Locating and Estimating Air Emissions From Sources of Lead and Lead Compounds
Locating and Estimating Air Emissions From Sources of Lead and Lead Compounds
Locating and Estimating Air Emissions From Sources of Lead and Lead Compounds
AIR
EPA
L& E
EPA-454/R-98-006
May 1998
This report has been reviewed by the Office of Air Quality Planning and Standards, U.S.
Environmental Protection Agency, and has been approved for publication. Mention of trade
names and commercial products does not constitute endorsement or recommendation for use.
EPA-454/R-98-006
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TABLE OF CONTENTS
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TABLE OF CONTENTS, (CONTINUED)
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TABLE OF CONTENTS, (CONTINUED)
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TABLE OF CONTENTS, (CONTINUED)
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TABLE OF CONTENTS, (CONTINUED)
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TABLE OF CONTENTS, (CONTINUED)
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TABLE OF CONTENTS, (CONTINUED)
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TABLE OF CONTENTS, (CONTINUED)
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TABLE OF CONTENTS, (CONTINUED)
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APPENDICES
xii
LIST OF TABLES
Table Page
4-2 Lead Emission Factors for Primary Lead Smelting Facilities . . . . . . . . . . . . . . . . . . . . 4-6
4-3 U.S. Secondary Lead Smelters Grouped According to Annual Lead Production
Capacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-7
4-5 Lead Emission Factors for Primary Copper Smelting Facilities . . . . . . . . . . . . . . . . . 4-28
4-8 Lead Emission Factors for Secondary Copper Smelting Facilities . . . . . . . . . . . . . . . 4-37
4-11 Lead Emission Factors for Iron and Steel Foundries . . . . . . . . . . . . . . . . . . . . . . . . . . 4-58
4-12 Lead Emission Factors for Leadbearing Ore Crushing and Grinding . . . . . . . . . . . . . 4-62
4-15 Brass and Bronze Production and Lead Emissions in 1992 . . . . . . . . . . . . . . . . . . . . 4-67
xiii
LIST OF TABLES, (CONTINUED)
Table Page
5-3 Lead Emission Factors for Wood Waste-fired Utility Boilers . . . . . . . . . . . . . . . . . . 5-24
5-4 Lead Emission Factors for Wood Waste-fired Industrial Boilers . . . . . . . . . . . . . . . . 5-25
5-5 Lead Emission Factors for Wood Waste-fired Commercial/Institutional Boilers . . . 5-27
5-6 Lead Emission Factors for Natural Gas-fired Utility Boilers from AP-42 . . . . . . . . . 5-29
5-9 Lead Emission Factors for Coal-fired Utility Boilers from Utility Study . . . . . . . . . . 5-33
5-13 Lead Emission Factors for Oil-fired Utility Boilers from Utility Study . . . . . . . . . . . 5-40
5-16 Lead Emission Factors for Waste Oil-fired Industrial Boilers . . . . . . . . . . . . . . . . . . 5-41
5-17 Lead Emission Factors for Waste Oil-fired Commercial/Institutional Boilers . . . . . . 5-42
5-18 Lead Emission Factors for Solid Waste-fired Utility Boilers . . . . . . . . . . . . . . . . . . . 5-43
5-21 Lead Emission Factors for Municipal Waste Combustion Sources . . . . . . . . . . . . . . 5-58
xiv
LIST OF TABLES, (CONTINUED)
Table Page
5-22 Lead Emission Factors for Sewage Sludge Incinerator Sources . . . . . . . . . . . . . . . . . 5-69
5-23 Lead Emission Factors for Medical Waste Combustion Sources . . . . . . . . . . . . . . . . 5-79
5-24 Lead Emission Factors for Drum And Barrel Reclamation Sources . . . . . . . . . . . . . . 5-93
5-25 Lead Emission Factors for Open Burning Of Scrap Tires . . . . . . . . . . . . . . . . . . . . . . 5-97
5-28 Distribution of Kraft Pulp Mills in the United States (1997) . . . . . . . . . . . . . . . . . . 5-102
5-29 Lead Emission Factors for Kraft Process Recovery Furnaces and Smelt Dissolving
Tanks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-109
5-31 Distribution of Sulfite Pulp Mills in the United States (1997) . . . . . . . . . . . . . . . . . 5-113
5-32 Lead Emission Factors for Sulfite Process Recovery Furnaces . . . . . . . . . . . . . . . . 5-116
5-34 Lead Emission Factors for Portland Cement Manufacturing Facilities . . . . . . . . . . . 5-127
6-1 Glass Manufacturers (SIC 3229) in the United States Reporting Lead and Lead
Compound Emissions Under SARA 313 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-3
6-6 Characteristics of Uncontrolled Exhaust Gas from Lead Oxide Ball Mill and
Barton Pot Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-25
6-7 Performance Test Results on Baghouses Serving Lead Oxide Facilities . . . . . . . . . . 6-26
xv
LIST OF TABLES, (CONTINUED)
Table Page
6-8 Lead Emission Factors for Manufacture of Lead Oxide in Pigments . . . . . . . . . . . . . 6-27
6-20 Manufacturers of Resins and Plastics Reporting Lead and Lead Compound
Emissions in the 1992 Toxic Chemicals Release Inventory . . . . . . . . . . . . . . . . . . . . 6-61
6-22 Lead Emission Factors for Batch-Mix Hot-Mix Asphalt Plants . . . . . . . . . . . . . . . . . 6-73
6-23 Lead Emission Factor for Drum-Mix Hot-Mix Asphalt Plants . . . . . . . . . . . . . . . . . . 6-74
6-26 Rubber Product Manufacturing Facilities in the United States Reporting Lead And
Lead Compound Emissions in 1992 Under SARA 313 . . . . . . . . . . . . . . . . . . . . . . . 6-82
xvi
LIST OF TABLES, (CONTINUED)
Table Page
7-5 Typical Values for Paved Road Industrial Augmentation Factor (I) . . . . . . . . . . . . . . 7-11
7-6 Typical Silt Content Values of Surface Material on Industrial and Rural Unpaved
Roads . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-13
xvii
LIST OF FIGURES
Figure Page
4-2 Simplified Process Flow Diagram for Secondary Lead Smelting . . . . . . . . . . . . . . . . . 4-9
4-13 Typical Process Diagram for Pretreatment in the Secondary Aluminum Processing
Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-46
4-14 Typical Process Flow Diagram for the Secondary Aluminum Processing Industry . . 4-47
4-15 Process Flow Diagram for a Typical Sand-Cast Iron and Steel Foundry . . . . . . . . . . 4-54
xviii
LIST OF FIGURES, (CONTINUED)
Figure Page
5-3 Simplified Atmospheric Fluidized Bed Combustor Process Flow Diagram . . . . . . . . 5-13
5-6 Simplified Process Flow Diagram, Gas Cycle for a Mass Burn/Rotary Waterwall
Combustor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-51
5-15 Typical Process Component Options in a Hazardous Waste Incineration Facility . . . 5-84
xix
LIST OF FIGURES, (CONTINUED)
Figure Page
5-23 Process Diagram for Magnesium-Based Sulfite Pulping and Chemical Recovery . . 5-114
6-9 General Process Flow Diagram for Batch-Mix Asphalt Paving Plants . . . . . . . . . . . . 6-67
6-10 General Process Flow Diagram for Drum-Mix Asphalt Paving Plants . . . . . . . . . . . . 6-69
6-11 General Process Flow Diagram for Counterflow Drum-Mix Asphalt Paving Plants . 6-70
xx
EXECUTIVE SUMMARY
The 1990 Clean Air Act Amendments contain a list of 188 hazardous air pollutants
(HAPs) which the U.S. Environmental Protection Agency (EPA) must study, identify sources of,
and determine if regulations are warranted. a Of these HAPs, lead and lead compounds are the
subject of this document. This document describes the properties of lead and lead compounds as
air pollutants, defines their production and use patterns, identifies source categories of air
emissions, and provides lead emission factors. The document is a part of an ongoing EPA series
designed to assist the general public at large, but primarily federal, state, and local air agencies,
in identifying sources of HAPs and developing emissions estimates.
Lead is primarily used in the manufacture of lead-acid batteries, lead alloys, lead oxides
in pigments, glass, lead cable coating, and a variety of lead products including ammunition and
radiation shielding. Lead is emitted into the atmosphere from mining and smelting; from its use
as a feedstock in the production of lead alloys, lead compounds and other lead-containing
products; from mobile sources; and from combustion sources.
In addition to the lead and lead compound sources and emission factor data, information
is provided that specifies how individual sources of lead and lead compounds may be tested to
quantify air emissions.
a
Caprolactam was delisted from the list of HAPs (Federal Register Volume 61, page 30816, June 18, 1996).
xxi
SECTION 1.0
PURPOSE OF DOCUMENT
The Environmental Protection Agency (EPA) and state and local air pollution
control agencies are becoming increasingly aware of the presence of substances in the ambient air
that may be toxic at certain concentrations. This awareness has led to attempts to identify
source/receptor relationships for these substances and to develop control programs to regulate
toxic emissions.
1-1
Substance or Source Category EPA Publication Number
Coal and Oil Combustion Sources EPA-450/2-89-001
Cyanide Compounds EPA-454/R-93-041
Dioxins and Furans EPA-454/R-97-003
Epichlorohydrin EPA-450/4-84-007j
Ethylene Oxide EPA-450/4-84-007l
Ethylene Dichloride EPA-450/4-84-007d
Formaldehyde EPA-450/2-91-012
Lead EPA-454/R-98-006
Manganese EPA-450/4-84-007h
Medical Waste Incinerators EPA-454/R-93-053
Mercury and Mercury Compounds EPA-453/R-93-023
Methyl Chloroform EPA-454/R-93-045
Methyl Ethyl Ketone EPA-454/R-93-046
Methylene Chloride EPA-454/R-93-006
Municipal Waste Combustors EPA-450/2-89-006
Nickel EPA-450/4-84-007f
Organic Liquid Storage Tanks EPA-450/4-88-004
Perchloroethylene and Trichloroethylene EPA-450/2-90-013
Phosgene EPA-450/4-84-007i
Polychlorinated Biphenyls (PCB) EPA-450/4-84-007n
Polycyclic Organic Matter (POM) EPA-450/4-84-007p
Sewage Sludge Incineration EPA-450/2-90-009
Styrene EPA-454/R-93-011
Toluene EPA-454/R-93-047
Vinylidene Chloride EPA-450/4-84-007k
Xylenes EPA-454/R-93-048
This document deals specifically with lead and lead compounds. Its intended
audience includes federal, state and local air pollution personnel and others who are interested in
locating potential emitters of lead and lead compounds and making gross emissions estimates.
1-2
The reader is strongly cautioned against using the emissions information contained
in this document to try to develop an exact assessment of emissions from any particular facility.
This document is intended to be used as a tool to assist in inventorying lead air emissions from
source categories, rather than specific facilities. Available data are insufficient to develop
statistical estimates of the accuracy of these emission factors, so no estimate can be made of the
error that could result when these factors are used to calculate emissions from any given facility.
The public's misinterpretation of these figures can lead to a gross exaggeration of lead air
emissions. It is possible, in some cases, that order-of-magnitude differences could result between
actual and calculated emissions, depending on differences in source configurations, control
equipment, and operating practices.1 Thus, in situations where an accurate assessment of lead
emissions is necessary, source-specific information should be obtained to confirm the existence of
particular emitting operations, the types and effectiveness of control measures, and the impact of
operating practices. A source test should be considered as the best means to determine air
emissions directly from a facility or operation.
A national ambient air quality standard (NAAQS) for lead of 1.5 micrograms per
cubic meter (µg/m 3) averaged over a calendar quarter was established in 1978. The EPA used
health effects criteria as the basis for arriving at this level for the NAAQS. As such, a large
amount of health-related information does exist in available literature for lead.
Since establishing the NAAQS for lead in 1978, EPA has periodically reviewed the
standard, again focusing on the health effects of lead. Although the NAAQS limit has remained
unchanged at 1.5 µg/m 3, evaluation of the standard is ongoing at EPA, generating additional
health-related and ambient air concentration data. However, data collected through ambient air
studies do not reveal specific lead emission contributions from individual sources, which is the
focus of this document.
With the 1990 Amendments to the CAA, lead and lead compounds were both
recognized for their toxic characteristics and included on the list of hazardous air pollutants
1-3
(HAPs) presented in Section 112(d) to be evaluated in the development of maximum achievable
control technology (MACT) standards. In addition, many states also recognize lead and lead
compounds as toxic pollutants, and some states may impose their own regulations, which can be
more stringent than federal standards. For example, under the state of California's air toxic
identification and control program, the California Air Resources Board (CARB) is proposing to
identify inorganic lead as a toxic air contaminant. The identification or risk assessment process
includes assessing the exposure and health effects of toxic air contaminants. Once a toxic air
contaminant is identified by the Board, it enters into the control or risk management phase of the
program. In this phase, the need for an appropriate degree of controls is evaluated with full
public participation.2
Lead air emissions have also been affected by regulatory activity from other
agencies, including: the Occupational Safety and Health Administration (OSHA), which has
enacted regulations for reducing lead exposure to a variety of worker categories; the U.S.
Consumer Product Safety Commission, which has prohibited lead paints on toys and furniture; the
Food and Drug Administration (FDA) has guidelines for levels of lead that can leach out of
ceramics; and the Toxic Substances Control Act (TSCA) which proposed reducing lead in the
manufacture of certain products, such as fishing sinkers.
The MACT standards development program at the Office of Air Quality Planning
and Standards (OAQPS) has served as a means of providing source-specific information on lead
and lead compound emissions. A concerted effort was made during the development of this
document to coordinate with the work underway at OAQPS. Data were available through this
program for the metallurgical industry, which is a significant emitter of lead. However, many of
the MACT standards were in the preliminary stages (e.g., secondary aluminum, iron and steel
foundries), and emissions information was not available.
As a result of California's “Hot Spots” source testing program and other state
source testing efforts, data were available for incorporation into this document. Information and
1-4
test data from these reports are maintained in EPA's Source Test Information Retrieval System
(STIRS) database and the Factor Information Retrieval (FIRE) System.3,4 However, despite the
data generated by these programs, the available data on some potential sources of lead emissions
are limited and the configurations of many sources will not be the same as those described in this
document. Therefore, this document is best used as a primer to inform air pollution personnel
about the following: (1) the types of sources that may emit lead, (2) process variations that may
be expected within these sources affecting emissions, and (3) available emissions information that
indicates the potential for lead to be released into the air from each operation. This document
does not contain any discussion of health or other environmental effects of lead, nor does it
include any discussion of ambient air levels.
Group Leader
Emission Factor and Inventory Group (MD-14)
Office of Air Quality Planning and Standards
U. S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
1-5
SECTION 2.0
OVERVIEW OF DOCUMENT CONTENTS
This section briefly outlines the nature, extent, and format of the material
presented in the remaining sections of this report.
Section 3.0 provides a brief summary of the physical and chemical characteristics
of lead and lead compounds and an overview of its production, uses, and emission sources. This
background section is useful in developing a general perspective on lead, how it is manufactured
and consumed, and identifies potential sources of lead emissions.
Section 4.0 focuses on air emissions of lead from the metallurgical industry. For
each major production source category described in Section 4.0, a list of individual companies
identified in that particular industry is provided, where available. An example process
description and a flow diagram with potential lead emission points are given. Emission factors
for potential lead emissions, before and after controls employed by industry, are given where
available.
Section 5.0 describes various combustion source categories where lead emissions
have been reported. For each type of combustion source, a description(s) of the combustor is
given and potential lead emission points are identified on diagrams. Emission factors for
potential lead emissions, before and after controls, are given where available.
Section 6.0 summarizes other source categories that use and potentially emit lead.
The manufacture of lead-acid batteries is discussed in this section. The majority of the other
source categories discussed use lead as an additive in various products such as glass, paint,
2-1
pigments, glazes, solders, and stabilizers. Limited information on many of these sources is
available; therefore, varying levels of detail on the processes, emissions, and controls are
presented. Locations of facilities in each source category are provided, where available.
Section 7.0 discusses lead emissions from mobile sources. Both on-road and
off-road sources, as well as aircraft are addressed. This section also includes a discussion of
emissions from lead deposited in soil by mobile sources and reentrained in road dust.
Section 8.0 summarizes available procedures for source sampling, ambient air
monitoring, and analysis of lead. This section provides an overview of applicable sampling
procedures and cites references for those interested in conducting source tests. References for
the entire document are listed in Section 9.0.
Each emission factor listed in Sections 4.0 through 7.0 was assigned an emission
factor rating (A, B, C, D, E, or U) based on the criteria for assigning data quality ratings and
emission factor ratings as required in the document Procedures for Preparing Emission Factor
Documents.5 The criteria for assigning the data quality ratings to source tests are as follows:
A - Tests are performed by using an EPA reference test method, or when not
applicable, a sound methodology. Tests are reported in enough detail for
adequate validation, and, raw data are provided that can be used to
duplicate the emission results presented in the report.
2-2
D - Tests are based on generally unacceptable method, but the method may
provide an order-of-magnitude value for the source.
Once the data quality ratings for the source tests had been assigned, these ratings
along with the number of source tests available for a given emission point were evaluated.
Because of the almost impossible task of assigning a meaningful confidence limit to industry-
specific variables (e.g., sample size vs. sample population, industry and facility variability,
method of measurement), the use of a statistical confidence interval for establishing a
representative emission factor for each source category was not practical. Therefore, some
subjective quality rating was necessary. The following quality ratings were used in the emission
factor tables in this document:
C - Average. Emission factor is developed primarily from A-, B-, and C-rated
test data from a reasonable number of facilities. Although no specific bias
is evident, it is not clear if the facilities tested represent a random sample
of the industry. As with the A rating, the source category population is
sufficiently specific to minimize variability.
D - Below average. Emission factor is developed primarily form A-, B-, and
C-rated test data from a small number of facilities, and there may be
reason to suspect that these facilities do not represent a random sample of
the industry. There also may be evidence of variability within the source
population.
E - Poor. Factor is developed from C- rated and D-rated test data from a very
few number of facilities, and there may be reasons to suspect that the
facilities tested do not represent a random sample of the industry. There
also may be evidence of variability within the source category population.
2-3
U - Unrated (Only used in the L&E documents). Emission factor is developed
from source tests which have not been thoroughly evaluated, research
papers, modeling data, or other sources that may lack supporting
documentation. The data are not necessarily “poor,” but there is not
enough information to rate the factors according to the rating protocol.
2-4
SECTION 3.0
BACKGROUND
Pure lead is a silvery-white metal that oxidizes and turns bluish-gray when
exposed to air. It is soft enough to be scratched with a fingernail. It is dense, malleable, and
readily fusible.6 Its properties include a low melting point; ease of casting; high density; low
strength; ease of fabrication; acid resistance; electrochemical reaction with sulfuric acid;
chemical stability in air, water, and earth; and the ability to attenuate sound waves, atomic
radiation and mechanical vibration. 7 The physical properties of lead are presented in Table 3-1.
Lead in its elemental or pure form rarely occurs in nature. Lead most commonly
occurs as the mineral galena (lead sulfide [PbS]), and is sometimes found in other mineral forms,
which are of lesser commercial importance, such as anglesite (PbSO4 ) and cerussite (PbCO3).6
Table 3-2 presents properties of these three mineral compounds.
3-1
TABLE 3-1. PHYSICAL PROPERTIES OF LEAD
Property Value
Atomic weight 207.2g
Melting point 327EC
Boiling point 1770EC
Specific gravity
20EC 11.35 g/cm3
327EC (solid) 11.00 g/cm3
327EC (liquid) 10.67 g/cm3
Specific heat 130 J/(kg-K)a
Latent heat of fusion 25 J/ga
Latent heat of vaporization 860 J/ga
Vapor pressure
980EC 0.133 kPab
1160EC 1.33 kPab
1420EC 13.33 kPab
1500EC 26.7 kPab
1600EC 53.3 kPab
Thermal conductivity
28EC 34.7 W/(m-K)
100EC 33.0 W/(m-K)
327EC (solid) 30.5 W/(m-K)
327EC (liquid) 24.6 W/(m-K)
Thermal conductivity
(relative to Ag = 100) 8.2
Coefficient of linear expansion, at 20EC per EC 29.1x10-6
Surface tension at 360EC, mN/m (= dyn/cm) 442
Source: Reference 8
a
To convert J to cal, divide by 4.184.
b
To convert kPa to mm Hg, multiply by 7.5.
3-2
TABLE 3-2. PHYSICAL PROPERTIES OF THE PRINCIPAL LEAD-ORE
COMPOUNDS
Source: Reference 9
Lead in its compound form also has many uses in manufacturing processes,
primarily as pigments. Lead compounds can be classified into the following general categories:
C Organolead compounds;
C Lead oxides;
C Lead salts.
Each of these classes of lead compounds is discussed briefly below. Table 3-4 presents a
summary of the chemical formulas and end uses of the most commonly used lead compounds.
