EPA-450/2-73-001
EMISSION FACTORS
FOR TRACE
SUBSTANCES
U.S.-ENVIRONMENTAL PROTECTION AGENCY
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EPA-450/2-73-001
EMISSION FACTORS
FOR TRACE SUBSTANCES
David Anderson
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Water Programs
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
December 1973
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This report has been reviewed by the Office of Air Quality Planning and Standards, Environmental Pro-
tection Agency, and approved for publication. Approval does not signify that the contents necessarily
reflect the views and policies of the Environmental Protection Agency, nor does mention of trade names
or commercial products constitute endorsement or recommendation for use.
Document is available to the public through the
National Technical Information Service,
Springfield, Virginia 22151.
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PREFACE
This document presents emission factors that can be used to estimate emissions of eight trace sub-
stances: arsenic, asbestos, beryllium, cadmium, manganese, mercury, nickel, and vanadium. The limita-
tions and applicability of emission factors, as presented in the Introduction to this report, should be
kept in mind in applying the factors presented.
Throughout the document, some source classifications or industrial categories appear much more
frequently than others. This is not intended to imply that these sources are necessarily more serious
polluters than others. The imbalance is partially due to the availability of data from some more minor
sources and the unavailability of equivalent data from other more obvious or more serious sources. When
source tests are run, the emissions are normally analyzed for a wide range of constituents by the Envi-
ronmental Protection Agency. Data from such analyses should aid considerably in the assessment of the
relative importance of sources of a particular pollutant.
As additional data become available, they will be incorporated in this document as supplements. The
availability of these supplements will be indicated in the publication, Air Pollution Technical Publica-
tions of the Environmental Protection Agency, which is available from the Air Pollution Technical
Information Center, Research Triangle Park, N. C. 27711.
ACKNOWLEDGMENTS
The author would like to thank the people of the Environmental Protection Agency who have provided
helpful suggestions and comments in preparing this document. These people are: James H. Southerland,
John McGinnity, Mike Jones, Robert E.Neligan, John Copeland, Dr. Robert E.Lee, Darryl Van Lehmden,
Dale Slaughter, Gill Wood, D. E. Caldwell, and Susan Anna. Susan Watson, Joan Currin, Vivian Dailey,
Fannie Lee, and Cynthia Pendergrass were also very helpful in the production of the draft report.
iii
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CONTENTS
Chapter Page
ABSTRACT x
1. INTRODUCTION 1-1
References for Chapter 1 1-1
2. ARSENIC 2-1
Mining 2-1
Metallurgical Processing 2-1
Cast Iron 2-1
Nonferrous Alloys ' 2-1
Phosphoric Acid, Thermal Process 2-2
Processing and Utilizing Arsenic and Its Compounds 2-2
Agricultural Uses 2-2
Glass Production 2-2
Wood Preservative 2-2
Others 2-2
Consumptive Uses 2-3
Agricultural 2-3
Detergents 2-3
Fuel Combustion 2-3
Coal 2-3
Oil 2-3
Waste incineration 2-3
References for Chapter 2 2-3
3. ASBESTOS 3-1
Mining 3-1
Milling 3-1
Processing of Asbestos 3-1
Friction Products 3-1
Asbestos Cement Products 3-1
Textiles 3-1
Asbestos Paper 3-2
Floor Tile 3-2
Asbestos Insulation 3-2
Others 3-2
Consumptive Uses 3-2
Solid Waste Incineration 3-2
References for Chapter 3 3-2
4. BERYLLIUM 4-1
Mining 4-1
Metallurgical Processing 4-1
Beryllium Hydroxide 4-1
Beryllium Oxide 4-1
Beryllium-Copper Alloys 4-1
Beryllium Metal 4-1
Cement Plants 4-2
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Chapter
Dry Process 4-2
Wet Process 4-2
Processing or Uses of Beryllium and Its Compounds 4-2
Beryllium Alloys 4-2
Ceramics 4-2
Rocket Propellants 4-3
Beryllium Metal Fabrication 4-3
Fuel Combustion 4-3
Coal 4-3
Oil 4-3
Waste Incineration 4-3
Others 4-4
References for Chapter 4 4-4
5. CADMIUM 5-1
Mining of Zinc-Bearing Ores 5-1
Metallurgical Industry 5-1
Zinc, Lead, and Copper Smelters 5-1
Secondary Copper 5-1
Secondary Lead 5-1
Galvanized Metals 5-2
Cement Plants 5-2
Dry Process 5-2
Wet Process 5-2
Processing or Utilization of Cadmium 5-2
Electroplating 5-2
Pigments 7 5-2
Plastics 5-3
Alloys 5-3
Batteries 5-3
Miscellaneous 5-3
Consumptive Uses 5-3
Fuel Combustion 5-3
Oil 5-3
Coal 5-3
Gasoline 5-4
Waste Incineration 5-4
References for Chapter 5 5-'
6. MANGANESE 6-
Mining 6-1
Production of Manganese Metal 6-1
Production of Manganese Alloys 6-1
Ferromanganese — Blast Furnace 6-1
Ferromanganese — Electric Furnace 6-1
Siliconmanganese — Electric Furnace 6-1
Processing of Manganese and Its Compounds 6-1
Steel Production 6-1
Cast Iron 6-2
Welc:ag Rods 6-2
Nonferrous Alloys 6-3
Batteries 6-3
Chemicals , .. 6-3
Others 6O
vi
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Chapter Page
Cement Plants 6-3
Dry Process 6-3
Wet Process 6-3
Fuel Combustion 6-3
Coal 6-3
Oil 6-4
Waste Incineration 6-4
References for Chapter 6 6-4
7. MERCURY 7-1
Mining 7-1
Ore Processing 7-1
Secondary Production of Mercury 7-1
Processing and Utilization of Mercury and Its Compounds 7-1
Instruments 7-1
Production of Chlorine and Caustic Soda 7-1
Paints 7-2
Pharmaceuticals 7-2
Pulp and Paper 7-2
Amalgamation 7-2
Electric Apparatus 7-4
Others 7-4
Consumptive Uses 7-4
Paints 7-4
Agricultural Spraying 7-4
Pharmaceuticals 7-4
Dental Preparations 7-4
General Laboratory Losses 7-4
Fuel Combustion , 7-4
Coal 7-4
Oil 7-5
Solid Waste Incineration 7-5
References for Chapter 7 7-5
8. NICKEL 8-1
Mining and Metallurgical Processing 8-1
Processing of Nickel and Its Compounds 8-1
Stainless and Heat-resisting Steels 8-1
Alloy Steel 8-1
Nickel Alloys 8-1
Electroplating 8-1
Batteries .8-1
Catalysts 8-1
Cement Plants 8-2
Dry Process 8-2
Wet Process 8-2
Consumptive Uses of Nickel and Its Compounds 8-2
Fuel Combustion 8-2
Coal 8-2
Oil 8-2
Gasoline 8-3
Waste Incineration 8-3
References for Chapter 8 8-3
vii
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Chapter Page
9. VANADIUM 9-1
Mining and Processing 9-1
Metallurgical Processing 9-1
Ferrovanadium 9-1
Vanadium Metal 9-2
Vanadium Carbide 9-2
Steel Production 9-2
Blast Furnace 9-2
Open-hearth Furnace 9-2
Basic Oxygen Furnace 9-2
Electric Furnace , 9-3
Cast Iron Production 9-3
Cement Plants 9-3
Dry Process 9-3
Wet Process 9-3
Processing of Vanadium and Its Compounds .- 9-3
Nonferrous Alloys 9-3
Catalysts .-^, 9-3
Ceramics and Glass 9-3
Miscellaneous 9-3
Fuel Combustion 9-4
Coal 9-4
Oil 9-4
Solid Waste Incineration x. 9-4
References for Chapter 9 9-4
viii
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LIST OF TABLES
Table Page
1-1 Emission Factor Symbols 1-3
2-1 Emission Factors for Mining and Industrial Sources of Arsenic 2-4
2-2 Emission Factors for Processing Arsenic and Its Compounds 2-4
2-3 Emission Factors for Consumptive Uses of Arsenic 2-4
2-4 Emission Factors for Arsenic from Fuel Combustion 2-5
2-5 Emission Factors for Arsenic from Solid Waste Incineration 2-5
3-1 Emission Factors for Abestos from Mining and Milling 3-3
3-2 Emission Factors for Processing of Abestos 3-4
3-3 Emission Factors for Consumptive Uses of Abestos 3-4
4-1 Emission Factors for Beryllium from Industrial and Solid Waste Incineration 4-5
4-2 Emission Factors for Beryllium from Fuel Combustion, Coal 4-6
4-3 Emission Factors for Beryllium from Fuel Combustion, Oil 4-7
4-4 Emission Factors for Beryllium from Waste Incineration 4-7
5-1 Emission Factors for Cadmium from Industrial Sources 5-6
5-2 Emission Factors for Processes Involving Cadmium 5-7
5-3 Emission Factors for Consumptive Uses of Cadmium 5-7
5-4 Emission Factors for Cadmium from Fuel Combustion 5-8
5-5 Emission Factors for Cadmium from Waste Incineration 5-9
6-1 Emission Factors for Manganese from Industrial Sources 6-6
6-2 Emission Factors for Manganese from Fuel Combustion, Coal 6-8
6-3 Emission Factors for Manganese from Fuel Combustion, Oil 6-9
6-4 Emission Factors for Manganese from Waste Incineration 6-10
7-1 Emission Factors for Mercury from Mining, Primary and Secondary Sources 7-7
7-2 Emission Factors for Processing and Utilization of Mercury and Its Compounds 7-8
7-3 Emission Factors for Consumptive Uses of Mercury and Its Compounds 7-9
7-4 Emission Factors for Mercury from Fuel Combustion, Coal 7-10
7-5 Emission Factors for Mercury from Fuel Combustion, Oil 7-12
7-6 Emission Factors for Mercury from Solid Waste Incineration 7-14
8-1 Emission Factors for Nickel from Industrial Sources 8-4
8-2 Emission Factors for Nickel from Fuel Combustion, Coal 8-6
8-3 Emission Factors for Nickel from Fuel Combustion, Oil 8-7
8-4 Emission Factors for Nickel from Waste Incineration 8-9
9-1 Emission Factors for Vanadium from Industrial Sources 9-6
9-2 Emission Factors for Vanadium from Fuel Combustion, Coal 9-7
9-3 Emission Factors for Vanadium from Fuel Combustion, Oil 9-8
9-4 Emission Factors for Vanadium from Solid Waste Incineration 9-9
IX
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ABSTRACT
This document presents emission factors for eight trace pollutants: arsenic, abestos, beryllium, cadmium,
manganese, mercury, nickel, and vanadium. Emission data on which these factors are based, obtained .from
source tests, material balance studies, engineering estimates, etc., have been compiled for use by individuals
and groups responsible for conducting air pollution inventories. Emission factors given in this document
cover most of the common emission categories for the eight trace substances: mining, metallurgical,
secondary metal industry, processing and utilization, consumptive uses, fuel combustion, and waste
incineration. When no source test data are available, these factors can be used to estimate the quantities of
the trace pollutants being released from a source or source group.
Key words: air pollution, arsenic, asbestos, beryllium, cadmium, emissions, emission factors, manganese,
mercury, nickel, pollution, vanadium.
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EMISSION FACTORS
FOR
TRACE SUBSTANCES
1. INTRODUCTION
The purpose of this document is to present
emission factors that can be used to estimate emis-
sions of eight trace substances: arsenic, asbestos,
beryllium, cadmium, manganese, mercury, nickel,
and vanadium. It would be difficult and extremely
costly to monitor suspect sources of large amounts
of trace substances within the United States. The
only feasible method of determining trace sub-
stance emissions for a given community is to make
generalized estimates of typical emissions from
each of the source types.
The emission factor is an estimated average of
the rate at which a pollutant is released to the
atmosphere as a result of some activity, such as
combustion or industrial production, divided by
the level of that activity.1
The limitations and applicability of emission
factors must be understood. While the emission
factors presented in this report are sufficient,
under most conditions, for estimating emissions for
such purposes as emission inventories, their
accuracy is uncertain and in most cases unknown.
They should not be used as a basis for establishing
control regulations, standards, or similar mea-
sures. In general, particle size distribution and
chemical structure were not considered in
developing the factors because of the lack of such
data.
The emission factors presented in this document
were estimated by the whole spectrum of tech-
niques available for determining such factors;
these included: questionnaire surveys, plant visits,
source testing, process material balances,
analytical work to determine the content of trace
substances, and literature search. Obviously, the
varying accuracies of the techniques employed in
developing the emission factors affect the accuracy
of the emission factors themselves. To give some
indication of this variation, the tables include an
"emission factor symbol" that indicates the
technique employed to determine each emission
factor. Emission factor symbols commonly used in
this document are defined in Table l-l2-16 and the
accuracy normally associated with the related
techniques is indicated. In some instances,
analytical techniques not included in Table 1-1
were used to determine emission factors for a
specific trace substance or the accuracy of the
technique differed for a specific substance from
that given in Table 1-1. These exceptions are
identified in the introduction to the chapter per-
taining to the particular substance involved.
In using these factors, the following procedure is
recommended. First, the user should read Table
1-1. Next, the text description of the emission
source should be read. Finally, based on this
information, the factor can be intelligently applied
to the area of concern.
Unless otherwise noted in the tables, the
emission factors are for uncontrolled processes. In
some cases, however, it was impossible to develop
uncontrolled factors, and in these instances, factors
were developed based on emissions from control
equipment. No attempt should be made to back
calculate to obtain the uncontrolled value since this
could lead to large errors and possibly to undue
concern. Therefore, factors of this type should only
be applied to controlled processes.
REFERENCES FOR CHAPTER 1
1. Compilation of Air Pollutant Emission Factors
(Revised). U.S. Environmental Protection Agency.
Research Triangle Park, N.C. Office of Air
Programs Publication No. AP-42. February 1972.
149 p.
1-1
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2. Brown, H.S. Unpublished data from Purchase
Order No. 3-02-00710. Geological Resources, Inc.
Raleigh, N.C. December 1972.
3. Barnett, W.B. and H.L. Kahn. Comparison of
Atomic Fluorescence with Atomic Absorption as
an Analytical Technique. Anal. Chem. 44(6): 935-
939. May 1972.
4. Schlesinger, M.D. and H. Schullz. An
Evaluation of Methods for Detecting Mercury in
Some U.S. Coals. Pittsburgh Energy Research
Center. Pittsburgh, Pa. RI 7609. 1972.
5. Schlesinger, M.D. and H. Schultz. Analysis for
Mercury in Coal. Bureau of Mines Managing Coal
Wastes and Pollution Program, U.S. Department
of the Interior. Washington, D.C. Technical
Progress Report 43. September 1971.
6. Levy, A., S.E. Miller, R.E. Barnett, E.J. Schulz,
R.H. Melvin, W.H. Axtman, and D.W. Locklin. A
Field Investigation of Emissions from Fuel Oil
Combustion for Space Heating. Battelle.
(Presented at American Petroleum Institute
Committee on Air and Water Conservation
meeting. Columbus, Ohio. November 1, 1971.)
7. Air Pollution Engineering Manual. Danielson,
J.A. (ed.). National Center for Air Pollution
Control, Public Health Service, U.S. Department
of Health, Education, and Welfare. Cincinnati,
Ohio. Publication No. 999-AP-40. 1967. p. 728.
8. Diehl, R.C., E.A. Hottnan, H. Schultz, and R.J.
Heron. Fate of Trace Mercury in the Combustion
of Coal. Pittsburgh Energy Research Center,
Bureau of Mines. Pittsburgh, Pa. Technical
Progress Report No. 54. May 1972.
9. Caban, R. and T.W. Chapman. Losses of
Mercury from Chlorine Plants: A Review of a
Pollution Problem. Amer. Inst. Chem. Engr. J.
18(5):892-901, September 1972.
10. Test No. 71-MM-06. Emission Testing Branch,
Environmental Protection Agency. Research
Triangle Park, N.C. March 29, 1972.
11. Dams, R., J.A. Robbins, K.S. Rahn, and J.W.
Winchester. Nondestructive Neutron Activation
Analysis of Air Pollution Particulates. Anal. Chem.
42(8):861-867, July 1970.
12. Morrison, G.H. and N.M. Potter. Multielement
Neutron Activation Analysis of Biological Material
Using Chemical Group Separations and High
Resolution Gamma Spectrometry. Anal. Chem.
44(4):839-842, April 1972.
13. Ruck, R.R., HJ. Gluskotes, and E.J. Kennedy.
Mercury Content of Illinois State Geological
Survey. Urbana, 111. No. 43. February 1971.
14. Liebermann, K.W. and H.H. Kramer.
Cadmium Determination in Biological Tissue by
Neutron Activation Analysis. Anal. Chem.
42(2):266-267, February 1970.
15. Nandi, M., D. Stone, H. Jick, S. Shapiro, and
S.P. Lewis. Cadmium Content of Cigarette. Lancet.
December 20, 1969. p. 1329-1330.
16. Zuboric, P., T. Stadnichenko, and N.B.
Sheffey. Distribution of Minor Elements in Coal
Beds of the Eastern Interior Region. U.S. Govern-
ment Printing Office. Washington, D.C.
Geological Survey Bulletin 117-B. 1964.
1-2
EMISSION FACTORS FOR TRACE SUBSTANCES
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Table 1-1. EMISSION FACTOR/SYMBOLS
Emission
factor
symbol
Technique
Estimated accuracy
PV
E
Q
MB
Source
sampling
CAA
DM
ES
EST
FAA
NA
OES
S
SC
SSMS
UK
Plant visits
Engineering judgement
Questionnaire surveys
Material balances
Flame atomic absorption
Dithizone
Emission spectroscopy
Emission spectrometry
Flameless atomic absorption
Neutron activation
Optical emission spectrography
Saltzman's colorimetric
Spectrochemical analyses
Spark source mass spectrography
Unknown, reported in literature
based on unspecified analy-
tical technique
Unknown.
Unknown.
Unknown.
Unknown.
Precision is 1, 3, and 10% for minimum detectable
levels of 1, 0.5, and 0.1 ppm, respectively, for
beryllium and for nickel in oil samples.2 Minimum
detectable level is 0.4 ppm for cadium in oil
samples.2 Minimum detection limit is 0.001
/*g/ml of prepared sample for cadmium generally.3
Less accurate than FAA for mercury.4
Comparable to FAA for mercury analysis.5
Semiquantitative.6
Semiquantitative.7
±5% with minimum resolution of 2 ppb for
analysis of mercury. 8-9
±25% for one sample of particulate analyzed.11
Arsenic in biological materials had an average
deviation of about ±6.9%.12 ±20% precision for
mercury in coal.13 Accuracy of ±5% for
biological tissues analyzed for cadmium.14
Considered to be Semiquantitative. Reported to
have a precision of ±25% for samples from
cement plants.10
Unknown.15
Limit of detection is 0.0001 % with an accuracy of
±15% for beryllium analysis in coal.1"
Precision ±100%.10
Unknown.
Introduction
1-3
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2. ARSENIC
MINING1
Arsenic is widely distributed in the earth's crust.
It occurs mainly as an impurity in copper, lead,
cobalt, nickel, iron, gold, and silver ores. Emission
of arsenic is a by-product of mining for these ores.
Processing is basically the same for all mining
operations: ore removal, ore handling, crushing,
grinding, and concentration. Emissions of arsenic
occur from these operations, but the major part is
from tailings (wind losses). The emission factor for
mining operations is given in Table 2-1.
METALLURGICAL PROCESSING1
Arsenic is produced commercially from flue
dust, speiss, and sludges as a by-product of copper
smelting and other smelting operations. It is
produced in the form of arsenic trioxide or
arsenous oxide (As2O3). The arsenic trioxide is
volatilized during smelting and is, therefore, a
main constituent of flue dust. Crude flue dust can
carry up to 30 percent by weight of arsenic trioxide.
To recover arsenic trioxide from the flue dust (or
from the other sources mentioned), the crude flue
dust is mixed with a small amount of pyrite or
galena. The hot gases from the roasting
(about 220°C) are passed through brick cooling
chambers called kitchens (about 100°C). Arsenic
trioxide will condense out of the gas as a result of
cooling, and the condensate is 90 to 95 percent
pure arsenic trioxide.
If higher purity is necessary, the arsenic trioxide
is refined in a reverberatory furnace (at 540 °C).
The vapors pass through settling chambers and
kitchens. The temperature (from 120 to 180 °C) in
the settling chambers is above the condensation
point of the trioxide. Most of the trioxide is thus
•caught in the kitchens and is about 95 percent
pure. A baghouse is used for exit gases from the
kitchens.
Emissions occur as a result of gas losses during
processing. Some dust is also lost. In processes in
which arsenic content of the ore is high, control
equipment is an essential part of the process. Other
smelters dump the flue dust or sell it to refining
smelters.
Emission factors are provided in Table 2-1 for
copper, lead,and zinc smelters. No emission factors
are provided for gold and silver reduction plants.
These values can be considered uncontrolled
emissions since the arsenic is usually collected as
flue dust. The emission factors are based upon
material balances and stack sampling data.
CAST IRON1
Dust samples from foundries have been
analyzed by spectrographic methods for arsenic
content. Foundries and steel mills emit arsenic, the
quantity depending upon the content of the raw
materials.
The cupola is used most extensively in the
production of cast iron. Based on information
obtained from the industry, the particulate
emission factor is 9 to 11 kilograms of particulate
per 1000 kilograms of process weight. This value
includes melting and nonmelting operations.
Arsenic constitutes about 0.7 percent of this
particulate matter.1 Therefore, from the above
information, the emission factor for this industry
was estimated as shown in Table 2-1.
NONFERROUS ALLOYS1
Arsenic is alloyed with copper (arsenical
copper), lead, and sometimes brass. Arsenical
copper can contain from 0.3 to 0.5 percent arsenic.
Certain lead alloys contain from about 1 to 2.5
percent arsenic.
Uses for arsenical copper are for building
automobile radiators, heat exchangers, and
condenser tubes. Batteries, babbits, and munitions
use lead containing a small quantity of arsenic.
Arsenic is also added to small quantities of brass to
prevent dezincification and reduce season
cracking.
Alloying and melting operations for the pro-
duction of these alloys result in emissions, and no
air pollution equipment is reported in use. The
2-1
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emission factor (Table 2-1), based on information
obtained from industry, is therefore, considered an
uncontrolled value.
PHOSPHORIC ACID, THERMAL
PROCESS *
Some phosphoric acid produced by the thermal
process is used in detergents, foods, and drugs.
