and la largely excreted In the feces
(134,87).
The amount of cadmium uptake from material
In the lungs depends on the concentration,
particle size, solubility of the particu-
late matter and phyalologlcal considerations.
However, under normal conditions, inhala-
tion does not contribute significantly to
intake. Moat cadmium salts have a ahort
retention tine In the lunga (84,116).
Acute lethal concentration for root fresh-
water fish vsries from 0.01 to 10 mg/t (133).
Reduced reproduction of Daphnla magna at
0.0005 mg/t.
Seven day I.Ds# for rainbow trout (Salmo
galrdnerl) ia 0.008-0.010 ppm.
Oysters may concentrate cadmium.
Certain plant* nay take up Cd from soil (121).
Yields of beana, turnips, and beeta
reduced by 0.10 ng/1 In nutrient aolutlon (85).
The concentration of chromium in aolls
varies greatly; however, the aoll
chemistry of chromium is largely unknown (138).
In some agricultural crops, high level8
of chromium can cauae reduced growth or
death of the cropa, whereas adverse
effects of low concentrations of chromium
on corn, tohacco and augar beeta have also
been documented (132). The oxides of
-------
TABLE 6-7.
F.loment. Ccnernl Information
Chromium
(contd.)
ON
SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS
lltimnn Health Effects
Also, It does not appear to concentrate
In any particular mammalian tlnaucs or to
incrcose in these tissues with age (87,115).
Mont human exposure to chromium occurs
vl.i intake of food and water. However*
the presence of chromium in these sub-
stances Hun not produced any significant
adverse effects In either man or experi-
mental animals (84). It should be noted
that chromium pauses through the plocenta
and enters the fetus, where it is
selectively concentrated In the lung
tissue. There Is also the possibility
of ocrupaiionally Induced lung cancer
due to the Inhalation of hexavalent
chromium (84,116).
F.xposure to chromium In air results in
Injury to nasal tissues.
At high concentrations, concer of the
respiratory trace has resulted (88).
Tulmonary effects Reported with Inhala-
tion of 4,500 Ug/m Cr for 5 years (108).
I.Djo (oral, rat): 1,870 mg/kg for
Crcl« equivalent to 615 mg/kg for
Cr1 .
Cancer has resulted from exposure to
110 UR/m1 of tro, (137).
Lowest dosage resulting In carcinogenic
response Is 1 mg/kg.
Ecological Health Effects
chromium In the soil sre very Insoluble
and generally unavailable to plants.
As with other metnln, the toxicity of
chromium salts for aquatic life varies
with the species, temperature, pH, valence,
and the presence of synergistic and antago-
nistic substances (87). Chromium toxicity
Is especially sensitive to water hardness (134).
Fish are relatively toleront to chromium
salts, but lower forms of aquatic life
are extremely sensitive. Chromium also
Inhibits the growth of algae. The reported
lethal limits of hexavalent chromium for
fish are 17 and 17 ing/i as compared to
0.05 ng/1 for macroinvertehraten and
0.032 to 6.4 ng/1 for algae (87).
Chromluai is only biologically Important
In the tri- and hexavalent states. In
manna1s, there Is a conversion of hexa-
valent to trlvalent chromium. Trlvalent
chromium is postulated to be an essential
element to manuals (84).
Even In its sont soluble fonts, chromium
is not absorbed by nanmals and 1s largely
excreted In the feces (134,87). Also, It docs
not appear to concentrate in any particular
mammalian tissues or to increase In these
tissues with age (87,135).
Toxic to aquatic life.
Oysters most sensitive to effects: 10-12
Ug/t may be lethal.
-------
TABLE 6-7.
Element. General Information
Chromium
(contd.)
Cobalt
(Co)
Cobalt and its salts are
cumulative poisons.
SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS
Human Health Effects
Ecological Health Effects
In man, cobalt salts are well absorbed
by the small intestine. However, slgnl-
fleant retention of cobalt by humans
doea not occur. Approximately BOX of
the Ingested cobalt is excreted in urine
and 15Z is removed in the feces
Exposure to cobalt and its compounds ban
resulted in some pulmonary effects, an
allergic-type dermltltls, digestive
changes, and liver and kidney damage (BB-,83)
(oral, rat): 1,500 mg/kg, for cobalt.
LD.
L0
LDso (oral, rat): equivalent to 36 mg/kg
as Co+?.
Ingestion of 1,500 mg/kg of CoClj has
caused the death of a child.
Oncogenic effects minimum TD^o is 2.5
mR/kg of Co (108).
Exhibits a hlocumulatlve effect in aquatic
organ lams.
Sons phytoplankton can accumulate chromium
2,300 times the concentration in water.
Soybean yields reduced by concentrations
of 0.5 mg/t in water solutions and 10
mg/kg In soil cultures (85).
Cobalt has been reported to increase
In concentration in the soil around
coal-fired power plant from 2.3 Pg/g
in background soil to 4.6 Pg/g in
enriched aoila near the plant (26).
Cobalt la an essential element for both
plants and animals. In mammals it in
required for activation of vitamin Hi? (84).
Tks. difference between nutritional
requirements and toxic dosage in plants
may be very small.
A concentration of 0*1 mg/1 of cobalt in
nutrient solutions in irrigation waters
is near the threshold toxicity level of
plants, whereas a concentration of 0.05
mg/1 appears to be satisfactory for
continuous application on all soils (139).
For wildlife and domestic animals, such as
sheep and cattle, a wide margin of
safety (a factor of 100) exists between
the required and toxic leve)s(87).
the slow accumulation of cobalt, at n
concentration of 1 ug/g» over a period
of time as short as a month, results in
-------
TABLE 6-7.
I'lcmcnt. General Information
Cobalt
(contd)
Coppet
(Co)
Concentration of calcium and
nagneslun influence toxicity
of copper In water.
SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS
Human Health F.ffects
Ecological Health Effect*
cardiomyopathy (symptoms similar to
congestive heart failure) In laboratory
organisms (84).
Growth of carp (Cyprlnus cnrplo) inhibited
by 0.05 ag/l.
Growth In Chlorella (algae) and Euglena
retarded by 0.04 mg/l.
Cumulative In several aquatic species.
At 0.1 mg/l, toxic to tomato planta^®*)*
Even when man is exposed to excessive
concentrations of copper, chronic symptoms
do not result (84). For humans, the only
limiting factor of copper In domestic
water supplies is taste (87).
Copper Is an eeaentlal element for most
organisms. However, It can be strongly
toxic to planta and aquatic organisms even
at very low concentrations then present
In its Ionic form (140, 141).
In form of salts, may irritate gastro-
intestinal tract if Ingested.
Chronic exposure may result In anemia.
Exposure to metallic copper fumes may
cause respiratory, eye, and skin Irrata-
t ions (fl8,83).
LO^o (Intraperitoneal, mouse): 3,500
uB/e..
I.D*o (oral, r.it): equivalent to 66 mg/kft
an Oi .
In general, copper concentrations less than
1 mg/1 have been reported to be toxic
to many kinds of fish, crustaceans, molluscs
Insects, phytoplankton and zoopl.inkton
The toxicity of copper varies among
organisms. For example, diatoms, dlnoflagel
lates and blue green algae arc reported
to be more sensitive than green algae
to polsunlng by copper (4(1J:
Thus the enrichment of copper to an aquatic
ecosystem would be expected to result In
a reduction in primary productivity and
the standing crop of many species of
phytoplankton. The toxicity of copper
to aquatic organisms Is also affected
-------
Element.
Central Information
TABLE 6-7. SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS
Human Health Effects
Ecological Health Effect*
Copper
(rontd)
On
I
V£>
hy the physical and chemicnl characteristics
of the water Including temperature., hardness,
turbidity, and carhnn dioxide content.
In hard water, the toxicity of copper 9nlta
la reduced by the precipitation of copper
carbonate or other Insoluble compounds (134).
Also* the sulfates of cupper and zinc, and
of copper and cadmium, are synergistic In
their toxic effect on fish (87).
Copper le accumulated by many marine organisms,
with concentration factors of 30,000 reported
In phytoplankton, 5,000 In the noncalcnreous
tissues of molluscs and 1,000 in fish muscle.
It Is also concentrated In m.iny aquatic
Invertebrates In which the copper Is attached
to their blood protein hemocyanln which
serves aa an oxygen carrier (134,07,101).
96-hour LCjo for fathead minnow (Plephates
promelas) It 0.05 ppm for CuSo* In soft
water, 1.5 ppra In hard water.
Inhibits photosynthesis of glsnt kelp at
0.06 mg/fc.
Toxic to oysters at 0.1 mg/l.
Concentration factor of 30,000 In marine
phytoplankton and of 1,000 In marine floh.
Concentrations of 0.1-1.0 ng/1 In nutrient
solutions are toxic to a number of plants (65).
-------
__ TABLE 6-7.
I'lrmcnt General Information
FluorIne
(F)
SUHHARt OF ECOLOGICAL_AND HEALTH gFFtcTS
Human Health Effects Ecological Health Kffccta
In vertebrates, fluoride In stored pri-
marily In the skeletal tissue. Data from
field studies on the levels and hloaccumu-
l.-Hlon of fluoride show that a level of
2.0 mg/fc In livestock drinking water may
result In some tooth mottling. This concen-
tration la not excessive from the stand-
point of animal health or the deposition of
fluoride In meat, milk or eggs. Chronic
fluoride poisoning of livestock has been
observed when water contained 10 to 15 mg/iof
fluoride (142). Concentrations of 30 to 50
mg/1 of fluoride In the total ration of dairy
cows la considered by the F.PA to be the tipper
safe limit (87). Fluoride Is transferred
only to a very small extent Into the milk and
to a Romewhat greater extent Into eggs (87).
However, fluoride uptake In ruminants can
lend to prenatal skeletal defects. The
presence of aluminum may mitigate the effect
of fluorosis and It ahould be noted that
aluminum comprises a farlly large portion
of coal ash. Fluoride may be transformed
by some organisms in the natural environ-
ment Into for more toxic organic fluorides.
If thin transformation occurs to any signi-
ficant degree. It could have profound
ecological effects (143).
Host studies of fluorine In the environment
have been on Its effects on food crops.
It has been shown the airborne fluoride
can damage either the foliage or the fruit
of a wide range of plants. Citrus trees,
apricot, cherry, plum, grape. Douglns
fir and many species of pine, corn,
sorghum, and ornnmental flowers, In parti-
cular, are extremely susceptible to fluoride
damage (144) .
As a result of fluoride pollution and Its
entry Into food chalnn bv arcumiilat Ion
In forage crops, extensive damage to
grazing livestock has occurred. Some plant
varieties have been found to build up
fluoride concentrations In their tissue
to leveln that are millions of times that
found In the surrounding air (144).
in contrast to terrestrial studies, data
from field studlea on htnaccumulatIon of
fluoride In aquatic organisms are virtually
nonexistent. However, It Is know that
fluoride le taken up hy some aquatic plants
and Is dtored In the skeletons of fish (143).
In vertebrates, fluoride la stored primarily
-------
TABLE 6-7. SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS
Element General Information Human Hcnlth Effects Ecological Health F.ffeetn
Fluorine
(contd.)
eggs. Chronic fluoride poisoning of live-
stork has been obaerved when water contained
10 to 15 «g/l of fluoride (142). Concentration
of 30 to SO mg/1 of fluoride In the total
ration of dairy cows In conntdercd by the
F.PA to be the upper safe limit (97).
Gall lum
(Ca)
There are no reported adverse effects
of gallium In humans following Indus-
trial exposure. Galllm In not readily ab-
sorbed by mammals from the oral route (R4).
In humann, gallium has cauned metallic
taste, skin rashes, and bone mArrow
depression (145).
Fluoride Is transferred only to a very small
extent Into the milk and to a nome
what greater extent Into eggs (87). However,
fluoride uptake in ruminants can lead
to prenatal skeletal defects. The prenence
of aluminum nay mitigate the effect of
fluoronlR and it should be noted that alu-
minum comprises a fairly Jrirge portion of
coal nnh.
Fluoride may be transformed by nome organisms
In the nstural environment Into far more
toxic orgAnlc fluorides. If this trans-
formation occurs to Any significant degree.
It could have profound ecological effects (143)
Little Is known of the toxicity of
gallium to either plants or animals.
Gallium In not readily absorbed by manuals
from the oral route (84).
t,Di~ (subcutaneous, rat): HO mg/kg for
gallium. Gallium compounds* generally
have a low order of toxicity. Intravenous
Injections up to 15 mg/kg body weight are
tolerated without harm by experimental
animals; however, larger doses produce
-------
Element
Genera) Information
TABLE 6-7. SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS
Human Health Effects
Ecological Health Effects
Calllum
(contd.)
Germanium
(Ce)
Germanium compounds are generally The toxicity of germanium and Its compound**
of a low order of toxicity. They Is low to mammals even when present at
are thought to resemble other organo- very high leveln. Inhalation exposure of
metals, which are usually mure toxic rats to germanium and germnnlum oxide
than Inorganic forms. Animal- results In rapid clearance from their
studies Indicate that germanium bodies (86),
after absorption Is widely distributed
throughout the body and Is not
selectively retained In any tissue
(104).
On
I
Ln
N)
Iron
(Fe)
Becau.se Iron Is homeostat lea 1 ly controlled.
It In not toxic to man (86).
hemorrhagic nephritis. Calllum is slowly
eliminated from the body of animals after
Injection of soluble gallium salts. It
is similar to the tissue distribution of
bismuth and mercury in the hody (165).
The toxicity of germanium and Its compounds
Is low to maimals even when present at
very high levels. Inhalation exposure of
rats to germanium and germanium oxide
results in rapid clearance from their
bodies (86).
At high exposure levels germanium disturbs
the water balance In mammals leading to
dehydration, henoconcentratIon, fall In
blood pressure, and hypothermia (106). Ger-
man turn hydride is considered moderately
toxic, but can cause death of experimental
animals at 150 ppm. It Is similar to,
hut less toxic than, arslne and stlblne
and causes a hemolytic response (88,03).
Germanium dioxide stimulates generation
of red blood cells (83).
rabbit)
(Intraperitoneal, rat): 750 mg/kg for
germanium dioxide. Cermanlum In taken up
by cereals, especially oats, from Cermanlum
bearing soils (106).
Iron Is widely distributed in the environ-
ment with animal tissues usually hovlng
higher concentrations than plants. In
mammals. Iron is an easentlal element
needed for the formation of hemoglobin
and myoglobin. The addition of soluble
iron Raits In irrigation water may lead
to Increasing soil acidification (87).
D^o (subcuta nemi s)
586 mg/kg for germanium. LD;o
-------
TABLE 6-7.
Element. Cenersl Information
Lead Lead compounda usually polaonoua
(Pb) in proportion to eolublllty«
Toxoclty of particulate lead la
dependent oo particle size.
Lead la a cumulative polaoo.
a>
I
Ln
LO
SUHHART OF ECOLOGICAL AND HEALTH EFFECTS
Human Health Effects Ecological Health Effects
Leod has many detrimental effects on humane
which range greatly |n severity. Acute tox-
icity, however. Is most common ln children (84).
Moat lead enters man ln the following
component0 of the human diet: legumes (3Z),
garden frulta (192), other frulta (16Z),
root vegetables (61), grain and cereal
(7Z), meat, fish and poultry (7X), and
leafy vegetables (5Z) (94.) The major
routes of lead uptake ln man are through
the gastrolntestinal tract and lungs.
Of the lead Ingested, 5 to 10Z Is absorbed
and about 37Z of the Inhaled lead reaalna
ln the lungs. Once absorbed, lead accumu-
lates primarily ln the bones, with lesser
amounts ln other organs (64).
Ingested lead Is largely captured by the
liver and excreted ln hlle.
Lead absorbed by Inhalation yellds toxle
effects from small amounta«
Lead poisoning produces hemolyala of red
blood cells, lesions of the kidneys,
liver, male gonads, nervous system, and
blood vessels.
Lowest dosage, aa lead, of lead compounds
producing tumors ln animals Is 555 mg/kg.
Exposure to lead Increases Incidence of
abortiona and atlll births. Lead Is
transferred across human placenta (105).
Teratogenic effects ln anlmala have bean
produced from exposure; lowest dosag*
21 mg/kg.
Lead Is present ln all soils and planta.
Soil contalna an average of 10 to
15 Ug/g and ranges from 2 to 200 Ug/g of
lead. The availability of lead ln
soils to plants Is not understood. Rovcvn;
soil type and pH have been found
to affect lead uptake. At low pH,
lead Is more available to planta.
Plants are able to translocate lead
from the soil to the roots but poorly
transport It to the leaves and fruits.
This occurs even when the soil lead
la soluble and available In the eoll (146).
For example, the lead content of straw-
berries does not change when the lead
content of soil Is increased from 8
to 59 Ug/g. ln radishes 3 ten-fold
Increase In soil lead content
Increases the lead concentration by a
factor of less than two (147). Thus la
appeara that soil lead may not be
readily Incorporated Into the food
chain via the soil plant pathway.
There la some evidence that lead may
be phytotoxlc aa It haa been shown
to decrease tranaplratIon and photo-
aynthesls ln sunflowers (148). Roadside soils
planta, earthworms, trout, and mice have
been ahown to have elevatfed lead levela
which decrease rapidly with lncreaalag
distances from the hlghwaya (149,150).
The toxicity of lead to freshwater
organlsma varies with lta solubility
which la a function of water hardness.
-------
TABLE 6-7
Tlrmcnt Ccnrr.il Information
Lend
(contd.)
0n
I
Lithium Very reactive and water soluble.
(LI) Lithium Is noncumulatIve (153).
HAgnr8iun
(Mr)
Concentration of magnesium and
calcium In varer Influences the
toxicity of heavy mineral* (1)3)
SUMMARY OF ECOLOCICAL AND HEALTH EFFECTS
Human Health F.ffecta
Highly toxic to humans, partially Inversely
dependent on sodium Intake (105).
Levels above 75 Ug/m' of lithium hydride
cause sncrzlnR (133).
Teratogenic dosage In rate reported to be
350 mg/kg.
Metallic magnesium may cause local skin
effects (84).
Inhalation of magnesium dust can cause
mrtal fume fevrr (145).
For example, brook trout arc adversely
Affected by lead at 0.10 ng/1 In soft
water, whereas in hard waters the 96-hour
LCit value Is 44? ng/1 (81)
Little la known of the biological effect*
of lead on marine organisms although
the connon marine mussel haa been found
to concentrate lead without showing
detrimental effects (151). In addition
some marine plants may concentrate each
up to 40,000 times (87).
Reproductive Impairment of Paphnla magnla
occurs at concentrations of 30ug/t (102).
Toxic effects In plants produced by
>25 mg/l In nutrient solutions (85).
Lithium is phytotoxic.
The most sensitive plant species Is
citrus. A slight toxicity is produced
by 60 to 100 Ug/t In Irrigation water (85).
At 7.2 ppmv Inhibits growth of Botry-
ococcus. 24-hour LCs«: equivalent to 866
ppm as Kg*' for Paphnla magna (85).
L^lq (oral, dog): 320 mR/kg.
-------
__ TABLE 6-7^ SUMHAFT OF ECOLOGICAL ANP^HRALTH EFFECTS^
Dement General Information Hum.™ Health Effecta Ecological Health Effects
Manganese
(Hn)
ON
I
Ln
Mercury
(llg)
Manganese compound* nor highly
poisonous due to manganous Ion
atone (155).
Hay produce acute and chronic
effecta. Food, especially flah,
la greateat contributor to the
human body burden of mercury (85).
Flsh-estlng blrda and manmala, at
the top of the food chain, auscep-
tlble to excessive mercury ln
water.
Manganese la an essential element for
mORIfflfl 19 , being required aa a cofsctor
for a number of enzymea. It la preaent
In all living organlams and la abaorhed
from food via the gaatrolnteatIna1 tract.
In general. It la not toxic to man, except
from chronic inhalation of HnOj during
occupational exposure over long perloda
of tine (2 yeara) (84).
Strong oxidising properties of manganates
and permanganates can catiae akin irritation.
Exposure may cause reaplratory damage.
tnhatatlon of Hn or ita compounda may
rauae chronic poisoning (156).
Lowest concentration cnualng toxic effect*
ln humans (central nervoua ay at em effecta.
due to inhalation) reported to be 11 mg/m
(108). LDj* (Intraperitoneal, mouse)t 53
i"hAr.
Mercury la a particularly dangerous
toxicant due to ita volatility and trana-
formatlon by bacterial action into an
akytated form (159.) It la stated that
all of the organic forma of mercury
(atkoxl, alkyl, and aryl) are toxic, hut
these mercurials ln the nervous system,
the ease of their transmittal across the
placenta and their effect on developing
tissue make them particularly dangeroua
Manganese la toxic la very low concentrations
to many crop plants. However, its phyto-
toxlclty is dependent upon acidic soil condl-
tlons (87). Manganese primarily affects lover
trophic levela of aquatic organisms. It
haa been shown to decreaae growth and repro-
duction in aome species of plankton, and
cause Increases in growth and reproduction
ln others (157).
Hanganeae Is an essential element for mammals,
being required aa a cofactor for a number
of encymes. It Is present ln all living
organisms and is absorbed from food vis the
gaatrolnteatlnat tract.
Marine mollusc bloaccumulatlon factor of
12,000 reported (102).
Acute dose of 96-hour LCj# of 1,400 ppm Is
reported for rslnbow trout (Salmo gslrdnerl).
carp, (Cyerlnua carplo)~ and Daphnla (145).
Soil concentrations of 2.5 ppm have
affected soybeans, but soil effects depend
on variables such aa pH and molature (158).
Mercury Is a particularly dangerous toxicant
due to its volatility and tranaformation by
bacterial action Into an alkylated form (159).
The mercury content In soils of the United
Ststes ranges from 10 to 500 ng/g (108).
Mercury tenda to be retained ln the surfsce
layers of the soil due to adsorption by
organic and inorganic materlatrf and the low
solubilities of mercury sslts/phosphates.
carbonate, sulfide)(loft). Mercury haa been
-------
rlemonl
Genernl Information
TABLE 6-7. SUMMARY OF EC01.0C1CAL ANT) HEALTH EFFECTS
Human Hcolth Effects
Ecological Health Effects
Hercury
(contd)
0
1
Ln
On
Exposure to mercury vapor results In ahsorp-
tton by the lung*, with none secondary
amount* taken In by the akin. Absorption
of elemental mercury After oral Indention
Is mlnlm.il compared to the uptake of methyl-
mercury which Is quickly abaurbed through
the nkln, lungs and gaatrolnteatInal tract.
Hethylmercury tenda to accutmifnte In the
kidney, brain and blood. In addition*
methylmercury nay pass through the placental
wall Into the fetua, concentrating In
the brain tlsRue (84).
Acute lllneas hag reaulted from Inhalation
of 1.2 to 8.5 ffijj/m' (109). Human death haa
resulted from Ingestion of 1,629 mg/kg (108).
Central nervous system effects have resulted
from Inbnlatlon of 169 lig/m' for 40 years(lo8)
Certain compounds have demonstrated nn-
cengenlc potential (108,105). The lowest
dosage producing tumors la 600 mg/kg.
Certain compounds have demonstrated
teratogenic potential. The loweat dosage
producing a teratogenic response Is
500 iir/Kr.
reported to Increase In concentration
ln the soils around a coal-fired power
plant from 7.9 ng/g In background
soils to 4.6 Ug/g in enriched soils near
the Installation (85).