Organolead compounds are distinctive with at least one lead-carbon bond. Only
two types of organolead compounds have found large-scale commercial applications:
tetramethyllead (TML) and tetraethyllead (TEL). However, with the removal of lead from
3-3
TABLE 3-3. USES OF LEAD ALLOYS
Alloy Uses
Lead - Copper
<0.10% copper by wt. Lead sheet
Lead pipes
Sheathings for electric power cables
Wire and other fabricated lead products
Tank linings
Tubes for acid-mist precipitators
Steam heating pipes for acid-plating baths
60 to 70% copper by wt. Bearings and bushings
(leaded brass or bronze)
Lead - Antimony Lead-acid battery positive grids, posts, and connectors
Flashings and roofing materials
Cable sheathings
Ammunition
Tank linings, pumps, valves, pipes, and heating and cooling coils in chemical
operations using sulfuric acid or sulfate solutions at elevated temperatures
Lead sheet
Anodes in metal-plating and metal-electrowinning operations
Collapsible tubes
Wheel-balancing weights for automobiles and trucks
Special weights and castings
Battery cable clamps
Lead - Antimony - Tin Printing-type metals
Bushing and sleeve bearings
Journal bearings in freight cars and mobile cranes
Decorative, slush, and special castings (e.g., miniature figures, casket trim, belt
buckles, trophies, and holloware)
Lead - Tin Solders for sealing and joining metals (e.g., electronic applications including
printed circuit boards)
Automobile radiators
High-temperature heat exchangers
Terne-steel sheets for radio and television chassis, roofs, fuel tanks, air filters,
oil filters, gaskets, metal furniture, gutters, and downspouts
Coating of copper sheet used for building flashings
Coating of steel and copper electronic components
Electroplating
Lead - Calcium Grids for large stationary stand-by power, submarine, and specialty sealed
batteries
Original equipment automotive batteries
Negative grids for replacement batteries
Electrowinning anodes
Cable sheathing, sleeving for cable splices, specialty boat keels, and lead-alloy
tapes
Lead - Calcium - Aluminum Negative battery grids
3-4
TABLE 3-3. USES OF LEAD ALLOYS (CONTINUED)
Alloy Uses
Source: Reference 10
a
Alloys that melt at very low temperatures (i.e., 32EF to 361.4EF [0EC to 183EC]).
3-5
TABLE 3-4. LEAD COMPOUNDS
Lead borosilicate Composed of a mixture of the borate and silicate of A constituent of optical glass
lead
Lead carbonate, basic 2PbCO 3@Pb(OH)2 Exterior paint pigments, ceramic glazes
Lead chloride PbCl2 Preparation of lead salts, lead chromate pigments,
analytical reagent
Lead chromate PbCrO4 Pigment in industrial paints, rubber, plastics, ceramic
coatings; organic analysis
Lead cyanide Pb(CN) 2 Metallurgy
Lead dimethyldithiocarbamate Pb[SCSN(CH3)2]2 Vulcanization accelerator with litharge
Lead dioxide PbO2 Oxidizing agent, electrodes, lead-acid storage batteries,
curing agent for polysulfide elastomers, textiles (mordant,
discharge in dyeing with indigo), matches, explosives,
analytical reagent.
Lead fluoborate B2F8@Pb Salt for electroplating lead; can be mixed with stannous
fluoborate to electroplate any composition of tin and lead
as an alloy
TABLE 3-4. LEAD COMPOUNDS (CONTINUED)
silica
Lead silicochromate A yellow lead-silicon pigment Normal lead silicon chromate is used as a yellow prime
pigment for traffic marking paints. Basic lead silicon
chromate is used as a corrosive inhibitive pigment for metal
protective coatings, primers, and finishers. Also for
industrial enamels requiring a high gloss
Lead sodium thiosulfate PbS2O3@2Na2S2O3 Matches
Lead stannate PbSnO3@2H2O Additive in ceramic capacitors, pyrotechnics
Lead stearate Pb(C18H35O2)2 Varnish and lacquer drier, high-pressure lubricants,
lubricant in extrusion processes stabilizer for vinyl
polymers, corrosion inhibitor for petroleum, component of
greases, waxes, and paints
Lead subacetate 2Pb(OH) 2Pb(C2H3O2)2 Decolorizing agent (sugar solutions, etc.)
Lead suboxide Pb2O In storage batteries
Lead sulfate PbSO 4 Storage batteries, paint pigments
Lead sulfate, basic PbSO 4@PbO Paints, ceramics, pigments
TABLE 3-4. LEAD COMPOUNDS (CONTINUED)
Lead thiocyanate Pb(SCN) 2 Ingredient of priming mix for small-arms cartridges, safety
matches, dyeing
Lead titanate PbTiO3 Industrial paint pigment
Lead tungstate PbWO4 Pigment
Lead vanadate Pv(VO3)2 Preparation of other vanadium compounds, pigment
Lead zirconate titanate PbTiZrO3 Element in hi-fi sets and as a transducer for ultrasonic
cleaners, ferroelectric materials in computer memory units
Litharge PbO Storage batteries, ceramic cements and fluxes, pottery and
glazes, glass, chromium pigments, oil refining, varnishes,
paints, enamels, assay of precious metal ores, manufacture
of red lead, cement (with glycerol), acid-resisting
compositions, match-head compositions, other lead
compounds, rubber accelerator
Source: Reference 11
gasoline, these compounds are no longer produced in the United States, although they are
imported for special applications such as use in aircraft fuel.
Lead oxide is a general term and includes lead monoxide or “litharge” (PbO); lead
tetraoxide or “red lead” (Pb 3O 4); and black or “gray” oxide, which is a mixture of 70 percent lead
monoxide and 30 percent metallic lead. Litharge is used primarily in the manufacture of various
ceramic products. Because of its electrical and electronic properties, litharge is also used in
capacitors and electrophotographic plates, as well as in ferromagnetic and ferroelectric materials.
It is also used as an activator in rubber, a curing agent in elastomers, a sulfur removal agent in the
production of thiols and in oil refining, and an oxidation catalyst in several organic chemical
processes. It also has important markets in the production of many lead chemicals, dry colors,
soaps (i.e., lead stearate), and driers for paint. Another important use of litharge is the production
of lead salts, particularly those used as stabilizers for plastics, notably polyvinyl chloride
materials.12
Lead dioxide (PbO2) is a brownish, black powder. Because of its strong oxidizing
properties, it is used in the manufacture of dyes and to control burning in incendiary fires. It is
also used as a curing agent for liquid polysulfide polymers and low molecular weight butyl and
polyisopropane.13
3-10
Lead titanate (PbTiO3) and lead zirconate (PbZrO3 ) are two lead oxides that are
frequently mixed, resulting in highly desirable piezoelectric properties that are used in
high-power acoustic radiating transducers, hydrophones, and specialty instruments.14
Lead sulfide (PbS) or galena is one of the most common lead minerals, appearing
black and opaque. It is an efficient heat conductor and has semiconductor properties, making it
desirable for use in photoelectric cells. Lead sulfide is used in ceramics, infrared radiation
detectors, and ceramic glaze.14,15
Most lead salts are white or colorless and are used commercially as pigments.
Basic lead carbonate (Pb(OH)2@2PbCO3), basic lead sulfate (Pb(SO4)@PbO), and basic lead
silicates (3PbO@SiO2) are well known white pigments. Basic lead carbonate is used as a
component of ceramic glazes, as a curing agent with peroxides to form improved polyethylene
wire insulation, as a color-changing component of temperature-sensitive inks, as a component of
lubricating greases, and as a component of weighted nylon-reinforced fish nets made of
polyvinylchloride (PVC) fibers.10
Basic lead sulfate helps provide efficient, long-term, economic heat stability to
flexible and rigid PVC. It can be dispersed easily, and has excellent electrical insulation
properties. It is also an effective activator for azodicarbonamide blowing agents for vinyl
foams.10
Basic lead silicates are used by the glass, ceramic, paint, rubber, and plastics
industries. Lead monosilicate (3PbO@3SiO2) is used in formulating lead-bearing glazes for the
ceramics industry and as a source of PbO in the glass industry. Lead bisilicate
(PbO@O@[email protected]) was developed as a low solubility source of lead in ceramic glazes for
foodware. Tribasic lead silicate (3PbO@SiO2) is used primarily by glass and frit producers.10
3-11
Lead chromates (PbCrO 4), colored salts, are used frequently as orange and yellow
pigments.11
In 1992, domestic lead ore mining in the United States accounted for about
13 percent of the total world lead mine production for that year. Australia, Canada, China, and
Kazakhstan (formerly part of the U.S.S.R.) accounted for nearly 47 percent of the world's lead
mine production in 1992. Other major lead ore producing countries include Mexico, North
Korea, Morocco, Peru, South Africa, Sweden, and other nations part of the former U.S.S.R.16
Most of the lead ore mined in the United States comes from the “lead-belt” in
southeast Missouri. The recoverable lead mine production from Missouri was about 76 percent
of the total lead mine production in the United States in 1992. In Missouri, lead is primarily
recovered from lead, zinc, and lead-zinc ores. Lead is also mined in Alaska, Arizona, Colorado,
Idaho, Illinois, Montana, New Mexico, New York, and Tennessee. In these states, lead is
recovered from zinc, lead-zinc, copper, gold, and fluorspar ore deposits.16
3-12
Lead ore is mined underground except when it is mined with copper ores, which
are typically mined in open pits. The lead content of ores typically ranges from 3 to 8 percent.
The ores are processed at the mine site to produce a lead ore concentrate of 55 to 70 percent lead.
Once dried, the lead-ore concentrates are shipped to primary lead smelter/refinery plants for
further processing.
Lead is among the most recycled nonferrous metals in the world. Secondary
production (from recycled materials) has risen steadily, such that in 1992, secondary output
surpassed primary output in the United States by about a factor of three. This growth reflects the
favorable economic conditions associated with lead recycling and the ability of lead to retain its
physical and chemical properties when recycled.17
Secondary lead smelters and refineries recover and refine metal from lead-bearing
scrap materials and residues to produce lead and lead alloy ingots, lead oxide, and lead pigments.
About 86 percent of recycled scrap was from lead-acid battery plates.16
As shown in Figure 3-1, the manufacture of storage batteries is the major end use
of lead (accounting for 81 percent of domestic lead use). About 63 percent of the total storage
battery consumption is for manufacturing battery posts and grids, and 37 percent was for
manufacturing lead oxides used in battery paste.16
3-13
Storage batteries
SIC 3691
1,098,002 tons (998,184 Mg)
Ammunition
SIC 3482
71,330 tons (64,845 Mg)
Sheet lead
SIC 15, 3443, 3693
23,107 tons (21,006 Mg)
Casting metals
SIC 36, 371, 37, 3443
18,822 tons (17,111 Mg)
Cable covering
SIC 36
17,591 tons (15,992 Mg)
Miscellaneous uses
14,310 tons (13,009 Mg)
Bearing metals
SIC 35, 36, 37
5,264 tons (4,785 Mg)
3-14
The manufacture of ammunition and “other oxides” are the next largest uses of
lead, each accounting for 5 percent of the total domestic lead consumption in 1992. “Other
oxides” include the manufacture of pigments and chemicals, paints, glass, and ceramic products.
The manufacture of pigments and chemicals account for 16 percent, and the manufacture of
paints and glass and ceramics account for 84 percent of the total lead consumption for the “other
oxides” category.16
The manufacture of casting materials, solder, sheet metal, and cable covering each
accounted for 1 to 2 percent of total lead consumption in 1992.16
Some uses of lead experiencing increased growth over the past few years with
continued growth expected are the use of lead in cathode ray tubes for television and computer
screens (to protect viewer and service technicians from harmful radiation), and use of lead solder
in the microelectronics industry.17
3-15
SECTION 4.0
EMISSIONS OF LEAD AND LEAD COMPOUNDS FROM THE METALLURGICAL
INDUSTRY
Lead is recovered from a sulfide ore, primary galena (lead sulfide), which also
contains small amounts of copper, iron, zinc, and other trace elements. A description of the
process used to manufacture lead and a discussion of the emissions resulting from the various
operations are presented below.
A list of primary lead smelters currently in operation within the United States is
given in Table 4-1. Primary lead smelters produced 449,800 tons (408,000 Mg) of refined lead
in 1990.19
1990 Production
Smelter Refinery tons (Mg)
ASARCO, East Helena, MT ASARCO, Omaha, NE 72,500 (65,800)
ASARCO, Glover, MO Same site 123,200 (112,000)
Doe Run (formerly St. Joe), Same site 254,100 (231,000)
Herculaneum, MO
Source: Reference 19
4-1
4.1.1 Process Description
Figure 4-1 presents a typical process flow diagram for primary lead smelting.
The recovery of lead from the lead ore consists of three main steps: sintering, reduction, and
refining.20
The blast furnace reduces the lead oxide produced in the sintering machine to
elemental lead and removes undesirable impurities as a slag. Reduction reactions to elemental
lead occur around 2,900(F (1,600(C). The resulting metal, called bullion, assays 94 to
98 percent lead. The furnace is a rectangular, water-cooled steel shell or shaft atop a
refractory-lined crucible or hearth. Both sides are equipped with tuyeres through which
pressurized combustion or blast air is introduced. Furnace capacities range from 500 to
1,000 tons (454 to 910 Mg) per day. The charge to the furnace includes sinter, coke, slags from
drossing and refining processes, silica, limestone, and baghouse dust. About 80 percent of the
charge consists of sinter that may contain from 28 to 50 percent lead. Blast air is introduced
through the side-mounted tuyeres, resulting in partial combustion of coke and formation of
carbon monoxide, and providing the heat required to reduce lead oxide to lead bullion.
Most of the impurities react with the silica and limestone and form a slag. The
slag is skimmed continuously from the furnace and is treated either at the smelter or is shipped
4-2
4-3
Figure 4-1. Typical Primary Lead-Processing Scheme
The lead bullion is tapped from the furnace periodically, and is usually treated in
a drossing kettle before undergoing final refining. In the kettle, the bullion is cooled and the
higher melting impurities, primarily copper, float to the surface and form a dross which is
skimmed off and subsequently treated in a reverberatory furnace. The bullion undergoes a final
refining in a series of cast iron kettles. The final lead product, typically 99.99 percent or more
pure, is then cast into pigs or ingots for shipping.18
The function of the dross reverberatory furnace is to separate lead bullion carried
over in the dross from other metals of economic value or contaminants in the dross. The dross
lead content may be as high as 90 percent. Although much smaller, the reverberatory furnace
used is similar in construction to the reverberatory furnace used in copper smelting. Where
applied, end-products usually include lead bullion, which is recycled; matte, which is rich in
copper and usually sent to a copper smelter for copper recovery; and speiss, which is high in
arsenic and antimony.18
Emission controls on primary lead smelter operations are used for controlling
(PM) and sulfur dioxide (SO2) emissions resulting from the blast furnace and sintering machines.
Centrifugal collectors (cyclones) may be used in conjunction with fabric filters or electrostatic
precipitators (ESPs) for PM control. Because lead emissions generally are associated with PM
emissions, devices used to control PM emissions should also control lead emissions. However,
no data on the effectiveness of fabric filters and ESPs in controlling lead emissions are
available.20
4-4
4.1.3 Emissions
Lead can potentially be emitted from each unit operation within a primary lead
smelting facility. Table 4-2 presents lead emission factors for specific primary lead operations.
Since lead is generally emitted as PM, lead will be some fraction of total PM. The lead content
of particulate emissions ranges from 20 to 65 percent. For blast furnaces, the lead content of
total PM ranges from 10 to 40 percent. The lead content of particulate emissions from dross
reverberatory furnaces ranges from 13 to 35 percent. For processes where the operating
temperature is near the boiling point of lead, such as the sinter machine, lead fume may be
emitted.
The secondary lead smelting industry produces elemental lead and lead alloys by
reclaiming lead, mainly from scrap automobile batteries. Blast, reverberatory, rotary, and
electric furnaces are used for smelting scrap lead and producing secondary lead. Smelting is the
reduction of lead compounds to elemental lead in a high-temperature furnace, which requires
higher temperatures (2200 to 2300(F [1200 to 1260(C]) than those required for melting
elemental lead (621(F [327(C]). Secondary lead may be refined to produce soft lead (which is
nearly pure lead) or alloyed to produce hard lead. Most of the lead produced by secondary lead
smelters is used in the production of lead-acid batteries.21
4-5
TABLE 4-2. LEAD EMISSION FACTORS FOR PRIMARY LEAD SMELTING FACILITIES
Average Emission
Factor Emission Factor Range Emission
SCC Emission Source Control Device in lb/ton (kg/Mg) in lb/ton (kg/Mg) Factor Rating Reference
-4
3-03-010-02 Blast Furnace None 1.0x10 --- U 22
(5.0x10-5)a
Baghouse 6.7x10-2 --- E 20
(3.4x10-2)b
Spray 1.7x10-2 --- U 22
Tower/FF (8.5x10-3)a
3-03-010-04 Ore Crushing None 3.0x10-1 --- U 23
(1.5x10-1)c
Baghouse 2.0x10-3 --- E 20
(1.0x10-3)d
4-6
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of lead produced.
b
Emission factors are expressed in lb of pollutant emitted per ton bullion processed.
c
Emission factors are expressed in lb of pollutant emitted per ton of ore crushed.
d
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of lead in ore.
e
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of sinter produced.
f
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of ore processed.
Smelter Location
Small-Capacity Group:a
Delatte Metalsb Ponchatoula, LA
General Smelting and Refining Company College Grove, TN
Master Metals, Inc.b Cleveland, OH
Metals Control of Kansasb Hillsboro, KS
Metals Control of Oklahomab Muskogee, OK
Medium-Capacity Group:c
Doe Run Company Boss, MO
East Penn Manufacturing Company Lyon Station, PA
Exide Corporation Reading, PA
GNB, Inc. Columbus, GA
Frisco, TX
Gulf Coast Recycling, Inc. Tampa, FL
Refined Metals Corporationb Beech Grove, IN
Memphis, TN
RSR Corporation City of Industry, CA
Middletown, NY
Schuylkill Metals Corporation Forest City, MO
Tejas Resources, Inc.b Terrell, TX
Large-Capacity Group:d
Exide Corporation Muncie, IN
Gopher Smelting and Refining, Inc. Eagan, MN
GNB, Inc. Vernon, CA
RSR Corporation Indianapolis, IN
Sanders Lead Company Troy, AL
Schuylkill Metals Corporation Baton Rouge, LA
4-7
Lead-acid batteries represent about 90 percent of the raw materials used at a
typical secondary lead smelter, although this percentage may vary from one plant to the next.
These batteries contain approximately 18-20 lb (8.2-9.1 kg) of lead per battery consisting of
40 percent lead alloys and 60 percent lead oxide. Other types of lead-bearing raw materials
recycled by secondary lead smelters include drosses (lead-containing byproducts of lead
refining), which may be purchased from companies that perform lead alloying or refining but
not smelting; battery plant scrap, such as defective grids or paste; and scrap lead, such as old
pipes or roof flashing. Other scrap lead sources include cable sheathing, solder, and babbitt-
metal.21
Paste desulfurization, an optional lead recovery step used by some secondary lead
smelters, requires the separation of lead sulfate and lead oxide paste from the lead grid metal,
polypropylene plastic cases, separators, and hard rubber battery cases. Paste desulfurization
involves the chemical removal of sulfur from the lead battery paste. The process improves
furnace efficiency by reducing the need for fluxing agents to reduce lead-sulfur compounds to
lead metal. The process also reduces sulfur dioxide (SO2) furnace emissions. However, SO2
emissions reduction is usually a less important consideration because many plants that perform
paste desulfurization are also equipped with SO2 scrubbers. About one-half of smelters perform
paste desulfurization.21
4-8
Figure 4-2. Simplified Process Flow Diagram for Secondary Lead Smelting
Source: Reference 21
4-9
After removing the lead components from the batteries, the lead scrap is
combined with other charge materials, such as refining drosses and flue dust, and is charged to a
reverberatory furnace. Reverberatory furnace slag, coke, limestone, sand, and scrap iron are fed
to a blast, rotary or electric smelting furnace. Smelting furnaces are used to produce crude lead
bullion, which is refined and/or alloyed into final lead products. In 1994, there were
approximately 15 reverberatory furnaces, 24 blast furnaces, 5 rotary furnaces, and 1 electric
furnace operating in the secondary lead industry in the United States.21 Blast and reverberatory
furnaces are currently the most common types of smelting furnaces used in the industry,
although some new plants are using rotary furnaces.
Reverberatory Furnaces
Reverberatory furnace charge materials include battery grids and paste, battery
plant scrap, rerun reverberatory furnace slag, flue dust, drosses, iron, silica, and coke. A typical
charge over one hour may include 9.3 tons (8.4 Mg) of grids and paste to produce 6.2 tons
(5.6 Mg) of lead.21
Charge materials are often fed to a natural gas- or oil-fired rotary drying kiln,
which dries the material before it reaches the furnace. The temperature of the drying kiln is
about 400(F (200(C), and the drying kiln exhaust is drawn directly into the reverberatory
furnace or ventilated to a control device. From the rotary drying kiln, the feed is either dropped
into the top of the furnace through a charging chute, or fed into the furnace at fixed intervals
with a hydraulic ram. In furnaces that use a feed chute, a hydraulic ram is often used as a stoker
to move the material down the furnace.
4-10
Charge Chute
Flue
Source: Reference 21
Burner
Slag Tap
Slag Layer
Molten
Lead
The PbSO4 and PbO also react with the alloying elements to form lead bullion and oxides of the
alloying elements, which are removed in the slag.
The molten lead collects in a pool at the lowest part of the hearth. Slag collects in
a layer on top of this pool and retards further oxidation of the lead. The slag is made up of
molten fluxing agents such as iron, silica, and lime, and typically has significant quantities of
lead. Slag is usually tapped continuously and lead is tapped intermittently. The slag is tapped
into a mould. The slag tap and crucible are hooded and vented to a control device.