Phosphates used to produce the phosphoric acid
will, from natural sources, contain arsenic. The
phosphates are reduced in an electric furnace, and
during this step, arsenic emissions may be quite
significant. However, no emission factor is
available to date.
PROCESSING AND UTILIZING ARSENIC
AND ITS COMPOUNDS1
About 70 percent of the arsenic and its
compounds consumed is for agricultural purposes,
20 percent is used in glass production, and the rest
(about 10 percent) goes for wood preservatives,
nonferrous alloys, animal dips, paints,
pyrotechnics, poultry feeds, and other products.
Emission factors are provided in Table 2-2.
Agricultural Uses *
The principal use of arsenic is in the application
of various arsenic compounds as pesticides. All
compounds are produced from arsenic trioxide.
The processing of the pesticides depends upon
the size of operation. Small operations conduct all
reactions in closed batch reactors. Emissions occur
only as handling losses before the arsenic trioxide is
added to the reactor vessel. In large operations,
arsenic trioxide is handled in bulk quantities. In
some cases, for example, trioxide is received in
railroad cars and dumped directly into a reactor
tank containing nitric acid to produce arsenic acid.
The chemical reactions involving the trioxide with
various other reactants do not result in significant
emissions. Most handling operations are controlled
by hoods, ducts, exhaust fans, and baghouses.
The emission factor presented in Table 2-2 is
based on information obtained from industrial
sources. The value is considered a controlled
emission factor.
Glass Production *
Arsenic is used in almost all types of glass. It
aids the processing by removing bubbles during
manufacturing and acts as a stabilizer of selenium
in decolorizing crystal glass. About 1 to 5
kilograms of arsenic per 1000 kilograms of glass
produced is used. Soda-lime glass, the most widely
used glass, will contain about 3 kilograms of
arsenic per 1000 kilograms of glass.
The process normally involves a direct-fired
regenerative furnace that operates continuously.
Raw materials are charged at one end of the
furnace and molten glass exits at the other end.
The operating temperature inside the furnace is
about 1480°C, and the exit temperature of the
glass is about 1200°C. Emissions are mainly from
the furnace as combustion gases, and volatilized
materials from the molten mass. The mass of
particulates emitted is directly proportional to the
production rate of the furnace.
No stack information or material balance
information is available to yield emission factors.
However, 7.71 percent of the particulate emitted
(about 1 kilogram per 1000 kilograms of glass) has
been reported to contain arsenic trioxide. The
emission factor based on this information is
presented in Table 2-2. Samples from baghouses
yielded this value; however, the value 7.71 percent
is considered an uncontrolled emission, and the
emission factor given should be used for
uncontrolled processes only.
Wood Preservatives
1
Several arsenic compounds are used as wood
preservatives. These compounds are used to
preserve mine timbers, telephone poles, and other
wood materials. Emissions from this source are
considered negligible.
Others l
Other uses of arsenic and its compounds are
represented in paint pigments, pyrotechnics, cattle
and sheep dips, Pharmaceuticals, poultry feed
additives, semiconductors (alloyed with aluminum,
gallium, and indium), and other miscellaneous
products.
Industrial sources felt that emissions from these
applications in industry resulted from handling of
the dry arsenic or its compounds. The emission
factor is based on information from these sources
and should be used for the individual industries
(see Table 2-2).
2-2
EMISSION FACTORS FOR TRACE SUBSTANCES
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CONSUMPTIVE USES
Agricultural
The uses of spray and dust pesticides containing
arsenic and its compounds are sources of emissions
as a result of application (consumptive use). No
emission factor is available at present on spraying
or dusting operations because of lack of data.
Another source of emissions from spraying or
dusting operations is from cotton ginning opera-
tions. Here pesticides adhere to cotton fibers, and
emissions result from the ginning operation. In one
study, particulates from a cotton gin were taken.
Particulate discharge was determined to be about
5.9 kilograms per bale of cotton ginned. The
arsenic content of the particulates average about
0.03 percent. Using the amount of particulate
emitted and the percent of arsenic present, the
emission factor was estimated (Table 2-3).
Detergents
Arsenic is not added to detergents intentionally.
The arsenic occurs naturally in the phosphates
used in producing detergents. Emissions are
considered negligible.
FUEL COMBUSTION
Coal *'2
The average content of arsenic in domestic coal
is about 5.44 parts per million. During combustion,
arsenic is emitted with the fly ash. A study of fly
ash samples showed an arsenic range of 25 to 370
micrograms per cubic meter (by emission spectro-
graphs). Based on an average value (147 micro-
grams per cubic meter) obtained from the fly ash
samples taken from stacks, the emission factor
(sample taken after fly ash collection) was
calculated (Table 2-4).
OH3
Imported fuel and crude oils and United States
crude oils have been analyzed by neutron
activation. All but one sample of the imported
residual oils analyzed contained arsenic. The
arsenic content of the residual oils ranged from 0.1
to 0.2 part per million with an average of 0.14 part
per million. All foreign crude oils analyzed showed
arsenic to be present. The arsenic content of the
crude oils ranged from 0.01 to 0.34 part per million
with an average of 0.13 part per million. Only five
out of nine U.S. crude oils analyzed showed arsenic
to be present.The arsenic content of the U.S. crude
oils ranged from 0.007 to 0.61 part per million with
an average of 0.15 part per million.
The emission factors given in Table 2-4 are
based on the arsenic content in the oils; a 100
percent combustion factor and densities of 850
(crude oil) and 944 grams per liter (fuel oil) were
assumed.
WASTE INCINERATION
1
Burning of products that contain arsenic is a
waste incineration source. No overall emission
factor for this source is available.
Two emission factor values are available: cotton
ginning waste burning and sewage and sludge
burning (Table 2-5). Waste from cotton ginning
operations will contain arsenic as a result of
pesticide application to cotton fields. The emission
factor for cotton ginning was estimated by Davis .*
For sewage and sludge, the arsenic content ranges
from 2 to 3.4 parts per billion. Based on these
values, the emission factor in Table 2-5 was
estimated by Davis.1
REFERENCES FOR CHAPTER 2
1. Davis, W.E. National Inventory of Sources and
Emissions; Arsenic, Beryllium, Manganese,
Mercury and Vanadium — Section I, Arsenic
(1968). W.E. Davis and Associates. Leawood,
Kansas. Contract No. CPA 70-128. May 1971.
2. Cuffe, S.T. and R.W. Gerstle. Emissions from
Coal Fired Power Plants. National Center for Air
Pollution Control, Public Health Service, U.S.
Department of Health, Education, and Welfare.
Cincinnati, Ohio. Publication No. 999-AP-35.
1967.
3. Sheibly, D. Unpublished data. Materials
Section, Lewis Research Center, Plum Brook
Station, National Aeronautics and Space
Administration. Sandusky, Ohio. August 1971.
Arsenic
2-3
-------
Table2-1. EMISSION FACTORS FOR MINING AND INDUSTRIAL
SOURCES OF ARSENIC
Source
Mining
Copper smelter
Lead smelter
Zinc smelter
Cast iron
Nonferrous alloys
Emission factor
0.1 kg/103kg (0.2 Ib/ton) of arsenic in ore
3 kg/103kg (5 Ib/ton) of copper
0.4 kg/103kg (0.8 Ib/ton) of lead
0.5kg/103kg (1 Ib/ton) of zinc
0.006 to 0.008 kg/103kg (0.01 to 0.02 Ib/ton)
of metal charged
0.5 kg/10-3kg (1 ib/ton) of arsenic processed
Emission
factor
symbol8
E
MB, UK
MB, UK
MB, UK
E
Q
a Defined in Table 1-1.
Table2-2. EMISSION FACTORS FOR PROCESSING
ARSENIC AND ITS COMPOUNDS
Source
Emission factor
Emission
factor
symbol
a
Pesticide production
for agricultural usesb
Glass production
Wood preservatives
Others (paint pigments,
pyrotechnics, pharma-
ceutical, semiconductors,,
etc.)
10kg/103kg(20lb/ton)of
arsenic processed
0.08 kg/103kg (0.2Ib/ton) of
glass produced
Negligible
2kg/103kg(3lb/ton)of
arsenic processed
Q
OESd)
Q
aDefined in Table 1-1; number in parentheses indicates the number of sam-
ples analyzed.
b Controlled emission factor.
Table2-3. EMISSION FACTORS FOR CONSUMPTIVE USES OF ARSENIC
Source
Emission factor
Emission
factor a
symbol
Cotton ginning processing
Detergents
2kg/103bales(4lb/103bales)
of cotton ginned
Negligible
UK
a Defined in Table 1-1.
2-4
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
Table 2-4. EMISSION FACTORS FOR ARSENIC FROM FUEL COMBUSTION
Fuel and source
Coal, domestic, controlled
Foreign residual oil
No. 6 fuel oil, Mexico
No. 6 fuel oil, Virgin Islands
No. 6 fuel oil, Trinidad
No. 6 fuel oil Curacao, N.A.
Average for foreign residual oil
Foreign crude oils
Neutral zone crude No. 24
Boscan crude oil, Morovia
Jabo crude oil, Venezuela
Kuwait crude oil, Kuwait
Boscan crude oil, Venezuela
Lagunillas crude oil, Venezuela
UMM Farvo, Libya
Average for foreign crude oils
U.S. crude oils
St. Tedesa, Illinois •
Maysville, W. Oklahoma
Hall-Gurney, Kansas
East Texas, Texas
Grass Creek, Walker Dome,Wyoming
Average for U.S. crude oils
Arsenic
content, ppm
5.44
0.1
0.1 to 0.2
0.095
0.16 to 0.2
0.14
0.079
0.34
0.053
0.01
0.31
0.12
0.02
0.13
0.61
0.031
0.047
0.007
0.04
0.15
Emission factor
kg/103 liters
2b
0.00009
0.00009 to 0.0002
0.00009
0.0002
0.0001
0.00007
0.0003
0.00005
0.000009
0.0003
0.0001
0.00002
0.0001
0.0005
0.00003
0.00004
0.000006
0.00003
0.0001
!H103 gallons
3b
0.0008
0.0008 to 0.002
0.0007
0.001 to 0.002
0.001
0.0006
0.002
0.0004
0.00007
0.002
0.0009
0.0001
0.0009
0.004
0.0002
0.0003
0.00005
0.0003
0.001
Emission
factor
symbol8
OESd)
NA(1)
NA(2)
NA(1)
NA(2)
NA(8)
NA(1)
NA(1)
NA(1)
NA(1)
NA(2)
NA(1)
NA(1)
NA(8)
NA(1)
NA(1)
NA(1)
NA(1)
NA(1)
NA(5)
a Defined in Table 1-1; numbers in parentheses indicate number of samples analyzed.
b Units for coal are kilograms per 103 kilograms and pounds per 103 tons, respectively.
Table2-5. EMISSION FACTORS FOR ARSENIC FROM SOLID WASTE
INCINERATION
Source
Cotton ginning waste burned
Sewage and sludge
Emission factor
9kg/103bales(17lb/103bales)
of cotton ginned
0.01 kg/103kg(0.02lb/ton)of
sewage and sludge
Emission
factor
symbol3
a Defined in Table 1-1.
Arsenic
2-5
-------
-------
3. ASBESTOS
MINING
Mineral abestos occurs in serpentine ore. The
most economical form of abestos is in the fibrous
form called chrysotile. The ore may contain up to
30 percent abestos, but the average is 4 percent. 2
The mining of abestos is normally open pit or
underground. The process for open-pit operations
consists of drilling, blasting, sorting and/or hand
cobbing, shovelling, transportation, and dumping
at the mill area. Underground operations involve
mining in drifts and stopes, using modified room-
and-pillar methods. '.2,3
Emissions are considered negligible for
underground operations, but emissions result from
all open-pit operations. Drilling operations are
controlled by cyclones or by filter bag collecters,
the latter being more effective. Controls for
blasting consist of wetting the blast area and sizing
the explosive charge. To reduce emissions from
trucks carrying the ore, tarpaulins are sometimes
employed. The emission factors presented in Table
3-1 were estimated by Davis1 and Harwood.2 Both
controlled and uncontrolled emission factors are
presented.
MILLING
1,2
Abestos milling processes consist mainly of
course crushing, drying, recrushing in stages,
screening for stages, fiberizing, grading, and
bagging. Emissions result from handling between
each process step of crushing, drying screening,
and bagging and from tailings. Completely
enclosing an operation is the most widely used con-
trol technique. This technique is used for crushing,
screening, fiberizing, and conveying. Exhaust
hoods, cyclones or a combination of these are also
used for all processes. A dumper unit or earth
covers and plantings are sometimes used to reduce
tailings emissions. The emission factors presented
in Table 3-1 are based on estimates made by
Davis i and Harwood.2
PROCESSING OF ASBESTOS
Friction Products1'2
Friction products, such as brake linings, consist
of asbestos fabric or molded asbestos in a specific
matrix. Processing consists of wet mixing,
grinding, drilling, and trimming. Each process
produces emissions, but because of the matrix
formation, complete fibers will usually not be
emitted. Emissions are controlled by capture
hoods, ductwork, fans, and bag filters. The
emission factor in Table 3-2 is based on a
manufacturer's estimated loss of 0.25 to 0.50
percent of asbestos from a bag filter.1-
Asbestos Cement Products1?2
Asbestos cement products contain from 15 to 20
percent by weight of asbestos. The largest use is in
asbestos-cement pipes. Asbestos cement is also
used in conduits for electric and telephone cables,
roofing shingles, insulation boards, etc. The
processing consists mainly of asbestos fibers being
dry-mixed with ground silica and portland cement.
Water is added to produce a slurry that is molded
or wound on a rotating metal cylinder to form
pipes. Shingles and siding products are sometimes
manufactured by a dry process in which a dry mix
is spread over a conveyor belt before water is
added. In the wet process, water is added before
forming. The last steps in all of the products are
the finishing steps: sawing, turning, drilling, and
sanding. Emissions result from handling, dry
mixing, and finishing steps. Emissions from
finishing steps are controlled by a complex
ventilation system consisting of capture hoods,
ductworks, fans, and filters. Wet and dry cyclones,
baghouse filters, or a combination of these reduce
emissions from mixing. The emission factor in
Table 3-2 for this industry is based on Davis'
estimate. 1
Textiles 1,2
Of the five varieties of commercial asbestos, only
chrysotile, crocidolite, and amosite can be used in
the textile industry. Asbestos is received by the
textile mill in milled form, or sometimes in crude
form. Crude asbestos is received in unopen bundles
and is cleaned by edge mills. The output from the
edge mills is screened, graded, and stored. The
milled and newly separated fibers from crude
asbestos are fed into "willowers" or "moody
3-1
-------
fluffers," which fluff up the fibers.2 Next the fibers
are mixed with a small amount of cotton or other
organic fiber just before the carding process. After
carding, the fibers are placed on lap aprons to yield
rovings. The rovings are spun into yarns, and the
yarns are sometimes further processed to produce
twine or cord.
Emissions result from the edge mills, willowing
process, spinning and weaving of the yarns, and
screening and conveying of the fibers. Air
ventilation systems to baghouse filters are
employed on almost all processes. For the spinning
and weaving process, emissions can be quite
significant. Emissions can be reduced by wetting
fibers and by adding organic fibers;. The
uncontrolled emission factor in Table 3-2 was
estimated by Harwood;2 the controlled factor was
estimated by Davis.1
Asbestos Paper *'^
Processing in the production of asbestos paper
is similar to the processing of wood pulp to obtain
paper.' Asbestos paper contains approximately 80
percent asbestos. 2 The other ingredients are china
clay and sodium silicate or starch. The mixture is
dried and mixed, then water is added to produce a
slurry. The slurry is conveyed to a paper machine
where sheets of paper are formed. The sheets are
rolled and dried. The handling and mixing of dry
products result in the various sources of emissions
from this industry. Emissions are controlled by
baghouses and cyclones. The uncor trolled
emission factor in Table 3-2 was estimated by
Harwood;2 the controlled factor was estimated by
Davis.1
Floor TUe1'2
In manufacturing floor tiles, asbestos fibers are
bonded with polymers or copolymers af vinyl
and/or vinylidene compounds. The processing
consists of mixing, milling, calendering,, water
spraying, buffering, punch pressing, and
packaging. The dust collected from each process is
recycled to the crusher and then to the punch press.
Emissions are collected for all processes by
cyclones or bag filters.1 The emission factors
presented in Table 3-2 were estimated by
Harwood.2
Asbestos IT sulation
1
A combination of calcium silicate with asbestos
produces an effective insulator, which is usually
employed on steam pipes. The process consists of
mixing calcium silicate (85 percent) \vith asbestos
and water. Not enough information is available to
obtain an accurate emission factor.
Others
The manufacture of asbestos-asphalt products,
paints using asbestos fibers, and some molded
articles can also result in asbestos emissions.
However, not enough information is available to
estimate emission factors for these processes.
CONSUMPTIVE USES
1,2
Emissions from the application of asbestos and
products containing asbestos are caused by
friction, cutting, handling, or spraying. The
emissions result from asbestos-asphalt road
surfacing, brake linings, insulation used in the
construction industry, steel fireproofing (spray-on
materials), and insulating cement. Emission factors
for each (except road surfacing) are presented in
Table 3-3. The emission factors for brake linings
are based on a 0.5 percent loss of the 1.4 kilograms
of asbestos in the lining. Steel fireproofing (mixture
of asbestos, cement, and mineral wool) is done in
an enclosed area in which it is assumed by Davis*
that 75 percent of the emissions are controlled.
Insulating cement is used extensively in al! types of
boilers. The emission factor presented in Table
3-3 is based on an assumed 89 percent control of 15
percent loss of abestos present in the cement.! The
basis for the emission factor given for construction
is unknown. *•
SOLID WASTE INCINERATION l
Various products that contain asbestos are
discarded, and the waste material may be
incinerated. This alone could become a large
emission source of asbestos; however, no accurate
information is, available to determine an emission
factor.
REFERENCES FOR CHAPTER 3
1. Davis, W.E. National Inventory of Sources and
Emissions: Cadmium, Nickel, and Asbestos —
Section HI, Asbestos (1968). W.E. Davis and
Associates. Leawood, Kansas. Contract No. CPA
70-128. February 1970.
2. Harwood, C.F. A Basis for National Air
Emission Standards on Asbestos. Illinois Institute
of Technology Research Institute. Chicago, Illinois.
Contract No. CPA 70-102. April 15, 1971.
3. Rozorshy, H. Air in Asbestos Mill:?!!-, '"an?. ian
Mining Journal. May 1957
3-2
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
Table 3-1. EMISSION FACTORS FOR ASBESTOS
FROM MINING AND MILLING a
Source b
Mining, total
Mining
Loading
Hauling
Unloading
Mining, total, 50% control
Milling
Milling, 50% control
Milling, 80% control
Emission factor,
kg/103kg(lb/ton)of
asbestos produced
5 (9 to 10)
2(3)
1(2)
1(2)
1 (2)
3(5)
50(100)
40 (80)
10(20)
Emission
factor
symbol0
E
E
E
E
E
E
E
E
E
aThe emission factors are based on engineering estimates and
no source sampling, These factors cannot be used to quantify
asbestos emissions.
bUncontrolled unless otherwise specified.
c Defined in Table 1-1.
Asbestos
3-3
-------
Table 3-2 EMISSION FACTORS FOR
PROCESSING OF ASBESTOS a
Sourceb
Friction material, controlled
Asbestos cement products,
controlled
Textiles
Textiles, controlled
Asbestos paper
Asbestos paper, controlled
Floor tile
Floor tile, controlled
Emission factor,
kg/1Q3kg (Ib/ton)
of asbestos processed
3(6)
0.5(1)
20 (40)
1 (2)
2(4)
0.5(1)
2(4)
0.5(1)
Emission
factor
symbol c
Q
E
E
E
E
E
E
E
aThe emission factors are based on engineering estimates
and no source sampling. These factors cannot be used to
quantify asbestos emissions.
b Uncontrolled unless otherwise specified.
c Defined in Table 1-1.
Table 3-3. EMISSION FACTORS FOR
CONSUMPTIVE USES OF ASBESTOS3
Source b
Brake linings
Steel fireproofing, controlled
Insulating cement, controlled
Construction industry
Emission factor,
kg/1 ()3kg( Ib/ton)
of asbestos applied
5(10)d
5(10)
13(25)
13 (25)
Emission
factor
symbol c
E
E
E
E
3-4
aThe emission factors are based on engineering estimates and no
source sampling. These factors cannot be used to quantify asbestos
emissions.
bUncontrolled unless otherwise specified.
c Defined in Table 1-1.
d A factor of 0.0005 pound per 103 vehicle miles can also be used.
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
4. BERYLLIUM
MINING1
Beryllium is found in beryl, bertrandite,
phenacite, chrysoberyl, and barylite ore. The main
commercial source in the United States is beryl ore.
Processing consists of a cycle of drilling,
blasting, cobbing, hauling waste to dumps, and
concentrating by hand-sorting. Emissions can
result from all of the processes mentioned. The
emission factor in Table 4-1 is based upon Davis'
estimation.l Emissions can also occur from copper
mining operations, but no emission factor is
available at present.
METALLURGICAL PROCESSING
Beryllium Hydroxide *2
The basic product from beryl ore is beryllium
hydroxide. Two processes are used for the
production of beryllium hydroxide: the Copaux-
Kawecki flouride process and the Sawyer-Kjillgren
process. In the former process, the beryl ore is
powdered by dry grinding, mixed with soda ash
and sodium flousilicate, and sintered at 760°C.
The product is then crushed, ground, and leached
with water. The insolubles in the water are filtered,
and the filtrate is treated with caustic soda to
precipitate the beryllium hydroxide.
In the Sawyer-Kjillgren process, a sulfate
extraction process, beryl ore is crushed, melted at
about 1760°C, and quenched in water to destroy
the crystaline structure. Next, the beryl glass is
placed in a gas-fired rotary kiln at 930°C, ground
in a ball mill to increase its activity, and then added
to sulfuric acid and water. Then soluble beryllium
and aluminum sulfate are extracted. Most of the
aluminum is removed by the addition of
ammonium hydroxide. The resulting solution is
cooled, and the alum is separated by centrifuging.
As the final steps for the production of beryllium
hydroxide ore, chelating agents are added to the
filtrate after centrifuging, sodium hydroxide is
added to produce sodium beryllate, beryllium
hydroxide is formed by hydrolysis, and the
beryllium hydroxide is separated by centrifuging.