In *ost plants, mercury concentrations
range from 10 to 200 ng/g (15 ng/g average),
but plants growing near mercury deposits
can contain 500 to 3,500 ng/g mercury*
TranalocatIon of Mercury occurs ln many
plant tlaaues, Including leaves, fruit
and tubers. Toxicity of mercury to
terrestrial plants apparently depends aore
on chemical form than on its concentration.
There are few studies svsllable on the
toxicity of mercury to specific plants (147).
The occurrence of Mercury is recognised
as nearly ublqultoua ln aquatic ecosystems.
Most of the mercury ln fish is ln the
methyl form (160). In addition numerous
laboratory studies hsve demonstrated the
toxicity of various mercury compounds
to birds.
Highest body burdens occur ln fish eating
birds, ss compared to insect eating birds (161).
Presently, little Is known about the overall
effects of mercury on ecosystems. However,
mercury Is known to cause alteration of the
behavior of various aquatic organisms (162,163).
Concentrations of mercury In'surface
waters have uaually been found to be
far leaa than 5 l»g/l. Natural methylatlon
-------
Crncrnl Information
TABLE 6-7. SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS
ttum.in lien 11li Rffcctn
Ecological Health Effects
Mercury
(contd. )
of bottom sediment mrrrury In areas
bordering mercury deposits results In n
continuous presence of the element In
solution (157).
Hcrcury fs actively taken up by lower
ordern of biota In freshwater quatlc
ecosystems. More than 75Z of nil the
methylmcrcury present In these lower
ordern In taken up directly from the water.
Higher orders of aquatic hlotn, such as
predatory fish, take up as much as 602 of
their methyImercury directly from the
water.
At each higher trophic level, the concen-
tration of methyImercury has been reported
to Increane due to binding In the muscle
tissue (166). The behavior of mercury In
the marine environment Is not completely
understood. However, organomercurlain
are concentrated by marine organisms to
a greater extent than are Inorganic
mercurlals (97,165).
Recently, It has been nhovn that the pre-
sence of selenium can decrease the toxicity
of methylmercury in birds and rats (16ft). The
presence of selenium may also result In
a decreased toxicity of methylmercury
In rfsh such as tuna, which contains
high levels of selenium (167) .
Oncorhynchua nerka, 0. gorbuscha, and
K.ilmon eggs killed by concentrations over
3 |ig/t (as mercuric sulfate).
0
1
Ui
•^1
-------
TABLE 6-
I'lcment Crneral Inform.it Ion
Mercury
(contd.)
Molybdenum Molybdenum compounds exhibit
(Ho) a low order of toxicity for
exposed workers. Molybdenum trl
oxide and ammonium molybdnte are
more toxic than the metal or
the dioxide (88).
SUMMARY OF ECOl-OCtCAL AND HEALTH EFFECTS
Human Health Effects
Ecological Health Effects
Holybdenum rtcriimulritfs In the kidneys
and adrenals In hum-ins. Excretion of
molybdenum In man Is rapid, occurring
primarily In the urine. Excess molybdenum
may be excreted in the bile. Nn data
are available documenting molybdenum
toxoclty in man due to Industrial exposure(8&)
Signs of molybdenum poisoning are loss
of appctIte, I1stlessness,dlarrhea,
and reduced growth rate (104).
Acute 96-hour LDso for fish I mg/t
of inorganic mercury (B5).
t.cfitons on roses at 10 Ug/m* (37).
Holybdenum Is needed by bacteria* higher
plants, and animals for a number of biologi-
cal processes. The accumulation of
molybdenum by plants Is proportional to
the amount added to the noil. It Is not
toxic to plants at natural hackground levoln(87).
It Is concentrated by many freshwater
and marine organisms Including hentMc
algae, phytoplankton, zooplankton, molluscs,
crustaceans. Insect larvae and fish (101,16R).
Molybdenum la also essential for the
fixation of elemental nitrogen by bacteria
and blue green algae (169).
Molybdenum exists In various valence forms.
In mammals, the soluble hexavalent
compounds are well absorbed, from the
gastrolntestlanl tract and tranaported
to the liver. Ruminants are particularly
sensitive to (Molybdenum which they may
ingest while grazing (170). A molybdenum
concentration of 5 to 10lJg/g Is considered
to be toxic to cattle (16f>). Sheep, horses
and swine are more tolerant to molybdenum.
LDie (Intraperitoneal, mouse): 160 mg/kg.
There 1s an Interrelation between moly-
bdenum and copper In the nutrition
-------
Tlement
Ccnrrol Information
TABLE 6-7. SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS
Human Health Effects
P.cologlrnl Health P.ffects
Molybdenum
(contd.)
On
I
Ln
VO
Nickel
(Nl)
Dietary intake from plant and
animal tissues are not harmful.
Nickel salts are highly toxic (104)*
Nickel salts reported to substan-
tially affect the biological oxi-
dation of sewage (85).
The chem1r.il species of nickel geratly
effect* Its toxicity to mammals. Nickel
cnrhonyl, N1(C0)*, is the most toxic of
all the nickel compounds to man. It causes
denth nfter exposure of 30 Ug/g for 30
minutes and has been Implicated as a respir-
atory carcinogen (84). Nickel carbonyl In
formed when hot carbon monoxide Is passed
over nlckeJ, both 09 which are waste products
of coal fired power plants. Dietary nickel
la excreted hy man largely In the feres,
whereas nickel carbonyl Is excreted In
the urine (80). As a particulate air
pollutant , nickel has been found to
have deleterloua health effects In both
humans and other mammals (172).
P.xpoaure may cause sennit lvlty to nickel
and dcrmlt1tIn.
Absorption through Inhalation mny be
associated with nasal, sinus, and lune
cancer (8fl).
requirements fro sheep and cattle. Copper
polnonlng Is associated with low molybdenum
levels In forage; copper starvation la
associated with high molybdenum levels (153).
Molyhdoals of cattle was associated with
l.islke clover grown in soils that had
0.01 to 0.10 mg/t of molybdenum In
aaturntlon extracts. Phytotoxlclty 1r
negligible, but plants accumulate molybdenum
In proportion to the amount In the soli.
Aquatic toxicity: Marine molluscs are
reported to have a concentration factor
of 60 times the concentration in water (AS).
96-hr I.Cjo for fathead minnow, Plmephales
promelas, Is 70 mg/fc (for molybdlr
onhydrlde).
Little Is known of either the soli
chemistry of biological activity of nickel (108).
Nickel la very toxic to many plants
especially citrus fruits. At concentra-
tlonn above 0.5 ng/1 It will Inhibit
plant growth (172).
Nickel is found in many soils In a generally
Insoluble for», but acidification may
render it soluble causing plant Injury or
death. It now appears that the toxicity
of nickel for plants may be caused by
a decrease In the oxygen exchange capacity
of the roots (173).
As a pure metal, nickel is not a problem
In water pollution because It Is not affected
hy, or soluble in water. Har\y nickel
salts, however, are highly soluble In
water (176). Nickel salts can kill fish at
-------
TABLE 6-7,
flcment Ceneml Inforawitton
Hickel
(contd.)
OS
ON
O
Phosphorous Yellow or white phosphorous 1®
(P) on# of the most highly toxic
inorganic substances (88).
Red phosphorous Is relatively
hornless unless white phosphorous
Is present as an Impurity.
SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS
Human Health Effects
Ecological Health Effects
Nickel tn some form la probably carcino-
genic in humans (173, 122).
Oncogenic response minimum dosage Is 16
mg/hg, as Nl.
Chronic effects in humans include liver
Injury, necrosis of jaw hone, anemia,
brittle bon#*s, snd tooth and eye damage (63).
Lowest lethal dose, administered orally,
for a human is 1.4 mg/kg (108).
Phosphorous may be absorbed through the
skin, an well as by ingestion or through
the respiratory tract (91).
very low concentrations. Data for the
fat head minnow show death occurring In
the range of 5 to 43 mg/1, depending upon
the alkalinity or the water (174).
Mttle Is known of the toxic effects of
nickel In marine systems. However, nickel
is toxic to phytoplankton and algae. Some
marine animals have been found to
contain up to 400 ug/l, and marine
plants up to 3,000 Mg/1 nickel (87). The
lethal limit of nickel has been reported
as low as 0.S mg/1 for some marine fish,
and 1.5 mg/1 for juvenile oystera (87).
Concentrstions 100 ug/fc may adversely
affect scversl aquatic species (102).
Aquatic toxicity for stickleback, 96+hour
LCs© : equivalent to 0.26 mg/f, as Hi
Concentrations of 0.5 to 1.0 mg/£ Hi+2are
toxic to tomato, oats, and other plants
In sand and solution culture (85).
F.lementa) phosphorous 1* highly toxic
and bioaccueulates In aquatic organisms.
A concentration factor as high as 25,000
has been reported with the largest con-
centration found In liver.
l.Cso (48 hour): 0.0105 ppm for l.epnmls
macrorhlrus (85).
LDso (skin, rat): !00 mg/kg.
-------
TABLE 6-7
FI client General Information
Potassium The toxicity of potassium compounds
(K) is almost always that of the anion
(83).
Scand lum
(SC) Toxic properties arc not
cstablIshed (81).
Selenium
(Se)
SUMMART OF ECOLOGICAL AND HEALTH[EFFECTS ^
Human Health Effects Ecological Health Effects
Exposure to du9t or mist of potassium
causes eye and respiratory trace
Irritation and nasal septum lesions(87).
I'D.q (oral, rat) potassium chloride - 2,630
mp,7kg. Aquatic toxicity; 432 ppm KC1 In
threshold of lowohlllzatIon for Daphnla
magna (85). This is equivalent to 210 ppm,
as K*.
The oral toxicity of all the rare
earth Is low In man due to poor
gastrointestinal absorption (84) .
The human Intake of selenium in food In
sclenlferous arras may range from 600
to 6,140 ug/day, which is stated ro he
close to the estimated levels at which
symptoms of chronic selenium toxicity
occur in man (87,84). Chronic symptoms in
man include gastrointestinal distress,
loss of hair and nails, and decayed teeth.
Also reported are fetal and teratogenic
effects, and fatty necrosis of the llver(84).
The toxicity of selenium to man depends
upon Kn chemical species. Elemental
selenium is probably not absorbed by the
gastrointestinal tract. The highest
concentration In man is found In the
kidneys and hair, and mainly eliminated
via the urine (86). Host selenium enters
the human diet through the Ingestion of
meat, fish and poultry (382), and grain
and cereal (62X) (94,175).
There Is no published information on
ecological effects of scandium.
LDso (oral, souse): 4,000 mg/kg for
scandadlum chloride, ScCh. This is equiva-
lent to 1,184 mg/kg on Sc.
Selenium varies greatly In its soil
concentration In the United States. Some
areas of very high selenium content in
the western U.S. have been purchased by
the U.S. Government and removed from
crop production. Other areas, such as
the Northeast are deficient in selenium
for good animal growth (23). It would thus
appear that additional selenium Input such
on from the combustion of fossil fuels,
might prove to he beneficial in certain
parts of the country and deleterious In
others (138,23).
The soil chemistry of selenium Is not
understood, so that predictions of nelenfum
uptake by plants from Its soil concentration
cannot reliably be made (138). In addition,
selenium has not been shown to be essen-
tial for plant growth although It is
concentrated by many plants to levels
which arc toxic to livestock (176).
-------
Flemcnt General Information
Sricnlum
(contd. )
On
I
CJN
ho
6-7. SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS
Human llenlth F.ffecta
Ecological Health Effects
Inhalation, Indention or absorption
through skin can cause acute and chronic
efferte (91).
Symptoms appear similar to ararnlc
pnlnonfng (10?).
Can cause respiratory tract Irritation
and systemic effects.
LDso (Intravenous, rat): 6 mg/kg; ^C^q
(Inhalation, rat): 33 mg/kg/8 hours.
No oncogenic effects from exposure reported.
Teratogenic response In chicks and mice,
minimum dosage 0.*> mg/kg (105).
For example, selenium at concentrations
exceeding 200 ug/g (dry weight) ha*
been found in sweet clover growing on
beds of fly ash (1-7). It Is stated that
a concentration of selenium between 0.04
and 2 Ug/g Is required to prevent defi-
ciencies In cattle, whereas concentrations of
4 to 5 ug/g are toxic (176). The deficiency
of selenium In mama Is results In a
degenerative muscle disease.
Thus, selenium Is essential to manna 1b,
but within a very narrow range and may
be so for man as well.
Information on the levels of selenium
In freshwater and marine Invertebrates and
fish are limited; although It Is known to
concentrate In some seaweeds (87), tooplank-
ton (178), Invertebrates (179), and fish (180).
ft Is believed that high selenium In
fishes may result from high selenium
content In the plankton upon which they
feed (lfll).
In addition, the selenium concentration
of some aquatic organisms has heen corre-
lated with thoae of mercury, araenlc, and
thallium (182). All of thene mihntances
Inhibit pulmonary selenium excretion. This
has suggested a possible regulating process
In the accumulation of these elements by
marine organisms (182).
Several cases of livestock polnonlng by
selenluB In waters have not beeti reported,
although some spring and Irrigation waters
-------
Flement
Selenium
(contd.)
ON
I
ON
u>
Sllvrr Silver Is cumulative In the body.
(Ap.)
TABLE 6-7
General Informal Ion
SUMMARY OF EOOLOCICAL AND BEAJ.TH EFFP.CTS
Human llenlth Effects
Ecological Health Effects
have been found to contain over 1 mg
per liter of selenium (07). Very little In
known of the potential toxicity of sele-
nium to humans when Ingested from water (97).
Dangerous to aquatic environment; passes
through food chain and accumulates In
Hah.
Silver does not occur normntly In animal
or human tlsauea. The major effect of
excessive exposure to silver Is a
loent or generalized Impregnation of
the tlasues known as argyrta. It Is
not known to harm Individuals In any
way other than its unsightly appearance.
Silver can be absorbed from the lungs
and gastrointestinal tract. Excretion
of Ingested stiver Is primarily via the
gastrointestinal tract (04).
2.0 rag/l of sodium selentte toxic to gold-
fish (Carasslum auratua) (102).
Concentration* of 0.2 kg/ha In soli can
produce 1.0 to 10.5 mg/kg In tissues of
forage and vegetable cropa.
Catfte are adversely affected by Se
concentrations >4 mg/kg forage.
Crop plants damaged by large accumulations.
Some grain crops exhibit chlorosis.
Plants exposed to Se usually show Inhibi-
tion of growth (14).
Silver Is toxic to marine organisms. It
has been found to be concentrated from
aeawater by factors ranging from 80 for
marine algae up to 1,000 (or marine mammals.
Concentrations of silver as low as 2pg/l
have been found to delay development and
cause deformations In sea urchins (07).
Sliver may also cause significant respira-
tory depression in marine teleosts after
exposures to concentrations as low as 0.12
Hg/g (103).
-------
TABLE 6-7.
riemrnt Cenetnl Information
S11 ver
(rond.)
Sodium Toxic properties And health effectn
(N.i) relate to sodium aa An Alk.il 1
cyanide, Na CN.
Among the most rapidly Acting of
al1 poisons.
qs Chronic poisoning Is rare or
•P* nonexistent (IRA).
St ront fum
(Sr)
The naturally occurring Isotopes are
not highly toxic (ISA).
SUMMARY OF ECOLOCICAL AND HEALTH EFFECTS
Hum,™ Health Effects
Ecological Health Effects
F.xpor.nre to minor amounts over long periods
produces permanent Rkln discoloration.
M.iny sliver p.iltn are Irritating to skin
and mucous membranes (145).
Skin effectn noted in human exposed to
1 mg/m1 (108).
M>so (oral, mouse): . 100 mg/kg for colloidal
silver. intrnvenous admlnlatratIon of 700
Iir/kg as colloidal silver has resulted In
human death (108). LDjg (oral, mouse):
50 mg/kg for AgNO) (32 mg/kg, mm Ag) .
Oncogenic effects produced hy 2,400 mg/kg
allver In rats.
Sodium cyanide Is acutely toxic by Inhala-
tion, akin absorption, and ingestion.
Cyanide toxicity Is an Inhibition of
oxygen metabolism.
Human ingestion of up to nearly 5 ag/day
over a long period did not result In harm-
ful effects (102).
Ingestion of 2.857 jtg/kg as sodium cyanide
has reoulted In human death.
LDse (oral, rat): 6,440 |ig/kg for NaCH.
The biological action and function of
strontium resemble those of calcium.
Strontium may be essential for the growth
of mammals, especially for the calcifica-
tion of bones and teeth (B4). Nn adverse
effects from the Industrial use of stron-
tium have been reported. Strontium Is ab-
sorbed from the gastrointestinal tract and
l.q excreted In the urine and fecea. Excess
strontium Is stored In the teeth and bones (R4).
Very toxic to aquatic species. Stickle-
back fish showed toxic effects at 0.005 ppm
as Ag
-------
TABLE 6-7
Flcment
General InformalIon
TI tan 1urn
(TO
Uranium
(U)
ON
I
Ln
Natural uranium In highly tonic by
virtue of It a biochemical activity
as well as Its radioactivity.
The most Important route of expo-
sure to uranium 1b Inhalation of
Insoluble particulate. Radia-
tion exposure Is considered
cumulative.
SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS
Human Health Effects Ecological Health Effects
Tltnnlum In classified as physiologi-
cally Inert to humnna. Tltnnlum is not
reported an an intoxicating agent;
tltnnlum oxide Hunts are considered
nulnnnccn. However, titanium tetra-
chloride Is Irritating and corrosive (83).
Approximately 3Z of an oral dose of titanium
la absorbed by man, and of that, most
Is excreted via the urine. The metal,
salts and oxides of titanium are nil non-
toxic to man, and most casen, are considered
physiologically Inert (84).
There Is no evidence linking exposure
to levels of 0.1S to 0.23 mg/m5 (both
soluble and Insoluble U compounds)
with Injury to kidney or to blood (88).
LC.. (Inhalation, mouse): 10 tug/m* for
TiCI* ; molecular wt: 189.7. Aquatic
toxicity: Titanium Is mildly toxic to
fish: 96-hr LCso for fathead minnow Is
8.2 ppm In noft water for tltsnlum sulfate (A.S),
Tlvn 96 (for titanium tetrachloride):
1,000 to 100 ppm (108). Tltnnlum Is effectively
excluded by plants (85).
There Is no published record of the
ecological effects of titanium.
There are no data on the concentration
of uranium compounds by fresh water and
marine organisms. In addition, the data
that are available suggest that uranyl
salts are somewhat less toxic to marine
than to freshwater organisms (87).
Inhalation or uranium dioxide dust at a
concentration of 5 mg/m' for five years
produces no evidence of toxicity In mammals.
However, uptake of the soluble uranyl
Ion may result In acute renal damage (84).
LD<0 (intravenous, rat): 400 mg/ka for
uranium chloride, (2S0 ng/kg as If* ).
The biological half life of uranium in
bone and kidney is reported as 300 days
(104). Aquatic toxicity: 96-hour LC«0
for fathead minnow, Plmephales
promelas: 2.8 mg/t (A3).
-------
TABLE 6-7
rIcment
General Informal Ion
Vnnadium
(V)
Vanadium Is toxic by all route*
of administration, with the
pentavAlent compounds exhibiting
the highest degree of toxicity.
SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS
Human Health Effects Ecological Health Effects
Vanadium lias fl very low order of oral toxi-
city to mammals. It dooR not affect
growth, life span, nor does It produce
tumors In rata or mice when given In
concentratlonn of 5 mg/1 In their dietary
water (116). Tn humonn. vanadium la excre-
ted primarily by the kidneys. The toxic
action of vanadium Is largely confined
to the resplrntory tract. At very high
concentratIons (Industrial exposure),
gastrointestinal disorders, kidney
damage, and cardiac palpitations
have been observed. Heart disease has also
been postulated to be related to the
vanadium concentration In the air (84).
inhalation cauaes respiratory system
effects. Including tracheitla, bronchitis,
pulmonary edema, and bronchial pneumonia.
Dermatitis and conjunctivitis may also
occur. Workers exposed to 0.5 to 2.2
mg/m' of V?0s had eye and bronchial
Irritation; 0x2 to 0.5 mg/a'has caused
respiratory symptoms (88). Eye effects
are reported at 100 Ug/m' (10R). Chronic
effects have not been reported (83).
Vanadium Is ubiquitous in the environment.
There is some evidence that vanadium
Is useful and possibly essential In both
mammalian and some plant systems (84,91).
Vanadium Is usually found In low concentra-
tions In most soil materials, although
It ranges from 20 to 500 Ug/R (10R).
enters the atmosphere through the combustion
of petroleum derivatives and coal, and then
settles out on the earth's surface including
the oceans (87)•
The osh of soae oils, In fact, has
been stated to contain more than 70Z
vanadium oxide (185). Thus, vanadium ran
serve as a uneful indicator of the pre-
sence of other pollutants in the environ-
ment which are associated with the com-
bustion of fossil fuels.
Vanadium has been shown to accumulate In
forent litter, humus* lichens, mosses
and the needles of spruce trees (1BA)>
However, when present In plant culture
solutions at concentrations of 0.5 |ig/g or
greater, vanadium is toxic to aome
plants (184). The accumulated vanadium. In
general, remains in the roots of plants
with very little reaching the stea and
lcavea. It Is stated that plant shoots
seldom contain Bore than 1 Ug/g of
vanadium (138).
-------
r I enifnt.
General Informal ton
TABLE 6-7. SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS
Human llrolth Effects
VnndJ turn
(contd.)
Ecological Health Effects
Information on the occurrence of vanadium
In freshwater biota la larking. There
ore alao no reports in the literature on
the toxicity of vanadium to marine orga-
ninms. However, several species of
marine algae (108)v invertebrate aacldlans
(189) and tunlcatcs (190) concentrate
vanadium to very high levels.
Vanadium has • very low order of oral
toxicity to unils. It does not affect
growth, life span, nor does It produce
tumors in rats or mice when given In
concentratIons of 5 mg/1 in their dietary
water (116).
o>
o>
SJ
Zinc
U n)
In humans, zinc is concentrated the
muscle, liver, kidney, and pancreas
and Is eliminated by the gastrointestinal
tract. Zinc has been shown to be
antagonist 1c to the detrimental effects
of endmtum. Exposure to high concen-
trations of zinc oxide fumes results
In fovrr In man, but this usually dis-
appears within 24 to '
-------
TABLE 6-7. SUMMARY OF ECOLOGICAL AND HEALTH EFFECTS
Flement Ccneral Information Human Health F.ffccts
hirmlcss except when ,-nlfnln J Rlon?d In
v«-ry high doaagrs. Host 7-lnr enters
the human diet through the Indention of
moat, flnh and poultry (J7Z), dairy pro-
ducts (21Z). grain and cereal (19Z),
and potatoes (72) (9/4).
Inhalation of fumc9 can caune metal fume
fever, with fever, nausea, vomiting,
aching, cough, and weakness (l'«5).
LI)50 (intraperitoneal, mouse) : 1) mg/kg.
o>
00
Ecological Ilealth F.ffccts
Tissues of plnnta deficient In zinc uaually
contain leas than 15 to 20 |t&/g r. Inc while
plant tleaucn containing an excess of 400
l*/g z lnc show toxicity symptoms (108,19)).
Lichens, In particular, ore very sensitive
to r.lnc and may nerve ah indicators of
excessive tine In the environment (19*).