Reverberatory furnace slag usually has a high lead content (as much as 70 percent by weight)
and is used as feed material in a blast or electric furnace to recover the lead. Reverberatory
furnace slag may also be rerun through the reverberatory furnace during special slag campaigns
before being sent to a blast or electric furnace. Lead may be tapped into a mold or directly into a
holding kettle. The lead tap is usually hooded and vented to a control device.21
Blast Furnaces
A blast furnace (Figure 4-4) is a vertical furnace that consists of a crucible with a
vertical cylinder affixed to the top. The crucible is refractory-lined and the vertical cylinder
consists of a steel water-jacket. Oxygen-enriched combustion air is introduced into the furnace
through tuyeres located around the base of the cylinder.
4-12
Figure 4-4. Cross-Section of a Typical Blast Furnace
4-13
Charge materials are pre-weighed to ensure the proper mixture and then are
introduced into the top of the cylinder using a skip hoist, a conveyor, or a front-end loader. The
charge fills nearly the entire cylinder. Charge material is added periodically to keep the level of
the charge at a consistent working height while lead and slag are tapped from the crucible. Coke
is added to the charge as the primary fuel, although natural gas jets may be used to start the
combustion process. Combustion is self-sustaining as long as there is sufficient coke in the
charge material. Combustion occurs in the layer of the charge nearest the tuyeres.
At plants that operate only blast furnaces, the lead-bearing charge materials may
include broken battery components, drosses from the refining kettles, agglomerated flue dust,
and lead-bearing slag. A typical charge over one hour may include 4.8 tons (4.4 Mg) of grids
and paste, 0.3 tons (0.3 Mg) of coke, 0.1 tons (0.1 Mg) of calcium carbonate, 0.07 tons
(0.06 Mg) of silica, 0.5 tons (0.4 Mg) of cast iron, and 0.2 tons (0.2 Mg) of rerun blast furnace
slag, to produce 3.7 tons (3.4 Mg) of lead. At plants that also have a reverberatory furnace, the
charge materials will also include lead-bearing reverberatory furnace slag.21
Blast furnaces are designed and operated to produce a hard (high alloy content)
lead product by achieving greater furnace reduction conditions than those typically found in a
reverberatory furnace. Fluxing agents include iron, soda ash, limestone, and silica (sand). The
oxidation of the iron, limestone, and silica promotes the reduction of lead compounds and
prevents oxidation of the lead and other metals. The soda ash enhances the reaction of PbSO4
and PbO with carbon from the coke to reduce these compounds to lead metal.
Lead tapped from a blast furnace has a higher content of alloying metals (up to
25 percent) than lead produced by a reverberatory furnace. In addition, much less of the lead
and alloying metals is oxidized and removed in the slag, so the slag has a low metal content
(e.g., 1 to 3 percent) and may qualify as a nonhazardous solid waste.
Because air is introduced into the blast furnace at the tuyeres, blast furnaces are
operated at positive pressure. The operating temperature at the combustion layer of the charge is
4-14
between 2200 and 2600(F (1200 and 1400(C), but the temperature of the gases exiting the top
of the charge material is only between 750 and 950(F (400 and 500(C).
A weir dam and siphon in the furnace are sometimes used to remove the lead
from beneath the slag layer. Lead is tapped from a blast furnace into either a crucible or directly
to a refining kettle designated as a holding kettle. The lead in the holding kettle is kept molten
before being pumped to a refining kettle for refining and alloying. The lead tap on a blast
furnace is hooded and vented to a control device.
Rotary Furnaces
4-15
Figure 4-5. Side View of a Typical Rotary Reverberatory Furnace
4-16
furnace opposite the jet allows charging of material to the furnace. Charge materials are
typically placed in the furnace using a retractable conveyor or charge bucket, although other
methods are possible.
Fluxing agents for rotary furnaces may include iron, silica, soda ash, limestone,
and coke. The fluxing agents are added to promote the conversion of lead compounds to lead
metal. Coke is used as a reducing agent rather than as a primary fuel. A typical charge may
consist of 12 tons (11 Mg) of wet battery scrap, 0.8 tons (0.7 Mg) of soda ash, 0.6 tons (0.5 Mg)
of coke, and 0.6 tons (0.5 Mg) of iron, and will yield approximately 9 tons (8 Mg) of lead
product.21
Electric Furnaces
4-17
Source: Reference 24
Electrode
Flue
Bath Level
Slag Tap
Lead Tap
Electrode
ERG_Lead_46.pre
Figure 4-6. Cross-Sectional View of an Electric Arc Furnace for Processing Slag
Source: Reference 24
In an electric furnace, electric current flows from the cathode to the anode
through the scrap charge. The electrical resistance of the charge causes the charge to heat up and
become molten. There is no combustion process involved in an electric furnace.
There is only one known electric furnace in operation in the United States for the
secondary lead industry. It is used to process second-run reverberatory furnace slag, and it
fulfills the same role as a blast furnace used in conjunction with a reverberatory furnace.
However, the electric furnace has two advantages over a blast furnace. First, because there are
no combustion gases, ventilation requirements are much lower than for blast or reverberatory
furnaces. Second, the electric furnace is extremely reducing, and produces a glass-like, nearly
lead-free slag that is nonhazardous .21
Three main strategies are used to control lead emissions and provide worker
protection in secondary lead smelters. These three control strategies involve engineering
measures, work practices, and personal protection. Engineering measures are the most effective
means of lead emissions abatement. Included in this category are control devices, material
substitution, process and equipment modification, isolation and automation, and local and
general ventilation. Good work practices and personal hygiene have become important in
reducing worker lead exposure. Included in these categories are housekeeping, administrative
controls, and the use of personal protective equipment such as respirators, gloves, goggles, and
aprons.25
4-19
4.2.4 Emissions
In secondary lead smelting operations, lead is emitted in some degree from each
unit operation. Measuring the level of lead in the blood of workers in each area is the most
readily available method of determining the operations that contribute the most to lead
emissions. Blood lead levels were highest among workers in the furnace area, clean-up area,
welding operations area, and the alloying and sawing areas. The lowest blood lead levels were
found in workers in the shipping area.25
Hazardous air pollutants and criteria air pollutants are emitted from secondary
lead smelters as process emissions from the main smelting furnace exhaust, process fugitive
emissions from smelting furnace charging and tapping and lead refining, and fugitive dust
emissions from materials storage and handling and vehicle traffic. Lead emission factors for
these processes are shown in Table 4-4.
The largest sources of process fugitive emissions are furnace charging, slag
tapping, and agglomerating furnace operation. Lesser sources are lead tapping and kettle
refining. Battery breaking and lead casting have fewer emissions. Lead casting is not a
substantial source of emissions because the temperature of molten lead is well below the fuming
temperature of lead.
Fugitive dust emissions contain lead emissions but are dependent upon the size of
the facility and the fugitive dust controls and practices in place at each facility. These emissions
cannot be measured and can only be roughly estimated using emission factors and facility
specific data.21
4-20
TABLE 4-4. LEAD EMISSION FACTORS FOR SECONDARY LEAD SMELTING
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of lead produced.
FF = Fabric Filter.
4-22
4.3 PRIMARY COPPER PRODUCTION
Seven primary copper smelters were operating in the United States in 1995 and
one additional was closed for modifications.27 The combined production capacity in 1995 for
the seven plants in operation was 1,728,043 tons (1,570,623 Mg).
4-23
Incoming concentrates are typically dried before input into a smelting furnace or
reactor. Several types of smelting furnaces/reactors are currently utilized in the United States,
including flash furnaces, CONTOP reactors, Noranda reactors, and IsaSmelt reactors.
Figure 4-7 illustrates basic smelting operations.
Molten copper matte is transferred by ladles from the furnace/reactor, and poured
into the converters. In the converters, further sulfur is removed from the matte, and in addition,
iron is oxidized and separated by skimming. The output from the converters is "blister" copper,
generally containing greater than 98 percent copper. Figure 4-8 illustrates a typical converter.
Molten blister copper is poured from the converter, and transferred by ladles to
anode furnaces, where further refining by removal of oxygen and other impurities takes place.
The resulting "anode" copper is generally greater than 98.5 percent pure. It is cast into anodes
for use in the final electrolytic refining step.
4.3.3 Emissions
Particulate matter and SO2 are the principal air contaminants emitted from
primary copper smelters. Actual emissions from a particular smelter will depend upon the
smelting configuration (type and mix of equipment used), control devices applied, and the
4-24
Figure 4-7. Typical Primary Copper Smelter Flowsheet
4-25
Figure 4-8. Copper Converter
4-26
operating and maintenance practices employed. Typically, lead will be emitted as PM. In
addition, actual lead emissions will vary depending on the quantity of lead introduced to the
smelter with the copper-bearing feed materials. The available emission factors for smelting and
converting are presented in Table 4-5. No factors are available for refining.
Control devices for particulate emissions from smelting and converting operations
typically consist of a dry (plate/wire) ESP, baghouses, scrubbers, and a wet (tube/wire) acid mist
ESP (to remove sulfuric acid and volatile heavy metals that condense during the cooling
process).
4-27
TABLE 4-5. LEAD EMISSION FACTORS FOR PRIMARY COPPER SMELTING FACILITIES
Source: Reference 32
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of concentrated ore processed and represent total process and fugitive emissions.
4-28
4-29
Composition (%)
Process Step Cu Fe S SiO2 Zn Cd Pb Other
Ore concentrate storage and handling 28 24 32 11 0.3 5
Slag handling 0.5 40 1.5 38 0.3 - 18 20
Roaster loading and operation 5 16 0.3 - 18 0.5
Reverberatory furnace loading 5 16 0.4 - 18 0.5
and operation
Matte transfer 42 32 25 1 0.25
Converter loading and blowing 1 8 4 2-6
Source: Reference 18
4-30
4.4 SECONDARY COPPER PRODUCTION
The principal processes involved in copper recovery are scrap metal pretreatment
and smelting. Pretreatment includes cleaning and concentration to prepare the material for the
smelting furnace. Smelting involves heating and treating the scrap to achieve separation and
purification of specific metals.
The feed material used in the recovery process can be any metallic scrap
containing a useful amount of copper, bronze (copper and tin), or brass (copper and zinc).
Traditional forms are punchings, turnings and borings, defective or surplus goods, metallurgical
residues such as slags, skimmings, and drosses, and obsolete, worn-out, or damaged articles,
including automobile radiators, pipe, wire, bushings, and bearings.
The type and quality of the feed material determines the processes the smelter
will use. Due to the large variety of feed materials available, the method of operation varies
greatly among plants. Generally, a secondary copper facility deals with less pure raw materials
and produces a more refined product, whereas brass and bronze alloy processors take cleaner
scrap
4-31
TABLE 4-7. DOMESTIC SECONDARY COPPER PRODUCERS
Source: Reference 33
and do less purification and refining. Figure 4-10 is a flowsheet depicting the major processes
that can be expected in a secondary copper-smelting operation.
4-32
Figure 4-10. Secondary Copper Smelting Processes
With zinc-rich feed, such as brass, the zinc oxide concentration in the exhaust gas
is sometimes high enough to make recovery for its metal value desirable. This process is
accomplished by vaporizing the zinc from the melt at high temperatures and then capturing the
oxide downstream in a process fabric filter.
The final step is always casting the alloyed or refined metal into a desired form,
e.g., shot, wirebar, anodes, cathodes, ingots, or other cast shapes. The metal from the melt is
usually poured into a ladle or a small pot (which serves as a surge hopper and a flow regulator)
and then continues into a mold.
4-34
The smelting process uses large volumes of air to oxidize sulfides, zinc, and other
undesirable constituents of the feed. This procedure generates considerable particulate matter in
the exhaust gas stream. The wide variation among furnace types, charge quality, extent of
pretreatment, and size of the charge is reflected in a broad spectrum of particle sizes and variable
grain loadings in the exhaust gases. One major factor contributing to differences in emission
rates is the amount of zinc present in scrap feed materials; due to its low boiling point, zinc
evaporates and combines with oxygen, producing zinc oxide fumes.
Metal oxide fumes from furnaces used in secondary copper smelters may be
controlled by fabric filters, ESPs, or wet scrubbers. Control efficiency by fabric filters may be
higher than 99 percent, but cooling systems are needed to prevent the hot gases from damaging
or destroying the bag filters. A two-stage system using both water jacketing and radiant cooling
is common. Electrostatic precipitators are not as well suited to this application, having a
low-collection efficiency for dense particulates, such as oxides of lead and zinc. Wet scrubber
installations also are relatively ineffective in the secondary copper industry. Scrubbers are
useful mainly for particles larger than 1 micron, but the metal oxide fumes are generally
submicron in size.
4-35
introduction of additional material onto the liquid metal surface produces significant amounts of
volatile and combustible materials and smoke, which can escape through the charging door.
Briquetting the charge offers a way to avoid fractional charges. When fractional charging
cannot be eliminated, fugitive emissions are reduced by shutting off the furnace burners during
charging. This reduces the flow of exhaust gases and enhances the ability of the exhaust control
system to handle the emissions.
Metal oxide fumes are generated not only during melting, but also during pouring
of the molten metal into the molds. Other dusts may be generated by the charcoal, or other
lining used in association with the mold. Covering the metal surface with ground charcoal is a
method used to make "smooth-top" ingots. This process creates a shower of sparks, releasing
emissions into the plant near the furnace and the molds being filled.
4.4.4 Emissions
Lead may be present in the scrap metals that are processed to recover secondary
copper, therefore, lead emissions can be expected from secondary copper-smelting operations.
Generally, lead will be emitted as particulate matter. Lead emission factors are presented in
Table 4-8.
Zinc is found primarily as the sulfide ore sphalerite (ZnS). Its common coproduct
ores are lead and copper. Metal impurities commonly associated with ZnS are cadmium and
minor quantities of germanium, gallium, indium, and thallium.35
Four primary zinc smelters were in operation in the United States in 1992. Three
of the smelters employed the electrolytic smelting process and one employed a pyrometallurgical
4-36
TABLE 4-8. LEAD EMISSION FACTORS FOR SECONDARY COPPER SMELTING FACILITIES
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of product, except as noted.
b
Emission factor is expressed in lb (kg) of pollutant emitted per ton (Mg) of material processed.
Source: Reference 36
4-38
4-39
Leaching is the first step of electrolytic reduction. In this step, the zinc oxide
reacts with sulfuric acid to form aqueous zinc sulfate in an electrolytic solution.
Single- and double-leach methods can be used, although the former exhibits
excessive sulfuric acid losses and poor zinc recovery. In double leaching, the calcine is first
leached in a neutral solution. The readily soluble sulfates from the calcine dissolve, but only a
4-40
portion of the zinc oxide enters the solution. The calcine is then leached in the acidic
electrolysis recycle electrolyte. The zinc oxide is dissolved as shown in reaction (3), as are
many of the impurities, especially iron. The electrolyte is neutralized by this process and it
serves as the leach solution for the first stage of calcine leaching. This recycling also serves as
the first stage of refining because much of the dissolved iron precipitates out of the solution.
Variations on this basic procedure include the use of progressively stronger and hotter acid baths
to bring as much of the zinc into solution as possible.
H2SO4
2 H2O 4H (aq) 4e O2 (4)
anode
4-41
Oxygen gas is released at the anode, metallic zinc is deposited at the cathode, and
sulfuric acid is regenerated within the electrolyte.
The final stage of electrolytic zinc smelting is the making and casting of the
cathode zinc into small slabs (59 lb [27 kg]) or large slabs (1,408 to 2,420 lb [640 to 1,100 kg]).
Sintering is the first stage of the pyrometallurgical reduction of zinc oxide to slab
zinc. Sintering removes lead and cadmium impurities by volatilization and produces an
agglomerated permeable mass suitable for feed to retorting furnaces. Down-draft sintering
machines of the Dwight-Lloyd type are used in the industry. Grate pallets are joined together
for a continuous conveyor system. Combustion air is drawn down through the grate pallets and
is exhausted to a particulate control system. The feed is a mixture of calcine, recycled sinter,
and coke breeze, which is low-sulfur fuel. Having a low boiling point, oxides of lead and
cadmium are volatilized from the sinter bed and are recovered in the particulate control system.
In retorting, because of the low boiling point of metallic zinc (1,663(F [906(C]),
reduction and purification of zinc-bearing minerals can be accomplished to a greater extent than
with most minerals. The sintered zinc oxide feed is brought into a high-temperature reducing
atmosphere of 1,652 to 2,730(F (900 to 1,499(C). Under these conditions, the zinc oxide is
simultaneously reduced and volatilized to gaseous zinc:
4-42
4-43
CO2 + C 2 CO (8)
The zinc vapor and carbon monoxide that are produced pass from the main
furnace to a condenser, where zinc recovery is accomplished by bubbling the gas mixture
through a molten zinc bath. Retorting furnaces can be heated either externally by combustion
flames or internally by electric resistance heating. The latter approach, electrothermic reduction,
is the only method currently practiced in the United States, and it has greater thermal efficiency
than do external heating methods. In a retort furnace, preheated coke and sinter, silica, and
miscellaneous zinc-bearing materials are fed continuously in the top of the furnace. Feed coke
serves as the principal electrical conductor, producing heat; it also provides the carbon monoxide
required for zinc oxide reduction. Further purification steps can be performed on the molten
metal collected in the condenser. The molten zinc finally is cast into small slabs (59 lb [27 kg])
or large slabs (1,408 to 2,420 lb [640 to 1,100 kg]). 35
4.5.3 Emissions
All four smelters treat the SO2-rich roaster exhaust gases in a sulfuric acid plant
for SO2 removal. As a result, particulate and lead emissions are negligible. The balance of the
processes performed at the electrolytic plants are wet and do not produce emissions.
Uncontrolled emissions from electrothermic reduction furnaces are also negligible. Thus, the
only potentially significant source of particulate and lead emissions from primary zinc smelting
operations in the United States is the one sinter machine operated at the pyrometallurgical plant.
The sinter machine at this plant is currently controlled by three ESPs and one baghouse in
series.18 Lead emission factors for primary zinc production are not available.
4-44
4.6 SECONDARY ALUMINUM OPERATIONS
a. charging f. demagging
b. melting g. degassing
c. fluxing h. skimming
d. alloying i. pouring
e. mixing
All of these steps may occur at each facility, with process distinctions being the
furnace type used and emissions characteristics. However, as with scrap treatment, not all of
these steps are incorporated into the operations at a particular plant. Some steps may be
combined or reordered, depending on furnace design, scrap quality, process inputs, and product
specifications.
4-45
Figure 4-13. Typical Process Diagram for Pretreatment in the Secondary Aluminum
Processing Industry
4-46
Figure 4-14. Typical Process Flow Diagram for the Secondary Aluminum
Processing Industry
4-47
Purchased aluminum scrap undergoes inspection upon delivery and is sorted into
the categories shown in Figure 4-13. Clean scrap requiring no treatment is transported to storage
or is charged directly into the smelting furnace. The bulk of the scrap, however, must be
manually sorted as it passes along a steel belt conveyor. Free iron, stainless steel, zinc, brass,
and oversize materials are removed. The sorted scrap then goes to appropriate scrap treating
processes, if necessary, or is charged directly to the smelting furnace. The more common scrap
treatment processes are discussed in the following paragraphs.
Sorted scrap is conveyed to a ring crusher or hammer mill where the material is
shredded and crushed, and the iron is torn away from the aluminum. The crushed material
passes over vibrating screens to remove dirt and fines, and tramp iron is removed by magnetic
drums and/or belt separators. Baling equipment compacts bulky aluminum scrap into bales.
Several types of residue from primary and secondary aluminum plants contain
recoverable amounts of aluminum. Aluminum is recovered from hot and cold drosses by batch
fluxing in rotary furnaces. In the dry milling process, cold aluminum dross and other residues
are processed by milling, screening, and concentrating to reduce oxides and non-metallic
materials to fine powders, yielding a product which is 60 to 70 percent aluminum.
Drosses, skimmings, and slags are treated by leaching to remove fluxing salts and
other nonrecoverable materials. First, the raw material is fed into a long, rotating drum or an
attrition or ball mill, from which soluble contaminants are leached. The washed material is then
screened to remove fines and dissolved salts and is dried and passed through a magnetic
4-48
separator to remove ferrous materials. The non-magnetic materials are then stored or charged
directly to the smelting furnace.
Cover fluxes are used to prevent oxidation of the melt caused by air contact.
Solvent fluxes react with non-metallic materials, such as burned coating residues and dirt, to
form insoluble materials that float to the surface as part of the slag. Alloying agents are charged
to the furnace in amounts determined by product specifications. Nitrogen or other inert gases
can be injected into the molten metal to help raise dissolved gases (typically hydrogen) and
intermixed solids to the surface.
4-49
through carbon lances to react with magnesium and aluminum as it bubbles to the surface. Other
chlorinating agents or fluxes, such as anhydrous aluminum chloride or chlorinated organic
compounds, are sometimes used.
Data for lead emissions from secondary aluminum processing facilities was
extremely limited. Currently, emissions data from secondary aluminum facilities are being
4-50
TABLE 4-10. LEAD EMISSION FACTORS FOR SECONDARY ALUMINUM PRODUCTION
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of aluminum produced, except as noted.
b
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of aluminum processed.
collected for inclusion in the secondary aluminum MACT, which may augment the information
provided here.
There were approximately 756 iron and steel foundries in the United States in
1992 based on a survey conducted by the EPA to support development of the iron and steel
foundry Maximum Achievable Control Technology (MACT) standard.42 In general, foundries
are located in areas of heavy industry and manufacturing, especially areas where iron and steel
are produced (e.g., the Great Lakes States).