Emissions are controlled from existing plants
using processes discussed. Ore storage, crushing,
melting, quenching, heat treatment, grinding, and
handling are all controlled by cyclones and
baghouses. Sulfation and dissolving are controlled
by a packed tower water scrubber. Crystallization
and beryllation, and sometimes leaching, are
controlled by ventilation. A venturi scrubber is
used on filtration and sintering processes and
sometimes leaching processes. No emission factor
is available for the production of beryllium
hydroxide.
Beryllium Oxide l
To produce beryllium oxide, beryllium
hydroxide is redissolved in water and sulfuric acid,
and ammonium sulfide is added to the solution.
The solution is then filtrated, evaporated, and
crystallized. Centrifuging is done to obtain
beryllium sulfate, which is then blended and
calcinated at 1040f)C to yield beryllium oxide.
Emissions are controlled by ventilating and by a
packed tower caustic scrubber (for the blending
and calcining step). No emission factor can be
determined at present.
Beryllium-copper Alloys
In the production of beryllium-copper alloys, a
master alloy is first produced. The process involves
beryllium hydroxide, which is calcined at 430°C to
produce beryllium oxide. Known quantities of
carbon powder, beryllium oxide, and copper are
mixed, melted in an electric arc furnace, and then
cast into ingots containing 4 percent beryllium.
Finally, the ingots plus more copper are melted in
an induction furnace to form 2 percent beryllium-
copper alloys. Emissions from calcining, mixing,
melting (induction furnace), and casting are all
controlled by baghouses. Arc furnace emissions are
controlled by a cyclone and baghouses. Not enough
information is available to determine an emission
factor.
Beryllium Metal*'2
Beryllium fluoride is used by the primary
producers for the production of beryllium metal.
One process used is the Schwenzfeir-Pomelee
purification process. Here, the feed contains sulfate
extraction product and various recycled products
4-1
-------
that are used to produce beryllium fluoride. The
feed is dissolved in ammonium bifluoride, calcium
carbonate is then added, and the solution is
thickened to remove heavy metals (except
manganese and chromium). Lead dioxide is added
to produce insoluble manganese dioxide and lead
chromate, which are filtered out. Next, the mixture
is sulfated, filtered again, placed in a vacuum
crystallizer, centrifuged, dried, and placed in a
decomposition furnace. Ammonium fluoride is
volatilized, and beryllium fluoride is removed and
solidified. An excess of beryllium fluoride is added
to magnesium, and a slag with a melting point
below the melting point of beryllium is produced.
The excess is essential for beryllium metal to be
obtained by water leaching. Solid beryllium is
obtained by raising the temperature above the
melting point of beryllium (1260°C). The mass is
then poured into a receiving pot, solidified,
crushed, and water-leached in a ball mill. To
eliminate the impure magnesium, the metallic
beryllium is melted again, and nonvolatiles are
removed in a dross. Emissions from each individual
process are controlled by a venturi scrubber,
packed tower scrubber, hydraulic scrubber,
baghouse, cyclone, or a combination cf these
control devices.1'2
No emission factor for the production of
beryllium metal can accurately be determined.
However, for the entire processing of beryllium
metal, alloys, and compounds (which is usually
done at one plant) an overall emission factor is
provided in Table 4-1. The emission factor is based
upon stack sampling information obtained by the
Environmental Protection Agency (EPA).1
CEMENT PLANTS
Dry Process '»4
Beryllium is present naturally in the initial
materials used to produce cement (pyrite,
limestone, clay, and shale). In the dry process,
limestone is crushed, then ground or ball milled
(sometimes with clay). Shale and pyrite are added,
and the product is pneumatically pumped into
blending silos. After the silos, the material is fed to
a kiln, then to a clinker cooler where gypsum (4.45
percent by weight) is added, and the product is fed
to a finishing mill. After the mill, the material
enters an air separator or classifier where the
finished cement is pneumatically pumped to silos.
Emissions from dry-process cement plants result
from all of these processes.
Two plants using the dry processing method
were visited, and particulate samples were obtained
by the EPA sampling train method.4 Baghouses at
both plants were employed as air pollution control
equipment. The probes for the sampling train were
placed in the stack area after each baghouse. Some
of the samples (total catch) were analyzed by
emission spectroscopy for trace metals. The
emission factors (Table 4-1) were calculated from
the percent of beryllium present in the sample and
the emission factor calculated for total particulates
emitted.3'4
Wet Process 5
The wet process is the same as the dry process,
except that a slurry is produced initially.
Particulate emissions were obtained by the EPA
sampling train method at two cement plants using
the wet process and employing, respectively,
baghouses and electrostatic precipitators. Samples
were taken at the exits of the control equipment,
and emission factors (Table 4-1) were estimated as
described for the dry process.
PROCESSING OR USES OF BERYLLIUM
AND ITS COMPOUNDS
Beryllium Alloys1'6'7
The beryllium-copper alloy from the production
plants is usually stamped and drawn into finished
shapes. The emission factor given in Table 4-1 was
estimated by Davis.1 It is not known whether
control equipment was employed.
Another use for beryllium-copper ingots is in
the production of beryllium-copper molds for
plastic casting. The process involves melting down
2 percent beryllium-copper ingots in a crucible
inside a furnace (1040°C). After melting, the
molten material is poured into molds and cooled.
Emissions are controlled by venting the areas of
concern to a baghouse.
A typical plant was visited, and an EPA
particulate train was employed at the inlet and
outlet of the baghouse.8 The samples were
analyzed by flame atomic absorption.<> Emission
factors based on the analytical results are shown in
Table 4-1.
Ceramics
1
A typical ceramic process begins with beryllium
oxide and other materials being mixed in a large
floor cistern containing water. The next steps are
milling, wet screening, and firing to produce a
glazed product. Emissions can result from
handling before processing and from machining
4-2
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
the finished product. Emissions are controlled by
hoods, central ventilation ducts, and absolute
filters. The emission factor presented in Table 4-1
is based on estimates by ceramic manufacturers.
Rocket Propellants *
Propellants that contain beryllium are mixed
with other propellant ingredients, vacuum cast,
cured, and sometimes machined. The
manufacture of beryllium-containing propellants
has virtually been discontinued, however, and this
emission source can therefore be neglected.
Beryllium Metal Fabrication
1
Beryllium metal is generally fabricated for use
in aircraft, computer, and spacecraft parts. The
operations usually consist of turning, milling,
drilling, reaming, grinding, honing, sawing, and
other high-precision machining. Emissions, usually
a fine particulate mist, can occur during any of the
operations described.
Emissions are controlled by some type of
ventilation system, usually coupled with a
baghouse or cyclone. The emission factor given in
Table 4-1 was obtained from questionnaire data.
FUEL COMBUSTION
Coaj 1,8-H
Stack analyses for beryllium have been
conducted at several power plants that burn coal as
the fuel. The sampling was done with an EPA
sampling train, and analysis was by emission
spectrometry. The probe for the sampling train was
placed in the stack in the area after the scrubber or
electrostatic precipitator control equipment. Four
plants were studied, average emission values for
two or three sampie runs were obtained, arid the
emission factors presented in Table 4-2 were
calculated. The emission factors ranged from
0.0001 to 0.002 kilogram per 1000 kiiograms of
coal burned. The content of beryllium in the coals
burned was also analyzed by emission
spectrometry. The values ranged from 1 to 2 parts
per million with an average value of 1.3 parts per
million,8'9
Two studies of coal bed samples from various
parts of the United Slates were conducted by a
geological survey team. The samples were ashed,
and the ash was analyzed by a quantitative
spectrochemical technique for beryllium and other
trace metals. The emission factors for this work are
based on the percent ash of the coal and the weight
percent of the beryllium found in the ash, assuming
65 percent of the ash is fly ash and assuming no
controls.! .10.11 The beryllium content reported in
Table 4-2 is the amount in the coal, not the amount
in the ash (see Reference 10).
Oil 12,13
The content of beryllium in oils has not been
well defined. An emission factor for residual oil
based on an estimate given by Davisl is included in
Table 4-3.
One oil burning power plant was visited, and
particulate samples were obtained with an EPA
sampling train. The particulate samples were then
analyzed by emission spectrometry for beryllium.
The emission factor given in Table 4-3 is based on
the percent beryllium found in the sample and the
particulate emission factor derived from the
sampling train results.12
Several oil samples were analyzed by flame
atomic absorption of beryllium. All samples ana-
lyzed showed beryllium below the detectable limit
(less than 0.3 part per million) of the technique. On
improving the technique, two No. 6 residual oils
showed beryllium to be present at 0.1 part per
million. The emission factor given in Table 4-3 is
based on the amount of beryllium present, 944
grams per liter of oil, and an assumed 100 percent
combustion factor.13
Both values based on analytical results in Table
4-3 agree reasonably well with the value estimated
by Davis.J
WASTE INCINERATION 14'15
Products that contain beryllium and its
compounds can become atmospheric emissions as
a result of waste incineration. There are two types
of sewage sludge incinerators: multiple hearth
furnaces and fluidized bed incinerators. The major
difference between the incinerators is that in the
multiple hearth all ash leaves through the bottom,
but in the Ouidized bed, ash is carried overhead
and removed by a scrubber. For sewage sludge
incinerators, a wet scrubber (impinjet, inertial jet,
or venturi) control device is part of the process.14
Three sewage sludge incinerators and one
municipal incinerator were visited by an EPA
sampling team. For sewage sludge incinerators,
particulate samples were collected and analyzed for
beryllium by emission spectrography. Beryllium at
one sewage sludge incinerator was found to be
below the detectable level of the analytical tech-
niques. Emission factors presented in Table 4-4 are
Beryllium
4-3
-------
based on the weight percent of beryllium (micro-
grams per gram) found in the samples from the
other two incinerators.14
The same sampling techniques were used for the
municipal incinerator, but the particulates
collected were analyzed by emission spectrometry.
The emission factor was calculated by the same
method as used for sewage sludge units.15
OTHERS
Foundries and steel mills may also be important
emission sources for beryllium. However, not
enough information is available to obtain emission
factors.
REFERENCES FOR CHAPTER 4
1. Davis, W.E. National Inventory of Sources and
Emissions; Arsenic, Beryllium, Manganese,
Mercury, and Vanadium — Section II, Beryllium.
(1968). W.E. Davis and Associates. Leawood,
Kansas, Contract No. CPA-70-128.
2. Schwenzfeir, C.W., Sr. Beryllium and
Beryllium Alloys. In: Kirk-Othamer Encyclopedia
of Chemical Technology (2nd Ed., Vol. 2. Stander,
A., ed.). New York, John Wiley and Sons, Inc.
1964. p. 450-474.
3. Test No. 71-MM-02. Emission Testing Branch,
Environmental Protection Agency. Research
Triangle Park, N.C. April 1972.
4. Environmental Protection Agency. Standards
of Performance for New Stationary Sources.
Federal Register. Vol. 36, No. 247. December 23,
1971. p. 24888-24890.
5. Tests No. 71-MM-01 and -03. Emission Testing
Branch, Environmental Protection Agency.
Research Triangle Park, N.C. March 1972.
6. Test No. 71-CI-23. Emission Testing Branch,
Environmental Protection Agency, Research
Triangle Park, N.C. Contract No. CPA-70-82.
August 1971.
7. Environmental Protection Agency. Hazardous
Air Pollutants; EPA Proposals on Standards for
Asbestos, Beryllium, and Mercury. Federal
Register. Vol. 36, No. 235. December 7, 1971 p.
23239-23256.
8. Tests No. 71-CI-01, -02, and -03. Emission
Testing Branch, Environmental Protection Agency.
Research Triangle Park, N.C. Contract No. CPA-
70-81. October 1971.
9. Test No. 71-CI-07. Emission Testing Branch,
Environmental Protection Agency. Research
Triangle Park, N.C. Contract No. CPA-70-131.
October and April 1971.
10. Stadnichenko, T., P. Zubovia, and N.B.
Sheffey. Beryllium Content of American Coals.
Department of the Interior. Washington, D.C.
Geological Survey Bulletin 1084-K. 1961.
ll.Zuboric, P., T. Stadnichenko, and N.B.
Sheffey. Distribution of Minor Elements in Coal
Beds of the Eastern Interior Region. Department
of Interior. Washington, D.C. Geological Survey
Bulletin 1117-B. 1964.
12. Test No. 71-CI-08. Environmental Protection
Agency. Research Triangle Park, N.C. Contract
No. CPA-70-131. April 1971.
13. Brown, H.S. Unpublished data from Purchase
Order No. 3-02-00710. Geological Resources, Inc.
Raleigh, N.C. December 1972.
14. Sewage Sludge Incineration. Environmental
Protection Agency. Research Triangle Park, N.C.
EPA-R2-72-040. August 1.972.
15. Test No. 71-CI-ll. Emission Testing Branch,
Environmental Protection Agency. Research
Triangle Park, N.C. Contract No. 70-81.
September 1971.
4-4
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
Table 4-1. EMISSION FACTORS FOR BERYLLIUM FROM
INDUSTRIAL AND SOLID WASTE INCINERATION SOURCES
Source
a
Emission factor
Emission
factor
symbolb
Mining
Production of beryllium
metal and its compounds,
overall value0
Cement plants0
Dry process
Feed to raw milld
Wet process
Kiln e'f
Clinker cooler6
Clinker cooler9
Processing or uses of beryl-
lium and its compounds
Beryllium alloys
(stamped and drawn)
Beryllium alloys (molding)
Uncontrolled
After a baghouse
Ceramics0
Rocket propellents
Beryllium metal
fabrication0
0.1 kg/103kg (0.2 Ib/ton) of Be
produced
15 kg/10dkg (30 Ib/ton) of Be produced
0.00002 kg/106kg (0.00003 lb/1000tons)
of feed
0.001 kg/106kg (0.002 Ib/1000 tons)
of feed
0.0004 kg/106kg (0.0008 lb/1000 tons)
of feed
0.0005 kg/106kg (0.0009 lb/1000 tons)
of feed
0.05 kg/103kg (0.1 Ib/ton) of Be processed
0.005 kg/103kg (0.01 Ib/ton) of alloy
melted
0.0002 kg/103kg (0.0004 Ib/ton) of alloy
melted
0.5 kg/103kg (1 Ib/ton) of Be processed
Negligible
0.05 kg/103kg (0.1 Ib/ton) of Be processed
CAA(?)
ES(1)
ES(1)
ES(1)
ES(1)
CAA (4)
CAA (2)
Q
Q
aUncontrolled unless otherwise specified.
bDefined in Table 1-1; numbers in parentheses indicate number of samples analyzed.
0 Controlled emission factor.
d Exit from baghouse.
e Exit from dectrostatic precipitator.
' At another plant, beryllium emissions from the kiln were below the detection limit of the
analytical technique.
9 Exit from two baghouse collectors in parallel.
hlt is not known whether this estimate is based on controlled or uncontrolled emissions.
Beryllium
4-5
-------
Table 4-2. EMISSION FACTORS IFOR BERYLLIUM FROM FUEL COMBUSTION, COAL
Source3
Power plants
Kansas0
South Carolina01
lllinoisd
Michigand
C . .il beds
Ma
-------
Table 4-3. EMISSION FACTORS FOR BERYLLIUM FROM FUEL COMBUSTION, OIL
Source
Residual oil
Power plant,
Connecticut15
Residual No. 6
Beryllium
content, ppm
0.08
0.024
0.1
Emission factor
kg/103 liters
0.00008
0.00002
0.00009
lb/103 gal.
0.0007
0.0002
0.0008
Emission
factor
symbol8
E
EST (2)
CAA (2)
a Defined in Table 1-1; numbers in parentheses indicate number of samples
analyzed.
bExit from «lff'"trostatic prpnipitato"
Table 4-4. EMISSION FACTORS FOR BERYLLIUM FROM WASTE INCINERATION
Source
Sewage sludge incinerator
Multiple hearth,
after wet scrubber
Fluidized bed,
after wet scrubber
Municipal incinerator,
uncontrolled
Municipal incinerator,
after electrostatic
precipitator
Emission factor
kg/IO^kg of waste burned
0.001 (0.0005 to 0.002)
0.001 (0.00005 to 0.001)
0.02
0.02
lb/103 tons of waste burned
0.002 (0.0009 to 0.003)
0.002 (0.0001 to 0.002)
0.03
0.03
Emission
factor
symbol
OES (3)
OES (3)
EST(1)
ESTd)
a Defined in Table 1-1; numbers in parentheses indicate number of samples analyzed.
Beryllium
4-7
-------
-------
5. CADMIUM
MINING OF ZINC-BEARING ORESl
Cadmium does not occur as a free mineral in
nature. It is found with zinc ores and other metal
ores that contain zinc compounds. The most
important mineral is sulfide greenockite, which is
found with zinc sulfide ores.
The processing is somewhat the same in all
mining operations — ore removal, ore handling,
crushing, grinding, and concentration. Concen-
tration is done by means of a flotation process in
this case.
Cadmium emissions are mainly due to wind
losses from tailing piles. No controls are employed
in such operations. The emission factors (which
include operations and tailing piles) for mining are
presented in Table 5-1.
METALLURGICAL INDUSTRY
Zinc, Lead, and Copper Smelters
Table 5-1 contains the emission factors for
cadmium for the metallurgical industry. The
sources of cadmium in this industry are mainly
zinc, lead, and copper smelters.
In the production of metallic zinc, the sulfur
present in the ore is removed by multiple hearth
(920°C) or Ropp roasting, followed by sintering
(1200°C). Metallic zinc is then produced in the next
step, which is a horizontal or vertical retort
smelting process. Roasting is sometimes followed
by an electrolytic process. Most of the cadmium is
emitted in the roasting and sintering process, and
particulates are normally collected in baghouses
and/or electrostatic precipitators. Cadmium
compounds emitted are cadmium chloride
(roasting) and cadmium oxide (sintering and
smelting). Refining of the cadmium collected in the
control equipment begins with a sulfuric acid leach
plus the addition of an oxidizing agent. Next,
cadmium is distilled in the conventional horizontal
retort (910°C) and then condensed as metallic
cadmium.3 The emission factors for both processes
(zinc smelter and refining) are shown in Table 5-1. *
Emissions from lead and copper smelters also
contain cadmium as a result of zinc and associated
cadmium present in the ores processed. The
emissions result from the roasting operation. As in
zinc production, cadmium is collected in bag-
houses on electrostatic precipitators. The cadmium
content in the collected material is low, so it is
recycled many times before the cadmium is refined.
The recycling allows opportunity for major
quantities of the cadmium to escape.
Emission factors for lead and copper smelters
are presented in Table 5-1. The factors do not
differentiate between emitted cadmium vapor and
particulate matter.
Secondary Copper1
Automobile radiators contain copper that has
been hardened by the use of about 0.2 percent
cadmium. When the radiators are melted for
copper recovery, the manufacturers do not recover
the cadmium. The emission factor given in Table
5-1 is based on the 0.2 percent value and the
amount of secondary copper obtained from
radiators.
4
Secondary Lead
The production of secondary lead mainly
consists of melting down lead batteries, lead oxide
drosses, recycled ducts, and metal scrap. The
process consists of melting the feed in a rever-
beratory or blast furnace (930°C). The molten mass
is then transferred to holding and refining kettles
and poured into ingots on a casting line.
Plants that employ controls usually use some
type of cooling system followed by cyclones, bag-
houses, and/or scrubbers. Emissions of particulate
matter result from all of the processes described,
but only the exit stream from a furnace has been
studied. Four plants were visited, and particulate
matter collected by an EPA sampling train was
analyzed by optical emission spectroscopy.
Cadmium was present in the samples from two
reverberatory furnaces. The samples from two blast
furnaces showed cadmium below the minimum
limit of the technique employed.
5-1
-------
Emission factors presented in Table 5-1 are
based upon the analytical results, process
conditions, and emission factors calculated for
particulate from probe and filter catch of the EPA
train.
Galvanized Metals *
Galvanized metal and steel scrap that is melted
down will contain some cadmium as an impurity in
the zinc galvanizing metal. Zinc used in
galvanizing averages about 3.7 kilograms per 1000
kilograms of steel produced. Cadmium content in
the zinc (for galvanizing) is about 0.04 percent. No
cadmium is reported to be recovered; and the
emission factor given in Table 5-1 is based on the
percent present.
CEMENT PLANTS
Cement manufacturing processes are described
in Chapter 4. Cadmium emissions from the
processes are due to the presence of cadmium as an
impurity in the initial chemicals used to produce
cement. Emissions from both dry and wet process
cement plants can result from all of the processes
described.
Dry Process 5
Two plants using the dry process were visited,
and particulate samples were obtained by the EPA
sampling train method. Baghouses at both plants
were employed as air pollution control equipment.
The probes for the sampling train were placed in
the stack area after each baghouse. Stacks from
which samples were taken included the kilns (at
one plant only), raw mill grinding systems, and
finish mill grinding systems. Some of the samples
were analyzed by emission spectroscopy for trace
metals. The emission factors (Table 5-1) were based
on percent of cadmium present in the sample and
the emission factor calculated for total
particulates.
Wet Process6
Particulate emissions were obtained from the
kilns, clinker cooler, and finishing mill of three
plants that employed the wet process. The same
analytical techniques described in the dry process
section were employed, except that one sample was
analyzed by spark source mass spectrograph and
optical emission spectrograph. Sampling was done
at the exits of the baghouses or electrostatic
precipitators employed at the individual plants.
Two samples analyzed (by emission spectroscopy)
at one plant showed cadmium below the detectable
level. The samples came from a kiln and clinker
cooler, each controlled by an electrostatic
precipitator. Emission factors (Table 5-1) were
calculated as described in the section for the dry
process.
PROCESSING OR UTILIZATION OF
CADMIUM1'7
Processing or utilization of cadmium and its
compounds is divided into six main categories: (1)
electroplating, (2) pigments, (3) plastics, (4) alloys,
(5) batteries, and (6) miscellaneous. Table 5-2 gives
emission factors for each.
Electroplating *
Cyanide baths are used for almost all
commercial plating. Emissions from the electro-
plating industry for cadmium are negligible. The
process involves setting up articles to be coated as
cathodes and the cadmium metal as an anode. As
electricity is passed through the bath, the metal is
coated with cadmium. If gassing rates are high in
the bath, emissions could become quite significant.
However, this process is quite efficient, and low
gassing rates prevail. On the average, electroplated
iron and steel contain about 0.025 kilogram of
cadmium per 1000 kilograms of steel or iron
produced.
Pigments *
Cadmium is used in pigments as a coloring
agent. The two compounds of importance are
cadmium sulfide and sulfoselenide.
Cadmium sulfide is prepared in many ways.