According to the Rnvlronmental Frotectlon
I Agency, In clnc mining arena, zinc has hcen
found in waters In concentrations as high
as 50 mg/1, and in effluentn from metal
plating worka and small anas ammunition
plant* it may occur in significant concen-
trat ions.
Ii. most surface and ground waters, it is
present only in trace amounts. There is
«ome evidence that zinc ions are adsorbed
strongly and permanently on silt, resulting
In the inactlvatlon of the metal (195.)
Concentrations of zinc In excess of 5 mg/1
In raw water used fro drinking water produces
nn underslrsble taste which persists through
conventional treatment (195).
The acute toxicity of zinc to freshwater
organisns varies greatly with the water
hardness, dissolved oxygen concentration,
pH, and temperature. Resistance to zinc
toxicity varies between species, and may
be different for Juvenile and adult
forma (196).
-------
F1ement
General Informat ion
TABLE 6-7. SUMMARY OF ECOLOCICAL AND HEALTH EFFECTS
Hum/in Health Effects
Ecological Health Effects
7. Inc
(contd.)
0>
I
On
VO
For example, zinc was found to be mo.it toxic
to freshwater minnows at n pll of 8 .ind
hardness of 50 ng/ft mid lenst toxic .it pH
of 6 nod hardner?4.of 200 ue/g (197). The
presence of copper in water may nlso
increase the toxicity of zinc to aquatic
organisms (195).
It is stated that the main concern of
zinc compounds in marine waters is not
one of acute toxicity, but rather the
long-term sublethal effects of the metallic
compounds and complexes (07). Invertebrate
marine organisms are reported to be more
sensitive thon vertebrates to acute zinc
toxicity (B7) . Must marine organism* often
concentrate zinc to levels greatly above
that present In neawater (19R).
While an increase in zinc intake In rats
results in sn increase in the concentra-
tion of zinc In their tlssuen, its accumu-
lation Is not great and leveln fall rapidly
noon after the termination of the experiment.
In hard water (200 ag/ as CaCO ), 0.18
iig/ of Zn reduced fertility of fathead
minnow, Plnephales promelae.
Rainbow trout eggs did not hatch in soft
water with a concentration of 0.06 mp,/?-
of Zn,
96-hour LCso for fathead minnowr 0.87 mg/£
Zn in soft water (20 mg/t an CaCOj).
Conrentrat ions of 0.4-1.6 mg/t In nutrient
solutions are toxic to certain varieties
of soybeans (85).
-------
REFERENCES
1. Wewerka, E. M., J. M. Williams, P. 0. Wanek, and J. D. Olsen. Envi-
ronmental Contamination from Trace Elements in Coal Preparation
Wastes. A Literature Review and Assessment. EPA-600/7-76-007,
PB-267 339, Los Alamos Scientific Lab., New Mexico, 1976. 69pp.
2. Altschuler, Z. S. Coal Resources - A Continuing Assessment. In: 5l.h
AIChE National Conference Proceedings on Energy and the Environment.
Cincinnati, Ohio, 1977. pp.249-263.
3. Jacobs, M. B. Air Pollution and Its Relation to Pulmonary Disease.
Archiv. Hig. Rada. Toksikol, 16(3):267-284, 1965.
4. Schulte, H. F. Effects of Chemical Pollutants on Man, Now and in the:
Future. In: Energy and the Environment-Cost Benefit Analysis, R. A.
Karam and K. J. Morgan, eds. Pergamon Press, Elmsford, New York,
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Metals on Plants: Part 1, Inhibition of Gas Exchange in Sunflowers
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149. Motto, H. L., R. H. Daines, D. M. Chilko, and C. K. Motto. Lead in
Soils and Plants: Its Relationship to Traffic Volume and Proximity
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150. Gish, C. D., R. E. Christensen. Cadmium, Nickel, Lead and Zinc in
Earthworms from Roadside Soil. Environ. Sci. Technol., 7:1060-1062,
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151. Schulz-Baldes, M. Lead Uptake from Seawater and Food and Lead Loss in
the Common Mussel Mytilus edulis. Mar. Biol., 25:177-193, 1974.
152. Welch, W. R., and D. L. Dick. Lead Concentrations in Tissues of
Roadside Mice. Environ. Pollut., 8:15-21, 1975.
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157. Arthur, D. Water Quality Criteria Data Book. Little, Inc., 1970.
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159. Abelson, P. H. Methylmercury. Science, 169:1, 1970.
160. Huckabee, J. W., and N. A. Griffith. Toxicity of Hg and Se to the
Eggs of Carp, Cyprinus Carpio. Trans. Amer. Fish Soc., 103:822-825,
1974.
161. Hess, L. W., R. L. Brown, and J. F. Heisinger. Mercury Contamination
of Birds from a Polluted Watershed. J. Wildlife Manage., 39:299-304,
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162. Doudoroff, P. Water Quality Requirements of Fishes and Effects of
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6-85
-------
SECTION 7
RADIOLOGICAL EMISSIONS FROM SCCP'S
The burning of conventional fuels can create several pollution problems.
The radiation hazard, however, is not commonly considered to be one of them,
and there are fewer papers in this area. Recently, because of continued
public interest in the environmental impact of nuclear power, comparisons
have been made between the radiological emissions from a nuclear plant and
a conventional coal power plant. The consensus of papers on this issue
reports that a conventional coal-fired facility is the greater radiological
polluter, (see Section 7.4). In fact, the radiological output of a lignite-
fired power plant exceeds allowable limits established for a comparable
nuclear facility (e.g., pressurized water or high temperature gas reactor).
The long-term radiological impact of such a power plant is unknown.
The addition to their pollution considerations, radioactive trace metals
have been involved with SCCP's in several other ways. Certain radioactive
isotopes have been used to follow specific elements through the fuel com-
bustion and gas cleaning and waste disposal processes. Neutron sources
have been used for instrumental neutron activation analysis (INAA) for trace
elements with detection in the gamma ray region. This is one of the more
reliable methods to measure trace element concentrations since no sample
preparation is required; see Section 8.3.5 for a complete discussion of
this technique. Also, different radioactive detection methods have been
used and compared. Finally, several papers address the specific environ-
mental and health effects of incinerated radiological wastes. Almost no
information was found on radioactivity associated with oil or gas combustion.
7-1
-------
7.1 CONCENTRATIONS IN FUELS
United States coals contain three principle radioactive species:
239U, 235U and 232Th, and their radioactive daughter products in (i.e.,
in the normal relative radioactive decay ratios) secular equilibrium. A
summary of a U.S. Geological Survey report (1) was made in a series of
similar articles of McBride et al. (2-4) and is reproduced in Table 7-1.
TABLE 7-1. KANGE Of DIABIOM AJTD THORIUM UIIICKHIXATIOHS AJID GE0METS1C HEADS (EXPECTED VALUES) FD»
COAL SAMPLES FROM VABIOOS RZCIONS OF IKE UNITED STATES* CN 15 THE HUMBER OF SAMPLES) .
Uranlua (ppa) Tborlua (ppp)
Region
Coal Rank
R
Range
Geo-
oettlc
¦un
fcanne
^ Geo-
metric
¦ean
Pennsylvania
Anthracite
S3
0.3-25.2
1.2
2.8-14.4
4.7
Applachlft
BlCuaiaoua
331
<0.2-10.5
1.0
2.2-47.6
2.8
Interior
Bituminous
143
0.2-43
1.4
< 3-79
1.6
Northern Great
Plains
Subbltiralnoup,
llgnlts
S3
<0.2-2.9
0.7
<2.0-8.0
2.4
Gulf
Lignite
34
0.5-16.7
2.4
<3.0-28.4
3.0
tacky fountain
Bituminous,
¦ubbltumlnou*
134
<0.2-23.8
0.8
<3.0-34.B
2.0
Alseka
Subbltimiooua
IB
0.4-5.2
1.0
<3.0-lB
3.1
SOURCE: (1)
They took 1 ppm of uranium and 2 ppm of thorium to be representative of U.S.
coals. Coles eit al_. (5) report similar levels of U and Th fron 15 western
(low-sulfur) coals; they also considered "
-------
Cooper and Dakik (6) report that the levels of U, Ra, Th, and other
radioactive isotopes in lignite appear to be significantly greater than for
Western coals. The concentrations of these elements is a function of the
geologic areas in which the coals are found, particularly their proximity
to uranium deposits. They report that the Conquista uranium mill in South
Texas roasts lignite to recover uranium. This lignite is believed to
run nearly 300 ppm. Moore (7) reports that a plant in North Dakota burns
lignite for the primary reason of extracing uranium from the ash residues.
Some work, focusing on other issues, has incidentally reported the con-
centration of radioactive elements. Tables 7-1 and 7-2 are representative
of the data reported elsewhere. Many elemental determination reports give
the concentrations of U and Th, but are not concerned with the level of
radioactivity present in the coal. Several other papers that do include
some discussion of the radiological aspects of coal are Lave (8), Martin
(9), Bedrosian (10), Goldman (11), and Van Hook (12). Styron (13, 14)
has also reported a radiation level from 210Pb, a 239U decay member, at
0.79 pCi/g for a certain western coal; he also discusses 210Po. Finally,
Krieger and Fishkorn at EPA (environmental Monitoring and Support Labora-
tory in Cincinnati) are studying the concentration of 226Ra in coal and
coal ash to determine the radiation hazard potential of coal burning.
No articles were found that discussed radioactive species in oil, gas,
wood, or municipal wastes.
7.2 EMISSION LEVELS
More attention and effort have been directed at measuring the levels
of emissions of radiological species than at source concentrations. Princi-
pally studies have looked at coal fly ash and bottom ash.
Coles et_ a^. (5) report a 5- to 10-fold increase in the radio
nuclide concentration in the fly ash over those given in Table 7-2 for the
source coal. They also reported concentrations by size, showing that
235U, 23SU, 226Ra, 229Ra, 210Pb, show increases in radiation levels with
decreasing particle size. Yet the most potent emitter was lf0K, ranging
7-3
-------
between 6 and 8 pCi/g, with 220Th, 226Ra, 22BRa, 21DPb, and 23BU all
emitting between 0.58 and 3.6 pCi/g.
McBride et. al. (3) modeled a 1000 MW coal-fired power plant burning
coal with 1 ppm U and 2 ppm Th. Their results are given in Curies per year
for airborne emission of each major decay chain: 230U chain, 8 x 10 3
Ci/yr; 235U chain, 3.5 x 10 k Ci/yr; 232Th chain, 5 x 10 3 Ci/yr. They
also report that radon, a short-lived decay products of Th, and U, accounts
for the majority of the airborne radiation released: 22 0Rn (1/2 life = 55
sec), 0.4 Ci/yr; 222Rn (1/2 life = 3.8 days), 0.8 Ci/yr. Lyon (15), in a
similar study, has developed data in agreement with McBride for U and Th
and, in general, supports McBride's data.
Cooper and Dakik (6) have compiled a table of radiation release rates
for the atmosphere from electrical power plants, including release rates
from nuclear plants; see Table 7-3. They show that radon (the noble gas
component) is the major, albeit short-lived, source of radiation emitted.
Also, the radon may escape during mining and grinding, so the exact point
of release is not always the same. The boiling water reactor in Table 7-3
is an old type reactor and is no longer being built . They also present
scenarios for radiation release in Texas based on various energy-mixes.
Lave and Freebrug (8) consider the most significant airborne element
from coal combustion to be radium; for example, 226Ra, 17.2 x 10 3 Ci/yr
and 2,L6Ra 10.8 x 10 3 Ci/yr for a 1000 MW plant. They also report values
for a 1000 MW oil burning plant: 226Ra, 0.15 x 10 3 Ci/yr and 22BRa,
0.35 x 10 3 Ci/yr. The Code of Federal Regulations (16) set the allowable
standard for ambient air at: 226Ra, 2 pCi/m3 and 22BRa 1 pCi/m3. In the
worst case for coal, this would necessitate only a ten-fold dilution of
emissions; oil plant emissions are below ambient levels.
Other articles have addressed various specific aspects of the coal-
generated radiological emissions problem. • Martin et^ al_. (9) have com-
pared radioactivity released from coal- and oil-fired steam plants (data
gathered by the Bureau of Radiological Health). Bedrosian e_t al. (10)
and Styron and Robinson (14) also have investigated some radioactive
7-4
-------
TABLE 7-3 RADIOACTIVE ISOTOPE RELEASES TO THE
ATMOSPHERE FROM ELECTRIC POWER PLANTS
Type of Plant
Radiation release Rate
-Curies/1,000 Mw(e)
-Year
Noble Gas
Components
Halogens and
Particulates
Average
Range
Average
Range
Nuclear Plant
Boiling Water Reactor
2,600
,000.0
180,000-9,300,
000 7.200
0.33-21.20
Pressurized Water
12
,000.0
40-60,000
1.300
0.00007-9.10
Reactor
High Temp. Gas Reactor
312.0
200-324
0.0018
0.0015-0.0020
Lignite Plant
69.0
0-475
2.000
0.050-326.00
Coal Plant
2.2
0-82
0.148
0.037-3314
Oil Plant
0.2
0-1
0.005
0.003-0.010
Gas Plant
116.0
1-232
0
0
SOURCE: 6
-------
materials emitted from coal-fired plants. Furr ejt al^. (14) have reported
the radioactivity levels in certain fly ashes while studying the uptake
of trace metals by plants grown on fly ash-soil mixtures. Of course, many
studies report elemental concentrations of U and Th without reference to their
radioactivity. Such data were reported in Sections 3 and 5 of this report.
Finally, several studies have looked at emissions from incinerators
that burn radiologically contaminated wastes. Forster (17) summarizes
practices used at three plutonium-contaminated-waste facilities. He also
reports that a survey of manufacturers revealed that no commercial incinera-
tor is designed specifically for this use. Lachapelle (18) has reported
work on a 50 lb/hr incinerator and associated gas-cleaning equipment as a
means to concentrate low-level radioactive wastes. Optimum conditions
have been achieved and atmospheric discharges were always below emission
limits. Radiologically contaminated animals were also test incinerated.
Finally, Krieger and Frishkorn at EPA in Cincinnati have developed and
tested a methodology to quantify discharges from nuclear medicine facilities.
This included radio-pharmaceuticals not removed by tertiary sewage treat-
ment that subsequently wind up in power plant coolant waters. However,
their work has not yet been published.
7.3 HEALTH AND ENVIRONMENTAL EFFECTS
The majority of articles concerning radiation and combustion ultimate-
ly address the ecological or health impact of the process under study.
McBride al_. (3) most recently have combined empirical data and modeling
to assess the impact on human health from a hypothetical 1000 MW mid-
western coal-fired power plant. Radium turns out to be the major source of
whole-body radiation, with ingestion being the main exposure pathway; in-
halation is the second major exposure pathway. Whole-body population ex-
posures (^20 man-rem/yr) do not exceed regulations (19) except for bone
dose ("-200 man-rem/yr) nearby the plant. The U.S. average annual dose
from nautral sources is 130 man-rem/year. The conclusion is that the
health effects are very slight (0.002 to 0.005 health effects per year of
operation per million people) , and the health effects from other emissions
(particulates, N0X, SO^) would be many times more significant.
7-6
-------
Cooper and Dakik (6) also discuss the potential health effects of radia-
tion from coal-fired power plants. They assumed a worst case dosage based
on a hypothetical person standing 500 meters downwind from a 1000 MW
power plant for an entire year. They included inhalation and ingestion of
water and sediments from rainfall and settling. Different types of coals
were also considered, and Table 7-4 summarizes their results. Also see Table
7-5 for regulation levels. They conclude that the whole body dosage due to
national average coal-fired power plants is within (about 75%) the most
stringent NRC (Nuclear Regulatory Commission) guidelines, and only the bone
marrow NRC limit is exceeded; however, worst case lignite would require 99.5
to 99.8% removal efficiencies to achieve compliance.
Martin et^ a!l, (9) have taken fly ash data generated by the Bureau
of Radiological Health on oil- and coal-fired steam stations and compared them
in tabular form with limits recommended by the Inaternational Commis-
sion on Radiological Protection (ICRP) . Moore e_t al_. (21) have looked at
sources of 21 °Po in the atmosphere. They concluded that the major sources
are dust, plant exudates and phosphate fertilizer production. They judged
SCCP's to be minor contributors,
Bedrosian _et al. (10) have made a radiological survey around fossil
fuel plants (principally coal). Their primary focus was on air sampling
techniques, especially those remote to the facility. But they were con-
cerned with estimation of critical dosage to organs, particularly the lungs.
Furr et al. (17) studied the uptake of many trace metals, including
radioactive species, by cabbages grown in soil-fly ash mixtures. Goldman
(11) has studied the impact of radioactivity in fly ash and concludes that
it is important enough to be factored into a total assessment of coal
combustion environmental impact.
Isom, Gooch and Neill (at TVA, Division of Environmental Planning,
Water Quality and Ecology Branch in Sheffield, Alabama) are studying the
impact of aquatic trace metals, including radiological species, released
to the environment by energy generating systems (coal and nuclear). Speci-
fically, they are looking at the bio-accumulation in the tissues and fluids
of mollusks and other aquatic animals.
7-7
-------
TABLE 7-4 MAXIMUM INDIVIDUAL RADIATION DOSE COMMITMENT LEVELS FROM TYPICAL
1,000 MEGAWATT COAL AND NUCLEAR POWER PLANTS.0,b
Eastern0 Wstern0 National0 South0 Pressurized^ Boiling1' 10 CFR 50
Organ
Bituminous
Coal
Subbltuinlnous
Coal
Average
Coal
Texas
Lignite
Water
Reactor
Water
Reactor
0
Appendix 1
Design Guides
Whole Body
1.7
2.4
3.7
5.1
1.8
4.6
5.0
Bone
16.6
' 23.4
36.4
49.8
2.7
5.9
15.0
Lung
1.7
2.5
3.9
5.4
1.2
4.0
15.0
Thyroid
1.7
2.4
3.7
5.1
3.8
36.9
15.0
Kidneys
3.0
4.0
6.7
9.2
1.3
3.4
15.0
Liver
2.1
3.0
4.7
6.4
1.3
3.7
15.0
Spleen
2.6
3.5
5.4
7.4
1.1
3.7
15.0
Notes: a. All dosage values are reported In mllllrems per year to a person located 500 meters down-
wind of the plant.
b. All dosage levels are based on calculations and data from Oak Ridge National Laboratory.(20)
c. Particulate removal efficiencies are 99.0Z for all coal-fired power plants.
d. Particulate removal efficiencies are 99.99Z + (DF-10.000+) for all nuclear power plants.
e. (19)
SOURCE: 6
-------
TABLE 7-5 REGULATIONS FOR LIMITING RADIATION DOSE COMMITMENTS
TO INDIVIDUAL ORGANS BY THE U.S. NUCLEAR REGULATORY
COMMISSION (20).
Allowable Radiation Dose Commitment-mrem/year^
Organ 10 CFR 20* 40 CFR 190 10 CFR 50(AI)"
Whole Body
500
25
5
Bone
500
25
15
Lung
1,500
25
15
Thyroid
1,500
75
15
Kidneys
1,500
25
15
Liver
1,500
25
15
Spleen
1,500
25
15
Gonads
500
25
15
Notes: a. Currently in effect. (16)
b. To become effective December 1, 1979. (26)
c. For halogens and particulates. (19).
d. Millirems per year of radiation dose.
-------
Morris (22) has done a modeling study to compare the risk of popu-
lation exposure from a coal burning and a nuclear power plant. All of hi3
input data are theoretical and the results predict changes in mortality
in the vicinity of such plants. Braunstein e_t _al_. (23) have published
several documents for ER£)A on the subject of radiological impact. In one
report, the environmental pathways critical to exposure are considered for
^C, 3H, radio-iodine, transuranics and certain other materials. They also
published a bibliography entitled "Geochemical Aspects of the Behavior of
Uranium and Thorium in the Environment," an in-house ORNL publication.
Styron and Robinson (14) have undertaken research on four topics;
(1) to delineate the scope of potential environmental and human health
problems associated with radioactivity in Western coals; (2) to establish
a data base for 23SU, 2:oPb, 210Po, 2 3 3Th and 2Z6Ra in Western
coals; (3) to assess the release, fate and accumulation of radionuclides
from a western coal-fired power plant; and (4) to assess the need for addi-
tional controls. They focus particularly on 2I0Pb and found only slight
increases, with dosages still below current standards.
van Hook (12) has published a summary of the current (19 78) under-
standing of the health and environmental effects of trace elements including
radionuclides from all aspects of the coal industry. Synergistic and anta-
gonistic effects among trace contaminants are discussed. Future scenario;;
are considered. Finally, Cohen (24) has written an article which claims
that fears of radiological hazards are overstated and the other pollutant.;
from a coal-fired power plant are of much greater concern.
7.4 COMPARISON OF COAL AND NUCLEAR POWER
Several of the previously-cited articles ultimately compare the radio-
logical impact of coal and nuclear power plants. The consensus of these
authors is that the atmospheric emissions from a coal-fired facility are
from two to ten tines worse than from a nuclear power plant. There is also
general agreement that the other pollutants from coal combustion are of much
more concern than the radioactivity released. Specifically, these citations
7-10
-------
are (2, 9, 22, 23, 24). McBride e_t _al_. (3) specifically caution that all
aspects of the coal and nuclear power generation, from mining to disposal,
should be factored into any comparison of the two industries. A very compre-
hensive survey of the health effects of electrical generation is reported
by Lave and Freeburg (8). Although they do not consider radiological emis-
sions from SCCP's, the article directly compares health effects of coal,
oil and nuclear electrical generation from beginning (mining) to end (emis-
sions) as recommended by McBride et_ al.
7.5 REGULATIONS AND AMBIENT LEVELS
At the present time, there are no standards limiting radiation re-
leases or radioactive isotope emissions from fossil fuel power plants.
Nor are there any anibient air quality standards for radiation levels and
radioactive isotope concentrations from fossil fuel facilities. There
may be some type of standards set forth soon under the provisions of the
recently promulgated Federal Clean Air Act Amendments (25).
The nuclear power industry does have standards, and fossil fuel power
plant emissions are often compared to them, usually based on an equal amount
of power generated. The nuclear release rates (19) are analogous to the
Federal NSPS (New Source Performance Standards) administered by the EPA.
Ambient radiation standards are administered by the NRC, which limit down-
wind exposure levels for different types of radiation (alpha, beta, gamma);
these are analogous to the AAQS (Federal Ambient Air Quality Standards).
The total radiation levels in ambient air are difficult to determine
since individual isotopes must be specified; however, total beta radia-
tion, the dominant form from uranium and thorium decay processes, is often
taken as representative of radiation levels in the atmosphere due to its
ease of collection and measurement. Fossil fuel power plants are well
below the permissible values established by the AEC. For example, the
standard for total or gross beta radiation levels was set at 100 pCi/m3;
Cooper and Dakik (6) report levels in Texas range from 0.05 to 0.40 (average
0.08) pCi/m3.
7-11
-------
Regulations limiting radiation releases in terms of dose commitments
have also been set forth by the NRC (16, 19). New standards took ef-
fect December 1, 1979 (26). These include whole body and specific organ
dosages; (see Table 7-5).
The quantity of particulates released influences the total radiation
release. The current NSPS of 0.10 lbs/MBtu would result in a lung dosage
of 4 mrem/yr for national average coal (6), below the NRC standard (Table
7-5). However, reduction to the proposed standard of 0.05 lb/MBtu would
still not achieve compliance for bone dosage.