Iron and steel foundries can be defined as those that produce gray, white, ductile,
or malleable iron and steel castings. Both cast irons and steels are solid solutions of iron,
carbon, and various alloying materials. Although there are many types of iron and steel, groups
can be distinguished by their carbon content. Cast iron typically contains 2 percent carbon or
greater; cast steel usually contains less than 2 percent carbon. 40
4-52
Iron castings are used in most types of mechanical equipment, including motor
vehicles, farm machinery, construction machinery, petroleum industry equipment, electrical
motors, and iron and steel industry equipment.
The following four basic operations are performed in all iron and steel foundries:
A generic process flow diagram for iron and steel foundries is shown in Figure 4-15.
Figure 4-16 identifies the emission points in a typical iron and steel foundry.
4-53
4-54
Figure 4-15. Process Flow Diagram for a Typical Sand-Cast Iron and Steel Foundry
Source: Reference 44
4-55
Metal Melting Process
The highest amount of metal (by volume) in iron and steel foundries is melted in
cupolas. Electric arc furnaces (EAFs) and induction furnaces are also commonly used. Cupolas
are charged with alternate layers of coke, metallics, and fluxes. Combustion air is introduced
into the cupola through tuyeres located at the base. The heat produced by the burning coke
melts the iron, which flows down and is tapped from the bottom of the cupola. Fluxes combine
with non-metallic impurities in the charge and form slag, which is removed through tap holes
located above the level of the metal tap hole. Cupola capacities range mostly from 1 to 30 tons
(1 to 27 Mg) per hour, with a few large units capable of producing close to 100 tons (90 Mg) per
hour. Larger furnaces are operated for several days at a time with inspections and cleanings
between melt cycles.45
Iron and steel castings are produced in a foundry by injecting or pouring molten
metal into cavities of a mold made of sand, metal, or ceramic material. The use of EAFs and
induction furnaces is increasing. Steel foundries rely almost exclusively on EAFs or induction
furnaces for melting purposes.
In all types of foundries, when the poured metal has solidified, the molds are
separated and the castings removed from the mold flasks on a casting shakeout unit. Cutoff,
abrasive (shotblasting) cleaning, grinding, and heat treating are performed as necessary. The
castings are then inspected and shipped to plants of other industries for machining and/or
assembly into final products.43
In a typical foundry operation, charges to the melting unit are sorted by size and
density and cleaned (as required) prior to being put into the melter. Charges consist of scrap
metal, ingot, carbon (coke), and flux. Prepared charge materials are placed in crane buckets,
weighed, and transferred into the melting furnace or cupola. The charge in a furnace or cupola
is heated until it reaches a certain temperature and the desired product chemistry of the melt has
been attained. After the desired product is obtained, the molten metal is poured out of the
furnace into various-size transfer ladles and then into the molds holding furnaces.
4-56
Mold and Core Production
The casting or mold pouring and cooling operations in iron and steel foundries
are suspected to be a source of lead emissions. In addition to casting, mold preparation and
casting shakeout (removal from the mold) activities are also suspected as lead emission sources.
Lead emissions from these processes are believed to be small, although test data are not available
to quantify actual lead emissions.
Lead emissions depend mostly on the scrap metal quality and control
technologies. Control technologies commonly used to control lead emissions from iron and steel
foundry metal melting operations include baghouses and wet scrubbers. Additionally, lead
emissions due to coke combustion may be reduced by substituting natural gas for coke as a heat
source. Potential lead emissions from molding, casting, and shakeout are fugitive in nature.
Fugitive emissions from such sources are generally controlled with local hooding or building
ventilation systems that are ducted to a control device (predominantly baghouses).45
4.7.4 Emissions
Lead emission factors for several iron foundry processes were available. These
emission factors are presented in Table 4-11.
Lead emissions are generated by the mining, crushing, and grinding of three
primary nonferrous metal ores: lead, zinc, and copper. Lead and zinc ores are normally mined
underground, whereas copper ores are normally mined in open pits.46 Lead, zinc, and copper
occur in various amounts in all three ore types. If the metal content of two or more metals is
high
4-57
TABLE 4-11. LEAD EMISSION FACTORS FOR IRON AND STEEL FOUNDRIES
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of iron/steel produced, except as noted.
b
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of material processed.
Lead, zinc, and copper ores are generally concentrated in a liquid medium using
settling and flotation. In all but a few cases, the metal is combined with sulfur and/or oxygen in
the ore. Lead, zinc, and copper are usually found together in varying percentages in ore
deposits.46 Depending on the amount of each of these metals in the ore and on the potential
economic return, the metals are either separated from the ore or discarded in the tailings.
Lead and zinc ores are concentrated to 45 to 75 percent before going to the
smelter. Depending on the mineral and gauge material, the ore is crushed and ground to a size
based on an economic balance between the recoverable metal values and the cost of grinding.
Standard jaw, gyratory, and cone crushers, vibrating or trommel screens, and rod and ball mills
are used to reduce the ore to powder in the 65- to 325-mesh range. Through gravity and/or
selective flotation, the finely divided particles of copper, lead, and zinc are separated from the
gangue and are cleaned, thickened, filtered, and dried.
Copper ores are handled in essentially the same manner as zinc and lead ores.
Open-pit mining for copper, copper-lead, copper-zinc, and copper-lead-zinc ores is centered
4-59
Figure 4-17. Process Diagram for Ore Mining and Crushing
4.8.3 Emissions
Lead emissions are basically fugitive in nature and are caused by drilling,
blasting, loading, conveying, screening, unloading, crushing, and grinding operations. 46 The
emissions from actual ore mining operations are contained in underground mines. Lead
emission factors from available literature sources are presented in Table 4-12. Lead emissions
from lead, copper, or zinc ore mining are dependent upon the lead content of the ore. Ores with
greater lead content produce greater lead emission factors. Mixed-ore mining produces
relatively constant emission rates, although the lead content of the ore varies.
Brass and bronze are generally considered to be copper-based alloys, with zinc,
tin, and other metals such as lead, aluminum, manganese, and silicon as secondary components.
4-61
TABLE 4-12. LEAD EMISSION FACTORS FOR LEADBEARING ORE CRUSHING AND GRINDING
(6.00x10-2)
3-03-031-06 Copper-Zinc Ore (0.2% Pb content) None 1.20x10-2 --- B
(6.00x10-3)
3-03-031-07 Copper-Lead-Zinc Ore (2.0% Pb None 1.20x10-1 --- B
content) (6.00x10-2)
Source: Reference 49
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of ore processed.
Source: Reference 18
4-63
In 1987, the production of brass and bronze ingots totalled 203,934 tons (185,058 Mg).18 Of this
total, about 19 percent consisted of tin bronze, aluminum bronze, and nickel bronze, which do
not contain appreciable amounts of lead. The remaining 81 percent consisted of leaded red and
semi-red brass, high-leaded tin bronze, yellow brass, and manganese bronze, all of which
contain significant amounts of lead. Except where otherwise indicated, this section is derived
from Control Technologies for Lead Air Emissions.18
Figure 4-18 illustrates the processes involved in the production of brass and
bronze alloys. The principal processes include scrap metal pretreatment and smelting. Feed
materials consist primarily of high-grade copper and copper alloy (brass and bronze) scrap.
4-64
Figure 4-18. Brass and Bronze Alloys Production Processes
4.9.3 Emissions
Air pollutants emitted from brass and bronze smelting furnaces consist of
products of combustion, dusts, and metallic fumes resulting from the oxidation and condensation
of the more volatile metals such as lead, zinc, and others. The lead fraction of the PM generated
will vary according to fuel type, alloy composition, furnace type, smelting temperature, and
other operational factors. Exhaust gas parameters for an uncontrolled brass and bronze
reverberatory furnace are presented in Table 4-14. Table 4-15 shows production data and
emission factors.
4-66
TABLE 4-14. CHARACTERISTICS OF UNCONTROLLED EXHAUST GAS FROM
A BRASS AND BRONZE REVERBERATORY FURNACE
Source: Reference 18
a
Flow rates can vary according to the hooding arrangement. Volume given is at 250(F (120(C).
b
Temperature is usually reduced to 250(F (120(C).
TABLE 4-15. BRASS AND BRONZE PRODUCTION AND LEAD EMISSIONS IN 1992
a
The U.S. Bureau of Mines provided total lead alloy production for 1992. The breakdown of production for
each alloy type was not available. Therefore, the 1992 production estimates for each alloy type are based on
the breakdown of total lead production for each alloy type in 1986. Total lead alloy production was estimated
to be 163,073 tons (147,974 Mg). Source: Reference 18, 53
b
Source: Reference 18
c
Includes all production of high-leaded tin bronze; 90 percent of production for manganese bronze; and silicon
brass and bronze.
d
Includes all production of leaded red brass, semi-red brass, and yellow brass.
e
Includes all production for copper-base hardness and master alloys, miscellaneous alloys, 10 percent of
manganese bronze, and silicon brass and bronze.
4-67
SECTION 5.0
EMISSIONS OF LEAD AND LEAD COMPOUNDS FROM COMBUSTION SOURCES
This section contains process descriptions, available emission factor data, and
source locations for source categories that emit lead and lead compounds during combustion.
These source categories include fuel combustion in external and internal combustion engines;
incineration of various types of waste, including municipal waste, industrial waste, sewage sludge,
medical waste, hazardous waste, and scrap tires; and drum and barrel reclamation and
crematories.
There are few emission controls that are dedicated solely to reducing lead
emissions from combustion sources. However, the control strategies used to reduce PM
emissions have been found to be effective in controlling lead emissions in particulate form. Where
a specific emission control strategy has been identified to reduce lead emissions from a particular
combustion source discussed in this section, that control strategy is discussed as part of the
process description for that source. In many cases throughout this section, emission factor data
are provided for both controlled and uncontrolled combustion units that are typically found in a
particular source category.
The combustion of solid, liquid, and gaseous fuels such as coal, wood, fuel oil, and
natural gas has been shown to be a source of lead emissions. Lead emission rates depend on both
fuel characteristics and combustion process characteristics. Emissions of lead originate from lead
compounds contained in fuels and emitted during combustion.51,52,53 Because metals such as lead
only change forms (chemical and physical states) during combustion and are never destroyed, the
5-1
amount of lead in the original fuel or waste will be equal to the amount of lead found in the ash or
emitted in the effluent gas.54,55
Lead concentrations in coal depend on the type of coal. Example specific lead
concentrations in coal are as follows: anthracite coal contains approximately 7 ppm lead;
bituminous coal contains 14 ppm lead; subbituminous coal contains 6 ppm lead; and lignite coal
contains 7 ppm lead.56 Likewise, the lead concentration in fuel oil also depends on the type of oil.
Residual oil averages about 1 ppm lead by weight, while the lead content of distillate oil ranges
from 0.1 to 0.5 ppm lead by weight.57,58 Wood has been reported to have a lead content of
20 ppm.59
Lead and lead compound emissions may be reduced from combustion sources by
using PM control devices, lower combustion and control device temperatures, and controlling
feed chlorine content.60 Each of these lead reduction techniques is discussed briefly below.
During the combustion process, lead and other metals volatilize and then, upon
cooling, condense on all available particulate surface area. The submicrometer particles with very
high surface areas can carry a very high concentration of condensed lead. This phenomenon is
known as “fine particle enrichment.” There are three general factors favoring fine particle
enrichment of lead:55
5-2
C Low flue gas temperatures.
Another factor that influences the extent of lead emissions is chlorine content. The
chlorine content of the combusted fuel or waste increases the sensitivity of lead emissions to bed
temperature. When a high chlorine content is present, lead will volatilize at lower temperatures
due to the high volatility of lead chlorides (PbCl2) versus oxides (PbO). Monitoring and limiting
the feed chlorine content reduces the volatility of lead, allowing more lead to condense onto PM
for more effective lead emissions control.
The primary stationary combustion sources emitting lead compounds are boilers,
furnaces, heaters, stoves, and fireplaces used to generate heat and/or power in the residential,
utility, industrial, and commercial use sectors. A description of combustion sources, typical
emission control equipment, and lead emission factors for each of these major use sectors is
provided in the sections that follow.
Fuel economics and environmental regulations affect regional use patterns for
combustion sources. Most of the utility coal-firing capability in the United States is east of the
Mississippi River, with the significant remainder being in the Rocky Mountain region. Natural gas
is used primarily in the South Central States and California. Oil is predominantly used in Florida
and the Northeast. Information on precise utility plant locations can be obtained by contacting
utility trade associations, such as the Electric Power Research Institute in Palo Alto, California
(415-855-2000), the Edison Electric Institute in Washington, D.C. (202-828-7400), or the
U.S. Department of Energy (DOE) in Washington, D.C. Publications by EPA and DOE on the
utility industry are useful in determining specific facility locations, sizes, and fuel use.
5-3
Industrial and commercial coal combustion sources are located throughout the
United States, but tend to be concentrated in areas of industry and larger population. Most of the
coal-fired industrial boiler sources are located in the Midwest, Appalachian, and Southeast
regions. Industrial wood-fired boilers tend to be located almost exclusively at pulp and paper,
lumber products, and furniture industry facilities. These industries are concentrated in the
Southeast, Gulf Coast, Appalachian, and Pacific Northwest regions. Trade associations such as
the American Boiler Manufacturers Association in Arlington, Virginia and the Council of
Industrial Boiler Owners in Fairfax Station, Virginia can provide information on industrial boiler
locations and trends.61,62
Section 5.1.2 presents process descriptions and available emission factors for
residential heating. Section 5.1.3 presents process descriptions for utility, industrial, and
commercial fuel combustion. Section 5.1.4 presents available emission factors for utility,
industrial, and commercial fuel combustion.
The residential sector includes furnaces and boilers burning coal, oil, and natural
gas, stoves and fireplaces burning wood, and kerosene heaters. All units in this sector are
designed to heat individual homes. Residential combustion sources generally are not equipped
with PM or gaseous pollutant control devices. With coal- and wood-fired residential sources,
changes in stove design and operating practice in recent years have lowered PM, CO, and
hydrocarbon emissions from these sources. Changes include modified combustion air flow
control, greater thermal control and heat storage, and the use of combustion catalysts. Such
changes are also expected to reduce lead emissions.63,64
Process Description--Coal is not widely used for residential heating in the United
States. Only 0.3 percent of the total coal consumption in 1990 was for residential use.65
5-4
Although combustion units burning coal are minor sources of lead emissions, they may be
important local sources in areas where a large number of residences rely on coal for heating.
There are a wide variety of coal-burning stoves in use. These include boilers,
furnaces, and stoves that are designed to burn coal, and wood-burning stoves that burn coal.
These units may be either hand-fed or automatically-fed. Boilers and warm-air furnaces are
usually stoker-fed and are automatically controlled by a thermostat. Stoves are less sophisticated,
generally hand-fed, and less energy efficient than boilers and furnaces. Lead emissions from all of
these units depend on the concentration of lead in the coal.
Emissions--A 1979 EPA study reported average lead emission factors for a
residential coal-burning boiler and furnace. These emission factors, shown in Table 5-1, represent
total lead particulate emissions. Although these factors are dated, they should be representative
of current lead emissions from these sources for two reasons. First, these emissions depend on
the concentration of lead in the coal used and, second, emission controls still remain uncommon
among these sources.66
Process Description--Distillate oil is the second most important home heating fuel
behind natural gas. (Residual oil is seldom used in the residential sector.)67 The use of distillate
oil-fired heating units is concentrated in the Northeast. In 1991, Connecticut, Maine,
Massachusetts, New Hampshire, Rhode Island, Vermont, Delaware, District of Columbia,
Maryland, New Jersey, New York, and Pennsylvania accounted for approximately 72 percent of
residential distillate oil sales.68
Residential oil-fired heating units are available in a number of design and operating
variations. These variations include burner and combustion chamber design, excess air, and
heating medium. Residential systems typically operate only in an “on” or “off” mode and at a
constant fuel-firing rate, unlike commercial and industrial applications, where load modulation is
the general practice.70 In distillate oil-fired heating units, fuel oil is atomized into
5-5
TABLE 5-1. LEAD EMISSION FACTORS FOR RESIDENTIAL COAL COMBUSTION
Average Emission
Factor Emission Factor Range
in lb/ton in lb/ton
SCC Number Emission Source Control Device (kg/Mg)a (kg/Mg)a Emission Factor Rating
A21-04-002-000 Bituminous/ None 2.00x10-2 --- U
Subbituminous Coal - All (1.00x10-2)
Combustor Types
A21-04-001-000 Anthracite Coal - All None 1.60x10-2 --- U
Combustor Types (8.00x10-3)
Source: Reference 69
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of coal combusted.
Residential combustion units are less sophisticated than utility and industrial
combustion units. For this reason, they normally burn distillate oil to keep emissions to a
minimum.57,58 Average emission factors for residential distillate oil-fired furnaces are presented in
Table 5-2.
Process Description--Natural gas is the most widely used fuel for home heating
purposes. More than half of all homes in the United States are heated by natural gas
combustion.71 Gas-fired residential heating systems are generally less complex and easier to
maintain than oil-burning units because the fuel burns cleaner and no atomization is required.
Residential gas burners typically are built of the same basic design. Natural aspiration is used
where the primary air mixes with the gas as it passes through the distribution pipes. Secondary air
enters the furnace around the burners. Flue gases then pass through a heat exchanger and a stack.
As with oil-fired systems, there is usually no APCD installed on gas systems. Excess air,
residence time, flame retention devices, and maintenance are the key factors in controlling PM
(including lead) emissions from these units.
Emissions--Emissions testing data for lead from gas-fired residential units have
been extremely scarce, probably because the expected emissions are low and this source has not
5-7
TABLE 5-2. EMISSION FACTORS FOR RESIDENTIAL DISTILLATE OIL-FIRED FURNACES
Source: Reference 72
a
Emission factors are expressed in lb (kg) of pollutant emitted per MMBtu (Joule) of heat input.
5-8
been identified as a priority for testing. As a result, there are no available emission factors for this
source.
5.1.3 Process Descriptions for Utility, Industrial, and Commercial Fuel Combustion
Utility Sector
Utility boilers burn coal, oil, natural gas, and wood to generate steam for
electricity generation. Fossil fuel-fired utility boilers comprise about 72 percent [or
497,000 megawatts (MW)] of the generating capacity of U.S. electric power plants. Of these
fuels, coal is the most widely used, accounting for approximately 60 percent of the U.S. fossil
fuel-powered electricity generating capacity. Natural gas represents about 25 percent and oil
represents the remaining 15 percent.73
5-9
Figure 5-1. Simplified Boiler Schematic
5-10
along the furnace centerline. When coal is used as the fuel, the coal is pulverized in a mill to the
consistency of talcum powder (i.e., so that at least 70 percent of the particles will pass through a
200 mesh sieve), entrained in primary air, and fired in suspension.75 As fuel and air are fed to the
burners, a rotating “fireball” is formed. By tilting the fuel-air nozzle assembly, this “fireball” can
be moved up and down to control the furnace exit gas temperature and to provide steam
temperature control during variations in load. Tangentially-fired boilers commonly burn
(pulverized) coal. However, oil or gas may also be burned.73
Cyclone-fired Boiler--In the cyclone-fired boiler, fuel and air are burned in
horizontal, cylindrical chambers, producing a spinning, high-temperature flame. Cyclone-fired
boilers are almost exclusively (crushed) coal-fired. The coal is crushed to a 4-mesh size and
admitted with the primary air in a tangential fashion. The finer coal particles are burned in
suspension, while the coarser particles are thrown to the walls by centrifugal force.74 Some units
are also able to fire oil and natural gas.73
5-11
Figure 5-2. Single Wall-fired Boiler
5-12
Figure 5-3. Simplified Atmospheric Fluidized Bed Combustor Process Flow Diagram
5-13
Stoker-fired Boiler--Instead of firing coal in suspension as in the boilers described
above, the mechanical stoker can be used to burn coal in fuel beds. Mechanical stokers are
designed to feed coal onto a grate within the furnace. The most common stoker type used in the
utility industry is the spreader stoker (Figure 5-4). In the spreader stoker, a flipping mechanism
throws crushed coal into the furnace and onto a moving fuel bed (grate). Combustion occurs
partly in suspension and partly on the grate.75
Emission Control Techniques--Utility boilers are highly efficient and are among the
best controlled of all combustion sources. Existing emission regulations for total PM have
necessitated controls on coal- and oil-fired utility sources. Emission controls are not required on
natural gas boilers because, relative to coal and oil units, uncontrolled emissions are inherently
low.64 Baghouses, ESPs, wet scrubbers, and multicyclones have been used to control PM in the
utility sector. As described in other source category sections, lead condenses on PM, which is
easily controlled by PM control technologies. Particulate lead, specifically fine particulate, is
controlled most effectively by baghouses or ESPs. Depending on their design, wet scrubbers are
potentially effective in controlling particulate lead. Multicyclones are ineffective at capturing fine
particles of lead and, therefore, are a poor control system for lead emissions.63,64
Lead emissions from utility boilers are commonly controlled using an SO2 control
technology known as lime/limestone flue gas desulfurization (FGD). This technology employs a
wet scrubber for SO2 removal and is often preceded by an ESP, which accomplishes the bulk of
PM control. Wet FGD/ESP systems, while controlling lead condensed on PM at the entrance to
the ESP, are relatively inefficient for control of vapor-phase lead. However, most lead emissions
are condensed on PM and are not emitted in the vapor phase.63,64
A more recently applied SO2 control technique for utility boilers is spray drying.