One process involves heating cadmium oxide with
suflur and another dissolving cadmium oxide in
sulfuric acid and then precipitating the sulfide
from the solution with hydrogen sulfide.
Cadmium sulfoselenide lithopone is prepared by
mixing solutions of cadmium sulfate and barium
sulfide to obtain cadmium sulfide and barium
sulfate. The shade of color is then determined by a
calcining process. Cadmium sulfoselenide is
prepared by adding selenium to a solution of
barium sulfide or nitrate, reacting these with
cadmium sulfate, and calcining with sulfur to
remove unreacted selenium. Emissions from
pigment processing occur mainly from drying the
calcinated powder. For all processes described, bag
filters are normally employed as air pollution
control devices. The emission factor in Table 5-2,
based on a material balance analysis, is therefore
considered a controlled emission factor.
5-2
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
Plastics
CONSUMPTIVE USES1'9'10
Cadmium use in plastics is important and is
growing. Cadmium is used in plastics as a coloring
agent and sometimes as a stabilizer (as a barium-
cadmium compound). During processing of the
stabilizers, cadmium oxide is placed in a sealed
reactor to react with fatty acids to form cadmium
soaps. Emissions from this process only occur in
handling of the oxide before the reaction.
Since all plants investigated stated they used
bag filters to control emissions, the emission factor
in Table 5-2 is considered a controlled emission
factor.
Alloys J'3'8
In the United States, a large number of
companies produce alloys containing cadmium.
Their range of usage is from 450 to 68,000
kilograms. Their products are largely low-melting
solders, bearing alloys, and brazing alloys.
Aluminum solders are cadmium-zinc alloys in
which the composition of cadmium varies from 10
to 95 percent by weight.3 Brazing alloys contain
between 5 and 18 percent cadmium. Low-melting
or fusible alloys have a cadmium range of 8 to 40
percent by weight.8 Bearing alloys in which nickel
or silver and copper are alloyed with cadmium
contain 99 percent cadmium.3 In production of
these alloys, cadmium is applied by vacuum
deposition, dipping, spraying, or electrodeposition
(already discussed).3 The extent of the application
of air pollution control equipment in this industry
for these specific applications is not known. The
emission factor in Table 5-2 is based upon
manufacturers' estimates and is assumed to be for
a controlled operation.'
Batteries (Ni-Cd)l
Nickel-cadmium batteries are used extensively.
The battery grids of both positive and negative
plates consist of sintered carbonyl nickel powder.
The positive plate is nickel oxide and the negative
plate is cadmium. The process for producing these
plates is mainly sintering and electrochemical
depositing. The emission factor in Table 5-2 is
based upon manufacturers' estimates of emissions,
which are generally uncontrolled.
Miscellaneous1
Miscellaneous uses in which cadmium is
processed include x-ray screens, cathode ray tubes,
nuclear reactor components, etc. The emission
factor in Table 5-2 can be used as a rough approxi-
mation for these other uses.
Emission factors (Table 5-3) for consumptive
(i.e., nonmanufacturing) uses of cadmium have
been estimated for Pibber tire wear, fungicides,
superphosphate fes'Hizers, motor oil, and
cigarettes. In tires, cad-mum sulfide is used as a
curing agent. Cadmium salts are used in fungicides
on golf courses. Cadmium phosphate is used in
fertilizers. Cadmium is not added to motor oils, but
analysis of motor oils has shown an average content
of about 0.5 part per million. l-9>10
FUEL COMBUSTION
Oil 1,11-14
Foreign crude and residual oils and U.S. crude
oils have been analyzed by neutron activation and
flame atomic absorption. 12.14 Three of six No. 6
fuel oils analyzed by neutron activation contained
cadmium (3 to 5 parts per million). Cadmium in
the other three samples was below detectable levels
of the technique. All of 20 No. 6 fuel oil samples
analyzed by flame atomic absorption had cadmium
contents below the 0.4 part per million detection
limit of the technique. Eight foreign crude oils
from different sources were also analyzed by the
two techniques; only one (analyzed by neutron
activation) showed any cadmium present.
Cadmium was below detectable levels for all of
seven U.S. crude oils analyzed by neutron
activation.
In another study, a diesel oil and a heating oil
were analyzed by emission spectroscopy, and the
cadmium contents ranged from about 0.07 to 0.1
and 0.4 to 0.5 part per million, respectively.11
Emission factors for oil combustion are
presented in Table 5-4. The factors calculated are
based upon cadmium content of the oils analyzed,
an assumed 100 percent combustion factor, and a
density of 850 (crude) and 944 (residual) kilograms
per liter for oil. No data are available as to the
particle size of cadmium or the physical condition
(vapor or particulate) of cadmium upon emission.
Average values based on the analytical results are
not given because it seems cadmium may not be
present in all the oil types analyzed.
Coal15'16
Fly ash samples from four power plants were
analyzed by emission spectrometric methods to
determine trace metals present.15>16 The samples
were all taken by an EPA sampling train. The
probe of the train was placed in the stack after the
electrostatic precipitator or wet scrubber control
Cadmium
5-3
-------
equipment. Cadmium (20 to 170 j^g/g) was present
in only 4 of the 14 samples analyzed. The coal
burned at these plants was also analyzed for
cadmium, but because of the limits of the
analytical procedure, cadmium detection was
uncertain. The analyses indicated that not all coal-
burning boilers emit cadmium. The emission
factors presented in Table 5-4 are based on process
conditions and the amount of cadmium found in
the fly ash samples.
Gasoline •*
One out of six gasolines analyzed by emission
spectrographic analysis contained cadmium, about
6 parts per billion. Since only one of the gasolines
analyzed contained cadmium, no emission factor is
given for gasoline combustion.
WASTE INCINERATION M7-19
Emission factors for sewage sludge, municipal,
sewage sludge-mixed refuse, and waste lubrication
oil19 incineration are given in Table 5-5.
There are two main types of sewage sludge
incinerators: multiple hearth and fluidized bed.
Both incinerators have similar design, with the only
major difference being that ash is removed from
the bottom of the multiple hearth furnace, but in
the fluidized bed, all the ash is carried overhead
and is removed by a scrubber. Scrubbers (irnpinjet,
inertial jet, and venturi) are a part of the process
design of sewage sludge incinerators.
Three sewage sludge incinerations were visited,
and particulate samples were obtained by the EPA
sampling train method. The samples were analyzed
by emission spectroscopy.17 One incinerator that
handled mixed refuse and sewage sludge was
visited, and particulate samples were collected
using a null balance probe.18 The samples were
analyzed by atomic absorption for cadmium. The
emission factors presented in Table 5-5 are based
on amounts of cadmium found in the particulate
matter analyzed. The overall value for the munici-
pal incinerator in Table 5-5 was estimated in
Reference 1 for an uncontrolled process. It is
presented here for comparison with the source test
data and should not be used for emission estimates.
REFERENCES FOR CHAPTER 5
1. Davis, W.E. National Inventory of Sources and
Emissions; Cadmium, Nickel and Asbestos —
Cadmium (1968). W.E. Davis and Associates.
Leawood, Kansas. Contract No. CPA 22-69-131.
February 1970.
2. Compilation of Air Pollutant Emission Factors
(Revised). U.S. Environmental Protection Agency.
Research Triangle Park, N.C. Office of Air
Programs Publication No. AP-42. February 1972.
P. 149.
3. Howe, H.E. Cadmium and Cadmium Alloys.
In: Kirk-Othmer Encyclopedia of Chemical
Technology. (2nd Ed., Vol. 3. Stander, A., ed.).
New York, John Wiley and Sons, Inc., 1964. p. 884-
899.
4. Tests No. 72-CI-7, -8, -29, and -33. Emission
Testing Branch, Environmental Protection Agency.
Research Triangle Park, N.C. Contract No. 68-02-
0230. August 1972.
5. Tests No. 71-MM-02 and -05. Emission Testing
Branch, Environmental Protection Agency.
Research Triangle Park, N.C. March-April 1972.
6. Tests No. 71-MM-02 and -06. Emission Testing
Branch, Environmental Protection Agency.
Research Triangle Park, N.C. March 1972.
7. Anthanassiadis, Y.C. Preliminary Air Pollution
Survey of Cadmium and Its Compounds. Litton
Systems, Inc. Raleigh, N.C. Contract No. PH 22-
68-25. October 1969.
8. Mangold, C.A. and R.R. Beckett. Combined
Occupational Exposure of Silver Brazers to
Cadmium Oxide, Nitrogen Dioxide and Fluorides
at a Naval Shipyard. Amer. Ind. Hyg. Assoc. J.
32(2): 115-118, February 1971.
9. Nandi, M., D. Slone, H. Jick, S. Shapiro, and
S.P. Lewis. Cadmium Content of Cigarette. Lancet.
December 20, 1969. p. 1329-1330.
10. Trace Metals: Unknown, Unseen Pollution
Threat, Chemistry and Engineering News. July 19,
1971. p. 29-33.
11. Fagerwerff, T.V. and A.W. Specht. Occurence
of Environmental Cadmium and Zinc, and Their
Uptake by Plants. U.S. Soils Laboratory, United
States Department of Agriculture. Beltsville,
Maryland. Agriculture Research Science-swc.
1970.
12. Sheibly, D. Unpublished data. Materials
Section, Lewis Research Center, Plum Brook
Station, National Aeronautics and Space
Administration. Sandusky, Ohio.
13. Chemical Engineer's Handbook. (4th Ed.
Perry, J.H., ed.). New York, McGraw-Hill Book
Company, 1963. p. 9-6.
5-4
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
14. Brown, H.S. Unpublished data. Geological
Resources, Inc. Raleigh, N.C. September 1, 1972.
15. Tests No. 71-CI-01, -02, and -03. Emission
Testing Branch, Environmental Protection Agency.
Research Triangle Park, N.C. Contract No. CPA-
70-81. September-October 1971.
16. Test No. 71-CI-07. Emission Testing Branch,
Environmental Protection Agency. Research
Triangle Park, N.C. Contract No. CPA-70-131.
17. Sewage Sludge Incineration. Environmental
Protection Agency. Research Triangle Park, N.C.
EPA-R2-72-040. August 1972.
18. Cross, F.L., R.I. Drago, and H.E. Francis.
Metals in Emissions from Incinerators Burning
Sewage Sludge and Mixed Refuse. Environmental
Protection Agency. Research Triangle Park, N.C.
1969.
19. Waste Lube Oils Pose Disposal Dilemma.
Environ. Sci. Technol. 6(l):25-26, January 1972.
Cadmium
5-5
-------
Table 5-1. EMISSION FACTORS FOR CADMIUM FROM INDUSTRIAL SOURCES
Source**
Emission factor
Emission
factor
symbolb
Mining of zinc-bearing ore0
Zinc smeltersd
Copper smelters
Lead smelters
Cadmium refining units
Secondary copper0
Secondary lead
Rm/firberatory furnace6
Reverberatory furnace*
Steel scrap (galvanized metal )c
Cement plants
Dry process
Kiln 9
Raw mill9
Air separator after raw mill9
Feed to raw mill9
Feed to finish mill9
0.0005 kg/103kg (0.001 Ib/ton) of Zn
or 0.1 kg/103kg (0.2 Ib/ton) of Cd mined
150 kg/103kg (300 Ib/ton) of Cd charged
or 1.0 kg/103kg (2.0 Ib/ton) of Zn produced
650 kg/103kg (1300 Ib/ton) of Cd charged
or 0.4 kg/103kg (0.07 Ib/ton) of Cu produced
650 kg/103kg (1300 Ib/ton) of Cd charged
or 0.1 kg/103kg (0.2 Ib/ton) of Pb produced
13 kg/103kg (25 Ib/ton) of Cd produced
2 kg/l^kg (4 Ib/ton) of Cu scrap
0.05 kg/106kg (0.1 lb/103 tons) of Pb'
0.2 kg/106kg (0.4 lb/103tons) of Pb
0.001 kg/103kg (0.003 Ib/ton) of steel
0.2 kg/106kg (0.3 lb/103 tons) of feed
0.00005 kg/ 106kg (0.0001 lb/103 tons) of
feed
0.0005 kg/106kg (0.0009 lb/103 tons) of feed
0.0002 kg/106kg (0.0003 lb/103 tons) of
feed
0.003 kg/106kg (0.0005 lb/103tons) of
feed
Wet process
Kilnh
Raw mill9
Clinker cooler9
0.1 kg/106kg (0.2 lb/103 tons) of feed
0.01 kg/IO^g (0.02 lb/103 tons) of feed
0.00005 kg/1Q6kg (0.0001 lb/103 tons) of
feed
PV, MV, Q
PV, MV, Q
PV, MV, Q
PV, MV, Q
E
ES (3)
ES (2)
E
ES (1)
ES (1)
ES (1)
ES (1)
ES (1)
ES (1)
ES (1)
OES,SSMS (1)
a In this table, sources are controlled unless otherwise specified.
b Defined in Table 1-1; numbers in parentheses indicate number of samples analyzed.
c Uncontrolled emission factor.
d Factors should not be used for electrolytic process.
6 Exit from a cooling system, three cyclones, and a baghouse (121° C).
f Exit from a cooling system, cyclone, manifold, hopper, and baghouse (93°C).
9 Exit from baghouse.
h Exit from electrostatic precipitator. At another plant using an electrostatic precipitator, no cadmium was
using ES analytical method.
' Range, 0.02 to O.rkg/106kg (0.04 to 0.2 lb/103ton).
5-6
EMISSION FACTORS TO TRACE SUBSTANCES
-------
Table 5-2. EMISSION FACTORS FOR PROCESSES
INVOLVING CADMIUM
Source
Pigments0 /
Plastic stabilizers0
Alloys and soldersd
Batteries (Ni-Cd)
Miscellaneous (x-ray screens,
cathode ray tubes, nuclear
reactor components, etc.)
Emission factor.
kg/103kg(lb/ton)of
cadmium charged
8(15)
3(6)
5(10)
1(2)
1(2)
Emission
factor
symbol b
MB
PV
Q
Q
E
a Emission are uncontrolled unless otherwise specified.
b Defined in Table 1-1.
0 Controlled emissions (bag filters).
d Controlled emissions.
Table 5-3. EMISSION FACTORS FOR CONSUMPTIVE USES OF CADMIUM
Source8
Rubber tire wear
Fungicides
Superphosphate
fertilizers
Motor oil consumption
(in vehicle)
Cigarettes
Emission factors
0.003 kg/l^km (0.01 lb/106 vehicle miles)
0.02 kg/103 liters (0.05 lb/103 gal.)
of spray
0.0001 kg/103kg (0.0002 Ib/ton) of fertilizer
0.0006 kg/106km (0.002 lb/1Q6 vehicle miles)
1 6.0 ng/20 cigarettes
Emission
factor
symbolb
E
E
E
UK
S(15)
aAII sources are uncontrolled.
bDefined in Table 1-1; number in parentheses indicates number of samples
analyzed.
Cadmium
5-7
-------
Table 5-4. EMISSION FACTORS FOR CADMIUM FROM FUEL COMBUSTION
o
Source
Heating oil
(residual assumed)
Diesel oil
Foreign No. 6 residual fuel oil
Virgin Islands
Virgin Islands
(different oilfield)
Curacao, N.A.
Trinidad
Venezuela
Coal, power plant,
Kansas0
Coal, power plant,
Michigan d
Cadmium
content ppm
0.4 to 0.5
0.07 to 0.1
5
<0.4e
4
3
<0.4e
_ f
_e
Emission factor
0.004 to 0.0005 kg/103 liters
(0.003 to 0.004 lb/103 gal.) of oil
0.00007 to 0.00009 kg/103 liters
(0.0006 to 0.0008 lb/103 gal.) of oil
0.005 kg/103 liters (0.04 lb/103
gal.) of oil
—
0.004 kg/103 liters (0.03 lb/103
gal.) of oil
0.003 kg/103 liters (0.02 lb/103
gal.) of oil
—
0.1 kg/106kg (0.2 lb/103 tons)
of coal burned^
O.Bkg/IO^kg (1 lb/103 tons) of
coal burned9
Emission
factor
symbol13
ES(2)
ES(3)
NA(1)
CAA (3)
NA(1)
NA(1)
CAA (10)
EST(2)
EST (2)
a Uncontrolled emissions unless otherwise specified.
b Defined in Table 1-1; numbers in parentheses indicate number of samples analyzed.
cExit from limestone scrubber.
dExit from electrostatic precipitator.
e Below detectable limits of techniques.
fNot reported.
9Based on ash samples.
5-8
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
Table 5-5. EMISSION FACTORS FOR CADMIUM FROM WASTE INCINERATION
Source'
Emission factor
Emission
factor
symbol"
Sewage sludge incinerators
Multiple hearth °'
Fluidized bedc
Municipal incinerator
Refuse on lyc
Refuse and sludgec
Overall value for
uncontrolled solid waste
incineration (municipal)6
Lubricating oilf
0.004 kg/103kg (0.007 Ib/ton) of solid
waste incinerated9
0.0002 kg/103kg (0.003 lb/103tons) of
solid waste incinerated
0.4 kg/106kg (0.8 lb/103 tons) waste
incinerated
0.3 kg/106kg (0.6 lb/103tons) waste
incinerated
0.0002 kg/103kg (0.003 Ib/ton) of solid
waste incinerated
0.0002 kg/103 liters (0.002 lb/103 gal.)
of oil
OES (3)
OES (2)
CAA (3)
CAA (3)
E
UK
a In this table, emissions are controlled unless otherwise specified.
bDefined in Table 1-1; number in parentheses indicates number of samples
analyzed.
cExit from wet scrubber.
d Cadmium ratio of metal in particulate to metal in sludge was 2.6.
e This emission factor is presented for comparison only; it should not be used for
•emission estimates.
f Emissions of cadmium oxides.
9Range, 0.0005 to 0.01 kg/103kg (0.001 to 0.02 Ib/ton).
Cadmium
5-9
-------
-------
6. MANGANESE
MINING1
Most ore mined for manganese in the United
States is manganiferous ore (5 to 35 percent
manganese). Some manganese ore (35 or more
percent manganese) is also mined in the United
States, but this ore is usually imported from foreign
countries. Manganese is also found in iron ores but
is not recovered from this ore because of
economical reasons.
Processing at mining operations varies
considerably. All operations have crushing,
screening, and washing steps, and some also have
concentrating equipment, which many times will
include sintering and nodulizing equipment. At-
mospheric emissions result from ore handling,
crushing, and wind losses from tailings. The
emission factor presented in Table 6-1 is based
upon information obtained from mine operators.
No controls are used in the mining of ores
containing manganese.
PRODUCTION OF MANGANESE METALl
An electrolytic process is used to produce pure
manganese metal. The principal steps are grinding,
roasting the ore, leaching, purification of the leach
liquor, and electrodeposition of the manganese. In
the roasting step, the object is to convert all of the
manganese into the oxide form. After grinding and
roasting, the product is leached in leach liquor that
is first acidic but is later neutralized. The
neutralizing enables the extraction of about 98
percent of the manganese in the ore as a result of
the precipitation of iron and aluminum hydroxides.
The resultant product must be further purified
before electrolysis. The first step in purification is
the addition of hydrogen sulfides or ammonium
sulfide to precipitate the sulfides and some of the
impurities. The second step involves the addition of
iron (copperas), which oxidized the iron at a pH of
6.5 to 7.0 and precipitates ferric hydroxide. The
other impurities are removed with the hydroxide.
The purified solution is placed in the cathode
compartment of an electrolytic cell where the
manganese is deposited.
Emissions result from handling, grinding, and
roasting of the ore. The emission factor given in
Table 6-1 is based on manufacturers' estimates.
PRODUCTION OF MANGANESE ALLOYSl
Manganese ores are also used in the production
of ferromanganese, siliconmanganese, and
spiegeleisen. Ferromanganese is produced in blast
and electric furnaces, while siliconmanganese and
spiegeleisen are produced in electric furnaces.
Ferromanganese - Blast Furnace ^
The blast furnace is a large refractory-lined
chamber into which the manganese ore is charged.
About 65 percent of the ferromanganese is
produced from blast furnaces. Particulate
emissions from the blast furnaces are about 205
kilograms per 1000 kilograms of ferromanganese
produced,2 of which about 20 percent is
manganese.1 The emission factor is based on this
information and is considered to be uncontrolled.
Ferromanganese - Electric Furnace 1
Electric furnaces are furnished with heat from
arc type electrodes in the roof of the furnace.
Emissions result from the furnace, tapholes in the
furnace, handling, and mixing. The emission factor
(uncontrolled) presented in Table 6-1, estimated by
Davis,1 includes nonmelting operations as well.
Siliconmanganese - Electric Furnace 1
In the production of siliconmanganese,
emissions result from the same sources as
ferromanganese production in electric furnaces.
The emission factor presented in Table 6-1 is based
upon an internal EPA report referenced by Davis.1
PROCESSING OF MANGANESE AND ITS
COMPOUNDS 1
About 90 percent of the manganese used in the
United States is consumed by the steel industry.
The remainder is used to make cast iron,
nonferrous alloys, batteries, chemicals, and other
products.
Steel Production1
Manganese is used in the production of almost
every grade of steel. There are three main functions
6-1
-------
of manganese in the steel industry. It is a
deoxidizer and cleanser of molten steel, it improves
the hot-working properties of the steel, and it is an
important alloying agent. About 6.6 kilograms of
manganese are consumed per ton of steel
produced.1
The basic step in the production of steel is the
reduction of impurities in the blast furnace.
Further purification takes place in open hearth,
basic oxygen, or electric furnaces. Other operations
include ore crushing, handling, sintering,
pelletizing, and scarfing.
Blast Furnace li2
Manganese is part of each principal ingredient
charged into the blast furnace. It is present in the
iron and manganiferous ore (or other manganese
type ores), in the scrap, and in the recycled slag. Pig
iron from the blast furnace will contain about 70
percent of manganese initially present in the
charge. The remaining 30 percent is in the slag and
gases that are produced. In most cases, the gas by-
product is cleaned (about 97 percent efficiency) and
used as a fuel. The emission factor presented in
Table 6-1 is for an uncontrolled source and an
estimated 0.5 percentJ of manganese present in the
particulate material (75 kilograms per 1000
kilograms of pig iron produced).2
Open Hearth Furnace 1|2'3
Using pig iron (about 55 percent) from the blast
furnace, "home scrap," and purchased scrap, steel
is produced in an open hearth furnace. The
primary objective of the furnace is to reduce
impurities. Molten pig iron is added to the furnace,
then ore and lime boil are added. Next, a working
period is employed to lower the phosphorus, sulfur,
carbon (to desired level), and oxygen contents.