7.6 MISCELLANEOUS TOPICS
7.6.1 Speciation and Partitioning
The major topic of the Coles et^ a^L. paper (5) is to study the chemi-
cal form and elemental partitioning of the rationuclides during coal com-
bustion. Precipitator fly ash and bottom ash show no enrichment of
5 a j
Th and its decay-chain products. Thorium and radium do show a slight
size preference in fly ash. Generally, uranium shows depletion in fly as"i
and bottom ash and a preference for snail particles. 226Ra is more associa-
ted with the smaller size fly ash particles. 21t!Pb is depleted in all
ashes and shows a marked preference for small particles.
7.6.2 Atmospheric Radiation
Chamberlain (27) discusses several aspects of radioactive aerosols
and vapors. While SCCP emissions are not dealt with specifically, emperical
data and mathematical modeling are used to study the behavior of aerosols
associated with radiological species. Aerosols from combustion products
are included. Minor (28) has published a comprehensive report on many
aspects of radiological air pollution. Indirectly, many topics relating
to SCCP emissions are treated.
7.7 RESEARCH NEEDS
The general consensus of researchers in this field agrees that the
radiation from a coal burning SCCP's, while about equal to or greater than
from a comparable (in power) nuclear facility, is still not large; how-
7-12
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ever, any radiation emitted into the environment is a concern, and the total
amount produced by a 1000 MW coal-fired power plant is considerable. But
most of the radiation is contained in the massive amount of ash and is
well dispersed and believed to be of minor environmental concern.
Most researchers also agree that less than 10 1 Ci/yr are emitted from
a typical 1000 MW plant, although there is some difference of opinion as
to the major contributing species. While more research on the species
emitted and their subsequent involvement in the flora and fauna of the
immediate area would be useful, the radiation problem does not appear to be
dire. An area of possible concern would be the bone dosage from an SCCP,
particularly one burning lignite.
The long-term effects, particularly through food sources grown near
the plant, may be the most urgent concern in need of more research. Also,
monitoring of radiation levels in all phases of coal combustion should be
continued to insure that the current levels of emission do not increase.
No radiation research was found on non-fossil fuel types of SCCP emissions
but, justifiably, no hazard is anticipated from these fuel sources (wood
and refuse).
7-13
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REFERENCES
1. Swanson, V. E., J. H. Medlin, J. R. Hatch, S. L. Coleman, G. H. Wood,
Jr., S. D. Woodruff, and R. T. Hildebrand. Collection, Analysis, and
Evaluation of Coal Samples in 1975. U.S. Department of the Interior,
Geological Survey, 1976.
2. McBride, J. P., R. E. Moore, J. P. Witherspoon, and R. E. Blanco.
Radiological Impact of Airborne Effluents of Coal-Fired and Nuclear
Power Plants. ORNL-5315, Oak Ridge National Laboratory, Oak Ridge,
Tennessee, 1977. 43pp.
3. McBride, J. P., R. E. Moore, J. P. Witherspoon, and R. E. Blanco.
Radiological Impact of Airborne Effluents of Coal and Nuclear Plants.
Science, 202:1045, 1978.
4. McBride, J. P. Radiological Impact of Airborne Effluents of Coal-
Fired and Nuclear Power Plants. In : Trace Contaminants from Coal,
S. Torrev, ed., Noyes Data Corporation, Park Ridge, New Jersey, 197£.
pp.121-142
5. Coles, D. G., R. C. Ragaini, and J. M. Ondov. Behavior of the Natural
Radionuclides in Western Coal-Fired Power Plants. Am. Chem. Soc.
Div. Fuel. Chem. Prepr., 22(4):156-161, 1977.
6. Cooper, B. H. Jr., and G. A. Dakik. Releases of Radioactive Isotopes
from Coal and Lignite Combustion, Appendix D. In: Potential for In-
creased Coal Utilization in the State of Texas, University of Texas,
Austin, Texas, 1978. pp.1-31.
7. Moore, G. W. Extraction of Uranium from Aqueous Solution by Coal and
Other Materials. Economic Geology Bulletin No. 49, University of
North Dakota, Grand Forks, North Dakota, 1954. p.652.
8. Lave, L. B., and L. C. Freeburg. Health Effects of Electricity Gener-
ation from Coal, Oil, and Nuclear Fuel. Nucl. Saf., 14(5):409-428,
1973.
9. Martin, J. E., E. D. Howard, D. T. Oakley, J. M. Smith, and P. H.
Bedrosian. Radioactivity from Fossil-Fuel and Nuclear Power Plants.
In: Energy and Humane Welfare: The Social Costs of Power Produc-
tion, Volume 1, B. Commoner and H. Boksenbaum, eds. Macmillian
Information, New York, 1975. pp.103-118.
7-14
-------
10. Bedrosian, P. H., D. G. Easterly, and S. L. Cummings. Radiological
Survey Around Power Plants Using Fossil Fuel. EERL-71-3, PB 202 414,
Eastern Environmental Radiation Laboratory, Montgomery, Alabama,
1970. 27pp.
11. Goldman, M. Impacts of Heavy Metals and Radioactivity from Coal
Combustion. UCD--472-124, Unversity of California, Davis,
California, 1977.
12. Van Hook, R. I. Potential Health and Environmental Effects of Trace
Elements and Radionuclides From Increased Coal Utilization.
0RN1—5367, Oak Ridge, National Lab., Oak Ridge, Tennessee, 1978.
13. Stryon, C. E. Preliminary Assessment of the Impact of Radionuclides
in Western Coal on Health and Environment. CONF-780109-1. Presented
at Technology for Energy Conservation, U.S. Department of Energy,
Albuquerque, New Mexico, 1978. 6pp.
14. Styron, C. E., and B. Robinson. Preliminary Radiological Impact
Assessment of Western Coal Utilization. In: Joint Conference on
Sensing of Environmental Pollutants. American Chemical Society,
Kew Orleans, Louisiana, 1977. pp.336-338.
15. Lyon, W. S. Nuclear Methods in Coal Combustion Research.
CONT-771072-2. Presented at the International Conference on Nuclear
Methods in Environmental and Energy Research, Columbia, Missouri,
1977. 9pp.
16. U.S. Nuclear Regulatory Commission. Concentrations in Air and Water
Above Natural Background. Code of Federal Regulations, File 10, Part
20, Appendix B, Revised, 1978. pp.202-211.
17. Furr, A. K., T. F. Parkinson, R. A. Hinrichs, D. R. van Campen, C. A.
Bache, W. H. Gutenmann, and L. E. St. John. National Survey of Ele-
ments and Radioactivity in Flyashes: Absorption of Elements by
Cabbage Grown in Flyash-Soil Mixtures. Environ. Sci. Technol.,
11(133 :1194, 1977.
18. Lachapelle, D. G. An Engineering Evaluation of a Radioactive-Waste
Incinerator. C0NT-660904, In: Proceedings of the 9th Air Cleaning
Conference, Atomic Energy Commission, Boston, Massachusetts, 1966,
Volume I. pp.509-569.
19. U.S. Nuclear Regular Commission. Numerical Guides for Design Objec-
tives and Limiting Conditions for Operation to Meet the Criterion "As
Low as Practicable" for Radiactive Material in Light-Water Cooled
Nuclear Power Reactor Effluents. Code of Fedearl Regulations, Title
10, Part 50, Appendix I, revised, 1978. pp.369-373.
7-15
-------
20. Oak Ridge National Laboratory. Air Surveillance Network, September
1973. Radiation Data Reports, 15(l):22-25, 1975.
21. Moore, H. E., E. A. Martell, and S. E. Poet. Sources of Polonium-210
in Atmosphere. Environ. Sci. Technol., 10(6):586-591, 1976.
22. Morris, S. C. Comparative Effects of Coal and Nuclear Fuel on Mor-
tality. In: Proceedings of the Statistical Computing Section,
American Statistical Association, Chicago, Illinois, 1977. 7pp.
23. Braunstein, H. M., E. D. Copenhauer, and H. A. Pfudener. Environ-
mental, Health and Control Aspects of Coal Conversion: An Information
Overview, 2 Volumes. OENL/EIS-95, Oak Ridge National Laboratory, Oaii
Ridge, Tennessee, 1977. 1348 pp.
24. Cohen, B. L. Learning to Live with Radiation. Sci. Dig., 77(4):61,
1975.
25. Clean Air Act Amendments of 1977. Public Law 95-95, United States
Congress, Washington, D.C., August 7, 1977.
26. U.S. Environmental Protection Agency. Environmental Radiation Pro-
tection Standards for Nuclear Power Operations. In: 40 Code of
Federal Regulations Part 190 revised. G.P.O., Washington, D.C.,
1978.
27. Chamberlain, A. C. Radioactive Aerosols and Vapours. Contemp. Phys.,
8(6):561-581, 1967.
28. Miner, S. Air Pollution Aspects of Radioactive Substances.
PH-22-68-25, PB-188 092, Litton Systems, Inc., Bethesda, Maryland,
1696. 159pp.
7-16
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SECTION 8
ACCURACY OF DATA AND ANALYTICAL TECHNIQUES
In order to understand the quality of trace metal measurements over the
last 25 years, it is necessary to chronologically look at the development
of sampling and analytical technology. Many research teams have contributed
to the database since the 1950's using various sample preparation and
analytical techniques. Care must be exercised in the comparison of the
results of these efforts since different sampling, sample preparation, and
analytical techniques have been used. Also, advances made in these areas
have resulted in some of the more recent studies producing more accurate
results.
In the middle to late 1960's, the most prevalent method for measuring
trace element concentrations of coal, fly ash, and collected particulates
was by atomic absorption spectroscopy. Before the sample could be analyzed,
it was necessary to "prep" the sample for analysis. These preparation steps
could include sample fusion or ashing, followed by liquid extraction sequen-
ces or digestion. The elemental concentrations sought by researchers could
only be determined one element at a time. The element also had to be
solvated in some liquid before it could be subjected to atomic absorption
techniques. A commercial standard was manually prepared separately for
each element, and used to calibrate the atomic absorption instrument before
and after the samples were analyzed.
In the early 1970's computer technology made what appeared to be an
unrelated contribution. Large core memory, high speed, second generation
computers became more affordable to universities and large research centers.
It was possible to write programs that allowed the millions upon millions
of calculations required to translate the raw output data from X-ray
8-1
-------
diffraction (XRD), X-ray fluorescence (XRF), or instrumental neutron
activation analysis (INAA) directly into trace element concentration levels
in the sample. The major problem up to that time had been the accurate
correction of matrix interferences of the multiple elements present in the
sample. The advent of large capacity, high speed computers made such
calculations possible.
The distinct advantage of INAA and XRT was that no sample preparation
step was required before analysis, and all elements were analyzed for sinulta-
neously. The data obtained from these analyses often did not agree with
analysis of the same sample analyzed by atomic absorption or optical emission
spectroscopy. In the early 1970's programs involving round robin analyses
of the same samples were conducted by several research teams to resolve
the differences in analytical values (see Section 8.3 for detailed results).
As a result of these programs the following criteria were identified
for evaluating the accuracy of trace metal data:
• when (historically) were the results reported,
• by what analytical technique were the trace element
values determined,
• how accurate, in general, is the analytical method employed,
• what type of standards were used to compare reported
values in the study, and
• what types of internal quality assurance steps were employed
in the entire research program.
Only with the answers to these five questions can the accuracy of the
reported data be adequately assessed.
8.1 TYPES OF TRACE ELEMENT SAMPLING
8.1.1 Trace Element Sampling in Air
Air sampling for trace elements falls into two major categories,
sampling emissions from stack gases and ambient air sampling. A large mimber
of studies have looked at stack emissions from SCCP's, for example (1-16),
and see Section 5. All of these studies use a variety of analytical techni-
ques to obtain trace element concentrations. One study (10) used Laser-iaman
8-2
-------
spectroscopy to look at fly ash particles collected from coal- and oil-
fired power plants.
Several studies looked at ambient air concentrations in the vicinity
of SCCP's under evaluation (11,13). In addition, a number of ambient air
studies are discussed in Section 2.0 of the report.
8.1.2 Trace Element Sampling of Water
Methods of sampling water for trace elements is outlined in the manual
of Methods for Chemical Analysis of Water and Waste (17). The method out-
lined recommends atomic absorption spectroscopy of analysis. Other methods
that have been used to determine trace element concentrations in water
include spark source mass spectroscopy (18) and argon plasma emission sources
(19).
8.1.3 Trace Element Sampling of Soil
Soil sampling for trace elements requires some definition of what is
soil. If soil is considered as the upper layer of earth that may be dug
or plowed and in which plants grow, then few studies exist that have dealt
with this sampling. There has been a study done on plants and soils near
the Mohave generating station in southern Nevada (11). The other study was
a mass balance of trace elements in Walker Branch Watershed that included
some soil samples (13). One reason for the lack of such studies is given in
a panel discussion on the effects of trace contaminants from coal combustion
systems ERDA 77-64 (20) as follows.
The transport of trace elements within the soil hinges on water
movement and chemical reactions within the soil profile. The use of available
techniques for predicting and monitoring movements of soil water in the
vicinity of coal burning power plants depends upon accurate field determina-
tions of horizontal gradients in the water table and hydraulic conductivity
at the sites in question. Laboratory studies of soil columns, since they
do not represent field conditions, are of uncertain quality, but remain
the most practical method of study (20).
8-3
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8.2 ANALYTICAL TECHNIQUES USED IN TRACE ELEMENT ANALYSIS
8.2.1 Atomic Absorption Spectrophotometry
Atomic absorption spectrophotometry (AAS) can be used in determining
trace elements in a nonviscous solution. Conventional atomic spectroscopy
can be used to determine Li, Be, V, Cr, Mn, Co, Ni, Cu, Zn, Ag, Cd, and
Pb, after dry ashing and acid dissolution (21). A graphite furnace accessory
can be used for flameless AAS determination of Bi, Se, Sn, Te, Be, Pb, As.,
Cd, Cr, Sb, and Ge (21).
Before a solid can be quantitatively introduced into an atomic absorp-
tion spectrometer, it must be in the form of a solution, usually in water.
Depending upon the type of material, strong acids, bases and oxidizing
agents can be used. Acidic digestion is most common for coal, ash and
aerosols. This wet chemical procedure, although reasonably well standardized,
is comparatively slow and subject to error. For example, loss of volatile
elements and incomplete dissolution are the more frequent sources of error.
In atomic absorption spectroscopy, the sample in solution is atomized
by a flame or other energy source producing the atomic vapor of the element
being analyzed. Monochromatic light which has the same wavelength as that
of the element of interest is then passed through the sample vapor. The
atoms present in the ground (unexcited) state of the vapor absorb radiation
from the monochromatic light source in proportion to their concentration
present in the sample chamber (20,22).
Types of problems encountered in using atomic absorption spectroscopy
for coal and ash samples include interelement or chemical interferences,
matrix effects (which stem from the large concentrations of acids and solids
in solution), and molecular absorptions (which predominantly occur from
species such as strontium oxide (SrO) or calcium hydroxide (Ca[0H]2) thai:
result in a positive error in the absorption measurements) (23). Flameluss
atomic absorption spectroscopy achieves better sensitivity for some elements
than does atomic absorption spectroscopy, and they compliment one another
when used in tandem. Information on the background is necessary in addition
to separation and preconcentration of the sample; therefore, a standard in
8-4
-------
the same concentration range is usually run before and after the samples.
8.2.2 Optical Emission Spectroscopy
Optical emission spectroscopy (OES) involves excitation of the sample
in a spark or arc to produce a fluorescent line spectra of the elements
present (24), Once again, digestion of solid samples is required prior to
injection. Use of preconcentration techniques and/or a standard is required
to obtain sensitivity comparable to that of other techniques such as instru-
mental neutron activation analysis or spark source mass spectroscopy/iosotope
dilution. Nowadays, direct reading photoelectric spectrophotometers for
OES offer both faster analyses and somewhat greater precision than does
the use of photographic plates. Ruch _et_ al_. (25) achieved precision of
+10% for nine elements using direct reading detection and precision from 9%
to 30% for the same samples using photographic detection (26).
8.2.3 Selective Ion Electrodes
Selective ion electrode use in trace elements analysis has been rather
limited. Polarography and fluoride-ion selective electrode are methods
which normally require special preparation for analysis of individual elements.
Polarography is not used extensively for trace element analysis in coal or
fly ash, although its sensitivity for some elements (for example, cadmium)
makes it useful for trace analysis after interfering ions have been separated.
Trace fluoride determinations are commonly made by fluoride-ion selective
potentiometry (25).
8.2.4 Spark Source Mass Spectroscopy
Spark source mass spectroscopy (SSMS) is another analytical method
used in trace element analysis. In this method, the sample compounded in a
silver or graphite electrode, is ionized with a high intensity spark. A
determination is then made by monitoring the intensities of the ions of
different mass-to-charge ratios; different radial paths are defined in a
magnetic field, and therefore, come to a focus at varying points along a
photographic plate positioned on the focal plane of the magnetic analyzer.
Other modes of detecting individual isotopes include scanning of the ion
8-5
-------
species at a collector slit located at the principal focus or use of electric
static peak switching with static integration (18).
The method of spark-source mass spectrometry has several advantages,
including high sensitivity, comprehensive element coverage, and linearity.
Determinations may be made for many elements at concentrations as low as 1
ppb; also semiquantitative determinations as low as 100 ppb for some elemants
can be performed by electrical scanning. This technique allows detection of
all elements simultaneously during an electrical scan, (including interstitial
gases), with minimal spectral overlap, matrix, or inter-element effects.
Also, this method exhibits linear response for ionic species of any element
with the ion intensity being proportional to the concentration of that
element in the sample (18).
Although detection limits SSMS for most elements in coal and fly
ash are in the parts-per-billion range, accuracy may be only +50%,
varying with the concentration of interferents, as well as with data inter-
pretation. Accuracy may be improved with the use of standards or with the
use of stable isotope dilution (SSMS-ID). For elements having stable
isotopes, the accuracy of this method is restricted only by the percent
homogeneity of photographic emulsion on which ion intensity is recorded.
Without isotope dilution, the technique is considered to be only semi-
quantitative.
In one study by Carter et al. (27), isotope dilution by spark source
mass spectrometry and by thermal emission mass spectroscopy were used to
determine composition of coal, fly ash, gasoline, and fuel oil. The
average imbalance for the lower volatility elements measured by isotope
dilution mass spectrometry showed a precision range from -8% to +12% (28).
8-6
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8.2.5 X-Ray Fluorescence
X-ray Fluorescence (XRF) involves production of characteristic fluo-
rescence spectra by irradiation of the sample directly with X-rays. For
the analysis of air pollution particulates Birks (28, 29) cites the following
advantages for this method: no sample preparation is required for filter
collections, elements of atomic number 11 and greater can be analyzed with
fairly uniform detectability, the technique is nondestructive, and
several elements can be determined at one time with available commercial
equipment at fairly low cost, Although this method does not have the sub-
microgran sensitivities obtainable by instrumental neutron activation analysis
or spark source mass spectrometry/isotope dilution, its detection limits may
be improved by using preconcentration techniques or standard reference
materials. Natusch et al^ (31) showed that the use of X-ray fluorescence
in conjunction with other analytical techniques is a useful tool for
characterization of trace elements in fly ash.
8.2.6 Instrumental Neutron Activation Analysis
Instrumental neutron activation analysis (INAA) is a nondestructive
method of analysis. In this method, the sample is irradiated in a nuclear
reactor directly, without chemical dissolution or extraction. When
bombarded with slow neutrons, many elements give rise to radioactive
isotopes. When the other components of the sample do not interfere, it
is possible to identify the elements present and their concentrations from
measurement of intensities of different radiation peaks emitted in the gamma
ray spectrum. This method offers high sensitivity and the capability for
multi-element determinations (26).
The Oak Ridge National Laboratory study at the Tennessee Valley
Authority's Allen Steam Plant reported results by INAA with accuracies of
5 to 10% for submicrogram quantities (14). Garden reported accuracies of
2 to 3% in trace element studies at the Chalk Point Station using this
method (31), and Ondov et_ al_. (32) have attained accuracies in the same range.
In a recent study, four laboratories measured the concentrations of
37 elements in National Bureau of Standards standard coal samples (SRM 1632)
8-7
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and 41 elements in the standard reference for fly ash (SRM 1633), using
instrumental neutron activation analysis. Their conclusions were as
follows:
"In some cases where comparisons can be made, both the accuracy
and interlaboratory dispersion of results obtained in the analysis
of coal and fly ash by nuclear methods are generally superior to
other methods used in the round robin study. We suspect that the
major reason for this performance of the technique is the fact
that virtually no pretreatment of the samples is needed. Thus,
we avoid the difficulties encountered in dissolving samples that
can occur with the use of other methods such as AAS: loss of
volatile species, incomplete dissolution of certain fractions,
loss of elements on insoluble residues or container walls, and
contamination of samples by impurities in reagents or container
materials. Also, because of the long ranges of projectiles and
emitted X-rays, the nuclear methods are almost completely free
of matrix effects" (32).
For a few elements, the sensitivity of neutron activation can be much
improved by radiochemical separations to remove those elements that have
interfering radioactivities. Although these separations allow more oppor-
tunity for sample contamination, and are slower, it is possible to obtain
high precision and accuracy. Radiochemical separations on low-temperature
coal ash samples to determine As, Se, Zn, Cd, and Ga were carried out by
Ruch et al. (25). However, there are cases in which INAA gives a completely
false measurement due to the synthesis of elements in nuclear bombardment.
For example, National Bureau of Standards studies on strontium in granite
represent one such case (22).
8.3 EVALUATION OF VARIOUS ANALYTICAL TECHNIQUES
It is important to realize that data from studies using different
methods for analysis are not strictly comparable because of differences
in performance capabilities of various analytical methods used by different
researchers. To make the evaluation of results from different studies
more feasible, several investigations have been made to compare the
analytical performances of several methods on the same sample (24, 33-36).
In 1973, von Lehmden ej: a^. (24) undertook the comparison of six
analytical methods. In this study, nine laboratories were asked to determine
8-8
-------
the concentration of 28 elements in the same coal and ash samples. The
analytical methods employed were neutron activation analysis, atomic absorp-
tion, optical spectrometry and X-ray fluorescence. The determinations from
the different laboratories were evaluated to assess the comparability of
the various methods as applied to these matrices. Table 8-1 shows the results
for the coal samples, and the ash results are given in Table 8-2. Only
definitive concentrations were used for these conclusions (i.e., no "less-
than" values were considered). The following conclusions may be drawn
from this study:
• For at least eight trace elements in coal and ash, reported
concentrations varied by more than one order of magnitude.
For coal, these elements included Mn, Sb, Se, F, Li, Sn,
K, and Ba. For ash, these elements were As, V, Zn, Se, Li,
Ag, Sn, Na and Mag.
• Reported concentrations for three elements (Se, Li, and Sn)
varied by more than an order of magnitude in both coal and
ash matrices.
• Agreement was within an order of magnitude in both
matrices for only 9 of the 28 elements. These nine
were Si, Ca, S, Sr, Fe, Cr, Ni, Be and B.
• Standard samples must be prepared and standard methods of
analysis must be developed for a range of coal and ash
materials.
While this study is old by today's standard, the accuracy of these analytical
techniques have improved only slightly, and the results are presumably
still valid.