In this process, the gas stream is cooled in the spray dryer, but it remains above the saturation
temperature. A fabric filter or an ESP is located downstream of the spray dryer, thus controlling
both particulate-phase lead emissions and vapor-phase lead emissions that condense before they
reach the baghouse or ESP.63,64
5-14
5-15
Of the units included in the ICCR survey database, approximately 70% were
classified in the natural gas fuel subcategory, 23% in the oil (distillate and residual) subcategory,
and 6% in the coal burning subcategory. These fuel subcategory assignments are based on the
units burning only greater than 90% of the specified fuel for that subcategory. All other units
(accounting for the other 1% of assignments) are assigned to a subcategory of “other fossil
fuel.”259
Other fuels burned in industrial boilers are wood wastes, liquified petroleum gas,
and kerosene. Wood waste is the only non-fossil fuel discussed here since most lead emissions
are attributed to the combustion of wood fuel. The burning of wood waste in boilers is confined
to those industries where it is available as a by-product. It is burned both to obtain heat energy
and to alleviate possible solid waste disposal problems. Generally, bark is the major type of wood
waste burned in pulp mills. In the lumber, furniture, and plywood industries, either a mixture of
wood and bark, or wood alone, is frequently burned. As of 1980, the most recent data identified,
5-16
there were approximately 1,600 wood-fired boilers operating in the United States with a total
capacity of over 100,000 MMBtu/hr (30,000 MW thermal).78
Many of the same boiler types used in the utility sector are also used in the
industrial/commercial sector; however, the average size boiler used in the industrial/ commercial
sector is substantially smaller than the average size boiler used in the utility sector. In addition, a
few boiler designs are used only by the industrial/commercial sector. For a general description of
the major subassemblies and key thermal processes that occur in boilers, refer to Figures 5-1 to
5-4 in the section on Utility Sector Process Description and the accompanying discussion.
5-17
Fire-tube and Cast Iron Boilers--Two other heat transfer methods used in the
industrial/commercial sector are fire-tube and cast iron boilers. In fire-tube boilers, hot gas flows
through tubes that are surrounded by circulating water. Fire-tube boilers are not available with
capacities as large as water-tube boilers, but they are also used to produce process steam and
space heat. Most fire-tube boilers have a capacity between 1.4 and 25 MMBtu/hr (0.4 to 7.3 MW
thermal). Most installed fire-tube boilers burn oil or gas and are used primarily in
commercial/institutional applications.77
In cast iron boilers, the hot gas is also contained inside the tubes that are
surrounded by the water being heated, but the units are constructed of cast iron instead of steel.
Cast iron boilers are limited in size and are used only to supply space heat. Cast iron boilers range
in size from less than 0.34 to 9.9 MMBtu/hr (0.1 to 2.9 MW thermal).77
Various boiler firing configurations are used to burn wood waste. One
configuration that is common in smaller operations is the dutch oven or extension type of furnace
with a flat grate. This unit is used widely because it can burn very high-moisture fuels. Fuel is fed
into the oven through apertures in a firebox and is fired in a cone-shaped pile on a flat grate. The
burning is accomplished in two stages: (1) drying and gasification, and (2) combustion of gaseous
products. The first stage takes place in a cell separated from the boiler section by a bridge wall.
The combustion stage takes place in the main boiler section.78
In another type of boiler, the fuel-cell oven, fuel is dropped onto suspended fixed
grates and is fired in a pile. The fuel cell uses combustion air preheating and positioning of
secondary and tertiary air injection ports to improve boiler efficiency.78
5-18
In many large operations, more conventional boilers have been modified to burn
wood waste. These modified units may include spreader stokers with traveling grates or vibrating
grate stokers, as well as tangentially-fired or cyclone-fired boilers. Refer to Figures 5-1 to 5-4
and the accompanying discussion in the section on Utility Sector Process Description for more
detail on these types of boilers. The spreader stoker, which can burn dry or wet wood, is the
most widely used of these configurations. Fuel is dropped in front of an air jet that casts the fuel
out over a moving grate. The burning is carried out in three stages: (1) drying, (2) distillation
and burning of volatile matter, and (3) burning of fixed carbon. These operations often fire
natural gas or oil as auxiliary fuel. Firing an auxiliary fuel helps to maintain constant steam when
the wood supply fluctuates or to provide more steam than can be generated from the wood supply
alone.78
Sander dust is often burned in various boiler types at plywood, particle board, and
furniture plants. Sander dust contains fine wood particles with a moisture content of less than
20 percent by weight. The dust is fired in a flaming horizontal torch, usually with natural gas as
an ignition aid or as a supplementary fuel.78
A recent development in wood-firing is the FBC (refer to Figures 5-1 to 5-4 and
the accompanying discussion in Utility Sector Process Description for more detail on this boiler
type). Because of the large thermal mass represented by the hot inert bed particles, FBCs can
handle fuels with high moisture content (up to 70 percent, total basis). Fluidized bed combustors
can also handle dirty fuels (up to 30 percent inert material). Wood material is pyrolyzed faster in
a fluidized bed than on a grate due to its immediate contact with hot bed material.78
5-19
Waste Oil Combustion--Waste oil is another type of fuel that is burned primarily in
small industrial/commercial boilers and space heaters. Space heaters (small combustion units
generally less than 250,000 Btu/hr [0.1 MW] heat input) are common in automobile service
stations and automotive repair shops where supplies of waste crankcase oil are available.80 Waste
oil includes used crankcase oils from automobiles and trucks, used industrial lubricating oils (such
as metal working oils), and other used industrial oils (such as heat transfer fluids). Due to a
breakdown of the physical properties of these oils and contamination by other materials, these oils
are considered waste oils when they are discarded.81
The federal government has developed regulations for waste oil fuel under the
Resource Conservation and Recovery Act (RCRA). The EPA has determined that as long as
used oil is recycled (which includes burning it for energy recovery as well as re-refining it or other
processes), it is not considered a hazardous waste under RCRA 40 CFR 261.1.82 However, if a
facility does burn used oil, that facility is subject to certain requirements under RCRA.
If a facility is burning “on-specification” waste oil for energy recovery, that facility
is only subject to certain reporting and recordkeeping requirements (40 CFR 279.11).86 If a
facility burns the waste oil in a space heater with heat input capacity less than 0.5 million Btu/hr
(0.15 Mg) and vents the exhaust to the ambient air, that facility is not subject to any requirements
(40 CFR 279.23).84
A facility burning “off-specification” waste oil for energy recovery must comply
with additional requirements, including verification to EPA that the combusted oil was not mixed
with other hazardous wastes (40 CFR Subpart G).88
5-20
Boilers designed to burn No. 6 (residual) fuel oils or one of the distillate fuel oils
can be used to burn waste oil, with or without modifications for optimizing combustion. As an
alternative to boiler modification, the properties of waste oil can be modified by blending it with
fuel oil to the extent required to achieve a clean-burning fuel mixture.
Fly ash injection, one type of control commonly used in large wood-fired boilers to
improve fuel efficiency, may increase particulate lead emissions. With fly ash injection, a greater
amount of carbon is introduced into the boiler which, in turn, increases the amount of fine PM.
Fine PM is more difficult to collect with the APCD; the fine PM escapes through the APCD
uncontrolled, thereby increasing lead emissions.75
Emission controls for industrial boilers and their effectiveness in reducing lead
emissions are very similar to those previously described for utility boilers. PM control in the
industrial sector is achieved with baghouses, ESPs, wet scrubbers, and multicyclones. FGD
systems for SO2 control are used less frequently in the industrial sector than in the utility sector.
Generally, in the industrial sector, SO2 regulations are met by burning lower-sulfur-content
fuels.63,64
PM emissions from oil-fired industrial boilers generally are not controlled under
existing regulations because emission rates are low. Some areas may limit SO2 emissions from
5-21
oil-firing by specifying the use of lower-sulfur-content oils. Natural gas-fired industrial boilers are
also generally uncontrolled because of very low emissions.63,64
5.1.4 Emission Factors for Utility, Industrial, and Commercial Fuel Combustion
Extensive lead emissions data for utility, industrial, and commercial stationary
external combustion sources are available in the literature. Because state and federal air pollution
regulations often require emissions testing for toxic air pollutants, a current database of lead
emissions from these fuel combustion sources exists.
5-22
C Coal combustion:
C Oil combustion:
C Miscellaneous combustion:
Lead emission factors for wood waste combustion in utility, industrial, and
commercial boilers are presented in Tables 5-3, 5-4, and 5-5, respectively. These emission factors
are widely applicable to all utility, industrial, and commercial wood waste combustion SCC
categories.73 However, a wide range of boiler sizes, boiler and control device configurations, and
fuel characteristics is reflected by these composite emission factors. For this reason, if site-
specific information is available to characterize an individual combustion source more accurately,
it is recommended that the reader locate the appropriate process-specific emission factor
presented in the applicable table.
5-23
TABLE 5-3. LEAD EMISSION FACTORS FOR WOOD WASTE-FIRED UTILITY BOILERS
Reinjection (1.60x10-4)
1-01-009-03 Wood Waste-fired ESP 1.10x10-3 --- D 86
Boiler (Wood-fired) (5.50x10-4)
Multiple Cyclone without Flyash 3.10x10-4 --- D 86
Reinjection (1.55x10-4)
None 2.9x10-3 --- U 87
(1.45x10-3)
Limestone Injection, Thermal 4.49x10-6 lb/MMBtub 1.4x10-7 - 9.41x10 -6 U 88
de- NOx with Ammonia (1.93x10-15 kg/Joule) lb/MMBtub
Injection, Water Treatment, (6.00x10-17 - 4.10x10 -15
Multi-Cyclone, Fabric Collector kg/Joule)
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of wood waste combusted, except as noted. Emission factors are based on wet, as-
fired wood waste with 50 percent moisture and a higher heating volume of 4,500 Btu/lb.
b
Emission factors are expressed in lb (kg) of pollutant emitted per MMBtu (Joule) of heat input.
(1.75x10-4)
Multiple Cyclone without 3.20x10-4 --- D 86
Flyash Reinjection (1.60x10-4)
1-02-009-03 Wood Waste-fired Wet Scrubber - Medium 1.60x10-5 lb/MMBtub 1.10x10-5 - 2.50x10 -5 U 90
Boiler (Wood-fired, Efficiency (6.89x10-15 kg/Joule) lb/MMBtub
>50,000 lb steam) (4.74x10-15 - 1.08x10 -14
kg/Joule)
Multiple Cyclone without 4.00x10-5 lb/MMBtub 3.20x10-4 - 5.00x10 -4 U 91
Flyash Reinjection/Wet (1.72x10-14 kg/Joule) lb/MMBtub
Scrubber - Medium (1.38x10-13 - 2.15x10 -13
Efficiency kg/Joule)
Multiple Cyclone without 3.10x10-4 --- D 86
Flyash Reinjection (1.55x10-4)
ESP 1.10x10-3 --- D 86
(5.50x10-4)
TABLE 5-4. LEAD EMISSION FACTORS FOR WOOD WASTE-FIRED INDUSTRIAL BOILERS (CONTINUED)
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of wood waste combusted, except as noted. Emission factors are based on wet, as-
fired wood waste with average properties of 50 percent moisture and 4,500 Btu/lb higher heating value.
b
Emission factors are expressed in lb (kg) of pollutant emitted per MMBtu (Joule) of heat input.
Reinjection
1-03-009-03 Wood/Bark-fired Boiler Multiple Cyclone 3.10x10-4 --- D
(Wood-fired) without Flyash (1.55x10-4)
Reinjection
ESP 1.10x10-3 --- D
(5.50x10-4)
Source: Reference 86
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of wood waste combusted. Emission factors are based on wet, as-fired wood
waste with 50 percent moisture and a higher heating value of 4,500 Btu/lb.
Average emission factors for industrial wood waste-fired boilers are presented in
Table 5-4. Several of the emission factors are based on a comprehensive toxic air emission testing
program in California. The study, conducted by the Timber Association of California (TAC),
tested boiler types with capacities greater than 50,000 lb (22,680 kg) of steam per hour, including
fuel cell, dutch oven, stoker, air injection, and fluidized bed combustors. The summarized results
of the study were used to obtain the average lead emission factors. The emission factors
represent a range of boiler designs and capacities, control configurations, and wood waste
compositions. The range of control devices represented in the sample set included multiple
cyclones, ESPs, and wet scrubbers. Sampling was conducted using CARB Method 431, which
captures particulate lead.89,90,91
There were few data available for deriving lead emission factors for natural gas-
fired utility boilers. Based on the limited data available, it is unclear whether there are significant
lead emissions from these boilers. Tables 5-6 and 5-7 present lead emission factors for natural gas
fired boilers.
5-28
TABLE 5-6. LEAD EMISSION FACTORS FOR NATURAL GAS - FIRED UTILITY BOILERS FROM AP-42
a
To convert from lb/million ft3 to Kg/million m 3 multiply by 16.0.
b
Data for boilers controlled with overfire air and flue gas recirculation.
TABLE 5-7. LEAD EMISSION FACTORS FOR NATURAL GAS - FIRED BOILERS FROM UTILITY STUDY
Lead emission factors for coal-fired utility boilers are presented in Tables 5-8 and
5-9. The tables include composite emission factors for anthracite, bituminous pulverized
wet-bottom, and bituminous pulverized dry-bottom boilers. The emission factors include
particulate lead.55
AP-42, Section 1.1 also includes an equation for bituminous coal, subbituminous
coal and lignite combustion. This equation can be used for both controlled and uncontrolled
boilers. The equation is also applicable to all typical firing configurations of utility, industrial and
commercial/industrial boilers. The equation for lead is as follows:
0.8
C
Lead emissions (lb/1012 BTU) ' 3.4 ( PM
A
5-30
TABLE 5-8. LEAD EMISSION FACTORS FOR COAL-FIRED UTILITY BOILERS
Average Emission
Factor Emission Factor Range
Control in lb/ton in lb/ton Emission
SCC Number Emission Source Device (kg/Mg)a (kg/Mg)a Factor Rating Reference
1-01-001-02 Anthracite Coal Traveling Grate None 8.90x10-3 --- E 96
Overfeed Stoker (4.45x10-3)
1-01-002-01 Bituminous Coal: Pulverized: None 5.07x10-4 lb/MMBtub --- E 97
Wet Bottom (2.18x10-13 kg/Joule)
1-01-002-02 Bituminous Coal: Pulverized: None 5.07x10-4 lb/MMBtub --- E 97
Dry Bottom (2.18x10-13 kg/Joule)
ESP, FF or 4.20x10-4 lb/tonc --- A 97
venturi (2.10x10-4 kg/Mg)
scrubber
5-31
Average Emission
Factor Emission Factor Range
Control in lb/ton in lb/ton Emission
SCC Number Emission Source Device (kg/Mg)a (kg/Mg)a Factor Rating Reference
-4 b
1-01-002-22 Subbituminous Coal: None 5.07x10 lb/MMBtu --- E 97
Pulverized: Dry Bottom (2.18x10-13 kg/Joule)
ESP, FF or 4.20x10-4 lb/tonc --- A 97
venturi (2.10x10-4 kg/Mg)
scrubber
1-01-002-23 Subbituminous Coal: Cyclone None 5.07x10-4 lb/MMBtub --- E 97
Furnace (2.18x10-13 kg/Joule)
ESP, FF or 4.20x10-4 lb/tonc --- A 97
venturi (2.10x10-4 kg/Mg)
scrubber
5-32
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of coal combusted, except as noted.
b
Emission factors are expressed in lb (kg) of pollutant emitted per MMBtu (Joule) of heat input.
c
Emission factor should be applied to coal feed, as fired.
Average Emission
SCC Control Factor Emission Factor Range Emission
Number Emission Source Device in lb/ton (kg/Mg) a in lb/ton (kg/Mg) a Factor Rating Reference
1-02-001-04 Anthracite Coal Traveling Grate None 8.90x10-3 (4.45x10-3) --- E 96
(Overfeed) Stoker
1-02-002-01 Bituminous Coal Pulverized: Wet None 5.07x10-4 lb/MMBtub --- E 97
Bottom (2.18x10-13 kg/Joule)
1-02-002-02 Bituminous Coal Pulverized Coal: None 5.07x10-4 lb/MMBtub --- E 97
Dry Bottom (2.18x10-13 kg/Joule)
ESP, FF, or 4.20x10-4lb/tonc --- A 97
venturi (2.10x10-4kg/Mg)
scrubber
1-02-002-03 Bituminous Coal Cyclone Furnace None 5.07x10-4 lb/MMBtub --- E 97
(2.18x10-13 kg/Joule)
5-34
Average Emission
Control Factor Emission Factor Range Emission
SCC Number Emission Source Device in lb/ton (kg/Mg) a in lb/ton (kg/Mg) a Factor Rating Reference
1-01-002-22 Subbituminous Coal: Pulverized: None 5.07x10-4 lb/MMBtub --- E 97
Dry Bottom (2.18x10-13 kg/Joule)
ESP, FF, or 4.20x10-4lb/tonc --- A 97
venturi (2.10x10-4kg/Mg)
scrubber
1-01-002-23 Subbituminous Coal: Cyclone None 5.07x10-4 lb/MMBtub --- E 97
Furnace (2.18x10-13 kg/Joule)
ESP, FF, or 4.20x10-4lb/tonc --- A 97
venturi (2.10x10-4kg/Mg)
scrubber
1-01-002-24 Subbituminous Coal: Spreader Stoker None 5.07x10-4 lb/MMBtub --- E 97
5-35
(2.18x10-13 kg/Joule)
1-01-002-25 Subbituminous Coal: Traveling Grate None 5.07x10-4 lb/MMBtub --- E 97
(Overfeed) Stoker (2.18x10-13 kg/Joule)
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of coal combusted, except as noted.
b
Emission factors are expressed in lb (kg) of pollutant emitted per MMBtu (Joule) of heat input.
c
Emission factor should be applied to coal feed, as fired.
“---” means data are not available.
TABLE 5-11. LEAD EMISSION FACTORS FOR COAL-FIRED COMMERCIAL/INSTITUTIONAL BOILERS
Average Emission
Factor Emission Factor Range Emission
SCC in lb/ton in lb/ton Factor
Number Emission Source Control Device (kg/Mg)a (kg/Mg)a Rating Reference
1-03-001-02 Anthracite Coal Traveling None 8.90x10-3 --- E 96
Grate (Overfeed) Stoker (4.45x10-3)
1-03-002-08 Bituminous Coal Underfeed Multiple Cyclone 1.21x10-3 --- U 98
Stoker without Flyash (6.05x10-4)
Reinjection
1-03-002-03 Bituminous Coal Cyclone None 5.07x10-4 lb/MMBtub --- E 97
Furnace (2.18x10-13 kg/Joule)
ESP, FF, or venturi 4.20x10-4 lb/ton --- A 97
scrubber (2.10x10-4 kg/Mg)c
1-03-002-05 Bituminous Coal Pulverized: None 5.07x10-4 lb/MMBtub --- E 97
5-36
Average Emission
Factor Emission Factor Range Emission
SCC in lb/ton in lb/ton Factor
Number Emission Source Control Device (kg/Mg)a (kg/Mg)a Rating Reference
-4 b
1-03-002-22 Subbituminous Coal: None 5.07x10 lb/MMBtu --- E 97
Pulverized: Dry Bottom (2.18x10-13 kg/Joule)
ESP, FF, or venturi 4.20x10-4 lb/ton --- A 97
scrubber (2.10x10-4 kg/Mg)c
1-03-002-23 Subbituminous Coal: Cyclone None 5.07x10-4 lb/MMBtub --- E 97
Furnace (2.18x10-13 kg/Joule)
ESP, FF, or venturi 4.20x10-4 lb/ton --- A 97
scrubber (2.10x10-4 kg/Mg)c
1-03-002-24 Subbituminous Coal: Spreader None 5.07x10-4 lb/MMBtub --- E 97
Stoker (2.18x10-13 kg/Joule)
5-37
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of coal combusted, except as noted.
b
Emission factors are expressed in lb (kg) of pollutant emitted per MMBtu/Joule of heat input.
c
Emission factor should be applied to coal feed, as fired.
“---” means data are not available.
Oil Combustion
Lead emission factors for oil-fired utility boilers are presented in Tables 5-12 and
5-13. Lead emission factors for oil-fired industrial and commercial/institutional boilers are
presented in Tables 5-14 through 5-17.
Emission factors for specific utility boiler and control device configurations are
also listed in Table 5-12, as are emission factors for residual oil and distillate oil combustion.
Lead emission factors for oil-fired industrial boilers are presented in Table 5-14.
The data used in factor development came from the testing of two uncontrolled units. Testing
was conducted using CARB Method 436. The emission factors represent particulate lead.100
Lead emission factors for solid-waste fired utility boilers are presented in
Table 5-18.
Miscellaneous Combustion
Lead emission factors for industrial boilers firing other fuel types (i.e., solid waste
refuse-derived fuel) are presented in Table 5-19.
5-38
TABLE 5-12. LEAD EMISSION FACTORS FOR OIL-FIRED UTILITY BOILERS
a
Emission factors are expressed in lb (kg) of pollutant emitted per MMBtu (Joule) of heat input.
TABLE 5-16. LEAD EMISSION FACTORS FOR WASTE OIL-FIRED INDUSTRIAL BOILERS
a
Emission factors are expressed in lb (kg) of pollutant emitted per 1000 gallons (kL) of oil combusted.
b
L=weight % lead in fuel. Multiply numeric value by L to obtain emission factor.
“---” means data are not available.