During this work period, manganese losses are at a
maximum (70 to 80 percent in the fume and slag).1
Emissions for uncontrolled open hearth furnaces
with and without oxygen lancing are 11 arid 6 kilo-
grams of particulate per 1000 kilograms of steel
produced, respectively.2 Using qualitative data (by
emission spectrography), which indicated about 0.5
percent manganese present in the particulate
matter, emission factors were estimated as indi-
cated in Table 6-1.3
Basic Oxygen Furnace J '2
This furnace is a refractory-lined, cylindrical
vessel that is mounted on trunions. The furnace is
charged in the vertical, and a stream of oxygen,
supplied from overhead, is shot downward into the
converter. The oxygen causes agitation and mixing
action, which results in increased fume emissions.
For uncontrolled operations, the approximate
amount of particulate matter emitted per 1000
kilograms of steel produced is 23 kilograms.2 It has
been estimated that about 3.2 percent of this
emission is manganese (4.4 percent Mn3O4). The
uncontrolled emission factor is given in Table 6-1.
Electric Furnace 1>2
An electric furnace is a refractory-lined,
cylindrical vessel with large carbon electrodes
passing through the roof of the furnace. In
charging this type of furnace (preheated), the top is
opened to allow cold metal to be introduced. Large
amounts of fume result, and the fumes increase
throughout the process. Particulate emissions for
oxygen lancing and no lancing are 5.5 and 3.5
kilograms per 1000 kilograms of steel produced,
respectively.2 Using an estimated 3.1 percent of
manganese present in the particulate, uncontrolled
emission factors, presented in Table 6-1, were
calculated.J
Cast Iron J'2
Manganese is added to the cupola in • the
production of cast iron to reduce the sulfur content
in the final product. The charge into the cupola
contains coke, scrap, and pig iron, all of which
contain manganese. The manganese either reacts
with the air introduced into the cupola to form
oxides or with the sulfur to form manganese
sulfide. These compounds are removed in the slag.
The manganese present in the particulate material
is about 2 percent.* The emission factor in Table 6-
1 was calculated from the uncontrolled particulate
emission factor (8.5 kilograms per 1000 kilograms
of metal charged)2 and the percentage of
manganese present.
Welding Rods
1
Some welding rods and coatings contain
manganese. Aluminum welding rods contain about
1.5 percent manganese, and coatings of other rods
contain about 10 percent manganese. Manganese
is added to aluminum welding rods as a general
purpose alloy.
To make aluminum welding rods, aluminum-
rich alloy ingot containing the manganese is added
to a charge of aluminum and alloy scrap in a
reverberatory furnace (at 760°C). After melting,
the material flows to a trough and is tapped and
poured into ingots. The ingots are cooled, and then
reheated and rolled in a blooming mill. The
product is sent to a rod mill and finished by
forging, swaging, or drawbenching.
6-2
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
Emissions of manganese result from the furnace
and the hot ingots. The emission factor in Table 6-
1 is based on information obtained from industrial
sources.
Nonferrous Alloys
1
Manganese is alloyed with nonferrous metals
such as aluminum, magnesium, copper and zinc,
and copper and nickel. Aluminum-manganese
alloys will contain about 25 percent manganese.
Magnesium is alloyed with manganese chloride.
Bronze, produced from manganese alloyed with
copper and zinc, contains up to about 3.5 percent
manganese. The emission factor presented in Table
6-1 is based upon industrial sources.
Batteries
Manganese dioxide is used as a depolarizing
agent in the dry cell battery. Manganese dioxide,
calcined manganese, graphite carbon black,
ammonium chloride, and vita film are first added
to a ball mill. The ingredients are then wet mixed,
pulverized, and fed into battery cases in a paste
filling machine. To produce the final battery, the
battery cases are filled in a filling solution machine.
Emissions result mainly from the ball mill and
mixing. The emission factor given in Table 6-1 is
based upon manufacturers' estimates and is
considered uncontrolled.
Chemicals
1
Manganese ore, mainly the dioxide form, is used
in the chemical industry as an oxidizing agent in
the production of hydroquinore, potassium
permanganate, manganese sulfate, manganese
chloride, manganese oxides, and others. The
emission factor for the overall chemical industry
for the production of manganese chemicals (Table
6-1) is based upon information obtained from
various segments of the chemical industry.
Others 1
Manganese and its compounds are also used in
the production of fertilizers, animal and poultry
feed, pharmaceuticals, brits, glass, ceramics,
coloring effects to face bricks, paint driers, and
oxidants. They are also employed in air pollution
control, in water treatment, and as an experimental
fuel additive. No information is presently available
to determine emission factors for these sources.
CEMENT PLANTS
Cement manufacturing processes are described
in Chapter 4. Manganese is present in pyrite (as
manganese sulfide), and possibly in the limestone,
shale, and clay used in the production of cement.
Emissions from both dry and wet process cement
plants can result from all of the processes
described.
\
Dry Process
Two plants using the dry processing method
were visited, and particulate samples were obtained
by the EPA sampling train method. Baghouses
were employed at both plants as air pollution
control equipment. The probes for the sampling
train were placed in the stack area after each
baghouse. Some of the samples (total catch) were
analyzed by emission spectroscopy for trace metals.
The emission factors in Table 6-1 were based on
percent of manganese present in the sample and
the emission factor calculated for total particulates
emitted.4 Cement from one plant was analyzed and
found to contain 900 micrograms of manganese per
gram of sample analyzed.
Wet Process 5
Particulate emissions were obtained from three
cement plants using the wet process. The same
analytical techniques described in the dry process
section were employed, except that part of one
sample from one plant was analyzed by spark
source mass spectrography and optical emission
spectrography. Sampling was done at the exits of
the baghouses or electrostatic precipitators
employed at the individual plants. The emission
factor in Table 6-1 was also calculated as described
in the section for dry processing.
FUEL COMBUSTION
Coal1'6'7
Fly ash samples from five power plants were
analyzed by emission spectrometric methods to
determine trace metals present.6'7 The samples
were all taken by an EPA sampling train with the
probe of the train placed in the stack after the
electrostatic precipitator or wet scrubber control
equipment. Manganese was present in all samples
analyzed. The values of manganese ranged from 40
to 1400 micrograms per gram of sample analyzed
with an average value of 465 micrograms per gram.
The emission factors presented in Table 6-2 are
based upon the percent of manganese present in
the fly ash sample analyzed and on emission factors
estimated in the studies for particulates (based on
the EPA train).
In another study, fly ash samples from six power
boilers were analyzed by emission spectrometric
methods. Two of the boilers were fired with Illinois
Manganese
6-3
-------
coal, two with Pennsylvania coal, one with Ohio
coal, and one with West Virginia and Kentucky
coal. Manganese present before fly ash collection
was 966 to 3910 micrograms per cubic meter with
an average of 1950 micrograms per cubic meter.
After collection, the manganese present ranged
from 60 to 368 micrograms per cubic meter with an
average of 212 micrograms per cubic meter. Using
these average values, assuming uncontrolled
emissions and 9.9 cubic meters of flue gas per
kilogram of coal consumed, the emission factor for
this study was estimated (Table 6-2).l
OH *'8
Analyses of more than 400 samples of crude and
residual oils were obtained from major oil
companies and utilities along the east coast of the
United States. Almost all of the crude oils
contained some manganese (0 to 2000 parts per
million).1 Crude oils from the United States
contained manganese in the range of 0.005 to 1.45
parts per million. Residual fuel oils in the United
States average about 0.158 part per million. Middle
East residual oils contained an average of 0.120
part per million of manganese. Analysis of eight
South American residual oils showed no
manganese present as a result of the limit of the
analytical method employed. Emission factors pre-
sented in Table 6-3 are based on the manganese
conte it in the oils, assuming no control, a 100 per-
cent combustion factor, and densities of 850
(crude) and 944 (residual) grams per liter for oil.
In another study, several commercial and
residential boiler units were studied. Particulate
samples from the units were taken by EPA
sampling train (total catch) and analyzed by optical
emission spectrometry for trace metals.8 The
emission factors obtained in the study are
presented in Table 6-3.
WASTE INCINERATION 9'10
Emission factors for incineration of sewage and
sludge, and solid waste are presented in Table 6-4.
There are two main types of sewage sludge
incineration: multiple hearth and fluidized bed.
Both incinerators have similar designs with the
only major difference being that ash is removed
from the bottom of the multiple hearth furnace,
but in the fluidized bed, all ash is carried overhead
and is removed by a scrubber. Scrubbers (impinjet,
inertial jet, and venturi) are a part of the process
design of sewage sludge incinerators.
Three sewage sludge incinerators were visited,
and particulate samples were obtained by the EPA
sampling train method. The samples were analyzed
by emission spectroscopy and manganese was
found in all samples.9
The values presented for the solid waste
incinerated were based upon samples taken from a
large U.S. incineration unit (with a design rate of
363 x 103 kilograms per day). The samples were
taken by an EPA sampling train for particulates.
Sampling points were located at the inlet and outlet
of an electrostatic precipitator. The samples were
analyzed by emission spectrometry.10 The
emission factors are based on the manganese
content in the samples and the process weight rates
for each incinerator.
REFERENCES FOR CHAPTER 6
1. Davis, W.E. National Inventory of Sources and
Emissions; Arsenic, Beryllium, Manganese,
Mercury, and Vanadium - Section III, Manganese
(1968). W.E. Davis and Associates. Leawood,
Kansas. Contract No. CPA 70-128. August 1971.
2. Compilation of Air Pollutant Emission Factors
(Revised). U.S. Environmental Protection Agency.
Research Triangle Park, N.C. Office of Air
Programs Publication No. AP-42. February 1972.
p. 149.
3. Air Pollution Engineering Manual. Danielson,
J.A. (ed.). National Center for Air Pollution
Control, Public Health Service, U.S. Department
of Health, Education, and Welfare. Cincinnati,
Ohio. Publication No. 999-AP-40. 1967. p. 728.
4. Tests No. 71-MM-02 and -05. Emission Testing
Branch, Environmental Protection Agency.
Research Triangle Park, N.C. March-April 1972.
5. Tests No. 71-MM-01, -03, and -06. Emission
Testing Branch, Environmental Protection Agency.
Research Triangle Park, N.C. March 1972.
6. Tests No. 71-CI-01, -02, and -03. Emission
Testing Branch, Environmental Protection Agency.
Research Triangle Park, N.C. October 1971.
7. Test No. 71-CI-07. Emission Testing Branch,
Environmental Protection Agency. Research
Triangle Park, N.C. Contract No. CPA 70-131.
October 1971.
8. Levy, A., S.E. Miller, R.E. Barnett, E.J. Shulz,
R.H. Melvin, W.H. Axtman, and D.W. Locklin. A
Field Investigation of Emissions from Fuel Oil
Combustion for Space Heating. Battelle.
(Presented at American Petroleum Institute
Committee on Air and Water Conservation
meeting. Columbus, Ohio. November 1, 1971.)
6-4
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
9. Sewage Sludge Incineration. Environmental 10. Test No. 71-CI-ll. Emission Testing Branch,
Protection Agency. Research Triangle Park, N.C. Environmental Protection Agency. Research
EPA-R2-72-040. August 1972. Triangle Park, N.C. Contract No. 70-81.
September 1971.
Manganese 6-5
-------
Table6-1. EMISSION FACTORS FOR MANGANESE FROM INDUSTRIAL SOURCES
Sourcel
Emission factor
Emission
factor
symbolb
Mining
Manganese metal production
Production of manganese
alloys
Ferromanganese
Blast furnace c
Electric furnace
Siliconmanganese, electric
furnace
Processing of manganese and
and its compounds
Steel production (carbon
and alloy steels)
Blastfurnace
Open hearth furnace d
Oxygen lance
No lancing
Basic oxygen furnace6
Electric furnace
Oxygen lance
No lancing
Cast iron
Welding rods
Nonferrous alloys
Batteries
Chemicals
0.1 kg/103kg (0.2 Ib/ton) of Mn mined
13 kg/103kg (25 Ib/ton) of Mn processed
41 kg/103kg (82 Ib/ton) of ferromanganese produced
12kg/103kg(24lb/ton) of ferromanganese produced
35 kg/103kg (70 Ib/ton) of Siliconmanganese produced
0.4 kg/103kg (0.8 Ib/ton) of pig iron produced
0.06 kg/103kg (0.1 Ib/ton) of steel produced
0.3 kg/103kg (0.6 Ib/ton) of steel produced
0.7 kg/103kg (1 Ib/ton) of steel produced
0.2 kg/103kg (0.3 Ib/ton) of steel produced
0.1 kg/103kg (0.2 Ib/ton) of steel produced
0.2 kg/103kg (0.3 Ib/ton) of metal charged
8 kg/ 103kg (16 Ib/ton) of Mn processed
6 kg/103kg( 12 Ib/ton) of Mn processed
5 kg/103kg (10 Ib/ton) of Mn processed
5kg/103kg (10 Ib/ton) of Mn processed
Q
Q
E
E
OESd)
OES(1)
E
E
E
E
Q
Q
Q
Q
6-6
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
Table 6-1 (continued) EMISSION FACTORS FOR MANGANESE FROM INDUSTRIAL SOURCES
Source a
Cement plants
Dry process
Kilnf
Feed to raw mill
Air separator after
raw mill f
Raw mill
Feed to finish millf
Air separator after
finish mil|f
Wet process
Kiln9
Clinker cooler9
Clinker coolerh
Clinker cooler*
Air separator after
finish millf
Emission factor
0.04 kg/106kg (0.07 lb/103 tons) of feed
0.005 kg/106kg (0.01 lb/103 tons) of feed
0.01 kg/106kg (0.02 lb/103tons) of feed
0.004 kg/106kg (0.008 lb/103 tons) of feed
0.004 kg/106kg (0.008 lb/103 tons) of feed
0.005 kg/106kg (0.01 lb/103 tons) of feed
0.005 kg/106kg (0.01 lb/103 tons) of feed
0.02 kg/106kg (0.03 lb/103 tons) of feed
0.1 kg/106kg(0.2lb/103tons)offeed
0.0002 kg/106kg (0.0004 lb/103tons) of feed
0.00005 kg/ 106 kg (0.0001 lb/103 tons) of feed
Emission
factor
symbol6
ES(1)
ES(1)
ES(1)
ES(1)
ES(1)
ES(1)
ES(2)
ES(1)
ESd)
OES,SSMS(1)
OES.SSMSd)
Emissions are uncontrolled unless otherwise specified.
Defined in Table 1-1; numbers in parentheses indicate number of samples analyzed.
C 1
Average particle size of particulate matter is 0.3 micron.'
Mean particle size of dust is 0.5 micron.1
eMean particle size of particulate matter is 0.7 micron.1
txit from baghouse.
9 Exit from electrostatic precipitator.
Exit from two baghouses in parallel.
Manganese
6-7
-------
Table 6-2. EMISSION FACTORS FOR MANGANESE FROM FUEL COMBUSTION, COAL
Source
Power plant study
South Carolina6
Michiganb
Illinois'5
Average b
Kansas c
Six-boiler study
Manganese
content, ppm
_d
5
30 to 40
200
_d
Emission factor
0.0002 (0.0002 to 0.0003 kg/103 kg)
0.0004 (0.0003 to 0.0005 Ib/ton)
0.0002 to 0.005 kg/103kg
(0.0003 to 0.01 Ib/ton)
0.0004 to 0.0005 kg/ 103kg
(0.0008 to 0.0009 Ib/ton)
0.0005 kg/103kg
(0.001 Ib/ton)
0.001 kg/IO^g
(0.002 Ib/ton)
0.04 kg/103kg (0.08 Ib/ton)
Emission
factor
symbol3
EST (6)
EST (2)
EST (3)
EST (11)
EST (3)
EST (6)
Defined in Table 1-1; numbers in parentheses indicate number of samples analyzed.
b Exit from electrostatic precipitator.
c Exit from limestone wet scrubber.
Not reported.
6-8
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
Table 6-3. EMISSION FACTORS FOR MANGANESE FROM FUEL COMBUSTION, OIL
Source
U. S. crude oil
Arkansas
California
Colorado
Kansas
Montana
New Mexico
Oklahoma
Texas
Utah
Wyoming
U. S. crude oil,
average
U. S. residual
fuel oils,
average
Residential units
(distillate)
Commercial units
(residential No. 4)
Commercial units
(residential No. 5)
Commercial units
(residential No. 6)
Manganese
content, ppm
0.12
0.138
0.208
0.013
0.005
0.021
0.030
0.029
1.45
0.044
0.21
0.16
_ b
— b
_b
_b,c
Emission
kg/103 liters
0.0001
0.0001
0.0002
0.00001
0.000004
0.00002
0.00003
0.00003
0.001
0.00004
0.0002
0.0002
0.00001 to 0.00004
0.00002 to 0.00004
0.00005 to 0.00007
0.00005 to 0.00006
factor
to/103 gal.
0.0009
0.001
0.001
0.00009
0.00004
0.0001
0.0002
0.0002
0.01
0.0003
0.001
0.001
0.0001 to 0.0003
0.0002 to 0.0003
0.0004 to 0.0006
0.0004 to 0.0005
Emission
factor
symbol8
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
EST (2)
EST(2)
EST( 2)
EST (2)
a Defined in Table 1 -1; numbers in parentheses indicate number of samples analyzed.
b Not reported.
c Particle size range for paniculate collected with a cascade impactor was 25 percent by weight less than
0.21 micron and 80 percent less than 7.4 microns. Mass median particle size was approximately 1.2
microns.
Manganese
6-9
-------
Table 6-4. EMISSION FACTORS FOR MANGANESE FROM WASTE INCINERATION
Source'
Emission factor,
kg/103kg (Ib/ton) of waste burned
Emission
factor
symbol
Sewage sludge
incinerators
Multiple hearth0
Fluidized bedc
Solid waste
incineratord
Solid waste
incinerator6
0.0005 (0.001 )f
0.0003 (0.0005)9
0.02(0.03)
0.004 (0.007)
OES (4)
OES (3)
EST(1)
EST(1)
a In this table, all sources are controlled.
b Defined in Table 1-1; numbers in parentheses indicate number of samples analyzed.
c Exit from wet scrubber.
d Inlet to electrostatic precipitator (could be used as an uncontrolled emission factor).
e Exit from electrostatic precipitator.
f Range, 0.001 to 0.003 kg/1Q3kg (0.002 to 0.006 Ib/ton).
9 Range, 0.0002 to 0.0004 kg/103kg (0.0003 to 0.0007 Ib/ton).
6-10
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
7. MERCURY
MINING !
Cinnabar (HgS) is the main source of mercury.
This ore is mined by both open-pit and
underground methods. For open-pit operations,
emissions of mercury result from dust generated to
the ambient air by drilling, blasting, handling, and
ore removal. For underground operations,
emissions (particulate form) are carried out of the
mine by forced ventilation in which all units
discharge directly to the atmosphere. The emission
factor given in Table 7-1 is based on information
obtained from mine operators.
ORE PROCESSING
1-4
Two basic types of processes are used to re-
cover elemental mercury from the ore. In one pro-
cess, crushed cinnabar is placed in a retort (816
to 982°C). Mercury is volatilized, and air is allowed
to enter the retort to convert sulfur to sulfur
dioxide. The vapor is condensed, and mercury is
obtained from the condenser. Emissions result
from mercury (gaseous and particulate form) in the
gas stream discharged from the condenser and
from mercury remaining in the calcine. No
emission factor is available at present for this
process.
The second process emits more mercury than
the retort method. The process begins with crushed
cinnabar ore (1.75 to 3 kilograms of mercury per
1000 kilograms of ore) being fed to a fired rotary
kiln (593 to 760 °C). The resultant vapor is vented
through a cyclone (sometimes more than one) and
condensers before exiting through the stack at
temperatures between 32 and 43° C (gaseous and
particulate mercury). The mercury is extracted
from the condensers by a process called "hoeing"
(at atmospheric temperature). A fan usually draws
the vapors from the "hoe table" and vents them
directly to the atmosphere. After the hoe table, the
residual mercury is placed in retorts, which
sometimes exit the mercury vapor by way of a
condenser before the stack (19°C). Emissions result
from all of the stacks from the processes described
above.
Two smelter operations were visited, and an
EPA gaseous and particulate mercury train was
used to obtain stack samples for the smelter stack
and hoeing operations.2 Also, samples were
collected from the retort stacks by an EPA gaseous
mercury train. All samples were analyzed for
mercury by flameless atomic absorption.3 >4
The emission factors shown in Table 7-1 are
based on analytical results and process weight rate
of ore at the plants studied. The values are
considered uncontrolled factors since cyclones and
condensers are part of the recovery process for
mercury. The values obtained from the smelter
stack agree with Davis' estimate.1
SECONDARY PRODUCTION OF
MERCURYl
Mercury is recovered from battery scrap, dental
amalgams, and various sludges. Emissions result
from the furnace and calcine bin and from
handling and crushing. Davis1 estimated the
emission factor given in Table 7-1.
PROCESSING AND UTILIZATION
OF MERCURY AND ITS COMPOUNDSl
Most of the mercury recovered from cinnabar is
used as a working fluid in instruments and in the
production of chlorine and caustic soda. Mercury is
also used in the pulp and paper industry and in
paints, agricultural sprays, pharmaceutical
products, catalysts, etc.
Instruments
1
Manufacturers that produce switches and
relays, thermometers, thermal systems, and flow
measuring equipment usually use mercury as the
working fluid in the instruments. Emissions in the
production of these various instruments usually
occur as a result of breakage and spillage. The
emission factor in Table 7-2 is based on estimates
obtained from manufacturers of these instruments.
1,2,5-10
Production of Chlorine and Caustic Soda
About 30 percent of the chlorine produced is
produced by the mercury cell process (chlor-alkali).
Caustic soda is also produced by this cell. The
mercury cell is usually a horizontal trough
consisting of a electrolyzer and a denuder. A brine
7-1
-------
solution and liquid mercury (cathode) are fed
continuously into the electrolyzer where chlorine is
formed at the anode (graphite), which hangs above
the trough but is in contact with the brine. The
chlorine is cooled, dried, and liquefied. The sodium
forms an amalgam with the mercury. The amalgam
flows to the denuder where it becomes the anode to
a short-circuited iron or graphite cathode.
Hydrogen, mercury, and sodium hydroxide are all
formed after the amalgam reacts with water.