In an effort to resolve the analytical problems, the National Bureau
of Standards (NBS), in cooperation with the Environmental Protection Agency,
prepared Standard Reference Material (SRM) samples for coal (SRM #1632)
and ash (SRM #1633). Portions of these samples were sent to 85 laboratories
for analysis. "For many of the elements measured, there were surprisingly
wide variations of concentrations reported by the participating laboratories,
far outside the uncertainties usually quoted for the techniques used. For
this reason, it is clear that the standards are badly needed so that
laboratories can check their procedures for the elements they claim to be
able to measure." (32) Thus, one must still be cautious when comparing results
8-9
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TABLE 8-1. COAL ANALYSIS FOR TRACE ELEMENTS-COMPARISON OF METHODS
Laboratory Code
1 3 613 2345 33
Analytical Method
Flements SSMS* SSMS* SSMS* OES** OES** NAA*** NAA*** NAA*** NAA*** NAA*** AAS
Analyzed ppm (by weight)
Hg
< 2
< 2
< 0.10
NA
NA
< 0.
2
NA
< 0.02
0.
.03
NA
0.051+
Be
0.
4
NA
0.4
< 1
< 0.1
NA
NA
NA
NA
NA
NA
Cd
6
< 1
0.7
<30
<10
NA
< 3
< 40
NA
NA
NA
An
2
2
0.25
<100
<50
< 1
1.
.4
1.6
NA
< 1
NA
V
10
NA
7.7
10
10
7.
0
5.
,5
7
NA
6.
0
NA
Mn
20
3
1.9
10
20
7.
6
4.
.8
6.7
NA
5.
.0
NA
Ni
<'i0
4
6.0
<10
<20
NA
NA
< 20
NA
NA
NA
Sb
0.
6
NA
0.04
<10
<'0
0.
14
0.
,2
0.4
NA
NA
NA
Cr
<30
7
12
<10
<30
3.
4
5.
0
4.8
NA
NA
NA
7.n
<100
5
6.6
<100
<50
NA
NA
<100
NA
NA
NA
Cu
10
9
4.5
10
10
NA
NA
< 0.4
NA
NA
NA
Pb
< 4
4
1.8
<30
<10
NA
NA
NA
NA
NA
NA
Se
<15
< 8
0.1
NA
NA
1.
0
5.
0
2.0
1.
5
NA
NA
B
15
5
14
10
7
NA
NA
NA
NA
NA
NA
F
< 2
4
60
NA
NA
NA
NA
NA
NA
NA
NA
LI
0.
3
NA
. 2.8
<300
10
NA
NA
NA
NA
NA
NA
Ag
< 2
NA
< 0.1
< 1
< 1
NA
NA
< 2
NA
NA
NA
Sn
3
NA
0.19
<30
<10
NA
NA
NA
NA
NA
NA
Fe
2000
2000
1800
2000
3000
2400
2 700
3140
NA
8000
NA
Sr
100
50
46
<30
NA
160
NA
120
NA
80
NA
Na
600
100
660
300
500
800
870
840
NA
800
NA
K
100
50
200
150
20
NA
2200
280
NA
100
NA
Ca
10000
10000
5B00
8000
10000
NA
5500
7070
NA
NA
NA
SI
6000
10000
10000
3000
20000
NA
NA
NA
NA
NA
NA
Mg
2000
700
2000
600
100
2600
NA
920
NA
1000
NA
Ba
400
30
110
500
200
NA
220
430
NA
< 2.
0
NA
^Analysis on sample direct. *'DC arc on sample direct. ***lnstrumental NAA. +DlssolutIon followed by flaneslcss Ass.
Note: NAA, neutron activation analysis; SSMS, spark source mass spectrometry; OES, optical emission spectrometry; AAS,
atomic absorption spectrometry; and NA, no analysis.
SOURCE: (24)
-------
TABLE 8-2. FLY ASH ANALYSIS FOR TRACE ELEMENTS-COMPARISON OF METHODS
Laboratory code ' h * h ' h ^ h 1 d 1 H ' d 9 o ^ f ' f ^ f ®f '
Annlyt lcnl method SSMS SSMS SSMS SSMS OES OESC' OF.S DRES° DRES NAA NAA NAA NAA AAS
Elements
Analyzed,
ppma
"g
1
0.4
2
0.1
1
1
NA
NA
NA
1
18
0.
3
NA
0.21
Be
7
1
5
7
5
4
7
NA
3
NA
NA
NA
NA
NA
Cd
3
6
2
2.3
50
100
NA
NA
NA
NA
NA
90
NA
NA
As
40
100
15
2.8
100
200
50
NA
NA
30
70
54
40
NA
V
250
300
200
290
2000
400
200
NA
180
290
24 7
382
250
300
Mn
300
150
300
170
500
200
500
NA
NA
317
294
369
250
NA
N1
100
100
100
45
300
50
300
NA
NA
NA
NA
NA
NA
100
Sb
10
40
NA
5.6
50
100
NA
NA
NA
9.
2
7
19
NA
NA
Cr
200
100
100
330
500
100
300
NA
80
108
100
130
NA
150
Zn
200
70
1000
330
100
200
200
NA
350
NA
NA
NA
NA
600
Cu
100
150
200
45
300
200
300
NA
NA
NA
NA
33
NA
90
Fb
200
200
100
180
100
200
200
NA
440
NA
NA
NA
NA
95
Se
10
15
NA
0.77
NA
NA
NA
NA
NA
8.
2
40
12
NA
NA
B
500
200
300
190
300
300
500
NA
NA
NA
NA
NA
NA
NA
F
30
10
100 max 60
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Li
20
60
150
190
20
1C0
300
NA
NA
NA
NA
NA
NA
NA
Ag
1
2
NA
0.04
3
2
1
NA
NA
NA
NA
NA
NA
NA
Sn
6
15
NA
1.9
20
100
NA
NA
NA
NA
NA
NA
NA
NA
Fe
High
High
101
5.3*
20Z
10Z
5.0Z
10.
5X
13Z
17.
5X
18.3X
18.
1Z
26X
17.8Z
Sr
150
200
200
69
200
200
500
NA
400
520
NA
180
1000
NA
Na
2000
2000
500
6600
3000
4000
3000
1400
NA
2700
2300
2450
3500
2800
K
High
High
l.Z
1.7Z
2X
2X
0.5Z
NA
NA
NA
1.
5X
3.
IX
2.5Z
2.OX
Ca
HiRh
High
4.OX 1.3X
5Z
51
3.0Z
3.
7X
3.
7Z NA
2.
2X
3.
9X
NA
4.7X
Si
High
High
10Z
major
20X
15X
20Z
NA
NA
NA
NA
NA
NA
19.5X
Mg
10000
10000
5000
44000
5000
4000
5000
4000
2200
13700
7000
3000
4000
6000
Ba
200
600
700
110
200
300
500
NA
NA
NA
200
410
400
NA
a-ppn by weight, higher concentrations are specified as percent (Z).
b-Analysis on sample direct.
c-Dupllcate sample submitted for S6MS and OES analysis only.
d-DC arc on sample direct.
e-DiaaolutIon followed by RF spark analysis.
f-lnatrumental NAA SOURCE: (24)
Note: Analysis Code-NAA, neutron activation analysis;
SSMS, spark source mass spectrometry; OEC, optical
emission spectroaetry; DRES, direct reading emission
spectrometry; AAS, atomic absorption spectrometry;
NA, no analyals.
-------
from different labs — especially results before the availability of the
NBS standards in 1976.
In the study by Ondov £jt jil^ (32), four participating laboratories
measured the concentrations of 37 elements in the NBS standard coal sample
and 41 elements in fly ash. The analyses were performed by instrumental
neutron activation, photon activation and natural radioactivity. The latter
method was used by one laboratory to determine K, Th, and U. Both the
accuracy and interlaboratory dispersion of results for these methods are
generally superior to those for the other methods discussed.
While the results of the neutron activation analysis from this study
were good, there is still a need to develop standard procedures for the
other methods of analysis. To this end, a task group under the D-5 committee
of the American Society for Testing and Materials (ASTM) has been conducting
a round-robin analysis of coal and ash. Work has been essentially completed
on the development of standardized methods for the analysis for some trace
elements (F, Hg, Be, Cr, Cu, Mn, Ni, Pb, V, Zn) and for the major consti-
uents. It is expected that these methods will appear as ASTM standards
in 1980.
The data on trace element concentrations fror. research beginning in
1977 is probably generating the most accurate data to date. Standard Refer-
ence Materials (SRM's) for coal and fly ash have been made available by the
National Bureau of Standards since 1976. Most current studies make use of
these standards in their analytical programs. This provides a consistant
reference point to compare data from different studies. INAA and XRF analy-
sis programs are becoming more widespread in their usage; however, the ana-
lysis cost per sample is still relatively expensive.
Several examples of ongoing work are included here to give the reader
a feel for current areas of research. J.H. Steinfield, working at the
California Institute of Technology graduate school, is working to develop
a low-pressure impactor of fractionating particles below 0.5 micrometer
diameter. He wants to use this impactor in conjunction with combustion
studies and in measurements of trace metal concentrations in the vicinity of
8-12
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power plant plumes. C. E. Cushing, sponsored by Battelle Memorial Ecosystems
in Washington is studying the effects and behavior of fossil fuel effluents
in freshwater ecosystems. At the University of California Agriculture
Experiment Station at Riverside, California, G. R. Bradford is doing a trace
element study of soil-plant-water systems. The environmental fate of emissions
from coal plants is being examined by R. R. Turner ^ al_. at Oak Ridge,
Tennessee, under the sponsorship of ERDA, Division of Biomedical and
Environmental Research.
On the horizon is one of the most promising and least expensive
analytical techniques, ion plasma. Ion plasma allows simultaneous determina-
tion of up to 36 elements in a sample in less than two minutes. Most matrix
interferences are eliminated. Current research studies are evaluating the
elimination of any sample preparation before analysis to allow direct intro-
duction of the solid sample into the plasma. This method of analysis is
most promising for fast, low cost, reliable elemental analysis.
8.A AREAS WHERE FURTHER EVALUATION IS REQUIRED
Determination of adverse ecological or health effects of combustion-
derived trace contaminants is dependent upon characterization; that is, a
complete chemical and physical description of materials entering the environ-
ment from these systems is required. Anthropogenic contaminants enter the
environment via two primary pathways: (1) emission into the atmosphere with
the consequent potential for long-range transport and remote impact, and (2)
direct discharge via runoff and leaching into the aquatic and terrestrial
domain where impact might be expected to be more localized. Of primary im-
portance to the characterization process in either case is complete and
accurate analysis of selected representative samples obtained from the
various effluent streams of the combustion system.
8.4.1 Evaluation of Current Status
A degree of caution is necessary in preparing a general statement of
the current status of characterization and analysis of trace contaminants
from SCCP's. A number of careful characterization studies have been
completed (32, 37-43), and a statement stressing current limitations may tend
8-13
-------
to detract from this work. On the other hand, in virtually every aspect
of the problem, there are a variety of difficulties that remain to be
overcome.
8.A.2 Current Sampling Status
The problems associated with sampling atmospheric emissions from SCCP's
are substantial. Currently available information indicates that the chemistry
of fly ash and aerosols varies with particle size (37, 42-44), that some
elements tend to concentrate on particle surfaces (45, 43, 44), and that some
elements are present in the gas phase (46, 47, 43, 44). In addition, there
is evidence that the combustion and stack gas temperatures strongly influence
the distribution of elements between phases (46, 43).
A good deal of current interest and effort is on particle sizing. The
concentration of many trace elements is known to vary with particle size
(Sections 3, 4). Also, the efficiency of control devices is primarily a
function of size, as is the interaction of the particulates with the environ-
ment (Sections 4, 6). But none of the accepted sizing methods are fully
satisfactory. For SCCP sampling, differential impactors (e.g., Andersen
cascade impactor, Brink impactor, University of Washington impactor, etc.)
are nearly always used, but they are known to fall short of desired capability;
a series of reports by Southern Research Institute (48-50) adequately
discusses the problems. Better particle sizing data would improve understand-
ing in several areas of SCCP emissions: particle formation mechanisms; trace
metal distribution and activity; control technology; environmental transport,
residence time, and interaction material. Indeed, more research into sampling
techniques that provide for better sizing information would be welcomed by
several disciplines.
There is also evidence that organic materials of high molecular weight
and low volatility may be present in the gas phase at the temperature of the
flue gas, but that they rapidly condense on available surfaces (e.g., fly ash
in the stack plume) as the plume disperses and cools (42, 53). A similar
phenomenon occurs with certain trace metals which vaporize and condense on
fly ash particles. The partitioning of these materials, as with volatile
8-14
-------
organic materials, is a strong function of flue gas temperature. Thus, to
fully characterize stack emissions, it is necessary to sample both condensed
and gas phases and perhaps to sample at various distances from the mouth
of the stack for both organic and inorganic phases. The development of air-
craft-compatible sampling systems may well facilitate the study of power
plant emissions. In any event, the sampling trains currently being developed
and proposed for instack sampling are promising, but they are still in
development. They are probably not adequate for quantitative collection of
specific materials, but they may be adequate for the collection of sufficient
material for identification of the specific trace substances that may be
present in the gas and condensed phases.
As with atmospheric emissions, sampling and characterizing wastewater
streams, runoff, and aquatic/terrestrial systems appears to be a difficult
problem. In addition, there is often the questions as to whether the organic
materials and trace metals are dissolved in water or adsorbed on suspended
and sedimentary solids. Preservation of the samples prior to analysis is
often a problem; freezing samples seems to be the most effective procedure
at present. A better approach to overcoming the preservation problem may
be to develop more sensitive analytical procedures that require only a small
water sample (a few milliliters); then field sampling would be possible in
which the sample is fractionated and/or concentrated when collected and then
transported to the laboratory for study. The problems mentioned above
relating to subsequent sample analysis still need to be faced (51).
There are at present, no well-defined and standardized sampling
procedures that permit comparison of results obtained in different studies.
This is especially true for aqueous, soil, and biological sampling where
the difficulties associated with obtaining and preserving truly representative
samples are substantial. The sampling problems associated with inorganic
analysis of materials from aquatic or terrestrial environments appear, in
fact, to be related mainly to the representativeness of the sample. The
sampling strategy must assure that samples obtained can be used to estimate
the state of the system as a whole. By way of illustration, when the size
of coal piles and ash ponds associated with utility coal combustion systems
8-15
-------
is considered, the magnitude and complexity of obtaining a representative
sample is obvious.
8.4.3 Evaluation of Analysis and Instrumentation
Analytical methods are available for most elemental analyses and,
with few exceptions, their sensitivity and accuracy are adequate for the
characterization of trace contaminants. This statement Bhould not be
interpreted as suggesting that there is not a continuing need for improved
analytical techniques that can provide greater sensitivity, reduced cost,
and broader applicability. For example, there are few methods available
with the capability of multi-element analysis in a variety of matrices
without digestion. It is believed, however, that the characterization of
effluents is not prevented by any fundamental inability to perform elem€:ntal
analyses, but it should be recognized that the cost, in terms of skilled,
and highly trained personnel and sophisticated instrumentation, may be
very high.
Because the coal being burned provides the source for trace metal
emissions, a knowledge of the elemental concentration in the various coals
is vital. Work to date shows that there is considerable variation in trace
element composition not only with coal rank but also with geographical
origin (52) (see Section 3). Current techniques and instrumentation are
capable of assessing the concentrations of trace elements in the various
coal materials. Currently, only a few laboratories have a total trace element
capability. Problems still exist in dealing with the more volatile elements
at very low concentrations (53). While these determinations can be performed
at levels less than 1 ppm, the time and expense are prohibitive for all but
the most essential cases.
An analytical problem associated directly with coal analysis is that
of low temperature ashing (54, 51); standardized procedures and behavioral
characteristics for different coals have not yet been established. Because
such procedures are not widely used, an exchange of information is needed
to inform users of the significant variations in results that do arise as
a result of the variability of different coals; see Section 3.
8-16
-------
Over the next 10 to 20 years, ash from power plants will be one of
the most significant waste disposal problems in this country. It is known
that ash contains a large number of potentially toxic elements. In view of
this massive quantity of solid wastes, the possibility must be considered
that trace contaminants (principally heavy metals) will enter the environment,
and in order to predict the environmental contamination, something should
be known of the distribution of trace metals in ash. Bulk analyses are not
sufficient. In addition, the chemical form in which the metals occur in
ash should be known. At present, there exists a plethora of data on the
bulk composition of ash, but too little is known of the distribution of
elements and practically nothing is available on speciation of trace
contaminants.
Speciation studies are difficult at best. With a few exceptions, there
really is no direct means of identifying the species association(s) of a
trace element. Most techniques serve mainly to eliminate possibilities and
to indicate likely sites for an element. Electron spectroscopy for chemical
analysis provides information on the oxidation state of elements on the
surface but does not identify chemical species directly (55). Conclusions
are drawn to a large extent on circumstantial evidence. In simple 2-, 3-,
or 4-component systems, fairly precise information on speciation can be
obtained. This is not true, however, for complex systems. Inasmuch as most
heavy metals in ash are probably ionic, analysts are forced to study specia-
tion in the solid state and cannot employ analytical methods utilizing
solution chemistry.
In attempting to develop methods to determine the inorganic species
present, the use of physical separations as a pretreatment appears to offer
a partial solution. With soils and bottom sediments, considerable success
has been achieved by first separating the sample into a number of size
fractions, using standard methods (sieving, settling columns, centrifugation).
Further segregation is obtained on the basis of specific gravity using
continuous density gradient centrifugation (size segregation is essential
before using density procedures) (34, 56). Such techniques are capable
of separating particles with specific gravity differences as little as 0.05.
8-17
-------
The above two-fold physical separation yields fractions that are much more
homogeneous than the original sample, thereby making the interpretations
of speciation data more reliable. Speciation is also a problem in
characterization of atmospheric emissions. In this area, some progress has
been made on real-time monitoring of particles in-situ in aerosols by light
scattering (57-58). When plane-polarized light scattering is coupled with
ordinary light scattering, it is possible to measure particle size distribu-
tion and to obtain compositional information. This technique has a distinct
advantage in that it circumvents many of the current sampling problems while
providing real-time data and size-composition relationships.
Single particle analysis is applicable to speciation studies for both
atmospheric and aquatic/terrestrial samples. The state-of-the-art of single
particle analysis has advanced remarkably during the past several years.
Secondary ion mass spectrometry and Auger electron spectrometry have been
successfully employed in identification of trace elements in airborne
particles. Techniques have been developed and reference data have been
obtained that permit identification of inorganic particles by morphological
characterization or optical microscopy, often supplemented by scanning electron
microscopy.
The capability of X-ray fluorescence spectroscopy and X-ray diffraction
measurement of small particles is encouraging, but further development is
needed. A recent development in single particle analysis has been the
application of micro-Raman spectroscopy. Single particles in the respira'^le
range (i.e. <10 "jjm) have been examined for S0i» and NO3 (59). This
technique is promising and, with increased sensitivity, should provide im-
portant data relevant to coal combustion systems, including trace element
speciation.
8.4.A Standard Materials and Methods
For any large undertaking requiring the analytical efforts of a number
of laboratories, it is essential that sufficient attention be given to
quality assurance to establish that the data are sufficiently comparable
to neet the needs of the task. For the task of characterization and analysis
8-18
-------
of trace contaminants from coal combustion, very accurate data are probably
unnecessary; nevertheless, there is a need for widely accepted and used
(standard) methods and for suitable Standard Reference Materials (SRM).
Currently available SRM's for trace elements in coal and coal-related
substances may not be adequate (60).
In addition to the need for SRMs, the complexity and variability of
the materials to be analyzed in characterizing trace contaminants from coal
and coal combustion suggest the need for employing standard methods. This
is especially true when undertaking the comparison of emissions from various
combustion processes (e.g., conventional combustion compared with fluidized
bed combustion, and the influence of various operating parameters and
configurations on the nature of the effluents from combustion systems).
Documented standard methods are currently available for only a very
limited number of analyses and have been developed primarily for use
in commerce (ASTM). Standard sampling methods for the purpose of trace
contaminant measurement are essentially nonexistent (60, 53).
8.4.5 Characterization Studies
A greater emphasis has been placed on coal combustion because 5-20%
of the initial quantity of coal combusted remains as ash. Whereas for oil,
about 0.1% of the total quantity of oil combusted remains as ash (see
Section 3 of this report); therefore, the quantities of waste produced are
much larger in coal combustion as opposed to oil. Much less emphases has
been placed by researchers on characterization of the combustion of trash
or wood. These two fuel sources are just now being considered as alternate
fuels for use by industry and consumers to generate useful heat from their
combustion. Little emphasis has been placed on the study of gas-fired SCCP's
because gas is normally such a clean-burning fuel. Also, due to rising
price and Federal Regulations, the use of gas in industrial and utility
boilers is being phased out.
As noted in the introductory remarks for this section, a number of
field characterizations of trace element emissions have already been under-
taken. For the most part, these have been of limited scope with regard to
8-19
-------
the variety of contaminants measured, the diversity of effluent streams
investigated, and the range of operating parameters addressed by the study.
As a result, much valuable information has been gained on specific systeiis,
but the ability to generalize and predict is still quite limited.
By far, the greatest mass of inorganic trace contaminants leaving a
coal combustion system is deposited directly on the land and into surface
and ground waters through ponding of ash and the discharge of various
wastewater streams. Typical process waters or wastestreams generated in
coal combustion facilities that contain trace elements include: ash sluice
water, coal pile drainage, ash leachates, coal leachates, SO2 scrubber
sludges and supernatant, chemical cleaning wastes, and boiler blowdown (£1).
See Section 4 for a more complete description of these streams, and Section
5 for quantitative results on their trace metal content.
Many of these wastestreams have undergone initial characterization
(62); however, the results of the initial work in many cases is limited
in its predictive applicability due to differences in fossil fuels, in plant
operations, and in geographical-meteorological differences of study sites.
In addition, many of the characterization studies completed or under way
rely heavily on laboratory studies rather than full-scale field sampling
efforts.
To fully characterize trace contaminant emissions, it is necessary tD
conduct further studies aimed at identifying the effects of various firing
parameters, boiler designs, and emission control techniques (e.g., SO2
scrubbers, hot-side precipitators, etc.). In this connection there is a
role for basic research in combustion processes, reaction kinetics, and
thermodynamics that may provide insight into the fundamental processes that
determine the pathway of the various trace elements present in fossil fuels
through the entire SCCP.
In addition, controlled laboratory studies of those factors that
influence the availability of contaminants, such as leachability, should be
carried out in support of field studies. Such information could greatly
8-20
-------
reduce the Dumber of characterization studies needed to predict the emissions
that might be expected from a particular combustion system burning a
particular coal (43, 30).
8-21
-------
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of Automobile Exhaust Particulate. Memo Report 2350, Naval Research
Lab., 1971.
30. Natusch, D. F. S., C. F. Bauer, H. Matusiewicz, C. A. Evans, J.
Baker, A. Loh, R. W. Linton, and P. K. Hopke. Characterization of
Trace Elements in Fly Ash. In: International Conference Proceeding:;
on Heavy Metals in the Environment, Volume 2, Pact 2, Toronto,
Canada, 1975. pp.553-575.
31. Gordon, G. E. Study of the Emissions from Major Air Pollution Source:;
and Their Atmospheric Interactions. University of Maryland, College
Park, Maryland, 1974.
32. Ondov, J. M., W. H. Zoller, I. Olmez, et al. Elemental Concentration:;
in the National Bureau of Standards' Environmental Coal and Fly Ash
Standard Reference Materials. Anal. Chem., 47(7):1102-1109, 1975.