TABLE 5-17. LEAD EMISSION FACTORS FOR WASTE OIL-FIRED COMMERCIAL/INSTITUTIONAL BOILERS
Average Emission
Factor Emission Factor Range Emission
in lb/1000 gal in lb/1000 gal Factor
SCC Number Emission Source Control Device (kg/kL)a (kg/kL)a Rating Reference
1-01-013-02 Waste Oil None 1.68 --- U 23
(2.01x10-1)
1-05-002-13 Waste Oil Air Atomized None 50Lb --- D 106
Burner (6.0L)
a
Emission factors are expressed in lb (kg) of pollutant emitted per 1000 gallons (kL) of oil combusted.
b
L=weight % lead in fuel. Multiply numeric value by L to obtain emission factor.
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of waste combusted, except as noted.
b
Emission factors are expressed in lb (kg) of pollutant emitted per MMBtu (Joule) of heat input.
5-43
Source: Reference 23
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of waste combusted.
Internal combustion sources for electricity generation and industrial application are
grouped into two types: gas turbines and reciprocating engines.
Stationary gas turbines are applied in electric power generators, in gas pipeline
pump and compressor drives, and various process industries. Gas turbines greater than 3 MW are
used in electricity generation for continuous, peaking, or standby power. The primary fuels used
are natural gas and distillate (No. 2) fuel oil.107
The rated power of gasoline and diesel internal combustion engines covers a
substantial range: up to 250 hp (186 kW) for gasoline engines and greater than 600 hp (447 kW)
for diesel engines. The primary domestic use of large stationary diesel engines (greater than
600 hp) is in oil and gas exploration and production. These engines supply mechanical power to
operate drilling (rotary table), mud pumping, and hoisting equipment and may also operate pumps
or auxiliary power generators.112 Stationary natural gas-fired spark ignition engines of over
5,000 hp and natural gas-fired turbines of over 10,000 hp exist.
5-44
5.2.2 Emissions
Air emissions from the flue gas stack are the only emissions from electricity
generation, industrial turbines, and reciprocating engines. Turbines firing distillate or residual oil
may emit trace metals carried over from the metals content of the fuel.
If the fuel analysis is known, the metals content of the fuel should be used for flue
gas emission factors, assuming all metals pass through the turbine.107 The average fuel analysis
result can be used to calculate emissions based on fuel usage or stack exhaust flow measurements.
Potential emissions based on the trace element content of distillate oils have been calculated and
compared with measured stack emissions.110 In almost all cases, the potential emissions were
higher than the measured emissions. Limited lead emissions and lead emission factors were
available for the other emission sources indicated in this section.
As of January 1992, there were 160 municipal waste combustor (MWC) plants
operating in the United States with capacities greater than 40 tons/day (36 Mg/day), with a total
capacity of approximately 110,000 tons/day (100,000 Mg/day) of municipal solid waste (MSW).
It is projected that by 1997, total MWC capacity will approach 165,000 tons/day
5-45
(150,000 Mg/day), which represents approximately 28 percent of the estimated total amount of
MSW that will be generated in the United States by the year 2000.114 Table 5-20 lists the
geographical distribution of MWC units and statewide capacities.115
MWCs burn garbage and other nonhazardous solid waste, commonly called MSW.
Three main types of combustors are used to combust MSW: mass burn, refuse-derived fuel-fired
(RDF), and modular. Each type is discussed in this section.
In mass burn units, MSW is combusted without any preprocessing other than
removal of items too large to go through the feed system. In a typical mass burn combustor,
refuse is placed on a grate that moves through the combustor. Combustion air in excess of
stoichiometric amounts is supplied both below (underfire air) and above (overfire air) the grate.
Mass burn combustors are erected at the site (as opposed to being prefabricated) and range in size
from 50 to 1,000 tons/day (46 to 900 Mg/day) of MSW throughput per unit. Mass burn
combustors can be divided into mass burn/waterwall (MB/WW), mass burn/rotary waterwall
(MB/RC), and mass burn/refractory wall (MB/REF) designs.
The walls of a MB/WW combustor are constructed of metal tubes that contain
pressurized water and recover radiant heat for production of steam and/or electricity. A typical
MB/WW combustor is shown in Figure 5-5. With the MB/RC combustor, a rotary combustion
chamber sits at a slight angle and rotates at about 10 revolutions per hour, causing the waste to
advance and tumble as it burns. The combustion cylinder consists of alternating water tubes and
perforated steel plates. Figure 5-6 illustrates a simplified process flow diagram for a MB/RC.
MB/REF designs are older and typically do not include any heat recovery. One type of MB/REF
combustor is shown in Figure 5-7.
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TABLE 5-20. SUMMARY OF GEOGRAPHICAL DISTRIBUTION OF MWC FACILITIES
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TABLE 5-20. SUMMARY OF GEOGRAPHICAL DISTRIBUTION OF MWC FACILITIES
(CONTINUED)
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TABLE 5-20. SUMMARY OF GEOGRAPHICAL DISTRIBUTION OF MWC FACILITIES
(CONTINUED)
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Figure 5-6. Simplified Process Flow Diagram, Gas Cycle for a Mass Burn/Rotary Waterwall
Combustor
RDF-fired combustors burn processed waste that varies from shredded waste to
finely divided fuel suitable for co-firing with pulverized coal. Combustor sizes range from 320 to
1,400 tons/day (290 to 1,300 Mg/day). There are three major types of RDF-fired combustors:
dedicated RDF combustors, which are designed to burn RDF as a primary fuel; coal/RDF co-fired
combustors; and fluidized-bed combustors (FBCs), where waste is combusted on a turbulent bed
of limestone, sand, silica or aluminum.
Modular Combustors
Modular combustors are similar to mass burn combustors in that they burn waste
that has not been pre-processed, but they are typically shop-fabricated and generally range in size
from 5 to 140 tons/day (4 to 130 Mg/day) of MSW throughput. One of the most common types
of modular combustors is the starved-air or controlled-air type, which incorporates two
combustion chambers. A process diagram of a typical modular starved-air (MOD/SA) combustor
is presented in Figure 5-9. Air is supplied to the primary chamber at sub-stoichiometric levels.
The incomplete combustion products (CO and organic compounds) pass into the secondary
combustion chamber, where additional air is added and combustion is completed. Another design
is the modular excess air (MOD/EA) combustor, which consists of two chambers, similar to
MOD/SA units, but is functionally like the mass burn unit in that it uses excess air in the primary
chamber.
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Lead is present in a variety of MSW streams, including paper, inks, batteries, and
metal cans, but is most prevalent in plastics. Lead is used to make dyes and stabilizers that
protect plastics from thermal and photo degradation. Because of the wide variability in MSW
composition, lead emissions are highly variable and are independent of combustor type. Because
the vapor pressure of lead is such that condensation develops onto particulates in the flue gas,
lead can be effectively removed by a PM control device.114
Because lead is usually emitted from MWCs in particulate form, the control of lead
is most frequently accomplished through the use of an ESP or fabric filter (FF), which are
common PM control techniques. Although other PM control technologies (e.g., cyclones,
electrified gravel beds, and venturi scrubbers) are available, they are not as effective as the ESP or
FF at removing PM and so are seldom used on existing systems.114 Well-designed ESPs and FFs
operated at 450EF (230EC) or less remove over 97 percent of lead and other metals.116
The most common types of ESPs are plate-and-wire units, in which the discharge
electrode is a bottom-weighted or rigid wire, and flat plate units, which use flat plates rather than
wires as the discharge electrode. As a general rule, the greater the amount of collection plate
area, the greater the PM collection efficiency. After the charged particles are collected on the
grounded plates, the resulting dust layer is removed from the plates by rapping or washing and
collected in a hopper. As the dust layer is removed, some of the collected PM becomes
re-entrained in the flue gas. To ensure good PM collection efficiency during plate cleaning and
electrical upsets, ESPs have several fields located in series along the direction of flue gas flow that
can be energized and cleaned independently. Particles re-entrained when the dust layer is
removed from one field can be recollected in a downstream field. Because of this phenomenon,
increasing the number of fields generally improves PM removal efficiency.114
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5.3.3 Emissions
Available lead emission factor data for several types of MWCs are provided in
Table 5-21. The column labeled “Emission Source” identifies the main characteristics of each
incinerator type. For some types of incinerators, a range of factors is provided that represents
different sample test runs of the same source. Generally, there is a wide range in the emission
factors associated with MWCs. This range is attributable to the variability of waste compositions
and to the operating practices and effectiveness of control devices.117 Waste composition can
differ from one MWC unit to another, especially where the permit specifications for the accepted
waste are different. For example, an MWC with a permit that prohibits the burning of lead-acid
batteries will have lower lead emissions than an MWC with a permit that does not prohibit such
burning. Because of this variability, the factors shown in Table 5-21 must be used cautiously and
may not be representative of other MWCs.
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TABLE 5-21. LEAD EMISSION FACTORS FOR MUNICIPAL WASTE COMBUSTION SOURCES
Injection/ESP (1.45x10-3)
ESP 3.00x10-3 --- A 114
(1.50x10-3)
5-01-001-06 Mass Burn: Rotary None 2.13x10-1 --- A 114
Waterwall Combustor (1.07x10-1)
Spray Dryer/FF 2.61x10-4 --- A 114
(1.31x10-4)
Spray Dryer/ESP 9.15x10-4 --- A 114
(4.58x10-4)
Dry Sorbent 2.97x10-4 --- C 114
Injection/FF (1.49x10-4)
Dry Sorbent 2.90x10-3 --- E 114
Injection/ESP (1.45x10-3)
ESP 3.00x10-3 --- A 114
(1.50x10-3)
TABLE 5-21. LEAD EMISSION FACTORS FOR MUNICIPAL WASTE COMBUSTION SOURCES (CONTINUED)
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of waste incinerated.
About 1,500 of the estimated 3,800 industrial incinerators are used for volume
reduction, 640 units (largely in the petroleum and chemical industries) are used for toxicity
reduction, and the remaining 1,700 units are used for resource recovery, primarily at copper wire
and electric motor plants.64
Lead emissions from industrial and commercial waste incineration are a function of
waste composition, incinerator design and operating practices, and incinerator emissions control
equipment. Both the incineration of wastes and the combustion of incinerator auxiliary fuel may
be sources of lead emissions. Incinerator design and operating practices affect waste mixing,
residence time in the flame zone, combustion stoichiometry, and other factors that contribute to
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the amount of lead emissions generated. The type of emissions control used dictates whether lead
in the form of PM or a gaseous pollutant is controlled and to what extent. Generally, lead
emissions exist in both particulate and some gaseous forms, with available data indicating that
particulate lead emissions often predominate. Incinerators with emission controls designed
primarily for PM collection may be accomplishing most of the lead emissions control.
5.4.3 Emissions
At the time this report was compiled, there were no available emission factors for
lead emissions from industrial/commercial waste incinerators. Most of the incinerators used by
commercial and industrial facilities are multichamber designs. The process and control device
configurations for incinerators at industrial and commercial facilities are the same as those used by
municipalities. The emission factors for municipal incinerators, however, would not be accurate
to use for industrial and commercial facilities because these two types of facilities incinerate
different types of waste. The waste streams at industrial and commercial sites are highly variable.
One plant might burn wood protected with lead-based paint, which would yield high lead
emissions. Another plant might burn wooden boxes and pallets that have low lead content. As a
result, very little data has been developed that accurately characterizes lead emissions from
industrial/commercial incinerators.
There are approximately 200 sewage sludge incineration plants operating in the
United States.118 Most sewage sludge incinerators (SSIs) are located in the eastern United States,
although there are a significant number on the West Coast. New York has the largest number of
facilities with 33; Pennsylvania and Michigan have the next largest number with 21 and 19 sites,
respectively.119
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5.5.2 Process Description
The first step in the process of sewage sludge incineration is dewatering the
sludge. Sludge is generally dewatered until it is about 15 to 30 percent solids, at which point it
will burn without supplemental fuel. After dewatering, the sludge is sent to the incinerator for
combustion. The two main types of SSIs currently in use are the multiple-hearth furnace (MHF)
and the fluidized-bed combustor (FBC). Over 80 percent of the identified operating SSIs are
MHFs and about 15 percent are FBCs. The remaining SSIs co-fire MSW with sludge.120
Multiple-Hearth Furnaces
In most MHFs, partially dewatered sludge is fed onto the perimeter of the top
hearth. The rabble arms move the sludge through the incinerator by raking the sludge toward the
center shaft, where it drops through holes located at the center of the hearth. In the next hearth,
the sludge is raked in the opposite direction. This process is repeated in all of the subsequent
hearths. The effect of the rabble motion is to break up solid material to allow better surface
contact with heat and oxygen. A sludge depth of about 1 inch is maintained in each hearth at the
design sludge flow rate.
Under normal operating conditions, 50 to 100 percent excess air must be added to
an MHF to ensure complete combustion of the sludge. Besides enhancing contact between the
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Figure 5-10. Typical Multiple-Hearth Furnace
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fuel and the oxygen in the furnace, these relatively high rates of excess air are necessary to
compensate for normal variations in both the organic characteristics of the sludge feed and the
rate at which it enters the incinerator. When an inadequate amount of excess air is available, only
partial oxidation of the carbon will occur, with a resultant increase in emissions of CO, soot, and
hydrocarbons. Too much excess air, on the other hand, can cause increased entrainment of
particulate and unnecessarily high auxiliary fuel consumption.120
Fluidized-Bed Combustors
Partially dewatered sludge is fed into the lower portion of the furnace. Air injected
through the tuyeres at a pressure of 3 to 5 pounds per square inch gauge (20 to 35 kilopascals)
simultaneously fluidizes the bed of hot sand and the incoming sludge. Temperatures of 1,400 to
1,700EF (750 to 925EC) are maintained in the bed. As the sludge burns, fine ash particles are
carried out of the top of the furnace. Some sand is also removed in the air stream and must be
replaced at regular intervals.
Combustion of the sludge occurs in two zones. Within the sand bed itself (the first
zone), evaporation of the water and pyrolysis of the organic materials occur nearly simultaneously
as the temperature of the sludge is rapidly raised. In the freeboard area (the second zone), the
remaining free carbon and combustible gases are burned. The second zone functions essentially as
an afterburner.
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Figure 5-11. Fluidized-Bed Combustor
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Fluidization achieves nearly ideal mixing between the sludge and the combustion
air; the turbulence facilitates the transfer of heat from the hot sand to the sludge. A FBC
improves the burning atmosphere, such that a limited amount of excess air is required for
complete combustion of the sludge. Typically, FBCs can achieve complete combustion with 20 to
50 percent excess air, about half the excess air required by MHFs. As a consequence, FBCs
generally have lower fuel requirements than MHFs.120
The emission rates of lead in SSIs are affected by the following conditions:
Clearly, the quantity of lead in the feed sludge is the basic scalar of emissions.
Lead in sludge arises from several sources, including industrial discharges (especially plating
wastes), corrosion of outtake plumbing materials, street runoff (especially deposited lead
compounds from lead-containing paints), and numerous lesser domestic and industrial activities.
The lead content varies from day to day, reflecting a diversity of waste types.
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3. Collection of the lead condensed on the PM occurs while passing through
the APCD system.
5.5.3 Emissions
Table 5-22 presents lead emission factors for SSIs. The factors presented cover
the two main incinerator types: MHFs and FBCs. Again, as the emission factor tables for the
other types of incinerators (previously discussed) show, PM type control technologies offer the
greatest efficiency for reducing lead emissions.
Medical waste incinerators (MWIs) burn both infectious (“red bag” and
pathological) medical wastes and non-infectious general hospital wastes. The primary purposes of
MWIs are to (1) render the waste innocuous, (2) reduce the volume and mass of the waste, and
(3) provide waste-to-energy conversion.
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TABLE 5-22. LEAD EMISSION FACTORS FOR SEWAGE SLUDGE INCINERATOR SOURCES
There are an estimated 6,000 MWIs in the United States, located at such facilities
as hospitals, pharmaceutical companies, research facilities, nursing homes, and other institutions
and companies that incinerate medical waste.55 It is estimated that 90 percent of the nation's
6,872 hospitals (where the majority of MWIs are located) have some type of on-site incinerator, if
only a small unit for incinerating special or pathological waste.55
Controlled-Air Incinerators
Controlled-air incineration is the most widely used MWI technology, and now
dominates the market for new systems at hospitals and similar medical facilities. This technology
is also known as two-stage incineration or modular combustion. Figure 5-12 presents a schematic
diagram of a typical controlled-air unit.121
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Figure 5-12. Controlled-Air Incinerator
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At these conditions, combustion gas temperatures are relatively low (1,400 to 1,800EF [760 to
980EC]).121
In the second stage, excess air is added to the volatile gases formed in the primary
chamber to complete combustion. Secondary chamber temperatures are higher than primary
chamber temperatures--typically 1,800 to 2,000EF (980 to 1,095EC). Depending upon the
heating value and moisture content of the waste, additional heat may be needed. Additional heat
can be provided by auxiliary burners located at the entrance to the secondary (upper) chamber to
maintain desired temperatures.121
Excess-Air Incinerators
Excess-air incinerators are typically small, modular units. They are also referred to
as batch incinerators, multiple-chamber incinerators, or “retort” incinerators. Excess-air
incinerators are typically a compact cube with a series of internal chambers and baffles. Although
they can be operated continuously, they are usually operated in batch mode.121
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Figure 5-13. Excess-Air Incinerator
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are vaporized and pass (along with combustion gases) out of the primary chamber and through a
flame port that connects the primary chamber to the secondary or mixing chamber. Secondary air
is added through the flame port and is mixed with the volatile components in the secondary
chamber. Burners are also installed in the secondary chamber to maintain adequate temperatures
for combustion of volatile gases. Gases exiting the secondary chamber are directed to the
incinerator stack or to an air pollution control device. After the chamber cools, ash is manually
removed from the primary chamber floor and a new charge of waste can be added.121
Incinerators designed to burn general hospital waste operate at excess air levels of
up to 300 percent. If only pathological wastes are combusted, excess air levels near 100 percent
are more common. The lower excess air helps maintain higher chamber temperature when
burning high-moisture waste. Waste feed capacities for excess-air incinerators are usually
500 lb/hr (3.8 kg/min) or less.121
Rotary kiln incinerators are also designed with a primary chamber, where the waste
is heated and volatilized, and a secondary chamber, where combustion of the volatile fraction is
completed. The primary chamber consists of a slightly inclined, rotating kiln in which waste
materials migrate from the feed end to the ash discharge end. The waste throughput rate is
controlled by adjusting the rate of kiln rotation and the angle of inclination. Combustion air enters
the primary chamber through a port. An auxiliary burner generally is used to start combustion
and maintain desired combustion temperatures.
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Medical waste contains toxic metals such as lead. Lead is found in many materials,
including plastics, paper, inks, and electrical cable insulation. However, the primary source of
lead appears to be plastics. Lead is used to make dyes and stabilizers that protect plastics from
thermal and photo-degradation. The dyes made from lead are used to color plastic bags; thus,
some of the lead emissions from MWIs could be due simply to the “red bags” that infectious
waste is placed in. During incineration, lead only changes forms (chemical and physical states)
but is not destroyed. Lead can be emitted from incinerators on small particles capable of
penetrating deeply into human lungs.122
A majority of lead and other metal emissions is in the form of PM, and a minority
is in vapor form. Particulate emissions of lead from the incineration of medical wastes are
determined by three major factors:
Typically, two strategies are used to minimize metals emissions: (1) combustion
control in the primary chamber so as to inhibit vaporization or entrainment of metals, and
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(2) capture of any metals that do escape by APCDs. Both of these strategies are discussed below.
The key APCD parameters used are specific to the device that is used.
Most new incinerators are starved-air units. The primary chamber is designed to
operate at low temperatures and low gas flow rates. This minimizes the amount of materials
entrained or vaporized.
To ensure that lead emissions are minimized, operators must maintain the primary
chamber at the temperatures and gas flow rates for which it was designed. Usually the only
parameter that system operators can directly control is feed rate. High feed rates can lead to high
temperatures and high gas velocities. Thus, many operators carefully control the feed rate. The
feed rate is reduced when primary temperatures increase. Keeping the temperature low enables
the lead to condense on different sizes of particles, which are then easily trapped by PM control
devices.
APCD Control--When lead reaches the APCD, it is present in one of three forms.
Non-volatile lead is present on large entrained particles. Lead that has vaporized and recondensed
is usually enriched on fly-ash particles with diameters less than 1 micron. Extremely volatile lead
is present as vapor.122 The majority of lead emissions are in the first two forms and are controlled
by PM control devices. Generally, particulate control is a surrogate for lead control in an
incinerator/air pollution control system.55
5.6.3 Emissions
The available lead emission factors for MWIs are presented in Table 5-23. As with
the other types of incinerators, waste composition is a critical factor in the amount of lead emitted
from MWIs.
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TABLE 5-23. LEAD EMISSION FACTORS FOR MEDICAL WASTE COMBUSTION SOURCES
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of waste incinerated.
As with other combustion sources, the presented emission factors are highly
dependent upon the composition of the waste. For example, the difference in the emission factors
presented in Table 5-23 for both a high efficiency and medium efficiency wet scrubber applied to
an MWI is expected to be more a function of the lead content of the waste burned than scrubber
efficiency.
Hazardous waste, as defined by 40 CFR Part 261, includes a wide variety of waste
materials.124 Hazardous wastes are produced in the form of liquids (e.g., waste oils, halogenated
and nonhalogenated solvents, other organic liquids, and pesticides/herbicides) and sludges and
solids (e.g., halogenated and nonhalogenated sludges and solids, dye and paint sludges, resins,
and latex). The lead content of hazardous waste varies widely, but lead could be emitted from the
incineration of any of these types of hazardous waste. Based on a 1986 study, total annual
hazardous waste generation in the United States was approximately 292 million tons (265 million
metric tons).125 Only a small fraction of the waste (less than 1 percent) was incinerated. MACT
standards for hazardous waste combustors and Portland cement manufacturing were proposed
May 2, 1997 and March 24, 1998, respectively. These proposed standards should reduce lead
emissions.