Emissions of mercury result from the hydrogen
stream, cell end-box vent air, and cell room
ventilation air. In some plants, the hydrogen
stream is purified and employed in the production
of chemicals. In most plants, it is considered to be a
waste.' Control techniques include condensing the
hydrogen stream, condensing and contacting the
gas with carbon, packed adsorbent beds, mist
eliminators, and gas scrubbing. Mist eliminators
have been reported to reduce mercury emission
with an efficiency of 93 to 99 percent.5 Packed
adsorbent beds have been reported to be more than
99 percent effective.5'6 Mercury present in cell
end-box vent air and cell room air is usually vented
to the atmosphere.
Two chlor-alkali plants using the mercury cell
process were visited, and an EPA particulate and
gaseous mercury train was used to obtain samples
from the hydrogen stream and end-box ventilation
system. A gaseous mercury EPA train was
employed to obtain samples from the cell room
ventilation system. Samples from the hydrogen
stream (only 15 to 20 percent of the total stream)
were taken from the inlet and outlet of a carbon
adsorber unit (average efficiency was 48.5
percent).7'8 All samples taken were analyzed for
mercury by flameless atomic absorption.2
Emission factors based on these studies are
presented in Table 7-2. The values for the hydrogen
stream have been increased by 85 percent of the
inlet stream since the values reported in References
7 and 8 only represent 15 percent of the total
hydrogen stream.
In another study, the hydrogen stream capacity
for mercury in a 907-kilogram-of-chlorine-per-day
plant was determined based on equilibrium
concentration corresponding to various gas
temperatures.9 After plotting the experimental
data (based on tracer studies) and applying a least
squares fit to the data, the mathematical
relationship indicated by Equation 7-1 was ob-
tained.
y=0.2305(10-u) e
0.728T
where: y=emission factor,
kg Hg/103kg C12
T=temperature of the hydrogen
stream, °K
e = exponential function (2.72)
y = intercept
Actual source test data were also compared with
the plot (Figure 7-1), but not enough information
was available to obtain a relationship. A material
balance for the hydrogen stream exiting a heat
exchange is also provided in Reference 7. The
balance yields values that are larger (by a factor of
ten) than the values in Figure 7-1.
Emission factors based on information obtained
from industrial sources, material balances, and
other sources is also given in Table 7-2
for comparison. * '9'10In using the emission factors
for the chlor-alkali industry, it is recommended to
first use factors based on source test data.
Paints J
Mercurial compounds are added to paints as an
antifouling agent (mercuric oxides), as a mildew
proofing agent, and as a paint preservative
(mercuric sulfide). In the production of paints, the
compounds are added in the mixing stages, and
emissions are considered negligible.
Pharmaceuticals
In the production of various pharmaceuticals,
several mercuric compounds may be used (for
example, mercuric cyanide, mercuric bichloride,
mercuric iodide, and mercuric oxides). The
reactions are usually carried out in closed reactors.
Emissions during manufacturing are considered
negligible.
Pulp and Paper *
Emissions for the production of slimicides and
the usage of the slimicides in slurries of cellulose
fibers are considered negligible.
Amalgamation
Most metals can be amalgamated with mercury.
In this application, mercury is used mainly in
chemical manufacturing operations and in electro-
metallurgy. Emissions were estimated by Davis1 to
(7-D be negligible.
7-2
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
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NOISSIIIO
Mercury
7-3
-------
Electrical Apparatus *
In this category, the largest use of mercury is in
the manufacture of batteries employing the
mercury cell and alkaline energy cell. Mercury is
used in the form of mercuric oxide mixed with
graphite and as zinc-mercury alloy. Mercury is also
added to fluorescent and high intensity arc
discharge lamps. Emissions result from the
handling of the mercury or its compounds. The
emission factor in Table 7-2 is based on an
estimated 4 percent handling loss in which 10
percent of this loss became an atmospheric
emission.
Othersl
No emission factors can be estimated for the use
of catalysts (for example, mercuric bichloride and
mercuric sulfate) containing mercury that are
employed in chemical plants. Likewise, for the
production of agricultural sprays (for example,
mercuric bichloride and mercuric oxides) no
emission information is available.
CONSUMPTIVE USES
1
Emission factors for the consumptive or
nonmanufacturing uses of mercury and its
compounds are given in Table 7-3. These uses
include paints, agricultural spraying,
Pharmaceuticals, dental preparations, and general
laboratory applications.
Paints *
Emissions from paints result from their
application. Paints contain from 0.02 to 2.5 percent
mercury. Davis ' estimated the emission factor
presented in Table 7-3 based on the amount of
mercury present in paints.
Agricultural Spraying
The emission factor presented in Table 7-3 is
based on Davis'J assumption that about 50 percent
of the mercury present in sprays will become an
atmospheric emission.
Pharmaceuticals
1
Emissions from Pharmaceuticals result mainly
from the application of the antiseptics, skin
preparations, and preservatives that contain the
mercuric compounds. Davisl estimated the
emission factor given in Table 7-3.
Dental Preparations *
The emissions that result from mercury
amalgams used in filling teeth are considered to be
handling losses. Handling losses are about 4
percent, with about 1 percent being emitted.
General Laboratory Losses
Emissions from general laboratory use are
estimated to be 4 to 13 percent of the mercury used,
mainly as a result of handling and experimental
losses.
FUEL COMBUSTION
Coal Ul-15
A great deal of analytical work has been done on
mercury content in coals. In a study involving the
determination of mercury present in several coals
used for power generation, the average mercury
content was 0.2 part per million. '] The samples
came from Pennsylvania, West Virginia, Ohio,
Kentucky, Indiana, Missouri, Colorado, Montana,
and Arizona. The analytical methods consisted of
neutron activation and various atomic absorption
techniques. The content of mercury present in the
coals ranged from 0.05 to 0.38 part per million;
eastern coals contained more mercury than western
coals.
In another study, coal samples from two
Pennsylvania sites had mercury contents of
0.24±0.02 part per million and 0.31 ±0.03 part per
million.12 The analytical methods used were the
dithizone method, neutron activation, and
flameless atomic absorption.
In a third study, fly ash samples from New York
power plants were analyzed by atomic
absorption.13 The average amount of mercury
present was 0.13 part per million.
In a fourth study, 55 coal samples from Illinois
were analyzed. 14The mercury present ranged from
0.04 to 149 parts per million, with a mean of 0.18
part per million and a mode of 0.10 to 0.12 part per
million. Ohio coal and four western coals were also
analyzed in this study. The mercury content for the
western state coals ranged from 0.02 to 0.09 part
per million. The Ohio samples ranged from 0.1 to
0.15 part per million with an average of 0.13 part
per million. The analytical method used was
neutron activation.
Finally, results are presented for a study in
which fly ash samples from two bench scale coal
combustors (100 grams per hour and 227 kilograms
per hour) and two coal burning power plants were
7-4
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
analyzed by gold-amalgamation flameless atomic
absorption spectrophotometry. The flue gas from
the 100-gram-per-hour coal combustor was also
analyzed for mercury (same analytical method).
Mercury was found to be present in all fly ash and
flue gas samples. Coals from two different sources
(Pennsylvania and Missouri) were utilized in the
100-gram-per-hour combustor. The Pennsylvania
coal contained 0.15 ± 0.02 microgram of mercury
per gram (12 samples, by flameless atomic
absorption) before combustion. The Missouri coal
showed a mercury content of 0.24 ± 0.05
microgram of mercury per gram (21 samples, by
FAA) before combustion. Percent of total mercury
in the fly ash sample ranged from 31 to 37 and
from 55 to 66 for the Missouri and Pennsylvania
coals, respectively. After analysis of the flue gas
samples, the total amount of mercury accounted
for ranged from 62 to 96 percent.15
For the 227-kilogram-per-hour combustor, a
Pennsylvania type coal was utilized for combustion.
The mercury content for this coal was 0.019 to 0.04
microgram of mercury per gram of coal (23
samples, by FAA). Total mercury present in the fly
ash collected was 12 ± 3 percent. The fly ash
samples were collected by a 75 percent efficient
cyclone. Therefore, emission factors for this study
were increased and decreased, respectively, by 25
percent for the fly ash and flue gas.
The two power plants used Illinois coal with a
mercury content of 0.16 ± 0.07 microgram of
mercury per gram of coal (32 samples, by FAA).
Total mercury contents of the fly ash samples,
collected in a mechanical collector at one plant and
in an electrostatic precipitator at the other, were 7
and 19 percent, respectively.
The emission factors presented in Table 7-4
(arranged by area rather than individual study) are
based on the amount of coal consumed in the
United States for 1968 and the average mercury
content determined in References 1 and 11 through
14. The emission factors are considered to be the
total amount of mercury present in the fly ash and
flue gas if no control is applied to the boiler. For
comparison, the results for the bench scale
combustion and the associated fly ash flue gas
analyses15 have also been converted to emission
factors.
oa
1,16
All imported residual oils and foreign crude oils,
analyzed by neutron activation, contained
mercury,'6 the range being 0.005 to 0.30 part per
million, with an average of 0.13 part per million for
foreign residual fuel oils. The mercury content in
foreign crude oils ranged from 0.006 to 0.2 part per
million with an average of 0.04 part per million.
Most, though not all, U.S. crude oils contained
mercury, the range being 0.002 to 0.11 part per
million, with an average of 0.06 part per million.
Imported low-sulfur fuel oils had the lowest ranges
(0.001 to 0.02 part per million) and the lowest
average mercury content (0.01 part per million).
The emission factors in Table 7-5 are based on the
amount of mercury present in the samples,
assuming a 100 percent combustion factor and
densities of 850 (crude) and 944 (residual) grams per
liter for oil.
SOLID WASTE INCINERATION J'17
Various products that contain mercury are
burned annually. A typical incinerator that burned
refuse showed a 0.7 part per million mercury
content. The emission factor presented in Table 7-6
is based on this mercury content and on 272,000
kilograms per day of waste burned.
Sewage and sludge also contain mercury. Both
are burned at a rate of 1,814,000 kilograms per day
in the United States. The emission factor in Table
7-6 is based on an estimated average mercury
content of 15 parts per million. Three sludge
incinerators were visited, and a gaseous mercury
train was employed to collect samples at the
scrubber outlets. The samples were analyzed by
flameless atomic absorption. Mercury content was
found to be extremely low in all samples.
REFERENCES FOR CHAPTER 7
I.Davis, W.E. National Inventory of Sources and
Emissions; Arsenic, Beryllium, Manganese,
Mercury, and Vanadium - Section IV, Mercury
(1968). W.E. Davis and Associates. Leawood,
Kansas. Contract No. CPA 70-128. September
1971.
2.Environmental Protection Agency. Hazardous
Air Pollutants; EPA Proposals on Standards for
Asbestos, Beryllium, and Mercury. Federal
Register. Vol. 36, No. 235, December 7, 1971. p.
23239-23256.
3. Tests No 72-PC-08 and -09. Emission Testing
Branch, Environmental Protection Agency.
Research Triangle Park, N.C. Contract No. 70-132.
July 1972.
4. Test No. 71-PC-ll. Emission Testing Branch,
Environmental Protection Agency. Research
Triangle Park, N.C. Contract No. CPA-70-132.
November 19, 1971.
Mercury
7-5
-------
5. Brink, J.A., Jr., and E.D. Kennedy. Mercury
Air Pollution Control. Monsanto Enviro-Chem
Systems, Inc. (Clean Air Conference, Melbourne,
Australia. May 15-17, 1972.)
6. Wallace, R.A., W. Fulkerson, W.E. Shults, and
W.S. Lyon. Mercury in the Environment; The
Human Element. Oak Ridge National Laboratory.
Oak Ridge, Tennessee. ORNL NSF-EP-1. Contract
No. W. 7405-eng-26. January 1971.
7. Tests No. 72-PC-03 and -04. Emission Testing
Branch, Environmental Protection Agency.
Research Triangle Park, N.C. Task Order No. 3,
Contract No. CPA-70-132. November 1971.
8. Test No. 72-PC-10. Emission Testing Branch,
Environmental Protection Agency. Research
Triangle Park, N.C. Task Order No. 3, Contract
No. CPA-70-132. November 1971.
9. Caban, R. and T.W. Chapman. Losses of
Mercury from Chlorine Plants: A Review of a
Pollution Problem. Amer. Inst. Chem. Eng. J.
18(5):892-901, September 1972.
10. Atmospheric Emissions From Chlor-Alkali
Manufacture. Environmental Protection Agency.
Research Triangle Park, N.C. Publication No. AP-
80. January 1971.
11. Schlesinger, M.D., and H. Schultz. An
Evaluation of Methods for Detecting Mercury in
Some U.S. Coals. Pittsburgh Energy Research
Center, Bureau of Mines. Pittsburgh, Pa. RI 7609.
1972.
12. Schlesinger, M.D. and H. Schultz. Analysis for
Mercury in CqaL__Bureau_of_Mines Managing Coal
Wastes and Pollution Program, U.S. Department
of the Interior. Washington, D.C. Technical
Progress Report-43. September 1971.
13. Johnson, K.J. Mercury Analyses. Internal
Office Report, Region II Office, Environmental
Protection Agency, New York, N.Y. March 12,
1971.
14. Ruck, R.R., H.J. Gluskotes, and E.J. Kennedy.
Mercury Content of Illinois Coals. Illinois State
Geological Survey. Urbana, 111. No. 43. February
1971.
15. Diehl, R.C., E.A. Hattman, H. Schultz, and
R.J. Heron. Fate of Trace Mercury in the
Combustion of Coal. Pittsburgh Energy Research
Center, Bureau of Mines. Pittsburgh, Pa.
Technical Progress Report No. 54. May 1972.
16. Sheibly, D. Unpublished data. Materials
Section, Lewis Research Center, Plum Brook
Station, National Aeronautics and Space
Administration. Sandusky, Ohio.
17. Tests No. 71-CM 9, -20, and -24. Emission
Testing Branch, Environmental Protection Agency.
Research Triangle Park, N.C. Contract No. CPA-
70-131. September and December 1971.
7-6
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
Table7-1. EMISSION FACTORS FOR MERCURY FROM MINING, PRIMARY
AND SECONDARY SOURCES
Source*
Emission factor
Emission
factor
symbol13
Mining
Primary ore processing
Smelter stack
Hoeing operations
Retort operation
Secondary production
0.005 kg/103kg (0.01 Ib/ton) of ore mined
0.16 kg/IO^g (0.031 Ib/ton) of ore processed c
0.01 kg/103kg (0.02 Ib/ton) of ore processed
0.001 kg/IO^g (0.002 Ib/ton) of ore processed'
20 kg/IO^kg (40 ob/ton) Hg processed
Q
FAA(18)
FAA (3)
FAA (3)
E
All sources are uncontrolled.
Defined in Table 1-1; numbers in parentheses indicate number of samples analyzed.
c Range, 0.09to 0.22 kg/103kg (0.18to 0.44 Ib/ton).
Mercury
7-7
-------
Table 7-2. EMISSION FACTORS FOR
PROCESSING AND UTILIZATION OF MERCURY AND ITS
COMPOUNDS
Source{
Emission factor
Emission
factor
symbolb
Instruments
Electrolytic production of chlorine
Hydrogen stream
Uncontrolled
After one carbon
adsorber unit
End-box ventilation
Cell room ventilation
Ridge vent
Fan ventilation (1 fan)
Loss in hydrogen stream
Loss in ventilation
Comparative data
Loss in hydrogen stream
End-box ventilation
Cell room ventilation
Paints
Pharmaceuticals
Pulp and paper
Amalgamation
Electrical apparatus
9 kg/103kg (17 Ib/ton) of contained Hg
0.001 to 0.005 kg/103kg (0.002 to 0.01 Ib/ton)
of CI2 produced
0.0005 kg/103kg (0.001 Ib/ton) of CI2 produced
0.005 kg/103kg (0.01 Ib/ton) of CI2 produced0
0.002 kg/103kg (0.003 to 0.004 Ib/ton) of CI2
0.0003 kg/103kg (0.0005 Ib/ton) of CI2
produced
0.01 kg/103kg (0.02 Ib/ton) of CI2 produced
0.02 kg/103kg (0.04 Ib/ton) of CI2 produced
0.1 kg/103kg (0.2 Ib/ton) of CI2 producedd
0.04 kg/IO^g (0.075 Ib/ton) of CI2 produced
0.02 kg/IO^g (0.03 Ib/ton) of CI2 produced6
Negligible
Negligible
Negligible
Negligible
4 kg/103kg (8 Ib/ton) of Hg used
Q
FA A (5)
FAA (2)
FAA (6)
FAA (4)
FAA (2)
MB, Q
MB, Q
UK
UK
UK
Uncontrolled unless otherwise specified.
bDefined in Table 1-1; number in parentheses indicates number of samples analyzed.
c Range, 0.003 to 0.01 kg/103kg (0.006 to 0.02 Ib/ton).
d Range, 0.003 to 7.5 kg/103kg (0.006 to 15 Ib/ton).
eRange, 0.005to 0.027 kg/1Q3kg (0.01 to 0.054 Ib/ton).
7-8
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
Table 7-3. EMISSION FACTORS} FOR CONSUMPTIVE USES OF MERCURY AND ITS COMPOUNDS
Source
Paint
Agricultural
spraying
Pharmaceuticals
Dental preparations
General laboratory
handling
Emission factor
650 kg/103kg (1300 Ib/ton) of contained Hg
500 kg/103kg (1000lb/ton) of contained Hg
200 kg/103kg (400 Ib/ton) of Hg applied
10 kg/103kg (20 Ib/ton) of Hg handled
40 kg/103kg (80 Ib/ton) of Hg used
Emission
factor
symbol8
E
E
E
E
E
Defined in Table 1-1.
Mercury
7-9
-------
Table7-4. EMISSION FACTORS FROM FUEL COMBUSTION FOR MERCURY, COAL
Source3
Eastern states coals
Ohio
Belmont County
Harrison County
Jefferson County
West Virginia
Kanawha County
Pennsylvania
Washington County
Pittsburgh bed
Lower Kittanning
Washington County
100-g/hr
combustor
Fly ash
Flue gas
227-kg/hr
combustor
Fly ash
Flue gas
Missouri
Henry County
100-g/hr
combustor
Fly ash
Flue gas
Mercury
content, pprn
0.13
0.1 5 ±0.03
0.41 ± 0.06
0.24 ±0.04
0.07 ±0.02
0.12±0.04
0.24 + 0.02
0.31 + 0.03
0.1 5 ±0.02
0.83 to 0.97 ±0.1 3
—
0.18±0.04
0.22 + 0.04
—
0.24 ±0.05
0.31 to 0.37 + 0.06
—
Emission factor
kg/106 kg
0.1
0.15
0.41
0.24
0.07
0.12
0.24
0.31
—
0.09
0.06
—
0.05
0.2
—
0.08
0.16
lb/103tons
0.3
0.30
0.82
0.48
0.14
0.24
0.48
0.62
—
0.18
0.12
—
0.09
0.3
—
0.16
0.32
Emission
factor
symbol6
NA(3)
NA, FAA, CAA, (32)
NA, FAA, CAA (28)
NA, FAA, CAA (30)
NA, FAA, CAA (27)
NA, FAA, CAA (29)
NA, FAA, DM (?)
NA, FAA, DM (?)
FAA (12)
FAA (12)
FAA (12)
FAA (23)
FAA (17)
E(17)
—
FAA (21)
E(21)
7-10
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
Table7-4 (continued) EMISSION FACTORS FROM FUEL COMBUSTION FOR MERCURY, COAL
Source8
Kentucky
Muhlenberg County
Indiana
Clay County
Illinois
Power plants
Fly ash
Flue gas
New York
(fly ash only)
Western states coals
Montana
Rosebud County
Colorado
Montrose County
Arizona
Navago County
Utah
Average U.S. coalsc
Mercury
content, ppm
0.1 9 ±0.03
0.08 ±0.02
0.18
0.10 to 0.26 ±0.04
—
0.13
0.08
0.061+0.007
0.02
0.05 ±0.01
0.02
0.06 ±0.01
0.04
0.20
Emission factor
kg/106kg
0.19
0.08
0.18
0.02
0.2
0.2
0.08
0.061
0.02
0.049
0.02
0.06
0.04
0.20
lb/10dtons
0.38
0.16
0.36
0.04
0.3
0.3
0.2
0.122
0.04
0.098
0.04
0.12
0.08
0.40
Emission
factor
symbol b
NA, FAA, CAA (30)
NA,FAA(23)
NA (55)
FAA (32)
E
FAA (10)
NA(2)
NA, FAA, CAA (22)
NA(2)
NA, FAA, CAA (29)
NA(1)
NA, FAA, CAA (26)
NA(1)
NA, FAA, CAA (246)
a All sources uncontrolled.
b Defined in Table 1-1; number in parentheses indicates number of samples analyzed.
p
Based on results from Referencel 1.
Mercury
7-11
-------
Table7-5. EMISSION FACTORS FOR MERCURY FROM FUEL COMBUSTION, OIL
Source a
Oils
Imported residual oils
No. 6 fuel oil,
Mexico
No. 6 fuel oil,
Virgin Islands
No. 6 fuel oil,
Trinidad
W). 6 fuel oil,
Curacao, N.A.
No. 6 fuel oil,
St. Croix,V.I.
Bunker "C" fuel oil,
Venezuela
Average value for
imported residual oils
Imported No. 6 low-sulfur
fuel oils
Virgin Islands
Curacao, N.A.
Freeport, Bahamas
Average value for
imported low-sulfur
fuel oils
Foreign crude oils
Neutral Zone-Crude
No. 24, Nevada Zone
Mesa crude oil,
Venezuela
Monogas crude oil,
Venezuela
Mercury
content,
ppm
0.30
0.22
0.10
0.13
0.007
0,005
0.13
0.007
0.02
0.001
0.009
0.20
0.05
0.025
Emission factor
kg/103 liters
0.0003
0.0002
0.00009
0.0001
0.000007
0.000005
0.0001
0.000007
0.0002
0.0000009
0.000008
0.0002
0.00004
0.00002
lb/103 gal.