33. Miner, S. Preliminary Air Pollution Survey of Barium and Its Com-
pounds: A Literature Review. APTD 69-28, Litton Systems, Inc.,
1969.
8-24
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34. Christensen, H. E., and E. J. Fairchild. Registry of Toxic Effects of
Chemical Substances: 1976 Edition. NIOSH 76-191, Tracor Jitco Inc.,
Rockville, Maryland, 1976.
35. Campbell, J. A., J. C. Laul, K. K. Nielson, and R. D. Smith. Separa-
tion and Chemical Characterization of Finely-Sized Fly-Ash Particles.
Anal. Chem., 50(8):1032-1040, 1978.
36. Pollock, E. N. Trace Impurities In Coal by Wet Chemical Methods.
Adv. Chem. Ser., 141,23-34, 1975.
37. Block, C., and R. Dams. Study of Fly Ash Emission During Combustion
of Coal. Environ. Sci. Technol., 10(10):1011-1017, 1976.
38. Eisenbud, M., and T. J. Kneip. Trace Metals in Urban Aerosols.
EPRI-117-FR, PB-248 324, New York University, New York, 1975. 440pp.
39. Gordon, G. E., et al. Atmospheric Impact of Major Sources and Con-
sumers of Energy. University of Maryland, College Park, Maryland,
1975.
40. Gordon, G. E., and W. H. Zoller. Normalization and Interpretation of
Atmospheric Trace Element Concentration Patterns. CONF-730802. In:
Proceedings of the 1st Annual NSF Trace Contaminant Conference, 1973.
National Technical Information Service, Springfield, Virginia, 1974.
pp.314-325.
41. Klein, D. H., A. W. Andren, J. A. Carter, et al. Pathways of Thirty-
Seven Trace Elements through Coal Fired Power Plant. Environ. Sci.
Technol., 9(10): 973-979 , 1975.
42. Fennelly, P. F. Primary and Secondary Particulates as Pollutants: A
Literature Review. APCA J., 25(7):697-704, 1975.
43. Natusch, D. F. S. Characterization of Atmospheric Pollutants from
Power Plants. In: Second Federal Conference on the Great Lakes,
Proceedings, J. S. Marshall, ed. 1975. pp.114-129.
44. Pellizzari, E. D., J. E. Bunch, B. H. Carpenter, and E. Sawicki.
Collection and Analysis of Trace Organic Vapor Pollutants in Ambient
Atmospheres. Environ. Sci. Technol., 9 (6) *.552-555, 1975.
45. Andren, A. W., D. H. Klein, and Y. Talmi. Selenium in Coal Fired
Steam Plant Emissions. Environ. Sci. Technol., 9(9):856-858, 1975.
46. Linton, R. W., A. Loh, D. F. S. Natusch, C. A. Evans, Jr., and P.
Williams. Surface Predominance of Trace Elements in Airborne Par-
ticles. Science, 191 (4229):852-854, 1976.
8-25
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47. Jones, P. W. , R. D. Giammar, P. E. Strup, and T. B. Stanford. Effi-
cient Collection of Polycyclic Organic Compounds from Combustion
Effluents. Environ. Sci. Technol., 10(8):806-810, 1976.
48. Southern Research Institute. Field Measurements of Particle Size
Distribution with Internal Sizing Devices. EPA 650/2-73-035.
Birmingham, Alabama, 1973.
49. Southern Research Institute. Particle Sizing Techniques for Control
Device Evaluation. EPA 650/2-74-102. Birmingham, Alabama, 1974.
50. Southern Research Institute. Particle Sizing Techniques for Control.
Device Evaluation: Cascade Impactor Calibration. EPA 600/2-76-280,
Birmingham, Alabama, 1976.
51. Mizuike, A. Separations and Preconcentrations. In: Trace Analysis:
Physical Methods, G. H. Morrison, ed. Wiley, New York, New York,
1970.
52. Swanson, V. E., J. H. Medlin, J. R. Hatch, S. L. Coleman, G. H. V/ocd,
Jr., S. D. Woodruff, and R. T. Hildebrand. Collection, Analysis, and
Evaluation of Coal Samples in 1975. U.S. Department of the Interior,
Geological Survey, 1976.
53. Lisk, D. J. Recent Development in the Analysis of Toxic Elements.
Science, 184(4142):1137-1141.
54. Gorsuch, T. T. The Destruction of Organic Matter. Pergamon Press,
New York, 1970.
55. Electron Microscopy. Trace Element Measurement in a Coal-Fired Steam
Plant, CRC Press, Cleveland, Ohio, 1977. pp.45-49.
56. Linton, R. W., P. Williams, C. A. Evans, and D. F. S. Natusch. Deter-
mination of the Surface Predominance of Toxic Elements in Airborne
Particles by Ion Microprobe Mass Spectrometry and Auger Electron
Spectrometry. Anal. Chem., 49(11):1514-1520, 1977.
57. Bhardwaja, P. S., J. Herbert, and R. J. Charlson. Refractive Inde;: of
Atmospheric Particulate Matter: An In Situ Method for Determination.
Appl. Opt., 13(4):731-734.
58. Butcher, S. S., and R. J. Charlson. An Introduction to Air Chemistry.
Academic Press, New York, 1972.
59. Etz, E. S., and G. J. Rosacso. Identification of Small Single Par-
ticle with a New Laser Raman Microprobe. Presented at the Inter-
Micro-76 meetings, Chicago, Illinois, 1976.
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60. American Society for Testing and Materials, Annual Book of ASTM
Standards. Race Street, Philadelphia, Pennsylvania.
61. Hart, F. C., and B. T. DeLaney. The Impact of RCRA (PL 94-580) on
Utility Solid Wastes. EPRI FP-878, EPRI TPS 78-779, Fred C. Hart
Associates, Inc., New York, 1978.
62. Klein, D. H., A. W. Andren, and N. E. Bolton. Trace Element Dis-
charges from Coal Combustion for Power Production. Water, Air, Soil
Pollut., 5(1):71-77, 1975.
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SECTION 9
REGULATIONS
It is the purpose of this chapter to present to the reader a brief
history of Federal environmental acts and regulations since 1970. Only
acts and regulations that have bearing upon SCCP's will be considered.
After the reader is aware of the actions that have taken place to estab-
lish regulations for SCCP's in areas other than trace metal emissions, then
the current regulatory climate and the possible need to take further Federal
action to limit trace metal emissions can be evaluated. As the scenario
is presented, the informed reader can assure himself that a definite rela-
tionship exists between point source SCCP's particulate emissions and trace
metal emissions. Currently there does not exist a Federal regulation
that specifically limits the emission of trace elements from SCCP's.
However, in the current regulatory climate, this could be negated in the
near future.
Since regulations already exist for total suspended particles in
ambient air, the regulatory framework already exists if trace metal emission
regulations are deemed necessary. This regulatory framework can support the
enforcement of trace metal emissions through such vehicles as the issuing of
permits and source compliance sampling, already in effect.
The real decision that must be made is whether information gathered
thus far under current regulatory sanctions is sufficient to determine
if other trace metal emissions regulations are needed. If not, then what
areas of further study and evaluation are necessary to make an intelligent
decision?
9-1
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9.1 FEDERAL ENVIRONMENTAL REGULATORY ACTS SINCE 1970
9.1.1 Clean Air Amendments of 1970
In 1963 the Clean Air Act was promulgated. In part echoing the 1955
act, this new act provided for matching funds to state and local agencies
for air quality control, research and training programs. Additionally, the
act called for control of air pollution from Federal facilities, and the
supervision of interstate transport of pollution. In 1965, the 1963 act
was amended to include Federal emission standards for motor vehicles. The
amendment became known as the Motor Vehicle Air Pollution Control Act. In
1967 Congress passed the Clean Air Act. Its major objectives were to prctect
the public health and welfare and the productive capacity of its population,
to reduce harmful emissions, and to insure that air pollution problems will,
in the future, be controlled in a systematic way (1, 2). The act also
directed HEW to designate air quality control regions, develop air quality
criteria documents, publish reports on control techniques, establish air
quality standards and initiate the development of implementation plans.
It was not until the establishment of the Environmental Protection
Agency (EPA) in 1970 that an organized effort to protect the nation's
environment was undertaken. The control steps as prescribed by the
amendments (3) are briefly reviewed below.
9.1.1.1 Air Quality Control Regions (Sec 107) —
A systematic control of air quality can only be conducted effectively
in areal entities with common problems (2). For this reason air quality
control regions were designated on the basis of meteorological data and
topographic features including the types of functional areas and juris-
dictional boundaries which are important in the implementation of air quality
standards. EPA established the boundaries in consultation with local
authorities and concerned citizens.
Once approved, the boundaries were published in the Federal Register
and the air quality control regions were officially designated (A). In
order to get this process off to a quick start, the Clean Air Amendments
9-2
-------
gave the EPA 90 days Co complete this task (2). To date, 247 air quality
control regions have been established, of which 65 are interstate and 182
are intrastate regions (5). Figure 9-1 shows the distribution of air
quality control regions in the U.S. (6).
9.1.1.2 Air Quality Criteria (Sec 108) (3)—
As a next logical step, EPA was required by the amendments to develop
air quality criteria for the pollutants, particulate matter, sulfur dioxide,
carbon monoxide, hydrocarbons, photochemical oxidants and nitrogen oxides
(7-9). These criteria were based on the latest scientific knowledge,
given concentrations at which specific pollutants, either by themselves
or in combination with other pollutants, produce identifiable adverse
effects on the health and welfare of the public (2). Air quality criteria
merely describe the effects which are likely to occur when a certain pol-
lutant concentration is exceeded for a specific length of time. Air quality
standards, on the other hand, legally prescribe the pollutant concentrations
which cannot be exceeded more than once per year in a certain air quality
control region for a specified standard setting time.
Additionally, the EPA was required by law to publish reports on the
latest control techniques available for emission reduction of regulated
pollutants (10). These reports had to not only discuss the latest technology,
but also had to include the costs of control devices, and the costs and
feasibility of alternative control measures. From time to time the EPA
was required to revise these documents as new information became available (2).
9.1.1.3 Ambient Air Quality Standards —
Air quality criteria were defined and numerical concentration levels
were established. When promulgated, these values become ambient air quality
standards (AAQS's). There are national primary AAQS's which are set to
protect the public health, and secondary AAQS's which are set to insure
the public welfare. The national AAQS's set the upper limit and apply to
all air quality control regions. But each control region has the option to
set standards which are more stringent than the federal standards (11).
Table 9-1 gives the list of national ambient air quality standards with
sampling methods (12).
9-3
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VO
•o
NOT SHOWN
6 Cook Inlet (Alaska)
Figure 9-1. Boundaries of air quality control regions.
uuUbii liqocclu mascva
SOURCE: (6)
60 Hawaii
-------
TABLE 9-1. IAIIOKAL AMBIENT All QUALITY STARQAXDS
Pollutant
'Averaging
Time
National Standards
Primary Secondary
Sampling
Method
Annual
geometric
75pg/m' 60ug/m'
Suspended
mean
Particulates
24-hr.
1BBT JjaiBB*
260yg/ms lSUyg/m1
Annual
arithmetic
SOpg/m' 60ug/m3
Sulfur dioxide
mean
(0.03 ppm) (0.02 ppm)
365pg/m1 260vg/m>
24-hr.
maximum*
(0.14 ppm) (0.10 ppm)
3-hr.
maxlouD*
1300ug/m'
(0.50 ppm)
S-hr.
llgXilMB*
lOmg/m*
Carbon
(9 ppm)
monoxide
1-hr.
maximum*
40mg/m3
(35 ppm)
Hydrocarbons
(corrected for
3-hr.
maximum*
160pg/m3
methane)
(6-9
AM)
(0.24 ppm)
Photochemical
oxidants
1-br.
maximum*
160ug/m3
(corrected for
(0.08 ppm)
dioxide)
Nitrogen
Annual
arithmetic
100yg/m3
dioxide
TO?*"
(0.05 ppm)
high-volume
modified
pararosanillne
or equivalent1
nondisperslve
Infrared
spectroscopy
or equivalent2
Flame Ionization
decaction using
gas chromato-
graphy
Chemilumlnes-
cence or
equivalent3
Jacoba-Hochhelser
or equivalent*
Mot to be exceeded more than once per year,
coulometrlc and flame photometric methods,
gas chromatography and mercury replacement.
neutral potassium Iodide colorimetrlc and coulometrlc methods.
Saltzman and coulometrlc methods.
Data Source: (11).
9-5
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9.1.1.4 Standards of Performance (Sec. Ill)—
Under the amendments, the EPA is also required to set standards of
performance, as emission standards, for all new and modified stationary
pollution sources (13, 14). In contrast to AAQS's which set limits to the
ambient pollutant levels, standards of performance constitute limits at
the source in such a way that AAQS's for the respective pollutants should
not be exceeded. Table 9-2 presents standards of performance for twelve
source categories currently identified (15, 16). These are the new
Source Performance Standards (NSPS). For all old and unmodified sources of
the categories in Table 9-2, states must set their own performance standards
using guidelines provided by the EPA.
9.1.1.5 Hazardous Air Pollutants (Sec. 112)—
Three pollutants, namely asbestos, beryllium and mercury have been
singled out as being potentially more toxic at concentrations found in
the atmosphere than those pollutants for which AAQS's have been set. A
technical report has been published for each of the three substances.
These reports address the nature of the substance, the adverse health
effects, the economic impacts if standards are enforced, and the difficulty
of identifying a potentially hazardous level for these substances which
are highly toxic at minute concentrations (17).
9.1.1.6 Air Quality Surveillance—
In 1961 a sophisticated air sampling network, the Continuous Air
Monitoring Program (CAMP) was established (19) . Fully automatic instruments
continuously recorded the concentrations of nitric oxide, nitrogen dioxide,
sulfur dioxide, total hydrocarbons, carbon monoxide, total oxidants
and ozone. The cities of Chicago, Cincinnati, New Orleans, Philadelphia,
San Francisco and Washington D.C. were initially selected for this study.
9-6
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7ABLE 9-2. KATIOKAL STAJOABDS OF PERFORMANCE FOR NEW STAIlOiAXY SCl'RCiS
Soarca
Pollutant
Ealeslon Standard
1. Fossil (uil'dred
steas generators
Particulars uttir
Sulfur dioxide
coal-fired
oll-flied
0.1 lb/101 Btu (auin 2-hr
•verage)
1.2 lb/10* Itu , , ,
(uxlBuB 2-hr
0.8 lb/101 Itu «»«•»•>
loclaeTacors
Nitrogen oxides
eaal-flrcd
oll-fIred
gas-fired
Visible pollutants
Particulate Mtltr
0.7 lb/10* Btu (*4x1bus 2-hr
0.3 lb/10* Btu averege as
0.2 lb/10* Btu altrugen dioxide)
<20X opacity, except lo uy
1-hr eslanlana uy be as
*ueh as A01 opacity for 2
nloutes
0.06 gr/scf
3. Portland cesent
plar ts
Particulate Bitter
klla&
clinker coolers
0.3 lb/t cf feed
0.1 lb/c of feee
Kitrlc acid
plants
5. Sulfuric ecld
p I a_T t s
6. Asphalt concrete
plants
Pstroleua
refineries
8. Storage vttscis
foi petroleum
liquids
9. Secondary lead
shelter*
Visible pollucaota
kilos
others
Nitrogen oxides
visible pollutants
Sulfur dloilde
Acid al«t
visiM* pol i
-------
Since 1968, most of the nation's air pollution monitoring has been
carried out by three National Air Surveillance Networks: the high-volumtt
network, the gas sampling network, and the CAMP station network. Since j.970,
these three networks have been part of the National Air surveillance
Network (NASN) operated under the auspices of the EPA. In 1971, the NASH
program consisted of some 7,000 air pollutant samplers, of which some 3,00
were of the static type (e.g., deposit gauges); some 2,400 were mechanical
devices of the integrating type (e.g., high-volume samplers); some 460 wt:re
spot tape samplers and some 235 were various types of automatic and con-
tinuous sampler/analyzers (20).
Monitoring and data analysis are carried out within the Office of Air
and Water Programs, which, with its Air Pollution Technical Information
Center, is a subdivision of the EPA. Processing and analysis of the huge
amounts of data is handled by an automated system for the Storage and
Retrieval of Aerometric Data (SAROAD) (2). The collection and dissemina-
tion of aerometric data to and from the National Aerometric Data Bank (NADB)
is handled through the National Aerometric Data Information Service (NADIS).
The data is transmitted from local to state agency, and then to NADB,
by data phone, magnetic tape, punched cards, or paper forms.
9.1.2 Resource Conservation and Recovery Act of 1976 (RCRA)
The 1976 amendments to the Solid Waste Disposal Act, titled the Resource
Conservation and Recovery Act of 1976 (RCRA), mandate national action for
the first time against solid waste management practices that lead to en-
vironmental and public health hazards (21, 22). They also seek to promote
resource recovery and conservation as waste management options. The main
provisions of RCRA for achieving these goals are as follows:
• Federal financial and technical assistance to State and local
governments is authorized for planning and development of
comprehensive solid waste management programs that include
environmental controls on all land disposal of solid wastes,
regulation of hazardous wastes from point of generation
through disposal, and resource recovery and conservation
activities.
9-8
-------
• Such programs would include schedules for upgrading or
closing all environmentally unacceptable land disposal
sites ("open dumps") identified according to EPA
criteria and a nationwide inventory. Open dumping is
prohibited except as covered by an acceptable schedule
for compliance under the State plan.
• Where states do not establish hazardous waste regulatory
programs that meet Federal standards, EPA will administer
regulatory control.
¦ A Cabinet-level interagency study of resource conservation
policies is mandated; findings and recommendations are to
be subaitted periodically to the President and the Congress.
• Public participation is required in the development of all
regulations, guidelines, and programs under the Act.
• Research, demonstrations, studies, and information
activities related to a wide range of solid waste problems
are authorized.
SOURCE: (21)
The Resource Conservation and Recovery Act of 1976 creates Federal
and State regulatory authority over both solid and hazardous wastes. Key
definitions in the Act which pertain to SCCP wastes include hazardous
waste, sludge, and solid waste. Relevant sections of these definitions
include:
• hazardous waste — "a solid waste, or combination of solid
wastes, which because of its quantity, concentration, or
physical, chemical, or infectious characteristics may ...
pose a substantial present or potential hazard to human
health or the environment when improperly treated,
stored, transported, or disposed or otherwise managed."
(23)
• solid — "any solid, semi-solid, or liquid waste generated
from an ... air pollution control facility ..."
(23)
• solid waste — "any garbage, refuse, sludge from an ... air
pollution control facility ... including solid, liquid,
semi-solid, or contained gaseous material ..." (23)
9-9
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Any waste that is not discharged under a Section 402 New Performance
Discharge Effluent Standard permit is considered a solid waste under RCRa.
Metal cleaning wastes would be a solid waste when disposed of in landfills
and an effluent when discharged under NPDES requirements.
9.1.3 Clean Air Amendments of 1977
Amendments to the Clean Air Act were enacted in August, 1977, setting
out extensive pollution control rules which differentiate between regions
with air not meeting national standards ("non-attainment areas"), and regions
with air cleaner than national standards require. "Clean air" regions are
divided into three "classes" of air quality according to the degree of
purity desired for them, with the most stringent pollution limitations
reserved for "Class I" areas, such as national parks, and the least stringent
limitations applicable to "Class III" areas, where substantial industrial,
development is to be permitted. "Class II" areas are those where moderate
development is desired.
The Environment Protection Agency has proposed regulations to implenent
the policy of preventing "significant deterioration" of air quality in
clean air areas as required by the Act. The EPA proposals were published
for public comment in November and December 1977, with final promulgation
an ongoing process.
In addition, EPA promulgated immediately effective regulations for
certain provisions of the Act, as required by Section 168. These include:
(1) a listing of mandatory Class I areas; (2) the sulfur dioxide and
particulate matter "increments" (additional pollution allowed beyond
existing pollution) for all classes; (3) the new statutory definition of
"baseline" (already existing) pollutant concentrations; (4) the exclusion
of some areas from consideration for Class III classification (24).
EPA also proposed to accelerate implementation of other "PSD" (Prevention
of Significant Deterioration) sections to make them effective on March 1, 1978.
These regulations are not in effect. Under accelerated implementation, a
number of new SCCP projects would fall under the new "best available control
technology" (scrubber) requirements which had expected to be able to comply
with low-sulfur coal under EPA's old, less stringent PSD rules.
9-10
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9.1.4 Revised New Source Performance Standards
The Environmental Protection Agency proposed New Source Performance
Standards (NSPS) in March, 1978, sharply limiting sulfur dioxide, particulate,
and nitrogen oxide emissions from steam electric generating plants.
New Source Performance Standards are based on Section III of the Clean
Air Act, which requires direct Federal emissions limitations for new, modified,
or reconstructed pollution sources. A 1976 Sierra Club and Navaho Tribe
petition for revision of the existing standards argued that technology advances
since 1971 call for stricter standards.
According to the recently revised NSPS (25), the new standards would
be: (1) for sulfur dioxide emissions, 1.2 lbs per million Btu and an across-
the-board requirement for 90% emission reductions unless emissions are less
than 0.6 lbs per million Btu. Reduction by 70% would be required below 0.6
lbs per million Btu. (2) For particulates, .03 pounds per million Btu; this
emission level is based on the controls achievable, EPA claims, with electro-
static precipitators and baghouses. (3) For the emission limitations
would be fuel specific, as follows:
Bituminous coals, certain lignites,
other solid fuels 0.6 lbs/106 Btu
N.D., S.D., Mont, lignite fired by
a slag tap furnace 0.8 lbs/106 Btu
Gaseous fuels (except low-Btu
synthetics) 0.2 lbs/106 Btu
Liquid fuels 0.3 lbs/106 Btu
Subbiturainous coals 0.5 lbs/106 Btu
Low-Btu synthetic gas 0.5 lbs/106 Btu
While none of these new regulations apply specifically to trace
elements, there is a relationship between trace element emissions and
particulate emissions; (See Sections A and 5 of this report). In the
present regulatory climate, particle control is the primary form of trace
element control.
9-11
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9.2 STATE ROLE IN COMPLIANCE WITH FEDERAL ENVIRONMENTAL REGULATIONS
9.2.1 State Implementation Plans
SIP's are important indirectly to the control of trace element
emissions because these plans force the states to act to achieve primary
ambient air standards. Primary ambient air standards contain a requirement
for suspended particulate matter. There is a strong correlation to th«:
level of suspended particles and trace element emissions (See Sections
4 and 5 of this report).
The SIP's continue to be amended to correct deficiencies found by the
courts as well as to meet the technical changes required by emerging
issues. The extent of approval of each SIP varies from state to state with
no state plan currently fully approved.
On July 22, 1975, new procedures for the development, review, and
approval of SIP revisions were initiated. These procedures will eliminate
any distinction between "state initiated" and "EPA initiated" SIP revisions
and will also eliminate the previous requirements for formal headquarters
concurrence on most SIP approval/disapproval actions. The Regional Ad-
ministrators now have authority to sign Federal Register notices proposing
EPA-initiated SIP revisions in addition to their existing authority to
sign such notices for state-initiated revisions.
The gap between the need for and availability of state and local air
pollution control resources to attain and maintain ambient standards con-
tinues to exist. Additional state and local resources are needed to
implenent relatively untried or innovative control techniques, especially
those pertaining to the siting of new sources and air pollution control
programs that are related to land use and transportation.