Based on an EPA study conducted in 1983, the major types of hazardous waste
streams incinerated were spent nonhalogenated solvents and corrosive and reactive wastes
contaminated with organics. Together, these accounted for 44 percent of the waste incinerated.
Other prominent wastes included hydrocyanic acid, acrylonitrile bottoms, and nonlisted ignitable
wastes.126
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Industrial kilns, boilers, and furnaces are used to burn hazardous waste. They use
the hazardous waste as fuel to produce commercial products such as cement, lime, iron, asphalt,
or steam. In fact, the majority of hazardous waste generated in the United States is currently
disposed of in cement kilns. Lead emissions from cement kilns are discussed in Section 5.13.
Hazardous waste, which is an alternative to fossil fuels for energy and heat, is used at certain
commercial facilities as a supplemental fuel. In the process of producing energy and heat, the
hazardous wastes are subjected to high temperatures for a sufficient time to volatilize metals in
the waste.
Currently, 162 permitted or interim status incinerator facilities, having 190 units,
are in operation in the United States. Another 26 facilities are proposed (i.e., new facilities under
construction or permitting).127 Of the above 162 facilities, 21 facilities are commercial facilities
that burn about 700,000 tons of hazardous waste annually.128 The remaining 141 are on-site or
captive facilities and burn about 800,000 tons of waste annually.
Five types of hazardous waste incinerators are currently available and in operation:
liquid injection, rotary kiln, fixed-hearth, fluidized-bed, and fume injection.129
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Figure 5-15. Typical Process Component Options in a Hazardous Waste Incineration Facility
Liquid injection combustion chambers are used for pumpable liquid waste,
including some low-viscosity sludges and slurries. Liquid injection units are usually simple,
refractory-lined cylinders (either horizontally or vertically aligned) equipped with one or more
waste burners. The typical capacity of liquid injection units is about 8 to 28 million Btu/hour
(8.4 to 29.5 GJ/hour). Figure 5-16 presents a schematic diagram of a typical liquid injection
unit.125,129
Rotary kiln incinerators are used for destruction of solid wastes, slurries,
containerized waste, and liquids. Because of their versatility, these units are most frequently used
by commercial off-site incineration facilities. Rotary kiln incinerators generally consist of two
combustion chambers: a rotating kiln and an afterburner. The rotary kiln is a cylindrical
refractory-lined shell mounted on a slight incline. The primary function of the kiln is to convert
solid wastes to gases, which occurs through a series of volatilization, destructive distillation, and
partial combustion reactions. The typical capacity of these units is about 10 to 60 million
Btu/hour (10.5 to 63.3 GJ/hour).
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Fluidized-Bed Incinerators
FBCs are suitable for disposing of combustible solids, liquids, and gaseous wastes.
They are not suited for irregular or bulky wastes, tarry solids, or other wastes that leave residues
in the bed.130 Fluidized-bed combustion chambers consist of a single refractory-lined combustion
vessel partially filled with inert granular material (e.g., particles of sand, alumina, and sodium
carbonate).125 The typical capacity of this type of incinerator is 45 million Btu/hour (47.5
GJ/hour).
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The types of incinerators used for hazardous waste combustion are similar to the
incinerators used by the other combustion sources discussed earlier in this section. However, the
components in the hazardous waste stream vary extensively. The hazardous waste stream may
include a variety of liquid, solid, or sludge wastes considered hazardous by RCRA. The
hazardous waste stream may also include wastes generated by a variety of sources (e.g., medical,
municipal, and sewage sludge).
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5.7.3 Emissions
Lead emissions have been detected in the stack gases from drum reclamation
facilities.132 These facilities typically consist of a furnace that is used to heat the drums to an
elevated temperature in order to destroy any residual materials in the containers. The drums are
then repaired, repainted, relined, and sold for reuse. The drums processed at these facilities come
from a variety of sources, such as the petroleum and chemical industries.133
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The furnaces are fired by an auxiliary fuel such as oil or natural gas. The used
drums are typically loaded onto a conveyor, which carries them through the heat treatment zone.
As the drums proceed through this process, any residual contents, paint, and interior linings are
burned off or disintegrated. Lead formation can occur from either the heat treatment of the
barrels or from the combustion of the auxiliary fuel.
5.8.3 Emissions
Only one test report was found that measured emissions of specific lead
compounds from a drum reclamation facility.132 The tested facility recycles 55-gallon drums. No
information was available concerning the physical or chemical characteristics of the residual waste
in the drums or of the auxiliary fuel type used to fire the furnace. The drum furnace consists of a
boiler at 1400EF (760EC) and an afterburner at 1600EF (871EC) as an emissions control device.
Table 5-24 shows the lead emission factor developed for this facility.
The emission factor for drum reclamation should be used cautiously because the
nature of the residual waste product can vary greatly from facility to facility, which will likely
affect lead emissions. The type of auxiliary fuel used can also have a significant effect on lead
emissions from these facilities.
Most facilities that burn scrap tires use the tires to supplement a primary fuel, such
as wood. This section addresses only those facilities that burn scrap tires as their sole fuel. The
primary purpose of these facilities is to recover energy from the combustion of scrap tires.
The EPA's Office of Solid Waste has estimated that approximately 26 million scrap
tires were incinerated in the United States in 1990.134 This equates to approximately
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TABLE 5-24. LEAD EMISSION FACTORS FOR DRUM AND BARREL RECLAMATION SOURCES
The tires are burned on reciprocating stoker grates in the combustion chamber at
the bottom of the boilers. The grate configuration allows air flow above and below the tires,
which aids in complete combustion. The boilers are operated above 2,000EF (1,093EC) to ensure
complete combustion of organic compounds emitted by the burning tires. The heat generated by
the burning of the tires causes the water contained in the pipes of the refractory brickwork that
lines the boiler to turn into steam. The high-pressure steam is then forced through a turbine for
the generation of power. After exiting the boiler chamber, exhaust gases pass through the large
fabric filter.
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5.9.3 Emissions
Although no lead emission factors were identified specifically for scrap tire
incinerators, this source category is included as a potential source of lead emissions. Lead
emission factors for open burning of scrap tires are identified in Section 5.10, “Open Burning of
Scrap Tires.” The data presented in that section show that lead is a component of tires and, as a
result, is emitted from the combustion of tires. It is expected that lead emissions are also present
in emissions from incinerators that burn scrap tires. However, because of differences in the
combustion and APCD design and operation, emission factors from open burning of scrap tires
are not representative of scrap tire incinerators.
Open burning of scrap tires can occur at permitted landfills that stockpile scrap
tires, at closed landfills that already contain scrap tires, and at illegal dumpsites where tires are
discarded. The fires can start by accident or are intentionally set by arsonists, and thus are often
unpredictable as to where and when they will occur.
Approximately 240 million vehicle tires are discarded annually.136 Although viable
methods for recycling exist, less than 25 percent of discarded tires are recycled; the remaining
175 million are discarded in landfills, stockpiles, or illegal dumps.136 Although it is illegal in many
States to dispose of tires by open burning, fires often occur at tire stockpiles and through illegal
burning activities. These fires generate a huge amount of heat and are difficult to extinguish
(some tire fires continue for months). Lead is a component of tires and is emitted from the
combustion of these tires.
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5.10.3 Emissions
Table 5-25 contains emission factors for the open burning of tires.137 The average
emission factor presented represents the average of tests performed on the simulated open burning
of chunk (defined as one-quarter or one-sixth of an entire tire) and shredded tires. When
estimating emissions from an accidental tire fire, note that emissions from burning tires are
generally dependent on the burn rate of the tire.
5.11 CREMATORIES
In 1991, there were about 400,000 cremations in more than 1,000 crematories
located throughout the United States. Table 5-26 lists the number of crematories located in each
State and the estimated number of cremations performed in each State.138
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TABLE 5-25. LEAD EMISSION FACTORS FOR OPEN BURNING OF SCRAP TIRES
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The human remains and cremation container, generally made of cardboard or
wood, are loaded onto the primary chamber hearth and the primary burner is ignited to begin the
cremation process. The remains may be raked at the midpoint of the cremation to uncover
unburned material and speed the process. The average cremation takes from 1 1/2 to 3 hours,
after which the incinerator is allowed to cool for a period of at least 30 minutes so that the
remains can be swept from the hearth.139
5.11.3 Emissions
Sampling, recovery, and analysis for lead were performed in accordance with
CARB Method 436. Emission factors developed from these data are presented in Table 5-27.
Four processes associated with the pulp and paper industry have been identified as
potential sources of lead emissions: chemical-recovery furnaces, smelt-dissolving tanks, lime
kilns, and power boilers. The following sections focus on the pulp mill thermal chemical-recovery
processes associated with potential lead emissions. Lead emissions from wood waste
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TABLE 5-27. LEAD EMISSION FACTOR FOR CREMATORIES
Note: Average weight per body incinerated: body = 141 lb (64 kg); wrapping material = 4 lb (2 kg) cardboard, 3 lb (1.4 kg) wood.
a
Emission factors are in lb (kg) per body.
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and fossil fuel-fired industrial power boilers are not specific to the pulp and paper industry; see
Section 5.1.
Source Location
The distribution of kraft pulp mills in the United States in 1997 is shown in
Table 5-28. Kraft pulp mills are located primarily in the southeast, whose forests provide over
60 percent of U.S. pulpwood.
Process Description
The kraft pulping process involves the cooking or digesting of wood chips at an
elevated temperature (340 to 360EF [about 175EC]) and pressure (100 to 135 psig) in white
liquor, which is a water solution of sodium sulfide (Na2S) and sodium hydroxide (NaOH). The
lignin that binds the cellulose fibers is chemically dissolved by the white liquor in a tall, vertical
digester. This process breaks the wood into soluble lignin and alkali-soluble hemicellulose and
insoluble cellulose or pulp. A typical kraft pulping and recovery process is shown in Figure 5-19.
Two types of digester systems are used in chemical pulping: batch and continuous.
In a batch digester, the contents of the digester are transferred to an atmospheric tank (usually
referred to as a blow tank) after cooking is completed (2 to 6 hours). In a continuous digester,
wood chips and white liquor continuously enter the system from the top while pulp is
continuously withdrawn from the bottom into a blow tank. In both types of digesters, the entire
contents of the blow tank are diluted and pumped to a series of brownstock washers, where the
spent cooking liquor is separated from the pulp. The pulp, which may then be bleached, is
pressed and dried into the finished product.
5-101
TABLE 5-28. DISTRIBUTION OF KRAFT PULP MILLS IN THE
UNITED STATES (1997)
5-102
5-103
In older recovery furnaces, the furnace's hot combustion gases concentrate the
black liquor in a DCE prior to combustion. NDCEs include most furnaces built since the early
1970s and modified older furnaces that have incorporated recovery systems that eliminate
conventional DCEs. These NDCEs use a concentrator rather than a DCE to concentrate the
black liquor prior to combustion. In another type of NDCE system, the multiple-effect
evaporator system is extended to replace the direct contact system.
The strong black liquor is sprayed into a recovery furnace with air control to
create both reducing and oxidizing zones within the furnace chamber. The combustion of the
organics dissolved in the black liquor provides heat for generating process steam and, more
importantly, for reducing sodium sulfate (Na2SO4) to Na2S to be reused in the cooking process.
Na2SO4, which constitutes the bulk of the particulates in the furnace flue gas, is recovered and
recycled by an ESP. After combustion, most of the inorganic chemicals present in the black
liquor collect as a molten smelt (containing sodium carbonate [Na2CO3] and Na2S) at the bottom
of the furnace, where they are continuously withdrawn into a smelt-dissolving tank. Molten smelt
in the smelt-dissolving tank is contacted with mill water or weak wash (the filtrate from lime mud
washing) to form green liquor.
5-104
5-105
Particulate emissions from the kraft recovery furnaces consist primarily of Na2SO4
and Na2CO3, with some sodium chloride. Particulate emissions also contain lead, but only in
minute quantities because lead is found as a contaminant in process chemicals and in trace
amounts in wood. Particulate control and, therefore, lead control on recovery furnaces is
achieved with ESPs, including both wet- and dry-bottom and, to a lesser extent, with scrubbers.
Further particulate control is necessary for DCEs equipped with either a cyclonic scrubber or a
cascade evaporator because these devices are generally only 20 to 50 percent efficient for
particulates.145 Most often in these cases, an ESP is employed after the DCE for an overall
particulate control efficiency range of 85 percent to more than 99 percent. At existing mills,
auxiliary scrubbers may be added to supplement older and less efficient primary particulate control
devices. No specific data were available in the literature documenting lead control efficiencies for
ESPs and scrubbers on kraft black liquor recovery furnaces.
Emissions
Emission factors for lead from kraft recovery furnaces were developed from data
provided by the National Council for Air and Stream Improvement, an industry environmental
research organization.147,148 Kraft furnace/control configurations represented included a DCE
recovery furnace equipped with an ESP and scrubber in series, a DCE recovery furnace equipped
5-107
with only an ESP, an NDCE recovery furnace equipped with an ESP and scrubber in series, and
an NDCE recovery furnace equipped with only an ESP. Emissions data were also provided for
smelt-dissolving tanks (3). Lead emission factors for kraft black liquor recovery furnaces and
smelt-dissolving tanks are presented in Table 5-29.
Source Location
Lime kilns are located at kraft process pulp mills. (See Table 5-28 for kraft pulp
mill source locations reported in 1993.)
Process Description
In the kraft process, green liquor from the smelt-dissolving tanks is clarified and
reacted with burnt lime (CaO) in a lime slaker. Following a series of causticizing vessels, the
resultant white liquor is clarified to yield Na2S + NaOH (aqueous white liquor) and lime mud or
calcium carbonate (CaCO3). The white liquor is recycled to the digestion process and the lime
mud is calcined in a lime kiln to regenerate CaO.146
A lime kiln is a counter current, inclined tube process heater designed to convert
lime mud (CaCO3) to CaO for reuse in the causticizing of kraft liquor. A process flow diagram
for a lime kiln is shown in Figure 5-22. The rotary kiln is the most common lime kiln design used
in the kraft pulp and paper industry. Rotary lime kilns range from 8 to 13 ft (2.4 to 4.0 m) in
diameter, and from 100 to 400 ft (30 to 120 m) in length. Lime kilns predominantly fire natural
gas, with some units firing distillate and/or residual fuel oil. Many facilities incinerate
non-condensible gases (NCG) from pulping source vents in lime kilns to control total reduced
sulfur (TRS) emissions. Temperatures in the kiln can range from 300 to 500EF (150 to 260EC) at
the upper or wet end to 2200 to 2400EF (1200 to 1300EC) at the hottest part of the calcination
zone near the lower or dry end.146,149
5-108
TABLE 5-29. LEAD EMISSION FACTORS FOR KRAFT PROCESS RECOVERY FURNACES AND
SMELT DISSOLVING TANKS
a
Emission factors are in lb (kg) of pollutant emitted per million tons (Mg) of black liquor solids (BLS) processed.
Emissions
Lead emission factors for uncontrolled and scrubber-controlled lime kilns are
presented in Table 5-30.
Source Location
Sulfite recovery furnaces are located at sulfite process pulp mills. Table 5-31
shows the distribution of sulfite pulp mills in the United States in 1997 according to information
compiled in support of EPA's pulp and paper industry MACT standard development.
Process Description
Although not as commonplace, the acid sulfite pulp production process is similar
to the kraft process except that different chemicals are used for cooking. Sulfurous acid is used in
place of a caustic solution to dissolve wood lignin. To buffer the cooking solution, a bisulfite of
sodium, magnesium, calcium, or ammonium is used. Digestion occurs under high temperature
and pressure, as in the kraft process, in either batch mode or continuous digesters. Following
digestion and discharge of the pulp into an atmospheric blow pit or dump tank, the spent sulfite
5-111
TABLE 5-30. LEAD EMISSION FACTORS FOR LIME KILNS
a
Emission factors in lb (kg) per air dry ton (Mg) of pulp produced.
b
Emission factors in lb (kg) per million tons (Mg) of calcium oxide (lime) produced.
liquor, known as red liquor, may be treated and discarded, incinerated, or sent through a recovery
process for recovery of heat and chemicals. Additionally, chemicals can be recovered from
gaseous streams such as those from red stock washers. The cost of the soluble bases, with the
exception of calcium, makes chemical recovery economically feasible.141,145 A simplified process
schematic of magnesium-based sulfite pulping and chemical recovery is shown in Figure 5-23.
Chemical recovery in the sulfite process involves the concentration of weak red
liquor in multiple effect evaporators and DCEs to strong red liquor (55 to 60 percent solids).
This liquor is sprayed into a furnace and burned, producing steam for mill processes. When
magnesium-base liquor is burned, magnesium oxide is recovered from the flue gas in a
multicyclone. The collected magnesium oxide is then water-slaked and used as circulation liquor
in a series of venturi scrubbers designed to absorb SO2 from the flue gas to form bisulfite solution
for use in the cook cycle.
5-113
5-114
Figure 5-23. Process Diagram for Magnesium-Based Sulfite Pulping and Chemical Recovery
Emissions
As with the kraft process, lead exists only as a contaminant in process chemicals
and in trace amounts in wood and is, therefore, found in minute quantities. Only one emission
factor was available in the literature for lead from an uncontrolled sulfite recovery furnace. The
lead emission factor is presented in Table 5-32.
Two processes, the wet and dry processes, can be used to manufacture Portland
cement. Based on 1990 U.S. cement kiln capacity data, an estimated 68 percent of Portland
cement is manufactured using the dry process. A description of the wet and dry processes and the
emissions resulting from the various operations is presented below.
In 1990, there were a total of 212 U.S. cement kilns with a combined total clinker
capacity of 81.1x106 tons (73.5x106 Mg). Of this total, 11 kilns with a combined capacity of
2.0x106 tons (1.8x106 Mg) were inactive. More than 30 raw materials are used to manufacture
Portland cement. These materials can be classified into four basic classes of raw materials:
calcarious, siliceous, argillaceous, and ferriferous. The 201 active kilns had a clinker capacity of
5-115
TABLE 5-32. LEAD EMISSION FACTORS FOR SULFITE PROCESS RECOVERY FURNACES
Figure 5-24 presents a basic flow diagram of the Portland cement manufacturing
process. The process can be divided into four major steps: raw material acquisition and handling,
kiln feed preparation, pyroprocessing, and finished cement grinding.
The second step involves preparation of the raw materials for pyroprocessing
(thermal treatment). Raw material preparation includes a variety of blending and sizing
operations designed to provide a feed with appropriate chemical and physical properties. The raw
material processing differs for wet processes and dry processes. At facilities where the dry
process is used, the moisture content in the raw material, which can range from less than
1 percent to greater than 50 percent, is reduced to less than 1 percent. Lead emissions can occur
during this drying process, but are anticipated to be very low because the drying temperature is
much below the boiling point of lead. At some facilities, heat for drying is provided by the
exhaust gases from the pyroprocessor. At facilities where the wet process is used, water is added
to the raw material during the grinding step, thereby producing a pumpable slurry containing
approximately 65 percent solids.
5-117
TABLE 5-33. PORTLAND CEMENT PRODUCTION FACILITIES
Clinker capacitya
Company and location No./type of kiln 103 Mg/yr 103 tons/yr
Alamo Cement Co.
San Antonio, TX 1-Dry 680 750
Allentown Cement Co., Inc.
Blandon, PA 2-Dry 844 930
Armstrong Cement & Sup. Co.
Cabot, PA 2-Wet 281 310
Ash Grove Cement Co.
Nephi, UT 1-Dry 544 600
Louisville, NE 2-Dry 872 961
Durkee, OR 1-Dry 454 500
Foreman, AR 3-Wet 857 945
Montana City, MT 1-Wet 254 280
Chanute, KS 2-Wet 450 496
Inkom, ID 2-Wet 191 210
Blue Circle, Inc.
Ravena, NY 2-Wet 1,390 1,532
Atlanta, GA 2-Dry 555 612
Tulsa, OK 2-Dry 544 600
Calera, AL 2-Dry 544 600
Boxcrow Cement
Midlothian, TX 1-Dry 907 1,000
Calaveras Cement Co.
Redding, CA 1-Dry 591 651
Tehachapi, CA 1-Wet 386 425
California Portland Cement
Mojave, CA 1-Dry 943 1,039
Colton, CA 2-Dry 680 750
Rillito, AZ 4-Dry 966 1,065
5-118
TABLE 5-33. PORTLAND CEMENT PRODUCTION FACILITES (CONTINUED)
Clinker capacitya
Company and location No./type of kiln 103 Mg/yr 103 tons/yr
Continental Cement Co., Inc.
Hannibal, MO 1-Wet 544 600
Dixon-Marquette
Dixon, IL 4-Dry 475 524
Dragon Products Company
Thomaston, ME 1-Wet 413 455
Essroc Materials
Nazareth, PA 1-Dry 874 963
Speed, IN 2-Dry 863 951
Bessemer, PA 1-Dry/1-Wet 295/191 325/211
Frederick, MD 2-Wet 336 370
Logansport, IN 2-Wet 367 404
Florida Crushed Stone
Brooksville, FL 1 - Dry 518 571
Giant Cement Company
Harleyville, SC 4 - Wet 789 870
Gifford-Hill & Co., Inc.