0.002
0.002
0.0008
0.001
0.00006
0.00004
0.001
0.00006
0.0002
0.000008
0.00007
0.001
0.0004
0.0002
Emission
factor
symbol b
NA(1)
NA(1)
NA(1)
NA(1)
NA(1)
NA(1)
NA(6)
NA(2)
NA(1)
NA(1)
NA(4)
NA(1)
NA(1)
NA(1)
7-12
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
Table7-5 (continued). EMISSION FACTORS FOR MERCURY FROM FUEL COMBUSTION, OIL
Source a
Jobo crude oil,
Venezuela
Bosean crude oil, Venezuela
Kenai Peninsula, Venezuela
UMM Tarvo, Libya
Gamba, Gabon
Tia Juanna, Venezuela
Ral Al Khafti, Kuwait
Durl, Sumatra
Darius, Iran
Average value for
foreign crude oils
U.S. crude oils
Wesson, Arkansas
Midland Farms, Texas
East Texas, Texas
Yates, Texas
Vacuum, New Mexico
St. Tedesa, Illinois
Maysville, Oklahoma
Hall-Gurney, Kansas
Huntington Beach,
California
Main Pass,
Louisiana
Average value for
U.S. crude oils
Mercury
content,
ppm
0.016
0.02
0.006
0.01
0.03
0.05
0.09
0.04
0.01
0.05
0.03
0.08
0.007
0.06
0.20
0.076
0.002
0.006
0.11
0.06
0.05
Emission factor
kg/103 liters
0.00001
0.00002
0.000005
0.000009
0.00003
0.00004
0.00008
0.00003
0.000009
0.00004
0.00003
0.00007
0.000006
0.00005
0.0002
0.00006
0.000002
0.000005
0.00009
0.00005
0.00004
lb/103gal.
0.0001
0.0001
0.00004
0.00007
0.0002
0.0004
0.0006
0.0003
0.00007
0.0004
0.0002
0.0006
0.00005
0.0004
0.001
0.0005
0.00001
0.00004
0.0008
0.0004
0.0004
Emission
factor
symbol b
NA(1)
NA(1)
NA(1)
NA(1)
NA(1)
NA(1)
NA(1)
NA(1)
NA(1)
NA(12)
NA(1)
NA(1)
NA(1)
NA(1)
NA(1)
NA(1)
NA(1)
NA(1)
NA(1)
NA(1)
IMA (10)
6 All sources uncontrolled.
bDefined in Table 1-1; numbers in parentheses indicate number of samples analyzed.
Mercury
7-13
-------
Table 7-6. EMISSION FACTORS FOR MERCURY FROM SOLID WASTE INCINERATION
Source
Emission factor
Emission
factor
symbol3
Solid waste incineration
Sewage sludge incineration
Uncontrolled
After wet scrubber
0.7kg/106kg (1 lb/103 tons) of refuse burned
0.02 kg/103kg (0.03 Ib/ton) sewage and sludge burned
Negligible
E
FAA (9)
Defined in Table 1-1; number in parentheses indicates number of samples analyzed.
7-14
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
8. NICKEL
MINING AND METALLURGICAL
PROCESSING 1
Open-pit mining is the only type employed in
the United States to recover nickel ore. The ore (1.4
percent nickel) is removed by digging or blasting
and then shipped to the smelter. The ore is then
smelted in electric furnaces and poured into ladles
where crushed ferrosilicon is added for the
reduction of the ore.
Secondary producers use scrap to prepare a
nickel case alloy. This product is sold principally to
steel mills. Another product, which is prepared to
exact specification, is sold to foundries.
The emission factor presented in Table 8-1 for
the mining and metallurgical industry (primary
and secondary) is based upon material balance
calculations. The value is a controlled emission
factor. Control equipment employed includes wet
scrubbers, bag filters, and electrostatic
precipitators.
PROCESSING OF NICKEL AND ITS
COMPOUNDS
Stainless and Heat-resisting Steels
The largest application of nickel is in the
production of stainless steels. The nickel contents
of stainless steels have an approximate range of 4.5
to 9.3 percent. Emissions of nickel (mainly as
nickel oxides) result from the melting process of the
various furnaces used in the steel industry. The
controlled emission factors (two) given in Table 8-1
are based upon the average of values estimated by
manufacturers. Some of the plants employ bag
filters as control equipment.
Alloy Steel
About 18.5 percent of all alloy steels produced
are nickel alloy steels with an average nickel
content of 1.8 percent. Emissions (nickel oxides
mainly) result from, the melting process in the
furnaces employed in the steel industry and from
steel or iron scrap, which contain about 1.3
kilograms of nickel per 1000 kilograms of scrap.
The emission factors (controlled) presented in
Table 8-1 are based on material balances.
Emissions are usually controlled by bag filters.
Nickel Alloys l
Alloys of this type are morel, sand and casting,
nickel-silver, electrical, and electrical resistance
alloys. Morel alloys contain more than 50 percent
nickel, and nickel silvers (copper-nickel-zinc) have
about 15 percent nickel by weight. All alloys have
various uses in several different industries.
Emissions from the production of these various
alloys result mainly from the melting process. The
emission factors (four values) given in Table 8-1 are
based upon estimates. Bag filters are employed as
control devices in the production of nickel alloys,
copper base alloys, and electrical alloys. Some
control is used in the production of cast iron, but
the value in Table 8-1 for cast iron is considered an
uncontrolled value.
Electroplating 1
The process consists of plating nickel with an
electrolyte solution. The anode is the nickel and the
nickel is deposited on the cathode (some other
metal). Emissions from this process are negligible.
Batteries l
Nickel-cadmium batteries have several
applications in heavy vehicles (diesel and buses)
and industry. The process is a sintering operation
in which the positive and negative plates consist of
sintered carbonyl nickel powder. The active
material of the plates is nickel oxide when the
battery is charged. Emissions result from handling
losses and sintering. Usually no controls are
employed in this industry. The emission factor
given in Table 8-1 is based upon manufacturers'
estimates.
Catalysts *
Nickel compounds are used in various industries
producing vegetable oils, ammonia, petrochemi-
cals, hydrogen, and many other products.
Emissions reported by manufacturers are con-
sidered negligible.
8-1
-------
CEMENT PLANTS
Cement manufacturing processes are described
in Chapter 4. Emissions from both dry and wet
process cement plants can result from all of the
processes described.
Dry Process
Two plants using the dry processing method
were visited, and particulate samples were obtained
by the EPA sampling train method. Baghouses
were employed as air pollution control equipment
at both plants on all processes described. The
probes for the sampling train were placed in the
stack area after each baghouse. Some of the
samples (total catch) were analyzed by emission
spectroscopy for trace metals. The emission factors
in Table 8-1 were based on percent of nickel
present in the sample and the emission factor
calculated for total particulates emitted. The final
cement from one plant was analyzed, and it also
contained nickel (80 micrograms per gram).
Wet Process3
Particulate emissions were obtained from the
kilns, clinker cooler, and finishing mill of three
plants that used the wet process. The same
analytical techniques were employed as described
in the dry process section except that part of one
sample was analyzed by spark source mass
spectrograph and optical emission spectrograph.
Sampling was done at the exits of the baghouses or
electrostatic precipitators employed at the
individual plants. Emission factors (Table 8-1) were
calculated as described in the section for the dry
process.
CONSUMPTIVE USES OF NICKEL AND ITS
COMPOUNDS
Nickel and its compounds are used in the pulp
and paper, petroleum, and chemical industries.
Emissions to the atmosphere are considered
negligible.
FUEL COMBUSTION
Several studies for trace metal emissions from
coal fired boilers have been done. In one study,
several boilers using coal from different parts of the
United States were studied. Fly ash samples were
collected and analyzed by emission spectrometry
for nickel and other trace metals. Nickel
concentrations ranged from 133 to 690 micrograms
per cubic meter. The emission factor given in Table
8-2 is based on the yearly consumption of coal, 75
percent control of particulates, nickel
concentration of 133 micrograms per cubic meter,
and 9.9 cubic meters per kilogram of coal.1
In another study, fly ash samples were collected
from five power plants and the samples were
analyzed by emission spectrometric methods for
trace metals.4'5 The samples were all collected by
an EPA sampling train with the probe of the train
placed in the stack after the electrostatic
precipitator or wet scrubber control equipment.
Nickel was present in all samples, the range being
50 to 290 micrograms per gram. Three coal
samples at three of the individual plants were also
analyzed, and nickel was again present, the range
being 10 to 30 micrograms per gram with an
average of 16 micrograms per gram. The emission
factors presented in Table 8-2 are based upon the
percent of nickel present in the fly ash samples
analyzed and emission factors estimated in the
studies for particulates, which were based on total
particulate catch.
1,6,7
According to Davis, * nickel content of U.S.
crude oils ranged from 1.4 to 64 parts per million
with an average of 15 parts per million. Nickel
content in imported crude oils ranged from 0.3 to
28.9 parts per million with an average of 10 parts
per million. The analytical method used to
determine trace metals present was not reported.
The emission factors given in Table 8-3 for this
study are based on the amount of nickel present,
assuming a 100 percent combustion factor and a
density of 850 grams per liter for crude oil.
In a second study, foreign crude and residual
oils from different oil fields were analyzed by flame
atomic absorption. All samples analyzed showed
nickel to be present. The nickel content in the
foreign crude oils averaged about 25.6 parts per
million (ranged from 1.8 to 59 parts per million).
The foreign crude oils showed an average nickel
content of about 36.3 parts per million (ranged
from 4 to 61 parts per million).6 The emission
factors for this study (Table 8-3) are based on the
amount of nickel found in the oil samples, an
assumed 100 percent combustion factor, and
densities of 850 (crude) and 944 (residual) grams
per liter for oil.
Another study in which residential (distillate
fuel) and commerical (residual fuel) oil burning
units were studied showed nickel being emitted to
the atmosphere.7 An EPA sampling train was
employed to catch particulates. The particulates
8-2
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
were analyzed for trace metals by optical emission
spectrometry. The emission factors based on this
study (Table 8-3) are lower than the values based
on nickel content alone. This would be the case if
some of the nickel or nickel compound were in the
vapor phase.
Gasoline
Nickel compounds may be present in some
gasolines. At present there is not enough
information available to give an accurate emission
factor.
WASTE INCINERATION 8'9'10
Sewage sludge and sewage sludge-mixed refuse
incinerators will be discussed in this section. Also,
an emission factor for waste lubrication oil is
provided in Table 8-4.
There are two main types, of sewage sludge
incinerators: multiple hearth and fluidized bed.
Both incinerators have similar designs, with the
only major difference being that ash is removed
from the bottom of the multiple hearth furnace,
but in the fluidized bed all the ash is carried
overhead and is removed by a scrubber. Scrubbers
(impinjet, inertial jet, and venturi) are a part of the
process design of sewage sludge incinerators.
Three sewage sludge incinerators were visited,
and particulate samples were obtained by the EPA
sampling train method. The samples were analyzed
by emission spectroscopy, and nickel was found in
all but one of the samples. 8
One sewage sludge-mixed refuse incinerator was
visited and particulate samples were collected
using a null balance probe. The samples were
analyzed by atomic absorption for nickel.9
The emission factors presented in Table 8-4 are
based on process conditions and amount of nickel
found in the particulate matter analyzed.
Several lubricating oils have also been analyzed
by EPA for trace metals. Nickel was present in all
oils and the emission factors ranged from 0.002 to
0.03 kilogram per 1000 liters of waste crankcase
oil, with an average value of 0.008 kilograms of
nickel oxides per 1000 liters of waste crankcase
oil.10
REFERENCES FOR CHAPTER 8
1. Davis, W.E. National Inventory of Sources and
Emissions; Cadmium, Nickel, and Asbestos -
Section II, Nickel (1968). W.E. Davis and
Associates. Leawood, Kansas. Contract No. CPA
70-128. February 1970.
2. Tests No. 71-MM-02 and -05. Emission Testing
Branch, Environmental Protection Agency.
Research Triangle Park, N.C. April 1972.
3. Tests No. 71-MM-03 and -06. Emission Testing
Branch, Environmental Protection Agency.
Research Triangle Park, N.C. March 1972.
4. Tests No. 71-CI-01, -02, and -03. Emission
Testing Branch, Environmental Protection Agency.
Research Triangle Park, N.C. Contract No. CPA
70-81. October 1971.
5. Test No. 71-CI-07. Emission Testing Branch,
Environmental Protection Agency. Research
Triangle Park, N.C. Contract No. CPA 70-131.
March 1971.
6. Brown, H.S. Unpublished data. Geological
Resources, Inc. Raleigh, N.C. September 1, 1972.
7. Levy, A., S.E. Miller, R.E. Barnett, E.J. Schulz,
R.H. Melvin, W.H. Axtman, and D.W. Locklin. A
Field Investigation of Emissions from Fuel Oil
Combustion for Space Heating. Battelle.
(Presented at American Petroleum Institute
Committee on Air and Water Conservation
meeting. Columbus, Ohio. November 1, 1971.)
8. Sewage Sludge Incineration. Environmental
Protection Agency. Research Triangle Park, N.C.
EPA-R2-72-040. August 1972.
9. Cross, F.L., R.I. Drago, and H.E. Francis.
Metals in Emissions from Incinerators Burning
Sewage Sludge and Mixed Refuse. Environmental
Protection Agency. Research Triangle Park, N.C.
1969.
10. Waste Lube Oils Pose Disposal Dilemma.
Environ. Sci. Technol. 6(l):25-26, January 1972.
Nickel
8-3
-------
Table 8-1. EMISSION FACTORS FOR NICKEL FROM INDUSTRIAL SOURCES
Source
Emission factor
Emission
factor
symbol13
Mining and metallurgical
Processing of nickel and
its compounds
Stainless steel
Nickel alloy steelsc
Iron and steel scrap
Nickel alloys (other)d
Copper base alloysd
Electrical alloys d
Cast iron
Electroplating
Batteries
Catalysts
Cement plants
Dry process
Kilnd
Feed to raw milld
Air separator after
rawmilld
Rawmilld
Air separator after
finish milld
Feed to finish mill
Ib/ton) of Ni produced
5 kg/103kg(10 Ib/ton) of Ni charged or
0.3 kg/103 kg (0.6 Ib/ton) of
stainless steel produced
5 kg/103kg (10 Ib/ton) of Ni charged
0.0008 kg/103 kg (0.0015 Ib/ton) of
steel and iron
1 kg/103kg (2 Ib/ton) of Ni charged
1 kg/103kg (2 Ib/ton) of Ni charged
1 kg/103kg (2 Ib/ton) of Ni charged
10 kg/103kg (20 Ib/ton) of Ni charged
Negligible
4 kg/103kg (8 Ib/ton) of Ni processed
Negligible
0.2 kg/106kg (0.3 lb/103tons) of feed
0.005 kg/106kg (0.01 lb/103 tons) of feed
0.0005 kg/106kg (0.001 lb/103 tons) of feed
0.0003 kg/106kg (0.0006 lb/103tons) of feed
0.002 kg/106kg (0.003 lb/103tons) of feed
0.005 kg/106kg (0.01 lb/103tons)of feed
MB
Q
MB
MB
E
E
E
E
Q
ES(1)
ES(1)
ES(1)
ES(1)
ESd)
ESd)
8-4
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
Table 8-1 (continued). EMISSION FACTORS FOR NICKEL FROM INDUSTRIAL SOURCES
Source1
Emission factor
Emission
factor
symbol5
Wet process
Kiln6 (2 different
plants)
Clinker cooler
Clinker cooler6
Clinker coolerf
Finishing mill after
air separatord
0.1 to 1 kg/106kg (0.2to2lb/103tons)of feed
0.002 kg/106kg (0.004 lb/103tons) of feed
0.05 kg/106kg (0.1 lb/103tons) of feed
0.1 kg/106kg (0.2 lb/103 tons) of feed
0.002 kg/106kg (0.004 lb/103tons) of feed
ES(2)
SSMS, OES (2)
ES(2)
ES(2)
SSMS, OES (1)
a Uncontrolled unless otherwise specified.
Defined in Table 1-1; numbers in parentheses indicate number of samples analyzed.
c Considered controlled.
d Exit from baghouse.
6 Exit from electrostatic precipitator.
Exit from two baghouses (in parallel).
Nickel
8-5
-------
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-a
8-8
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
Table 8-4. EMISSION FACTORS FOR NICKEL FROM WASTE INCINERATION
Source5
Emission factor
Emission
factor
symbol
Sewage sludge incinerators
Multiple hearth c
Fluidizedbedc
Municipal incinerator
Refuse only c
c
Refuse and sludge
Lubricating oil
0.002 kg/103kg (0.003 Ib/ton) of solid waste incinerated
0.0002 kg/103kg (0.0003 Ib/ton) of solid waste incinerated'
0.002 kg/103kg (0.003 Ib/ton) of solid waste incinerated
0.003 kg/103kg (0.005 Ib/ton) of solid waste incinerated
0.008 kg/103 liters (0.07 lb/103 gal.) of lubricating oilf
OES (4)
OES (2)
CAA (3)
CAA (3)
UK
In this table, all sources except lubricating oil are controlled.
b Defined in Table 1-1; numbers in parentheses indicate number of samples analyzed.
c Emission from wet scrubber.
d Range, 0.0003 to 0.004 kg/103kg (0.0006 to 0.008 Ib/ton).
e Range, 0.0001 to 0.0002 kg/103kg (0.0002to 0.0003 Ib/ton).
f Emission factor for nickel oxides.
Nickel
8-9
-------
-------
9. VANADIUM
MINING AND PROCESSING1'2
Vanadium occurs in many ores. It is found in
such minerals as pationite, bravoite, sulvanite,
davidite, and roscoelite. Vanadium is also present
in uranium-bearing sandstones, iron ores,
phosphate rock, and titaniferous magnetite ores.
The concentrations of vanadium in the ores range
from 0.01 to 25 percent. Vanadium is mainly
recovered from uranium and vanadium ores, and
from phosphate rock. The mining operations
consist of surface and underground ore recovery.
For underground operations, the process consists
of drilling, blasting, conveyance of ore to the
surface, and transportation to the mill. Surface
mining mainly consists of removing the overburden
by blasting and then transporting the ore to the
mill area.i Emissions result from all processes
described above. No controls are known by this
author to be employed.
In processing fo* the recovery of vanadium
pentoxide, the ores are first dry ground, mixed with
lime and salt, and roasted. Sodium vanadate is
produced from the roaster and is bleached with
water, acid, or a basic solution. The solution is
precipitated (sodium polyvanadate is produced)
and redissolved, thus causing the precipitation of
ammonium acetavanadate to take place. This
product is fused to yield vanadium pentoxide. The
product is of technical grade and contains 86
percent vanadium pentoxide (6 to 10 percent
sodium oxide). Emissions probably result from the
roasting operation and handling. The metal has a
low vaporization temperature and recovery rates
have been estimated at between 30 and 75 percent
of the metal present initially. 2 The emission factor
in Table 9-1 is based on information obtained from
the mining and milling industry.
METALLURGICAL PROCESSING
Ferrovanadium
1,3
The technical grade oxide, vanadium ore, or
slag is further reduced to ferrovanadium, which is
mainly used by the steel industry. The reduction is
carried out by carbon, ferrosilicon, or aluminum.
Reduction by carbon is done by an electric
reduction furnace or a vacuum furnace in which
charges are placed in the top of the furnace and the
molten product removed at the bottom. A vacuum
furnace product of ferrovanadium has been
reported to contain about 85 percent vanadium, 12
percent carbon, and 2 percent iron.3
Two processes are available for the production
of ferrovanadium by ferrosilicon reduction. In one
process about 90 percent grade ferrosilicon is
mixed with lime, vanadium pentoxide, and
fluorspar. The mixture is smelted in an electric
furnace lined with magnesite. The product
contains about 30 percent vanadium, iron, and
undesirable amounts of silicon. The silicon
concentration is reduced by adding more vanadium
pentoxide and lime. This step enables the silicon to
go into the slag phase, and the slag is recycled to
the first step of the process.
The second process in which silicon is employed
involves the reaction between vanadium bearing
slag, silica, carbonaceous reducer, and a flux inside
a submerged-arc electric furnace. The alloy
product, vanadium silicide alloy, is refined with
vanadium oxide until the concentration of silicon
present in the alloy is less than 20 percent. This
alloy is reacted with molten vanadiferous slag and
lime to yield a ferrovanadium alloy called Solvan
(28 percent vanadium, 11 percent other metals, and
the rest iron).
The reduction by aluminum can also be done by
two processes. In the first, the reactants of
vanadium pentoxide, aluminum, iron scrap, and a
flux are placed in an electric arc furnace. The
product from the reaction contains about 80
percent vanadium. In the second process, called
the thermite reaction, vanadium and iron oxide are
both reduced by aluminum granules. The reaction
is initiated by a barium peroxide-aluminum
ignition charge.
In each of the reduction processes discussed,
vanadium pentoxide is melted first before alloying
is done. The actual reduction process in the
furnace consists of the pentoxide going to
tetroxide, trioxide, oxide, and vandium metal.
Emissions from the above processes are from
the furnaces and from handling the molten
9-1
-------
material. The emission factor for electric furnaces
in Table 9-1 is based on uncontrolled emissions,
stack samples, and chemical analysis of the
particulates from the stack samples. The emission
factor for handling was estimated by Davis.'
Vanadium Metal 1>2
In one process used to obtain vanadium metal,
vanadium pentoxide is reduced by calcium (iodine
is also added). The reactants are all placed in a
sealed vessel, and calcium iodide, which serves as a
flux and thermal booster, is formed. The product is
about 99.5 percent pure vanadium. Another
process, called the alumino-thermic process,
produces 99 percent pure vanadium and employs
powdered vanadium pentoxide, which reacts with
aluminum in a sealed vessel. The molten alloy of
vanadium and aluminum settles to the bottom of
the vessel from a fused aluminum oxide slag. The
alloy is purified by crushing and melting by both
heat and an electron beam.
Vanadium metal can be further purified by
iodide refining, electrolytic refining in a fused salt,
or electrotransport. In the iodide refining process,
the iodide is reacted with vanadium metal to form
vanadium diodide, which is in vapor form. The
vanadium diodide is decomposed and deposited on
a hot filament. The electrolytic process involves the
cathodic deposition of vanadium from an
electrolyte in solution. Electrotransport consists of
a high-density current being passed through a
vanadium rod (heating to 1700 to 1850°C) with
migration of carbon, oxygen, and nitrogen atoms at
the negative end of the rod. Emissions result from
the handling of the molten mass, from crushing,
and possibly from the electron beam melting
employed in the alumino-thermic process. Most
reactions are inside sealed vessels that reduce
emissions. Not enough data are available to obtain
a reasonable emission factor for any process
discussed in this section.
Vanadium Carbide
Vanadium carbide is sometimes used as a
replacement for ferrovanadium in the steel
industry. The carbide is produced by heating
powdered vanadium metal, a hybride, and carbon
in a vacuum furnace (2000°C). Emissions can
result if a low carbon product is desired and low
temperatures are not employed in the heating. No
emission factor can be determined for this process
at present.