9-12
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9.2.2 Monitoring of Air Quality Maintenance Areas (AQMA)
Under the Clean Air Amendments, State Implementation Flans must include
a thorough emission inventory (2). Such an inventory is one of the most
essential Ingredients of an air quality control program because it pro-
vides :
• input data for diffusion models,
• input data for cost-benefit analysis,
• data for the development of control strategies, and
• information for state and regional planning authorities.
Emission inventories are now routinely compiled by use of question-
naires, interviews, on-site inspections, and a number of published approx-
imation techniques (26, 27). For easier comparison, the EPA prescribes
further a specific format according to which the above information has to
be presented (28) .
Again the strong correlation between suspended particles and trace
element concentrations should be remembered. Emission inventories can be
used to obtain data for determining particulate emissions from point sources.
If a trace element emission regulation should be promulgated, emission
inventories will be one part of a suitable framework for enforcement of
Federal regulations.
9.2.3 Effect of Permitting for New Source Performance Standards (NSPS)
The permit framework now used for NSPS is very relevant if actual
control of specific trace element emissions should arise. That is, this
permit framework will be a convenient mechanism already in place to imple-
ment new controls on trace metal emissions.
The permit system is specifically intended as a systematic means of
not only achieving mass compliance, but, just as important, preventing the
future growth in contaminant emissions. The permit system is a method which
accounts for all factors (e.g., design, operation, maintenance, and adminis-
tration) that must be considered in controlling any given source of air
pollution (29,30).
9-13
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The permit system provides for review of plans for construction, modi-
fication or operation of stationary source equipment or processes that aave
the potential to emit air contaminants. An application for a permit from
an owner is required in advance of construction or operation of the equip-
ment or process. The application provides the information necessary to
evaluate the potential emissions from the equipment. Permits (or certi-
ficates) to construct or to operate are issued if, after thorough evaluation,
inspection and source testing, it can be demonstrated that emissions wi.Ll
meet the standards of the agency throughout anticipated ranges and conditions
of equipment operation. In some instances, permits are conditioned to
assure that certain operational and maintenance practices are adhered to
in the routine operation of the equipment.
The distinguishing features of permit systems are: (1) the authority
such systems have over the construction and operation of all equipment
capable of emitting air contaminants is clearly defined; (2) the clarity
and specifics of the standards that must be complied with the procedure:;
that owners must follow in submitting applications; and (3) the amount
and type of technical information that must be supplied by the owner of
affected equipment to permit source evaluation and to assure compliance
with regulations (31, 32).
9.3 IMPACT OF ENVIRONMENTAL REGULATION ON SCCP's
9.3.1 Engineering Studies
A number of engineering studies have been done in response to environ-
mental regulations promulgated for SCCP's. The Environmental Protection
Agency (EPA) is preparing to establish a long-range schedule for promul-
gating New Source Performance Standards (NSPS). In order for future NSPS
to be most effective, an overall strategy or plan of action is being de-
veloped so that priorities for standard setting can be established (33).
A program to calculate the impact of NSPS on air pollutant emissions from
industry within the United States has been developed. These calculations
are performed using a generalized priority rating system known as Model
IV (33) which mathematically expresses the differentials in atmospheric
emissions that could be expected with and without NSPS.
9-14
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Several other important engineering studies have been performed (34-37).
One evaluation made by Jordan et al, (34) gives a review of the environmental
impact of the entire process of fossil energy production from exploration
to consumption. A focus is made on the specific industries for coal, oil
and gas and other hydrocarbon sources followed by a review of public poli-
cies on much needed research.
In another study conducted by Bernstein et al. (35), an indepth in-
vestigation of the pollution from intermediate-sized boilers was carried
out and consideration given to the possible methods of abating this pol-
lution. This category of boilers includes all units used in commercial
buildings, virtually all industrial units and some of the smaller utility-
size equipment. All fossil-fuels were included. All commercially feasible
means of controlling emissions were explored with respect to their effi-
ciency, capital cost requirements and operating costs; this includes fuel
switching, flue gas cleaning or treatment, combustion additives, and com-
bustion design techniques. Because these boilers are small, often unat-
tended, located in limited space and operated at low annual capacity,
fuel switching is the most effective control strategy, especially as it will
substantially reduce particulates and sulfur oxides. The four types of
particle control equipment considered were dry cyclones, wet scrubbers,
electrostatic precipitators and fabric filters.
A study done by Reiquam ejt al_. (37) reported that certain control
technologies aimed at achieving specific limits generate new waste streams
which, in turn, require controls. Without a systematic assessment of
these impacts, there is a substantial risk that pollution control strategies
for controlling pollution in one medium will cause problems in another
medium. For example, control of air emissions from coal-fired power stations
will probably have impacts upon other media (land and water) when controls
are imposed on the one medium (air). A complex methodology for assessing
the impact of specific control technologies or strategies has been developed
by Reiquam, et al (37). The assessment methodology consists essentially of
evaluating an index for each control strategy and comparing it to a corres-
ponding index for the uncontrolled case. The index is a function of the rate
9-15
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of production of pollutants, behavior of these pollutants in the environment,
and relative importance of each pollutant. The cross media concept somewhat
parallels the relationship between trace metals and particles since parricle
control impacts trace metal emissions.
9.3.2 Technology Advances
Some useful studies have been performed evaluating technologies th.it
have developed due to response of environmental regulations (38-49).
In a study issued by Franklin Institute Research Labs (38), a survey
of literature on control technology and regulatory aspects of sulfur oxLde
(SO^), nitrogen oxides (N0X) and particulate emissions from large, coal-fired
boilers (chiefly utility boilers) was presented. In a report by Dr. J. L.
Shapiro (AO) current power generation technology is reviewed. In another
study (41) models developed at Carnegie-Mellon University to systematically
address tradeoffs between energy and environmental impacts in the context
of conventional and advanced technologies producing electricity from co.al
are described.
9.3.3 Instrumentation Advances
Monitoring equipment to study and identify specific pollutants is .i
rapidly evolving technology. Trends in instrumentation are away from m.iny
older techniques using intermittant sampling or quick-sniff, grab samples.
Even the continuous analyzer using chemical techniques are being nudged
out by more advanced analyzers using physical measurement techniques (4 3).
9.3.4 Estimated Cost to Achieve Environmental Goals
The estimated cost to achieve environmental goals varies with the
source of the estimate (48). The Ford Foundation Energy Policy Project,
a two year study, projected the best way to achieve environmental goals
is through conservation of resources. This would result in saving $300
billion in capital investments for energy producing facilities in the next
25 years (48). Also, an older TVA environmental cost analysis may still be
informative (49).
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9.4 STATUS OF ENVIRONMENTAL COMPLIANCE
9.4.1 Evaluation of Compliance to 1977
Long-term progress (1970-1976) can be seen in achieving compliance
with the National Ambient Air Quality Standards (NAAQS) for total suspended
particulate, sulfur dioxide, and carbon monoxide nationally and for photo-
chemical oxidants in California. In the short-term, however, some reversals
have taken place for total suspended particles with many areas experiencing
increases between 1975 and 1976. Where photochemical oxidants are measured
outside California, the trend appears basically stable over the 1973-1976
period. Nitrogen dioxide trends are stable in California; nationally,
however, nitrogen dioxide levels tend to be increasing based mostly on three
years of data. There are still insufficient data, however, to draw any
definite conclusions on nitrogen dioxide levels outside California (34),
Air quality progress is measured by comparing the ambient air pollu-
tion levels with appropriate primary and secondary NAAQS for each of the
pollutants. Primary standards protect the public health, and secondary
standards protect the public welfare as measured by effects of pollution on
vegetation, material, and visibility. The standards are further categorized
for long- or short-term exposure. Long-term standards specify an annual
mean that may not be exceeded; short-term standards specify upper limit
values for 1-, 3-, 8-, or 24-hour averages that may not be exceeded more
than once per year (50, 51).
The major findings of these investigations which pertain to particulate
matter (and therefore trace metals) are as follows: (52-54)
• The general long-term improvement in total suspended parti-
culate reversed itself between 1975 and 1976 with many areas
experiencing increases. The likely explanation for this
phenomenon is meteorological. Large areas of the country
experienced drought during 1976. These extremely dry soil
conditions increased the likelihood of wind-blown dust con-
tributing to ambient particulate levels.
• A major decrease was observed in the population exposed to
high particulate levels in Metropolitan New York, Chicago,
and Denver. The greatest improvement occurred in the New
York-New Jersey-Connecticut Air Quality Control Region, where
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the percentage of the population exposed to particulate
levels above the annual primary health standard decreased
from 60 percent in 1970 to 0 percent in 1976. Similarly,
Chicago decreased from 100 percent in 1970 to 64 percent
in 1976; Denver decreased from 83 percent in 1970 to 74
percent in 1975.
9.4.2 Recent Regulatory Trends
The state of New Mexico now has in effect a recently passed regula-
tion on emission of particles from coal burning power plants (55). The
regulation as written allows a maximum particulate emission of O.05 lbs
per million Btu. More importantly, a limit of 0.02 lbs per million Btu
is set forth for particles with a mass median diameter less than two
microns- Elsewhere in this report (See Sections 4 and 5) it has been
shown that some trace metals may be enriched on particles less than two
microns emitted from coal combustion processes.
It is important to note that this regulation is part of the state ojr
New Mexico SIP's. It would therefore appear that regulatory acts already
in effect can be further utilized to start regulation of trace metal emis-
sions (See Sections 9.2 and 9.3 of this report). The strong correlation be-
tween fine particulate emissions and trace metal emissions may be one way to
indirectly control trace metal emissions without an additional statute that
limits trace metal emissions specifically. The reader should be cautioned
that further study into particle and trace metal emissions and correla-
tions must be done before such actions would be justifiable.
Just recently (October, 1978) lead has been made a criteria pollutar.t.
The National Ambient Air Quality Standard (NAAQS) is 1.6 yg/m3 averaged
over a three month period. SIP's for control of lead emissions were due as
of July 1979. Full attainment is scheduled for October 1982 (56).
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REFERENCES
1. Guidelines for the Development of Air Quality Standards and Imple-
mentation Plans. USDHEW, PHS, Nat. Air Poll. Contr. Adm.,
Washington, D.C., 1969.
2. Bach, W., and A. Daniels. Handbook of Air Quality in the United
States. Honolulu, Hawaii, Oriental, 1975.
3. Clean Air Amendments of 1970, PL 91-604.
A. Summary of Air Quality Control Regions (Interim Report). Air Poll.
Contr. Office, EPA, April 1971.
5. U.S. Environmental Protection Agency. Federal Air Quality Control
Regions. Rockville, Maryland, 1972.
6. Pechan, E. H. 1985 Air Pollution Emissions. D0E/PE--0001. Depart-
ment of Energy, Washington, D.C., 1977.
7. U.S. National Air Pollution Control Administration. Air Quality
Criteria for Particulate Matter, and for Sulfur Oxides, Arlington,
Virginia, 1969.
8. U.S. National Air Pollution Control Administration. Air Quality
Criteria for Carbon Monoxide, for Hydrocarbon, and for Photochemical
Oxidants. Washington, D.C., 1970.
9. U.S. Environmental Protection Agency. Air Quality Criteria for
Nitrogen Oxides. Washington, D.C., 1971.
10. National Air Pollution Control Administration. Control Techniques
for Emissions of CO, NO , HC, and Organic Solvents. Washington,
D.C., 1970. X
11. National Air Pollution Control Administration. Control Techniques
for Particulate Matter, and for S0~, 1969; Control Techniques for
Emissions of CO, NO , HC, and Organic Solvents, 1970; Control Tech-
niques for Emissions of CO, NO , and HC from Mobile Sources, 1970.
Washington, D.C. X
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12. U.S. Environmental Protection Agency. Guidelines for Designation ol
Air Quality Maintenance Areas, Vol. I, 1974.
13. U.S. Senate Committee on Public Works. A Legislative History of the
Energy Supply and Environmental Coordination Act of 1974, Volume 1.
Report 94-7, Washington, D.C., 1976.
14. Simon, C. Federal Regulations Relating to Stationary Combustion
Sources. Presented at the Air Pollution Control Association Pro-
ceedings, Mid-Atlantic States Session, Edision, New Jersey, 1972.
15pp.
15. U.S. Environmental Protection Agency. Performance Standards for New
Stationary Sources. Environ. Report., 2(16):477-495, 1971.
16. U.S. Environmental Protection Agency. Federal Register 38(111),
June 11, 1973, and 39(47), March 8, 1974. Washington, D.C.
17. U.S. Environmental Protection Agency. Proposed National Emission
Standards for Hazardous Air Pollutants: Asbestos, Beryllium,
Mercury. Research Triangle Park, North Carolina, 1971.
18. U.S. Environmental Protection Agency, Office of Water Program
Operations. Municipal Sludge Management: Environmental Factors.
EPA 430/9-77-004, Washington, D.C., 1977.
19. Jutze, G. A., and E. C. Tabor. The Continuous Air Monitoring Progran.
APCA J., 13(6):278-280, 1963.
20. Morgan, G. B., E. C. Tabor, and R. J. Thompson. Atmospheric Sur-
veillance-Past, Present and Future. In: Determination of Air
Quality, G. Mamatov and W. D. Shults, eds. Plenum Press, New York,
1972.
21. U.S. Environmental Protection Agency. EPA Activities Under the
Resource Conservation and Recovery Act of 1976, Annual Report to the
President and the Congress, Fiscal Year 1977. Washington, D.C.,
1978.
22. Resource Conservation and Recovery Act of 1976. C.P.O.,
Washington, D.C., 1976.
23. Hart, F. C., and B. T. DeLaney. The Impact of RCRA (PL 94-580) on
Utility Solid Wastes. EPRI FP-878, EPRI TPS 78-779, Fred C. Hart
Associates, Inc., New York, 1978.
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24. U.S. Environmental Protection Agency. Guidelines for the Interpreta-
tion of Air Quality Standards. 1977.
25. U.S. Environmental Protection Agency. New Stationary Sources Perfor-
mance Standards; Electric Utility Steam Generating Units. Fed. Reg.,
44(113):33580, 1979.
26. Air Quality Implementation Planning Program, Volume I, Operator's
Manual. EPA, Washington, D.C., 1970.
27. U.S. Environmental Protection Agency. Compilation of Air Pollution
Emission Factors and Supplements, 2nd ed. AP-42, Research Triangle
Park, North Carolina, 1973.
28. U.S. Environmental Protection Agency. Federal Register 36(158),
August 14, 1971 and 38(147), August 1, 1973. Washington, D.C.
29. Stein, A. Guide to Engineering Permit Processing. APTD-1164, Pacific
Environmental Services, Inc., Santa Monica, California, 1972. 380pp.
30. Nation Considers Strip Mining. Environ. Sci. Technol., 8(8):700-701,
1974.
31. Walsh, G. W., and D. V. von Lehmden. Resources for Air Quality Con-
trols Regions. Presented at the NAPCA Workshop on Regional Imple-
mentation Plans, 1969.
32. TRW Systems Group. Air Quality Implementation Planning Program,
2 Volumes. 1970.
33. Hooper, T. G., and W. A. Marrone. Impact of New Source Performance
Standards on 1985 National Emissions from Stationary Sources,
Volume 1, Final Report. TRC, 1975.
34. Jordan, A. R., M. Willrich, J. J. Schanz, R. L. Lowrie, and J. D.
Haun. Public Policy Toward Environment 1973: A Review and Appraisal
of Fossil Energy. Ann. N.Y. Acad. Sci., 216:63-78, 1973.
35. Berstein, F. H., J. R. Ehrenfeld, and T. R. Parks. Equipment for
Intermediate-Size Boilers, pp.72-74. Presented at the Air Pollution
Control Association 65th Annual Meeting, Miami, Florida, 1972.
36. Comparative Risk-Cost-Benefit Study of Alternative Sources of Elec-
trical Energy. Nucl. Saf., 17(2):171-184, 1976.
37. Reiquam, H., N. Dee, and P. Choi. Assessing Cross Media Impacts.
Environ. Sci. Technol., 9(2):118-120, 1975.
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38. Robinson, M. A Survey of Current U.S. and European Literature on Air
Pollutants and Cinders from Large, Coal-Fired Boilers: Control
Technology and Regulatory Aspects of Sulfur Oxides, Nitrogen Oxides,
and Particulate, and Disposal of Cinders. Franklin Inst. Research
Labs., 1798. 45pp.
39. Wagenet, R. J., W. J. Grenney, and J. J. Jurniak. Erosion Model for
Arid Wildland Watersheds. Paper 77-2510. Presented at the ASAE
Winter Meeting, Chicago, Illinois, 1977. 23pp.
AO. Rubin, E. S. A Systematic Approach to Characterizing Energy-
Environment Tradeoffs for Coal Utilization Technologies. In: Energy
and the Environment, Proceedings of the Fifth National Conference,
Cincinnati, Ohio, 1977, D. G. Nichols, et al., eds. AIChE, Dayton,
Ohio, 1978. pp.124-131.
41. McGlamery, G. G., R. L. Torstrick, W. J. Broadfoot, et al_. Detailed
Cost Estimates for Advanced Effluent Desulfurization Processes. Com-
bustion, 47(4):27-36, 1975.
42. Smil, V. Energv and Air Pollution: USA 1970-2020. APCA J.,
25(3):233-236, 1975.
43. U.S. Environmental Protection Agency, Office of Water Programs
Operations. Municipal Sludge Management: Environmental Factors.
EPA 430/9-77-004, Washington, D.C., 1977.
44. York, J. L. Environment vs. Western Coal. GFERC/IC-75/2. In:
Proceedings of the Symposium on Technology and Use of Lignite,
Grand Forks, North Dakota, 1975. ERDA, Oak Ridge, Tennessee, 1975.
pp.193-201.
45. Fisher, G. L., B. A. Prentice, and D. Silbennan. Morphology and
Chemistry of Size-Classified Fly Ash Collected from the Stack of a
Coal-Fired. University of California, Radibiology Laboratory, 1976.
46. Frankenberg, T. T. Trends in Air Pollution Legislation and in Precip-
itator Development. Presented at a meeing of the Southeastern Elec-
tric Exchange, Miami Beach, Florida, 1965.
47. Hamilton, L. D., and S. C. Morris. Risk Assessment for Energy Tech-
nology Development. Presented at the Specialty Conference on Toxic
Substances in the Air and the Environment, Cambridge, Massachusetts.
1977.
48. Hammond, A. L. Energy: Ford Foundation Study Urges Action on Conser-
vation. Science, 186(4162):426-428, 1974.
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SECTION 10
FUTURE RESEARCH
One of the objectives of this project was to identify areas where
research is needed. These needs are of two general types: one is merely
filling in gaps in the data, while the other need is for innovative, creative
research on problems of current and future interest. New analytical techniques
and instrumentation dictate in part the feasibility and practicality of meet-
ing some of these needs. Specifically for trace metals, the recent availa-
bility of simultaneous, multi-element analytical techniques, such as ICAP
(Inductively Coupled Argon Plasma) should greatly facilitate (in cost, time,
and number of samples) the investigation of trace metals in all types of
materials. For greatest accuracy INAA (Instrumental Neutron Activation
Analysis) is probably the preferred technique because no sample pretreatment
is required (see Section 8).
The directions in which technological research will be steered are
influenced by predictions of potential future problems. These scenarios,
coupled with a knowledge of current research, data, and available technology,
will be used to determine funding priorities. The Accuracy of Data section
of this report (Section 8) reviews current trace metal detection technology
and what is expected in the near future. At the end of each major section
is a subsection discussing the research needs specifically applicable to
that area. A summary of those subsections should reasonably well serve
to identify data gaps and areas for further research related to those fields.
This section will deal more with sources of current information and broad-
based, interdisciplinary research needs identified in the literature.
10-1
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10.1 SOURCES OF INFORMATION
To properly evaluate future research needs, one must first identify
all recent and current research in the field of concern. With the advert
of computerized bibliographic, statistical, granting and funding databases,
information is more readily available from a potpourri of database vendors;
prominent among them are:
• ORBIT — Systems Development Corporation,
• DIALOG — Lockheed Retrieval Services,
• MEDLARS — National Library of Medicine,
• DOE/RECON — U. S. Department of Energy, and
• STAR — (Scientific and Technical Aerospace Reports) —
by National Aeronautics and Space Administration
(available only to NASA contractors or in hard copy).
These services contain, in part, bibliographic references covering
about 130 databases. Many entries include abstracts, all are keyworded,
and many foreign entries are included. Most research libraries have accass
to one or more of these services. Included among the bibliographic data-
bases covered are Government Reports Announcements (by NTIS, National
Technical Information Services) and Chemcon (covering Chemical Abstracts).
U.S. patents are also covered.
Granting and funding reports are covered by SSIE (Smithsonian Science
Information Exchange), GRANTS (the Oryx Press, Phoenix, Arizona), and RI?
(Energy Reports in Progress), TIC (Technical Information Center) at ORNL,
(Oak Ridge, Tennessee). These reports contain summaries of research, either
in progress or completed within the last two years, and cover the physical,
social, engineering, and life sciences. Input is from over 1300 sources,
governmental and private, but about 90% is generated by the Federal govern-
ment and their funding. This service is designed to pick up most ongoing
federally supported research. All of the above-mentioned databases are
included in ORBIT and DIALOG; MEDLARS refers to the medical literature.
Government Reports Announcements is a monthly NTIS publication (Spring-
field, Virginia) which abstracts all Federally sponsored research report:;.
10-2
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Most of the entries refer to final reports and extend back to 1964. The
data from this publication are also included In the NTIS computerized data-
base. Monthly Catalogue, a USGPO (Washington, D.C.) publication, contains
information about most finalized research projects which were Federally
conducted. These data have been on-line since 1976.
STAR would be useful for ambient atmospheric data but it is not on-
line and is available only to NASA contractors. A hard copy is available to
anyone. GRANTS covers references to grants offered by federal, state, and
local government, commercial organizations and associations and private
foundations covering 88 academic disciplines. RIP has been developed at
ORNL in cooperation with the Energy Research and Development Inventory
Project of ORNL. The research, development or demonstration projects
covered include all types of funding, and the scope of interest includes
all energy sources (fossil, nuclear, unconventional), electric power (gen-
eration, transmission, distribution, storage), energy conservation and utili-
zation (heating, cooling, lighting, transportation, etc.), economic and
legal aspects, health and environmental effects, basic and applied research
and engineering development, and more.
Such services described above should enable anyone with a research
library access to identify with key word accuracy essentially all data or
research published up until about six months prior (the lag time for publica-
tions being entered into the data base). Also, most ongoing research can be
identified through granting records or interim reports.
There has not been a wholly successful effort to bring together all
information on research of specific concern, however. Most private re-
search laboratories (e.g., EPRI, Batelle, SRI, etc.) publish quarterly or
yearly summaries of research and current projects. For completeness, each
lab must be contacted individually. Also, each government agency generally
publishes a summary of work funded under its aegis. Examples which are rele-
vant to trace metal emissions from SCCP's include EPA (1, 2), DOE (30, and
interagency publications (4, 5). But again for completeness, each agencies'
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publication(s) should be reviewed. Finally, of particular interest to this
project is a Mitre report (6) reviewing current (July 1978) research projects
involved with the CCEA program.
10.2 ANALYTICAL TECHNIQUES
The pace of advancing technology to some extent dictates the rate of
research development. Until reliable, commercial atomic absorption spectro-
meters became available, extensive elemental determinations were difficult,
expensive and required a highly trained operator. Before 1960, fev elemental
determinations were reported. As technology evolved in the 1960's, data
on trace elemental studies became more common. But it was not until about
1970, when such determinations became reliable and more automated, that
trace metal studies began to proliferate. With the data becoming more
available, the scientific community was better able to define what problems
existed and channel the funding of research to the most pressing problems.
Little of the reliable trace metal information occurs in the databases
before 1970; coincidentally, most of the computerized information retrieval
systems began at about the sane time.
Today, new developments in analytical instrumentation are ushering
in a new era in trace metals research (7). Simultaneous multi-element
determinations are becoming the standard method. Isotope dilution-mass
spectrometry is now sufficiently accurate to provide reliable data. X-ray
fluorescence is quick and relatively inexpensive and reasonably accurate.
Neutron activation methods show a high degree of consistency between labs
which suggests a high degree of accuracy (8). And plasma fluorescence
has lowered the cost of a 35 element analysis below fifty dollars and
instrument time to five minutes. See Section 8 for a review of techniques.
The conclusion is that trace metal analysis of most types of samples
will become relatively easy and inexpensive. The number of trace element
determinations will profliferate, and soon, the existing data gaps will be
filled. Coal has received the most study among SCCP fuel alternatives,
and rightly so owing to the pollution load per Btu compared with other fuels;
10-4
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however, this project uncovered a relatively small amount of information
on trace metal emissions from oil, gas, wood or municipal refuse fuel sources.
Coal also accounts for nearly half the energy produced by electrical utilities.
Only a few studies have been reported in the United States on trace metal
emissions from package boilers (small, self-contained units) and from
residential combustion. With trace metal analysis becoming faster and
cheaper, many heretofore neglected sources will be more amenable to analysis.
Included among these are other types of incinerators (pathological, industrial,
waste disposal), fireplaces, open burning, etc.
Other techniques are beginning to attack the problem of chemical
speciation — that is, determining the molecular form of the trace metal under
study. Raman (19), auger (10), photoelectron (11), and photoacoustic spectro-
scopy (12) are being used or considered for the study of chemical species on
fly ash or ash-type particles. In the near future, as analytical techniques
improve and awareness of the problems they can solve evolves, information
about the molecular form of trace metals from combustion sources will grow.
Also, with trace metal analysis more available, increased efforts will
very likely be directed at emissions from process heating (heat used in
industrial processes). While this type of combustion is not strictly a SCCP
source, in many regions it accounts for a considerable fraction of the heat
produced and more than its share of pollutants, especially trace metal pollu-
tants. As an understanding of trace metal emissions and their environmental
fate develops, more attention will have to be paid to industry sources out-
side of the utility sector.
10.3 ALTERNATE FUELS
Fossil fuels make up the vast majority of combustion fuels today.
While this situation is not expected to change in the foreseeable future,
there will likely be a shift within the fossil fuel regime in the United
States towards more coal and coal by-products (liquefaction, gasification,
in-situ combustion, etc.) and possibly oil shale; generally, however, these
nonconventional processes are not commercially available at this time and
do not fall under the definition of an SCCP.
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Many studies predict the increased utilization of coal in the United
States (for example, see 13). While most speculate on the future particulate
load, few explicitly mention the parallel increased trace metal emissions
problem. Literature dealing only with particulate matter was not picked
up in this search unless trace metals were mentioned. However, the increase
in coal use implies a concomitant increase in the mobilization of trace
metals through the burning of coal. Control technologies (Section 4) and
regulations (Section 9) will simultaneously evolve and influence one another.
Thus, regulations and technologies directed at particle control will have an
impact on trace metal emissions as well. Anyone concerned about trace metal
pollution will therefore have to keep abreast of the status of particle
control.
Walker et al. (14) are interested in the catalytic conversion of coal
to more useful fuels, processes which they claim will become even more im-
portant. They report that it will be justifiable, indeed necessary, to spend
large sums of money learning to characterize coal. Their particular concern
is that trace metals play an important part in catalysis considerations, and
far too little is now know about the role of these trace metals in catalysis.
There are two candidates for non-fossil fuels that could make small
inroads into the nation's energy mix. The burning of municipal refuse, often
augmented by fossil fuels, is seen as a simultaneous solution to the disposal
of the burgeoning volume of trash and a novel, albeit small, fuel source
(15). Municipal refuse is much lower in sulfur than coal and somewhat
higher in chlorine; mixing of the two fuels will dilute the emissions per
BTU for both. An assessment of the trace metal content of refuse was presented
in Section 3.2, however, the enissions "resulting from the thermal conversion
of waste-to-energy are somewhat unknown." (16) Particulate emissions are the
most apparent problem, but cadmium, copper, iron, lead and zinc have also
been identified in the flue gas and fly ash; see Section 5.7. Devitt et al.
(16) also discuss the state-of-the-art (1978) control technologies available
for urban refuse, power generation boilers. Also, the need for research
into boiler types designed for refuse-generated power has been indicated by
Schwieger (17).
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Wood has also been proposed as a possibly significant fuel in the future.
However, only a few reports were identified in this study that dealt with
trace metals and wood (18). The trace metal content of paper products,
often due largely to the printing inks upon them, has been analyzed and
was presented in Table 3-11. In summary, the two possible alternate fuel
sources, trash and wood, remain largely unstudied as fuel sources with
regard to trace metals.
10.4 HEALTH AND ENVIRONMENTAL EFFECTS
The complete review of the health and environmental effects from
trace metals from SCCP is found in Section 6 of this report. Included at
the end of that section is an assessment of research needs, particularly
those designed to fill data gaps. However, several papers specifically
refer to research needs, and those are reviewed here.
The primary area of concern is the unknown chronic effects, both occu-
pational and public, attendant with the increased use of coal. Gibson (19)
has reported that safe exposure levels of hazardous substances from coal
combustion are mostly unknown; he urges toxocological studies as well as
monitoring and gathering more control data. Comar, et al. (20) discuss the
nature and measurement of health effects from energy production. Exposure-
response relationships, risks of death and health effects are considered
for all modes of energy production; coal is the most hazardous means of
energy production. But they conclude, "all data are, however, uncertain,
and massive research is needed." McBride, et_ al. (21) have cautioned to
include consideration of the total cost, monitary and environmental, of ener-
gy, mining to emissions, in any comparison of available types of energy.
Wittenberger (22) , recognizing the increased health hazards of coal-
generated power, has also warned that the health costs of the conversion to
coal should be factored into any total assessment. Since chronic effects are
largely unknown, such factors need to be determined. Comar and Nelson (23)
reported the results of a workshop that considered future energy needs and
the effects of fossil fuel combustion products on human health and well-being.
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Again, the conclusion is that not enough is known about the health effects to
accurately assess the magnitude of the problem and to pinpoint the areas
of acute concern. Eraak et al. (24) also recomirend a comprehensive assess-
ment for future power production in the Southwest, but noted that the paucity
of relevant data make such assessments unreliable.
Finally, a paper from Argonne National Labs (25) recommends a balanced
research program into the biomedical and environmental effects of coal ex-
traction, processing and combustion. Further, that research should be
integrated across all energy technologies to more capably direct and control
the energy mix in the future. They judged it necessary to group researcn
projects into broad program units (which they list) with objectives,
scopes, milestones and costs.
Vftile all these authors are dealing with the general need for more
health and environnental data on coal combustion, none specifically mention
trace metals. Yet all are concerned with the total pollution problem,
and many of the trace metal difficulties have not even been identified well
enough to be factored into the scenarios; however, all the papers, implicitly
or indirectly, relate to the trace metal health problem.
10.5 TECHNOLOGY ASSESSMENT
Closely related to health and environmental assessment and the
indicated research needs, is the area of energy technology assessment.
That is, studies which are trying to predict the energy picture for the
future are often ultimately directed at the health impact; however, such
predictions involve many guesses and estimations as input parameters, and
the results are not usually specific. Essentially none of them get down to the
level of trace metal pollution. The most popular method in assessment it;
to extrapolate current conditions against a demand axis to generate rough,
"ball-park" predictions of combustion and emission levels. For example,
several publications by the Interagency Task Force on Energy/Environment
Research and Development programs which this study reviewed (26, 67) faii.ed
to specifically mention trace metal pollution. They are concerned with
particles and total pollution loading from all potential energy sources and
10-8
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control technologies, but any trace metal predictions would be possible only
by inference. Other reports, typical of the discipline, reflect the same
level of predictive uncertainty (28-30). A recent book by Kash et al. (31)
on the role of research, development and demonstration in the nation's
energy future fails to even mention trace metals in the index. Rather than
reflecting on any author or study, the lack of specific consideration of the
trace metal emissions in the future simply reflects the state-of-the-arts
of pollution knowledge and assessment or prediction.
One study, which is specifically attempting to assess trace metal body
burdens that would result from increased coal utilization, was recently re-
ported by Gasper and Dauzvardia (32). They assume current levels of pollu-
tion will increase proportionally with increased power demand and coal use
in the Illinois River Basin. They conclude that by the hypothetical year of
2020 that trace metal body burdens will be about doubled.
Reiquam et al. (33) have warned that improved control technologies can
no more than transfer the pollution burden to another wastestream. Indeed,
controlling pollution in one medium will increase the severity of problems in
another. They present a methodology for assessing the cross-media impact of
specific control technologies and predicting the net effect of a particular
strategy on the environment. The methodology is demonstrated for a 1000
MW coal-fired power plant. The energy consumption, capital costs and opera-
ting costs are also considered.
10-9
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REFERENCES
1. TJ.S. Environmental Protection Agency. EPA Activities Under the
Resource Conservation and Recovery Act of 1976, Annual Report to the
President and the Congress, Fiscal Year 1977. Washington, D.C.,
1978.
2. U.S. Environmental Protection Agency, Office of Research and Develop-
ment. Research Highlights 1977. Washington, D.C., 1977.
3. U.S. Dept. of Energy. Fossil Power Systems R&D. G.P.O., Washington,
D.C., 1978.
4. Directory of Federal Environmental Research and Development Programs.
Government R&D Report, MIT Branch, 1978.
5. U.S. Environmental Protection Agency, et al. Second National Con-
ference on the Interagency Energy/Environment R&D Program,
Washington, D.C., 1977. Abstracts.
6. Thompson, W. E., and J. W. Harrison. Survey of Projects Concerning
Conventional Combustion Environmental Assessments. EPA 600/7-78-13S ,
Research Triangle Institute, Research Triangle Park, North Carolina,
1978.
7. Golightly, D. W. Atomic Emission Spectroscopy. Com-74-10469. In:
Survey of Various Approaches to the Chemical Analysis of Environ-
mentally Important Materials, B. Geifer and J. K. Taylor, eds.,
Nation Bureau of Standards, Washington, D.C., 1973. pp.144-172.
8. Ondov, J. M. , W. H. Zoller, I. Olmez, et al. Elemental Concentrations
in the National Bureau of Standards' Environmental Coal and Fly Ash
Standard Reference Materials. Anal. Chem., 47(7):1102-1109, 1975.
9. Etz, E. S., G. J. Rosasco, and W. C. Cumminghara. The Chemical Iden-
tification of Airborne Particies by Laser Raman Spectroscopy. In:
Environmental Analysis. Academic Press, New York, 1977. pp.295-34C.
10. Linton, R. W., P. Williams, C. A. Evans, and D. F. S. Natusch. Deter-
mination of the Surface Predominance of Toxic Elements in Airborne
Particles by Ion Microprobe Mass Spectrometry and Auger Electron
Spectrometry. Anal. Chem., 49(11):1514-1520, 1977.
10-10
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11. Hall, E. H., C. M. Allen, D. A. Ball, J. E. Burch, H. N. Conkle, W.
T. Lawhon, T. J. Thomas, and G. R. Smithson, Jr. Comparison of Fossil
and Wood Fuels, Final Report. EPA 600/2-76-056, PB 251 622,
Battelle-Columbus Laboratory, Columbus, Ohio, 1976.
12. Edwards, L. 0. Potential Applications of Photo-Acoustical Spec-
troscopy at Radian. DCN 78-290-403-46-01, Radian Corp., Austin,
Texas, 1978.
13. U.S. Comptroller General. Sixteen (16) Air and Water Pollution
Issues Facing the Nation. 3 Volumes. Washington, D.C., 1978.
14. Walker, P. L. Jr., N. C. Gardner, P. H. Given, H. J. Gluskoter, and
J. L. Johnson. Catalysis of Coal Conversion Processes and Characteri-
zation of Mineral Matter and Trace Elements in Coal. EPRI-207-0-0.
In: Research and Development Programs for Catalysis in Coal Con-
version Processes. Electric Power Research Institute, 1974. pp.
A86-A169.
15. Cho, P., and J. H. Chambers. Municipal Refuse: An Alternate Energy
Resource in Power Plants. In: Energy and the Environment, Pro-
ceedings of the Fourth National Conference, Cincinnati, Ohio, 1976.
AlChE, Dayton, Ohio, 1976. pp.204-211.
16. Devitt, T. W., C. J. Sawyer, and F. D. Hall. State-of-the-Art Assess-
ment of Air Pollution Control Technologies for Various Waste-as-Fuel
Processes. In: Energy and the Environment, Proceedings of the Fifth
National Conference, Cincinnati, Ohio, 1977, D. G. Nichols, et al.,
eds. AIChE, Dayton, Ohio, 1978. pp.167-173.
17. Schwieger, R. G. Utilities, Industry Burn Refuse to Generate Power.
Power, 119(2):15-23, 1975.
18. Hall, E. H., C. M. Allen, D. A. Ball, J. E. Burch, H. N. Conkle, W.
T. Lawhon, T. J. Thomas, and G. R. Smithson, Jr. Comparison of Fossil
and Wood Fuels, Final Report. EPA 600/2-76-056, PB 251 622,
Battelle-Columbus Laboratory, Columbus, Ohio, 1976.
19. Gibson, R. L. Toxicity of Coal and Shale Process Materials. In:
Proceedings of the 42nd American Petroleum Institute, Chicago,
Illinois, 1977. American Petroleum Institute, Chicago, Illinois,
1977. American Petroleum Institute, Washington, D.C., 1977.
pp.368-375.
20. Coroar, C. L., and L. A. Sagan. Health Effects of Energy Production
and Conversion. Ann. Rev. Ener., 1:581, 1976.
10-11
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21. McBride, J. P., R. E. Moore, J. P. Witherspoon, and R. E. Blanco.
Radiological Impact of Airborne Effluents of Coal and Nuclear Plants.
Science, 202:1045, 1978.
22. Whittenberger, J. L. Health Research Needs and Energy Development.
NP—20692, Harvard, 1976.
23. Comar, C. L., and N. Nelson. Health Effects of Fossil Fuel Combustion
Products Report of a Workshop in Indian Wells. PB-242 418,
EPRI-SR-11, Electric Power Research Institute, Palo Alto, California,
1975.
24. Ermak, D. L., J. R. Kercher, and D. L. Pitschard. Comprehensive
Approach for Evaluating the Environmental and Human Health Effects of
Coal-Fired Electricity Production in the Southwest. UCRL--77303,
CONF-751118-1, University of California, Livermore, California, 1975.
25. Argonne National Labs, (USA). Balanced Program Plan: Analysis for
Biomedical and Environmental Research, Volume 3, Coal Combustion.
ERDA--116, Argonne, Illinois, 1976.
26. Stryker, S. Interagency Energy/Environment R&D Program. Enviromental
Protection Agency, Office of Research and Development, 1977.
27. Stryker, S., et al. Interagency Energy/Environment R&D Program,
Status Report III. EPA, Office of Research and Development, 1977.
28. Amr, A. T., et al. Evaluation of Environmental Aspects of Selected
R,D&D Processes within the ERDA Fossil Energy Program. Mitre Corp.,
Metrek Div., McLean, Virginia, 1977.
29. Nichols, D. G., E. J. Rolinski, R. A. Servais, L. Theodore, and A. J.
Buonicore, eds. Energy and the Environment, Proceedings of the Fifth
National Conference, Cincinnati, Ohio, October 31-November 3, 1977.
AlChE, Dayton, Ohio, 1978.
30. Cheney, E. S. Limits on Energy Supply. Chem. Tech., 370-374, 1975.
31. Kash, D. E., M. D. Devine, J. B. Freim, M. W. Gilliland, R. W.
Rycroft, and T. J. Wilbanks. Our Energy Future. University of
Oklahoma Press, Norman, Oklahoma, 1976.
32. Gasper, J. R., and P. A. Dauzvarida. Assessment of Trace Element Body
Burdens Due to Projected Coal Utilization in the Illinois River
Basin. In: Proceedings of the 5th National Conference on Energy and
the Environment, American Institute of Chemical Engineers,
Cincinnati, Ohio, 1977. pp.350-354.
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Reiquam, H., N. Dee, and P. Choi. Assessing Cross Media Impacts.
Environ. Sci. Technol., 9(2):118-120, 1975.
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GLOSSARY
AAQS: Ambient Air Quality Standards (Federal)
ACFM: Actual Cubic Feet per Minute
AEC: Atonic Energy Commission
AEROS: Atmospheric and Emissions Reporting System
Aerosol: Fine particles (solid or liquid) suspended in a gas.
Ames Test: A short-term, in-vitro test for mutagenicity (DNA damage) in-
volving the reversion of a histadine requiring strain of bacterium
(Salmonella typhimurium) induced by a chemical agent.
Anthropogenic: Being caused or generated by man.
AQCR: Air Quality Control Region
BET: A method developed by Brunauer, Emmett, and Teller, to measure the
surface area of small particles by monitoring the adsorption of a
gas, assuming a monolayer; commercially available.
BTU: British Thermal Unit, equivalent to 1055.1 Joules.
CAMP: Continuous Air Monitoring Program
carcinogen: An agent that can cause cancer.
CCEA: Conventional Combustion Environmental Assessment (an EPA Program).
CFR: Code of Federal Regulations
Chalcophile: A mineralogical class of elements that are frequently found
as sulfides.
Curie: A unit of radioactivity equal to 3.7 x 1010 disintegrations per
second.
EPC: Estimated Permissible Concentration (a safe environmental level of a
pollutant).
G-l
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ESP: Electrostatic Precipitator (a device designed to remove particles
from a gaseous stream).
Fly ash: The solid particles resulting from the combustion of a fuel that
are entrained in the flue gas; sometimes meaning only the particles
that leave the process via the stack emissions.
ICRP: International Commission on Radiological Protection
IERL: Industrial Environmental Research Laboratory (EPA)
INAA: Instrumental Neutron Activation Analysis
LC-50: Lethal concentration; the concentration which causes fifty percent
mortality in a population
LD-50: Lethal Dosage; the dosage which causes fifty percent mortality.
Lithophile: A mineralogical classification for those elements frequently
found combined with oxygen (or frequently silicon dioxide).
MATE: Minimum Acute Toxicity Effluent; the minimum concentration in an
effluent that is believed to be acutely harmful.
MEG: Multimedia Environmental Goals
Micron: Common contraction of micrometer.
MMAD: Mass Mean Aerodynamic Diameter
NADB: National Aerometric Data Bank
NADIS: National Aerometric Data Information Service
NASN: National Air Sampling Network
NIOSH: National Institute for Occupational Safety and Health
NRC: Nuclear Regulatory Commission
Non-metal: Those elements in the upper right portion of the periodic table
having no metallic properties (H, C, N, 0, F, P, S, CI, Br, inert gases).
NSPS: New Source Performance Standards
NTIS: National Technical Information Service
Oncogenic: Tending to cause tumors.
ORNL: Oak Ridge National Laboratory
G-2
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ppm: Parts per million
PSD: Prevention of Significant Deterioration, or Particle Size Distribution
RCRA: Resource Conservation and Recovery Act (1976)
REM* A dosage of radiation that will cause the same biological effect as
one Roentgen of X-radation.
RTP: Research Triangle Park: an EPA/IERL
SAROAD: Storage and Retrieval of Aerometric Data
SCCP: Stational Conventional Combustion Process
Semi-metal: Those elements which exhibit some metallic characteristics,
but not all; B, Si, As, Se, Te, 1, At
SIP: State Implementation Plan
SRM: Standard Reference Material; a series of representative, quantified
reference materials available through National Bureau of Standards
Synergism: The interaction of two entities to produce an effect different
than merely the sum of their independent effects.
Teratogen: An agent that can cause fetal changes and birth defects.
TLV: Threshold Limit Value; refers to the maximum presumed safe level
for ambient concentrations; given in MEG's.
Trace element: those elements which are found in concentrations less
than 0.01 percent (100 ppm); not a sharp definition.
TSP: Total Suspended Particulate
TVA: Tennessee Valley Authority
WHO/FAO: World Health Organization/Food and Agricultural Organization
G-3
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|- TECHNICAL REPORT DATA
(Please reod JmUrucrions on the reverse before completing)
1. PEPOBT NO. 2.
EPA-600/7-80-155a
«. title and subtitle Trace Metals and Stationary Conven-
tional Combustion Processes;
Volume 1. Technical Report
6. REPORT DATE
August 1980 Issuing Date.
B. PERFORMING organization CODE
7. AuTHORIS}
L.O.Edwards, C.A.Muela, R.E.Sawyer, C.M.
Thompson, D.H.Williams, and R. D. Delleney
8. PERFORMING organization report no
S PERFORMING ORGANIZATION NAME AND ADDRESS
Radian Corporation
P.O. Box 9948
Austin, Texas 78703
ID. PROGRAM ELEMENT NO.
INE624
ii. contract/grant no.
68-02-2608, Task 54
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Develooment
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13 TYPE OF REPORT ANO PERJOD COVERED
Task Final; 5/79-5/80
14 SPONSORING AGENCY CODE
EPA/600/13
is supplementary notes ERL-RTP project officer C.J. Chatlynne is no longer with EPA;
for details, contact Michael C. Osborne, Mail Drop 62, 919/541-3996.
16 ABSTRACTThe report gives results of a search of U.S. literature to identify published
information about trace metals and Stationary Conventional Combustion Processes
(SCCPs). The search was initially computerized with later cross referencing from
identified reports. The report summarizes the information found in the literature and
includes specific references. It summarizes what has been published about ambient
trace metals in air, water, and soils. A survey, reporting the trace metal concen-
tration in combustible fuels, identifies coal as the fuel of most concern; generally,
trace metal levels in coal are similar to their crustal abundances. It reviews conven-
tional combustion technology. It discusses trace metal flows and partitioning around
various types of boilers and pollution control devices, and reports data from cited
studies. In addition to coal, the report gives data for oil, municipal refuse, and
wood. It also covers emissions to air, water, and soil, including trace metal leach-
ing. It documents the health and environmental effects of trace metals. Where pos-
sible, it assesses specific contributions from SCCPs. It covers environmental trans-
port systems, as well as special problems associated with radioactive metals and '
SCCPs.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
b.IDENTIFIERS/OPEN ENOEO TERMS
c. cosati Field/Croup
Pollution Fuel Oil
Trace Elements Wastes
Radioactive Materials Wood
Combustion Products Leaching
Coal
Boilers
Pollution Control
Stationary Sources
Trace Metals
Municipal Refuse
13B
06A 14 G
18H 11L
2 IB 07D,07A
21D
13A
19. DISTRIBUTION STATEMENT
Release to Public
1i SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
105
20 SECURITY CLASS {This page)
Unclassified
22 PRICE
CPA Form 2220*1
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