STEEL PRODUCTION l
Emissions of vanadium from the steel industry
are mainly due to impure vanadium or the
pentoxide being present in the iron ore. The
amount of vanadium present in the ore ranges from
0.01 to 0.1 percent. This range was estimated by
people contacted in the steel industry. Emissions
from alloying vanadium with steel are of less
importance in considering air pollution. The
vanadium is added to the melt at the end of the
refining process or after the steel is in the ladle.
Blast Furnace 1)4
In the production of steel, the first step involves
the removal of impurities from iron ore in a blast
furnace. Coke and limestone are also charged with
the iron ore in the furnace. Large amounts of
particulates are produced in this process.4 The gas
stream is usually cleaned with an estimated
efficiency of 97 percent.1 The emission factor in
Table 9-1 is based on an estimated vanadium
content of 0.03 percent in the iron ore (with 5
percent being lost). For further purification of the
pig iron into steel an open hearth, a basic oxygen,
or an electric furnace is used.
Open-hearth Furnacel^5
In the open hearth furnace, steel is made from a
mixture of scrap (which also contains vanadium)
and pig iron (about 55 percent pure) in a shallow
basin or hearth. The process consists of several
stages: tap to start, charging, meltdown (1650°C),
hot-metal addition, ore and lime boil, working,
tapping, and delay. Emissions of metal oxides are
continuous and varied during the operational
cycles described. For an uncontrolled process, the
particulate emitted is 6 (no oxygen lance) and 11
(oxygen lance) kilograms per 1000 kilograms of
steel produced.4 The amount of vanadium emitted
in the particulate matter is about 0.05 percent.1'5
The emission factor presented in Table 9-1 is based
on this value.
Basic Oxygen Furnace 1»^
The furnace consists of a refractory-lined
cylindrical vessel mounted on trunions. The charge
consists of steel scrap, molten pig iron, and
sometimes alloying materials. The furnace is
charged in the vertical position, and oxygen is
supplied, causing agitation and mixing of the
molten mass. Emissions result from the molten
mass and are usually controlled by scrubbers,
cyclones, or a combination of control equipment.
The emission factor presented in Table 9-1 is based
on an emission spectrographic study done on a
steel plant. A sample for particulates was taken by
an EPA sampling train and then was analyzed for
trace metals. The probe was placed in the stack of
the basic oxygen furnace after two venturi
9-2
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
scrubbers. The amount of vanadium present was
0.014 percent of the total particulate emitted
(which was determined to be 0.00675 kilogram per
1000 kilograms of steel). The emission factor is
small compared to Davis' value,1 which was based
on a 0.02 percent concentration of vanadium in the
particulate (23 kilograms of particulate per 1000
kilograms steel for uncontrolled value).
Electric .Furnace !
Electric furnaces are refractory-lined cylindrical
vessels with carbon electrodes passing through the
top of the furnace. Emissions from this furnace
result from charging, refining, and pouring of the
molten mass. Davis1 felt that emissions are
negligible for vanadium in electric furnaces.
CAST IRON PRODUCTION
1
The cupola is the method most widely used for
the production of cast iron. Emissions occur mainly
from the melting of the iron ore. The amount of
vanadium present in particulates, according to
industry sources, is about 0.001 percent. The
emission factor in Table 9-1 is based on this value.
CEMENT PLANTS
Cement manufacturing processes are described
in Chapter 4. Vanadium emissions from cement
plants are due to the presence of vanadium as an
impurity in one of the initial chemicals used to
produce cement. Emissions from both dry and wet
process cement plants can result from all of the
processes described.
Dry Process 7
Two plants using the dry process were visited,
and particulate samples were obtained by the EPA
sampling train method. Baghouses at both plants
were employed as air pollution control equipment.
The probes for the sampling train were placed in
the stack area after each baghouse. Stacks from
which samples were taken included the kilns (at
one plant only), raw mill grinding system, and
finish mill grinding system. Some of the samples
(total catch) were analyzed by emission
spectroscopy for trace metals. The emission factors
(Table 9-1) were based on percent of vanadium
present in the sample and the emission factor
calculated for total particulates.
Wet Process 8
Particulate emissions were obtained from the
kilns, clinker cooler, and finishing mill of three wet
process plants. The same analytical techniques
were employed as described in the dry process
section, except that part of one sample was ana-
lyzed by spark source mass spectrography and
optical emission spectrography. Sampling was
done at the exits of the baghouses or electrostatic
precipitators employed at the individual plants.
Basis for emission factor estimates (Table 9-1) is
also as described in the section for the dry process.
PROCESSING OF VANADIUM AND ITS
COMPOUNDS
Nonferrous Alloys *
Vanadium metal is also employed as an alloying
agent with nonferrous metals (aluminum and
titanium mainly) to control grain _size, ^thermal
expansion, and electrical resistivity.The emission
factor in Table 9-1 is based on two industrial
sources.
Catalysts 1
Catalyst manufacturers use vanadium
pentoxide or ammonium metavanadate as starting
reactants for the production of catalysts. In one
process, vanadic acid is produced and caustic
potash, dilute sulfuric acid, and water are added to
the acid. The mass is dried and placed in a
calcining furnace (at 800°C). The product is cooled
and sieved. The major source of emissions is the
furnace, and the emission factor in Table 9-1 is
based on manufacturers' estimates.
Ceramics and Glass
The use of vanadium in glass and ceramics is for
the production of a yellow stain for coloring pottery
and glass. Emissions of vanadium in this industry
are considered negligible.
Miscellaneous 1
Vanadium is also alloyed with magnetic alloys
and steel (already discussed). Compounds of
vanadium are placed in paint oil as a drying agent.
Vanadium chloride is used in toning silver bromide
in the development of color film.
In alloying, the vanadium is usually added in
the ladle. Emissions therefore are at a minimum.
For paint oils, the vanadium compounds can be
added in the paint-mixing process or during the
cooling period (230 to 316 °C). Emissions result
mainly during the cooling period. Vanadium
chloride, used in color film toning, is produced by
heating vanadium pentoxide with sulfur
monochloride to produce vanadium trichloride.
The trichloride is reduced by a nitrogen stream (at
800°C) to produce vanadium chloride. Emissions
result mainly from this stream. Emission factors
Vanadium
9-3
-------
for all of the processes described above are based
on losses estimated by manufacturers to range
from less than 0.25 to 5 percent.
FUEL COMBUSTION
Coal
1,9,10
Fly ash samples from five power plants were
analyzed by emission spectrometric methods to,
determine trace metals present. 9'10 The samples
were all taken by an EPA sampling train, with the
probe of the train placed in the stack after the
electrostatic precipitator or wet scrubber control
equipment. Vanadium was present in all samples
analyzed. The values of vanadium present ranged
from 70 to 180 micrograms per gram (weight
fraction) with an average value of 116 micrograms
per gram. The emission factors presented in Table
9-2 are based upon the percent of vanadium
present in the fly ash sample analyzed and emission
factors estimated in the studies for particulates.
The last value is based on the amount of
vanadium present in the coal initially. The range of
vanadium present was 16 to 35 parts per million
with an average of 22.5 parts per million. It was
assumed that 65 percent of the vanadium went with
the bottom ash. 1
Oil Ml
Analyses of over 400 samples of crude and
residual oils from major oil companies and utilities
on the east coast of the United States were
obtained. * The results showed vanadium to be
present in all samples. In crude oils (foreign and
domestic), the vanadium present ranged from less
than 1 to 1000 parts per million. The residual fuel
oils showed higher ranges (30 to 90 percent) than
the crude oils. Crude oils from the United States
showed a vanadium range of 0.1 to 78 parts per
million, with an average of 19.5 parts per million.
Residual oils of the United States average 30 parts
per million of vanadium, and the range was not
reported. Crude oils from Venezula ranged from
less than 1 to 1400 parts per million of vanadium,
with an average between 116 and 356 parts per
million. South American residual and crude oils
have an average vanadium content of 280 parts per
million. Crude oils from the Middle East contained
from 3 to 114 parts per million vanadium, with an
average of 43 parts per million. Residual oils from
the same area have an average content of 50 parts
per million vanadium. Emission factors based on
these values are presented in Table 9-3.
Another study in which residential (distillate
fuel) and commerical (residual fuel) oil burning
units were studied showed vanadium being emitted
to the atmosphere.11 An EPA sampling train was
employed to catch particulates. The particulates
were analyzed for trace metals by optical emission
spectrometry. The emission factors are given in
Table 9-3. The emission factors are lower than the
values obtained based on vanadium content alone.
SOLID WASTE INCINERATION 12
Incineration of waste material that contains
vanadium is another source of emissions for this
trace metal. However, there is limited information,
and the emission factors presented in Table 9-4 are
based on stack analysis of only one incinerator. The
analytical procedure employed to analyze for
vanadium was emission spectrography.
REFERENCES FOR CHAPTER 9
1. Davis, W.E. National Inventory of Sources and
Emissions; Arsenic, Beryllium, Manganese,
Mercury, and Vanadium — Section V, Vanadium
(1968). W.E. Davis and Associates. Leawood,
Kansas. Contract No. CPA-70-128. June 1971.
2. Athanassiadis, Y.C. Preliminary Air Pollution
Survey of Vanadium and Its Compounds. Litton
Systems, Inc. Contract No. PH 22-68-25. October
1969.
3. Carlson, O.N. ard E.R. Stevens. Vanadium
and Vanadium Alloys. In: Kirk-Othmer Encyclo-
pedia of Chemical Technology (2nd Ed., Vol. 21.
Stander, A., ed.). New York, John Wiley and Sons,
Inc., 1964. p. 157-167.
4. Compilation of Air Pollutant Emission Factors
(Revised). U.S. Environmental Protection Agency.
Research Triangle Park, N.C. Office of Air Pro-
grams Publication No. AP-42. February 1972. p.
149.
5. Air Pollution Engineering Manual. Danielson,
J.A. (ed.), National Center for Air Pollution Con-
trol, Public Health Service, U.S. Department of
Health, Education, and Welfare. Cincinnati, Ohio.
Publication No. 999-AP-40. 1967. p. 728.
6. Test No. 71-MM-24. Emission Testing Branch,
Environmental Protection Agency. Research
Triangle Park, N.C. Contract No. 68-02-0225.
March 7, 1972.
7. Tests No. 71-02 and -05. Emission Testing
Branch, Environmental Protection Agency.
Research Triangle Park, N.C. April 1972.
8. Tests No. 71-MM-01, -03, and -06. Emission
Testing Branch, Environmental Protection Agency.
Research Triangle Park, N.C. March 1972.
9-4
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
9. Tests No. 71-CI-01, -02, and -03. Emission Field Investigation of Emission from Fuel Oil
Testing Branch, Environmental Protection Agency. Combustion for Space Heating. Battelle. (Pre-
Research Triangle Park, N.C. Contract No. CPA sented at American Petroleum Institute Committee
70-81. October 1971. on Air and Water Conservation meeting.
in T * M -71 /-T m c • • T ^ o u Columbus, Ohio. November 1, 1971.)
10. Test No. 71-CI-07. Emission Testing Branch,
Environmental Protection Agency. Research
Triangle Park, N.C. Contract No. CPA 70-131. _ XT ^ _ r . . n
March 1971 ^- ^est ^O- '1-CI-H. Emission Testing Branch,
Environmental Protection Agency. Research
11. Levy, A., S.E. Miller, R.E. Barnett, E.J. Shulz, Triangle Park, N.C. Contract No. CPA 70-81.
R.H. Melvin, W.H. Axtman, and D.W. Locklin. A September 1971.
Vanadium 9.5
-------
Table 9-1. EMISSION FACTORS FOR VANADIUM FROM INDUSTRIAL SOURCES
Source
Emission factor
Emission
factor
symbol
Mining and processing
Metallurgical processing
Ferrovanadium,
electric furnaces c
Handling losses
Steel production
Blast furnace
Open-hearth furnace
No oxygen lance
Oxygen lance
Basic oxygen furnace d
Basic oxygen furnace
Electric furnace
Cast iron production
Cement plants
Dry process (for all
processes)
Wet process
Kijn (average of two)e
Clinker coolerf
Clinker cooler e
Clinker coolerg
Finishing mill after
air separator f
Processing of vanadium
and its compounds
Nonf errous alloys
Catalysts
Glass and ceramics
Miscellaneous (steel
alloying, magnetic
alloys, paint oils,
color film)
13 kg/103kg (25 Ib/ton) of vanadium processed
25 kg/103kg (50 Ib/ton) of vanadium processed
5 kg/103kg (10 Ib/ton) of vanadium processed
0.02 kg/103kg (0.03 Ib/ton) of pig iron produced
0.003 kg/103kg (0.006 Ib/ton) of steel produced
0.006 kg/103kg (0.01 Ib/ton) of steel produced
0.001 kg/106kg (0.002 Ib/ton) of steel produced
0.005 kg/103kg (0.009 Ib/ton) of steel produced
Negligible
0.1 kg/106kg (0.2 lb/103ton) of charge
_h
0.05kg/106kg (0.1 lb/103ton) of feed
0.0003 kg/106kg (0.0005 lb/1Q3ton) of feed
0.01 kg/106kg (0.02 lb/103ton) of feed
— h
0.0001 kg/106kg (0.0002 lb/103ton) of feed
6 kg/103kg (12 Ib/ton) of vanadium processed
10 kg/103kg (20 Ib/ton) of vanadium processed
Negligible
5 kg/103kg (10 Ib/ton) of vanadium processed
Q
UK
E
OES (1)
OES (1)
OES (1)
E
Q
ES (6)
ES (2)
OES, SSMS (1)
ES (1)
ES (1)
OES, SSMS (1)
Q
Q
Q
Uncontrolled unless otherwise specified.
bDefined in Table 1-1; numbers in parentheses indicate number of samples analyzed.
c Particle size, 0.1 to 1 micron.1
dExit from two venturi scrubbers.
e Exit from electrostatic precipitator.
f Exit from baghouse.
9 Exit from two baghouse collectors (in parallel).
h Emission below detection limit of analytical technique.
9-6
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
Table 9-2. EMISSION FACTORS FOR VANADIUM FROM FUEL COMBUSTION, COAL
Source8
Illinois0
South Carolina0
Michigan0
Average c
Kansas d
Based on vanadium
content in coal
Vandium
content,
ppm
20
e
10
15
10 to 20
22.5
Emission factor
kg/103kg
0.0003 (0.0003 to 0.0004)
0.0002 (0.0002 to 0.0003)
0.0003 (0.0002 to 0.0003)
0.0003
0.002
15
Ib/ton
0.0006 (0.0005 to 0.0007)
0.0004 (0.0003 to 0.0006)
0.0005 (0.0003 to 0.0006)
0.0006
0.003 (0.003 to 0.004)
30
Emission
factor
symbol6
EST (3)
EST (6)
EST (2)
EST(11)
EST (2)
UK
Controlled unless otherwise specified.
Defined in Table 1-1; numbers in parentheses indicate number of samples analyzed.
' Exit from electrostatic precipitator.
Exit from limestone wet scrubber.
e Not reported.
Vanadium
9-7
-------
Table 9-3. EMISSION FACTORS FOR VANADIUM FROM FUEL COMBUSTION, OIL
Source3
Crude oils, U.S.
Arkansas
California
Colorado
Kansas
Louisiana
Montana
New Mexico
Oklahoma
Texas
Utah
Wyoming
Average for U.S. crude oils
Average, residual oil - United States
Foreign crude and residual oil
Average, crude oil -
Western Venezuela
Average, crude oils -
Eastern Venezuela
Average, residual oil - Venezuela
Average, residual oil - Middle East
U.S. boilers
Residual units (distillate)
Commercial units (residual No. 6)c
Commercial units (residual No. 5)
Commercial units (residual No. 4)
Vanadium
content, ppm
9.3
50.0
00.44
15.1
0.5
78
0.1
4.0
2.6
4.6
49.7
19.5
30
356
116
280
50
— d
223
88
86
Emission factor
kg/103liters
0.008
0.04
0.0004
0.01
0.0004
0.07
0.00009
0.003
0.002
0.004
0.04
0.02
0.03
0.3
0.1
0.3
0.05
0.000008
0.04
0.01
0.02
lb/103 gal.
0.07
0.4
0.003
0.1
0.004
0.6
0.0007
0.03
0.02
0.03
0.4
0.1
0.2
3
0.8
2
0.4
0.00007
0.3
0.09
0.2
Emission
factor
symbol
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
UK
ES(2)
ES(1)
ES(1)
ES(1)
aUncontrolled unless otherwise specified.
b Defined in Table 1-1; numbers in parentheses indicate number of samples analyzed.
c Particle size range (paniculate collected with a cascade impactor): 20 percent (by weight) less than 0.21
micron, 80 percent less than 7.4 microns, mass mean particle size 1.2 microns.
dNot reported.
9-8
EMISSION FACTORS FOR TRACE SUBSTANCES
-------
Table 9-4. EMISSION FACTORS FOR VANADIUM FROM SOLID WASTE INCINERATION
Source
Uncontrolled
After electrostatic precipitation
Emission factor
0.0005 kg/103kg (0.001 Ib/ton) of waste
burned
_b
Emission
factor
symbol3
EST(1)
EST(1)
Defined in Table 1-1; numbers in parentheses indicate number of samples analyzed.
Emissions below detection limit of analytical technique.
Vanadium
9-9
-------
-------
BIBLIOGRAPHIC DATA
SHEET
1. Report No.
EPA-450/2-73-001
3. Recipient's Accession No.
4. Title and Subtitle
Emission Factors for Trace Substances
5. Report Date
December 1973
6.
7. Author(s)
David Anderson
8. Performing Organization Rept.
No.
9. Performing Organization Name and Address
U. S. Environmental Protection Agency
Office of Air and Water Programs
Office of Air Quality Planning and Standards
Research Traingle Park. N. C. 27711
10. Project/Task/Work Unit No.
11. Contract/Grant No.
12. Sponsoring Organization Name and Address
13. Type of Report & Period
Covered
Final report
14.
15. Supplementary Notes
16. Abstracts
This document presents emission factors for eight trace pollutants: arsenic, asbestos,
beryllium, cadmium, manganese, mercury, nickel, and vanadium. Emission data on which
these factors are based, obtained from source tests, material balance studies,
engineering estimates, etc., have been compiled for use by individuals and groups re-
sponsible for conducting air pollution inventories. Emission factors given in this
document cover most of the common emission categories for the eight trace substances:
mining, metallurgical, secondary metal industry, processing and utilization, consump-
tive uses, fuel combustion, and waste incineration. When no source test data are
available, these factors can be used to estimate the quantities of the trace pollutants
being released from a source or source group.
17. Key Words and Document Analysis. 17o. Descriptors
Air pollution *
Arsenic*+
Asbestos**
Beryllium*+
Cadmium*+
Emissions+
Emission factors*
17b. Identifiers/Open-Ended Terms
*Emission factors
+Air pollution
17c. COSATI Field/Group
Manganese**
Mercury**
Nickel**
Pollution**
Vanadium**
18. Availability Statement
Release unlimited
FORM NTIS-33 (REV. 3-72)
19. Security Class (This
Report)
UNCLASSIFIED
20. Security Class (This
Page
UNCLASSIFIED
21- No. of Pages
Rfl
22. Price
USCOMM-DC K8S2-P72
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INSTRUCTIONS FOR COMPLETING FORM NTIS-35 (10-70) (Bibliographic Data Sheet based on COSATI
Guidelines to Format Standards for Scientific and Technical Reports Prepared by or for the Federal Government,
PB-180 600).
1. Report Number. Each individually bound report shall carry a unique alphanumeric designation selected by the performing
organization or provided by the sponsoring organization. Use uppercase letters and Arabic numerals only. Examples
FASEB-NS-87 and FAA-RD-68-09.
2. Leave blank.
3. Recipient's Accession Number. Reserved for use by each report recipient.
4. Title and Subtitle. Title should indicate clearly and briefly the subject coverage ot the report, and be displayed promi-
nently. Set subtitle, if used, in smaller type o; otherwise subordinate it to main titK . When a report is prepared in more
than one volume, repeat the primary title, add volume number ,md include .submit for thi specific volume.
5- Report Date. !• ach report shall carry a date indicating at least month and year. Indicate the basis on which it was selected
(e.g., date of issue, date of approval, date of preparation,
6- Performing Organization Code. Leave blank.
7. Author(s). Give name(s) in conventional order 'e.g., John R, Doe, or J.Robert Doe). List author's affiliation if it differs
from the performing organization.
8- Performing Organization Report Number. Insert if performing organization wishes to assign this number.
9. Performing Organi zation Name and Address. Give name, street, c it y, state, and ? ip c ode. Lisi no more than two levels of
an organizational hierarchy. Display the name of the organization exactly as it should appear in Government indexes such
as USGRDR-I.
10. Project Tosk/Work Unit Number, list the project task and work unit numbers under winch the report was prepared.
11. Contract/Grant Number. Insert contract or grant number under which report was prepared.
12- Sponsoring Agency Name and Address. In<- lude / ip code.
13- Type of Report and Period Covered. Indit- ate interim, final, ( tc., and, if applicable, date s c overed.
14. Sponsoring Agency Code. Leave bJank.
15. Supplementary Notes. hntcr information not int luded e Isc where but useful, such a1- Prepared in cooperation with . . .
Translation of ... Presented at conference of ... To b< published in ... Supersedes . . . Supplements
16. Abstract. Include a brief (200 words or It ss) factual summary of the most significant information contained in the report.
If the report contains a significant bibliography or literature survey, mention it here.
17. Key Words and Document Analysis, (a). Descriptors. Select from the Thesaurus of Fngmeer ing and Scientific Terms the
proper authorized terms that identify the major concept of the research and are sufficiently specific and precise to be used
as index entries for cataloging.
(b). Identifiers and Open-Ended Terms. Use identifiers for project names, code name--, equipment designators, etc. Use
open-ended terms written in descriptor form for those subjects for which no descriptor exists.
(c). COSATI Field/Group. Field and Group assignments are to be taken from rhc 1965 COSATI Subject Category List.
Since the majority of documents are multid isc iphnary in nature, the primary Field/Group assignments ) wii be the specific
discipline, area of human endeavor, or type of physical object. The application(s) will be cross-referenced with secondary
Field/Group assignments that will follow the primary posting(s).
18. Distribution Statement. Denote rcleasability to the public or limitation for reasons other than security for example "Re-
lease unlimited'*. Cite any availability to the public, with address and price.
19 & 20. Security Classification. Do not submit classified reports to the National Technical
21. Number of Pages. Insert the total number of pages, including this one and unnumbered pages, but excluding distribution
list, if any.
22 Price. Insert the price set by the National Technical Information Service or the Government Printing Office, if known.
FORM NTIS-35 IREV. 3-72)
USCOMM-DC 14952-F
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