Harleyville, SC 1 - Dry 560 617
Oro Grande, CA 7 - Dry 1,041 1,148
Riverside, CA 2 - Dry 100 110
Glens Falls Cement Co.
Glens Falls, NY 1-Dry 450 495
Hawaiian Cement Company
Ewa Beach, HI 1-Dry 239 263
5-119
TABLE 5-33. PORTLAND CEMENT PRODUCTION FACILITES (CONTINUED)
Clinker capacitya
Company and location No./type of kiln 103 Mg/yr 103 tons/yr
Holnam, Inc.
Theodore, AL 1-Dry 1,308 1,442
Clarksville, MO 1-Wet 1,190 1,312
Holly Hill, SC 2-Wet 991 1,092
Mason City, IA 2-Dry 806 888
Florence, CO 3-Wet 780 860
Fort Collins, CO 1-Dry 448 494
Dundee, MI 2-Wet 880 970
Artesia, MS 1-Wet 457 504
Seattle, WA 1-Wet 429 473
Three Forks, MT 1-Wet 283 312
Ada, OK 2-Wet 544 600
Tijeras, NM 2-Dry 448 494
Saratoga, AR 2-Wet 335 369
Morgan, UT 2-Wet 298 328
Independent Cement Corp.
Catskill, NY 1-Wet 464 512
Hagerstown, MD 1-Dry 452 498
Kaiser Cement Corp.
Permanente, CA 1-Dry 1,452 1,600
Keystone Cement Company
Bath, PA 2-Wet 546 602
Kosmos Cement Co.
Louisville, KY 1-Dry 657 724
Pittsburgh, PA 1-Wet 357 394
LaFarge Corporation
New Braunfels, TX 1-Dry 865 954
Buffalo, IA 1-Dry 778 858
Demopolis, AL 1-Dry 655 722
Grand Chain, IL 2-Dry 1,076 1,186
Alphena, MI 5-Dry 1,773 1,954
Whitehall, PA 3-Dry 689 760
Sugar Creek, MO 2-Dry 437 482
Paulding, OH 2-Wet 445 490
Fredonia, KS 2-Wet 347 382
Lehigh Portland Cement
Mason City, IA 1-Dry 689 760
Leeds, AL 1-Dry 591 651
Cementon, NY 1-Wet 506 558
Union Bridge, MD 4-Dry 900 992
Mitchell, IN 3-Dry 689 760
York, PA 1-Wet 90 99
Waco, TX 1-Wet 73 81
5-120
TABLE 5-33. PORTLAND CEMENT PRODUCTION FACILITES (CONTINUED)
Clinker capacitya
Company and location No./type of kiln 103 Mg/yr 103 tons/yr
Lone Star Industries
Cape Girardeau, MO 1-Dry 1,002 1,104
Greencastle, IN 1-Wet 649 715
Oglesby, IL 1-Dry 422 465
Pryor, OK 3-Dry 623 687
Nazareth, PA 4-Dry 565 623
Sweetwater, TX 3-Dry 449 495
Medusa Cement Co.
Charlevoix, MI 1-Dry 1,237 1,364
Clinchfield, GA 1-Dry/1-Wet 508/187 560/206
Wampum, PA 3-Dry 638 703
Mitsubishi Cement Corp.
Lucerne Valley, CA 1-Dry 1,514 1,669
Monarch Cement Company
Humboldt, KS 3-Dry 611 674
Des Moines, IA 2-Wet 272 300
National Cement Company
Ragland, AL 1-Dry 767 845
Natl. Cement Co. of California
Lebec, CA 1-Dry 590 650
North Texas Cement
Midlothian, TX 3-Wet 816 900
Phoenix Cement Company
Clarkdale, AZ 3-Dry 640 705
Rinker Portland Cement Corp.
Miami, FL 2-Wet 512 564
River Cement Company
Festus, MO 2-Dry 1,070 1,179
RMC Lonestar
Davenport, CA 1-Dry 726 800
Roanoke Cement Company
Cloverdale, VA 5-Dry 1,013 1,117
Signal Mountain Cement Co.
Chattanooga, TN 2-Wet 408 450
South Dakota Cement
Rapid City, SD 1-Dry/2-Wet 408/287 450/316
5-121
TABLE 5-33. PORTLAND CEMENT PRODUCTION FACILITES (CONTINUED)
Clinker capacitya
Company and location No./type of kiln 103 Mg/yr 103 tons/yr
Southdown, Inc.
Victorville, VA 2-Dry 1,406 1,550
Brooksville, FL 2-Dry 1,089 1,200
Knoxville, TN 1-Dry 544 600
Fairborn, OH 1-Dry 553 610
Lyons, CO 1-Dry 408 450
Odessa, TX 2-Dry 499 550
St. Mary's Peerless Cement Co.
Detroit, MI 1-Wet 533 610
Tarmac Florida, Inc.
Medley, FL 3-Wet 933 1,028
Texas Industries
New Braunfels, TX 1-Dry 689 759
Midlothian, TX 4-Wet 1,139 1,256
Texas-Lehigh Cement Co.
Buda, TX 1-Dry 895 987
Total capacity reported 135-Dry/79-Wet 73,532 81,056
a
Kilns reported as inactive in 1990: Clinker capacity
103 Mg/year 103 tons/year
5-122
5-123
4. Reaction of the oxides in the burning zone of the rotary kiln to form
cement clinker at temperatures of about 2,750EF (1,510EC).
The rotary kiln is a long, cylindrical, slightly inclined, refractory-lined furnace. The
raw material mix is introduced into the kiln at the elevated end, and the combustion fuels are
usually introduced into the kiln at the lower end in a countercurrent manner. The rotary motion
of the kiln transports the raw material from the elevated end to the lower end. Fuel such as coal
or natural gas, or occasionally oil, is used to provide energy for calcination. Lead is present in
coal and oil. Use of other fuels such as chipped rubber, petroleum coke, and waste solvents is
becoming increasingly popular.
5-124
Pyroprocessing can be carried out using one of five different processes: wet, semi-
dry, dry, dry with a preheater, and dry with a preheater/precalciner. These processes essentially
accomplish the same physical and chemical steps described above. The last step in the
pyroprocessing is the cooling of the clinker. This step recoups up to 30 percent of the heat input
to the kiln system, locks in desirable product qualities by freezing mineralogy, and makes it
possible to handle the cooled clinker with conventional conveying equipment. Finally, after the
cement clinker is cooled, a sequence of blending and grinding operations is carried out to
transform the clinker into finished Portland cement.
With the exception of the pyroprocessing operations, the emission sources in the
Portland cement industry can be classified as either process emissions or fugitive emissions. The
primary pollutant resulting from the fugitive sources is PM, which contains a fraction of lead. The
control measures used for these fugitive dust sources are comparable to those used throughout
the mineral products industries.
Process fugitive emission sources include materials handling and transfer, raw
milling operations in dry process facilities, and finish milling operations. Typically, particulate
emissions from these processes are captured by a ventilation system vented to fabric filters.
Because the dust from these units is returned to the process, they are considered to be process
units as well as air pollution control devices. The industry uses shaker, reverse air, and pulse jet
filters, as well as some cartridge units, but most newer facilities use pulse jet filters. For process
fugitive operations, the different systems are reported to achieve typical outlet PM loadings of
0.02 grains per actual cubic foot (gr/acf) (45 milligrams per cubic meter [mg/m3]). Because the
lead is in particle form, the performance of these systems relative to lead control is expected to be
equivalent to this overall particulate performance. However, no data are available on lead
performance of fugitive control measures.
5-125
control kiln exhausts are reported to achieve outlet PM loadings of 0.02 gr/acf (45 mg/m3).
Clinker cooler systems are controlled most frequently with pulse jet or pulse plenum fabric filters.
A few gravel bed filters have been used on clinker coolers.
5.13.4 Emissions
Lead emission factor data are presented in Table 5-34. The principal source of
lead emissions is expected to be from the kiln. The majority of the lead input from the raw
materials and fuels is incorporated into the clinker. Lead volatilized from the kiln is either
removed in the bypass gases, the preheater, or the APCD. Small quantities of emissions would be
expected during raw materials processing and mixing in the form of fugitive dust containing
naturally occurring quantities of lead compounds in raw materials.
Processing steps that occur after the calcining process in the kiln would be
expected to be a much smaller source of emissions than the kiln. Emissions resulting from all
processing steps include particulate matter. Additionally, emissions from the pyroprocessing step
include other products of fuel combustion such as sulfur dioxide (SO2), nitrogen oxides (NOx),
carbon dioxide (CO2), and carbon monoxide (CO). Carbon dioxide from the calcination of
limestone will also be present in the flue gas.
5-126
TABLE 5-34. LEAD EMISSION FACTORS FOR PORTLAND CEMENT MANUFACTURING FACILITIES
Grinding (2.00x10-2)b
3-05-006-22 Dry Process Preheater FF 7.50x10-5 --- D 155
Kilns (3.75x10-5)a
ESP 7.10x10-4 --- D 155
(3.55x10-4)a
3-05-006-23 Dry Process Preheater/ FF 7.50x10-5 --- D 155
Precalcinator Kiln (3.75x10-5)a
ESP 7.10x10-4 --- D 155
(3.55x10-4)a
3-05-007-06 Wet Process Kilns ESP 7.10x10-4 --- D 155
(3.55x10-4)a
FF 7.50x10-5 --- D 155
(3.75x10-5)a
None 1.00x10-1 --- U 23
(5.00x10-2)b
TABLE 5-34. LEAD EMISSION FACTORS FOR PORTLAND CEMENT MANUFACTURING FACILITIES (CONTINUED)
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of cement produced.
b
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of clinker produced.
The most recent estimate available for the amount of lead used in the manufacture
of glass and ceramics in the United States is from 1986. During that year, 44,960 tons
(40,800 Mg) of lead were consumed.156 Based on an average lead content of 28 percent for
leaded glasses, an estimated 160,500 tpy (145,700 Mg/yr) of leaded glass were produced.
C Brilliance;
C High density;
C High durability.157
6-1
Lead glass is basically composed of silica sand and lead oxide. The lead oxide content usually
ranges from 12 to 60 percent, although some types may contain as much as 92 percent lead oxide.
The following three basic operations are performed in all leaded glass
manufacturing facilities:
C Melting; and
C Forming.
A generic process flow diagram for leaded glass manufacturing facilities is shown in Figure 6-1.
First, raw material, including silica sand, limestone, soda ash, and litharge (PbO)
are received separately at a production facility called a batch plant. The coarse materials are
crushed and stored in segregated bins, transferred to a weigher, and then mixed with cullet
(recycled glass) to ensure homogeneous melting. Batch weighing and mixing systems may be
operated manually or may be fully automated. In preparing the high-density components for
manufacturing leaded glass, most plants use high-intensity, rotating-barrel type mixers, which
tumble the batch upon itself in a revolving drum or double cone. The mixture is held in a batch
storage bin until it is fed to the melting furnace.
6-2
TABLE 6-1. GLASS MANUFACTURERS (SIC 3229) IN THE UNITED STATES
REPORTING LEAD AND LEAD COMPOUND EMISSIONS UNDER SARA 313
Facility Location
Corning Asahi Video Products Co.a State College, PA
Corning Inc. Fall Brook Plant Corning, NY
Corning Inc. Stueben Plant Corning, NY
Corning, Inc. Danville, VA
General Electric Company Niles, OH
GTE Products Corporation Central Falls, RI
Versailles, KY
Lancaster Glass Corporationb Lancaster, OH
Lenox Crystal, Inc. Mount Pleasant, PA
OI-NEG TV Products, Inc.a Columbus, OH
Perrysburg, OH
Pittston, PA
Schott Glass Technologies, Inc. Duryea, PA
St. George Crystal Ltd. Jeannette, PA
Thomson Consumer Electronicsa Circleville, OH
Total
6-3
6-4
Figure 6-1. Glass Manufacturing Process
Finally, the molten material is drawn from the furnace and worked on forming
machines by a variety of methods, including pressing, blowing, drawing, or rolling to produce the
desired product.
6.1.3 Emissions
Air emissions from leaded glass manufacturing occur in three areas: raw material
blending and transport, melting, and forming and finishing. Fugitive dust is produced by the
blending and transport process. In most cases, fabric filters are used on silos and the transport
system to confine the particulate emissions. Lead emissions from the raw material preparation
and forming and finishing operations are generally considered to be negligible.
The glass melting furnace is the principal source of lead emissions from a glass
plant. The main lead compounds found in the furnace discharges are lead carbonates from
6-5
gas-heated furnaces and lead sulfates from liquid fuel-fired furnaces.162 The composition and rate
of emissions from glass melting furnaces vary considerably, depending upon the composition of
glass being produced and, to a lesser extent, upon the design and operating characteristics of the
furnace. Emissions consist primarily of products of combustion and entrained PM.
The use of fully electric furnaces is estimated to reduce lead compound emissions
by a factor of 4 to 10.162 Other methods used to control emissions include:
If these techniques are inadequate for meeting desired emission levels, a baghouse
provides the most effective means of controlling particulate emissions. Collection efficiencies
have exceeded 99 percent on certain types of glass furnaces. Full-scale units are operating with
filtering velocities of 1 to 2 fpm (0.5 to 1 cm/s). Precautions must be taken, however, to address
problems associated with acid gases and high temperatures. SO2 and SO3 in the furnace exhaust
may cause severe acid corrosion, and hot off-gases cause deterioration of the bag material. Bags
made of felted Nomex, silicone-treated glass fiber, and Dacron have been used effectively in these
applications.163
6-6
scrubbers require a pressure drop of over 50 in. H20 (13 kPa) to achieve an efficiency of
approximately 97 percent.163
The composition and rate of emissions from glass melting furnaces vary
considerably, depending on the composition of glass being produced and, to a large extent, on the
design and operating characteristics of the furnace. Emissions consist primarily of products of
combustion and entrained PM.
One emission factor for uncontrolled lead emissions from leaded glass
manufacturing is presented in Table 6-2.160 Based on the type of controls currently used in the
glass manufacturing industry (baghouses, venturi scrubbers, ESPs), an overall control efficiency
of at least 90 percent is expected.
Average Emission
Emission Factor in Emission
SCC Number Source Control Device lb/ton (kg/Mg) Factor Rating
3-05-014 All processes Uncontrolled 5 (2.5) B
Today's major use of lead is in lead-acid storage batteries. The electrical systems
of vehicles, ships, and aircraft depend on such batteries for start-up and, in some cases, batteries
provide the actual motive power. The battery industry is divided into two main production
sectors: starting, lighting, and ignition (SLI) batteries and industrial/traction batteries.
6-7
The Battery Council International (BCI) reported a 1992 SLI battery production
of 81.07 million units. This total includes both original equipment market and replacement market
automotive-type batteries. Using the BCI estimate of about 18-20 lb lead per unit, the lead
consumption for this sector was 768,600 tons. The industrial/traction (stationary/motive power)
sector was estimated to have consumed 220,500 tons of lead.50
Figure 6-2 presents a flow diagram for lead-acid battery production. Lead-acid
storage batteries are produced from lead alloy ingots and lead oxide. The lead oxide may be
produced by the battery manufacturer or may be purchased from a supplier. Lead oxide is
produced either by the ball mill process or the Barton process. Both processes incorporate a
baghouse for product recovery and to control air emissions.
Battery manufacturing begins with grid casting and paste mixing. Battery grids are
manufactured by either casting or stamping operations. In the casting operation, lead alloy ingots
are charged to a melting pot; the molten lead then flows into molds that form the battery grids.
These grids may be connected in a continuous strip (concast) or cast into doublets. The stamping
operation consists of cutting or stamping the battery grids from lead sheets. The paste mixing
operation is conducted in a batch-type process to make paste for application to the grids. A
mixture of lead oxide powder, water, and sulfuric acid produces a positive paste. The negative
paste is made with the same ingredients in slightly different proportions with the addition of an
expander (generally a mixture of barium sulfate, carbon black, and organic fibers). Pasting
machines then force these pastes into the interstices of the grids to make plates. Concast plates
are then cut apart into single plates for curing in a controlled atmosphere.
6-8
TABLE 6-3. LEAD-ACID BATTERY PRODUCTION FACILITIES
Company Locationa
Battery Builders Inc. Naperville, IL
C&D Charter Power Systems, Inc. Leola, PA
Conyers, GA
Attica, IN
Hugeunt, NY
Daniell Battery Mfg. Co. Baton Rouge, LA
Douglas Battery Mfg. Co. Winston-Salem, NC
North Kansas City, MO
Eagle-Picher Ind. Inc. Socorro, NM
East Penn Manufacturing Co., Inc. Lyon Station, PA
Enpak, Inc. Memphis, TN
Exide Corp. Burlington, IA
Frankfurt, IN
Laureldale, PA
Harrisburg, PA
Manchester, IA
Salina, KS
Greer, SC
Bristol, TN
Hawker Energy Prods. Inc. Warrenburg, MO
GMC Delco Remy Division Fitzgerald, GA
Anaheim, CA
Olathe, KS
Muncie, IN
New Brunswick, NJ
6-9
TABLE 6-3. LEAD-ACID BATTERY PRODUCTION FACILITIES (CONTINUED)
Company Locationa
GNB Inc. City of Industry, CA
Farmers Branch, TX
Florence, MS
Kankakee, IL
Columbus, GA
Fort Smith, AR
GNB Inc. ABD Shreveport, LA
GNB Inc. Battery Technologies Inc. Dunmore, PA
GNB Industrial Battery Co. Kansas City, KS
Industrial Battery Eng. Sun Valley, CA
Interspace/Concorde Battery Corp. West Covina, CAb
Johnson Controls Battery Group, Inc. Canby, OR
Holland, OH
Middletown, DE
Geneva, IL
Forton, CA
Tampa, FL
St. Joseph, MO
Winston-Salem, NC
Milwaukee, WI
KW Battery Co. Skokie, IL
Power Battery Co., Inc. Paterson, NJ
Powerflow Sys. Inc. Terrell, TXb
Power Source Inc. Ooltewah, TNb
Ramcar Batteries Inc. City of Commerce, CA
Standard Ind. Inc. San Antonio, TXb
Superior Battery Mfg. Co., Inc. Russell Springs, KY
6-10
TABLE 6-3. LEAD-ACID BATTERY PRODUCTION FACILITIES (CONTINUED)
Company Locationa
Surrette America Northfield, NH
Teledyne Battery Prods. Redlands, CA
Trojan Battery Co. Santa Fe Springs, CA
Lithonia, GA
Universal Tool & Engineering Co. Indianapolis, INb
U.S. Battery Mfg. Inc. Evans, GA
U.S. Battery Mfg. Co. & Battery Corona, CAb
Voltmaster Co., Inc. Corydon, IAb
Yuasa-Exide Inc. Hays, KY
Richmond, KY
Laureldale, PA
Sumter, SC
a
These facilities reported lead emissions during 1993, unless otherwise noted. Lead emissions are in the form of
compounds, most often lead oxides. Lead emissions are not emitted to the air as elemental lead, but they are
measured as lead.
b
Facility reported emissions of lead compounds.
6-11
6-12
Figure 6-2. Process Flow Diagram for Lead-Acid Battery Production
During formation, the inactive lead oxide-sulfate paste is chemically converted into
an active electrode. Lead oxide in the positive plates is oxidized to lead peroxide; in the negative
plates it is reduced to metallic lead. The unformed plates are placed in a dilute sulfuric acid
solution. The positive plates are connected to the positive pole of a direct current (dc) source and
the negative plates are connected to the negative pole of the dc source. In the wet formation
process, the elements are assembled into the battery case before forming. After forming, the spent
acid may be dumped and fresh acid added, and a boost charge is added to complete the battery.
In the dry formation process, the individual plates may be assembled into elements first, and then
formed in large tanks of sulfuric acid or formed as individual plates. The formed elements from
either method are placed in the battery cases, the positive and negative parts of the elements are
connected to the positive and negative terminals of the battery, and the batteries are shipped dry.
Defective parts are either reclaimed at the battery plant or are sent to a secondary
lead smelter for recycling. Lead reclamation facilities at battery plants are generally pot-type
furnaces for non-oxidized lead. Approximately 1 to 4 percent of the lead processed at a typical
lead-acid battery plant is recycled through reclamation as paste or metal.
6-13
6.2.3 Emissions 165,166
Lead oxide emissions result from the discharge of air used in the lead oxide
production process. Fabric filtration is generally used as part of the process control equipment to
collect particulate emissions from lead oxide facilities.
Lead and other particulate matter are generated in several operations within
storage battery production, including grid casting, lead reclamation, slitting, small parts casting,
and during the three-process operation. These particulates are usually collected by ventilation
systems and ducted through fabric filters (baghouses).
Significant emissions of lead oxide may result during the first step of the paste
mixing operation when dry ingredients are charged to the mixer. These emissions are usually
collected and ducted through a baghouse (or impingement wet scrubber). Also, during the second
step, when moisture is present in the exhaust stream from acid addition, emissions from the paste
mixer are generally collected and ducted to either an impingement scrubber or fabric filter.
Emissions from grid casting machines, lead reclamation facilities, and the three-process operation
are sometimes processed by impingement wet scrubbers, but normally through a baghouse.
Sulfuric acid mist emissions are generated during the formation operation. These
emissions are significantly higher for dry formation processes than for wet formation processes
because wet formation takes place in battery cases and dry formation is conducted in open tanks
(a practice which is decreasing within the industry). Wet formation processes usually do not
require control. Emissions of sulfuric acid mist from dry formation processes can be reduced by
more than 95 percent by the use of mist eliminators or scrubbers. Also, acid mist emissions from
dry formation are commonly controlled by the application of surface foaming agents over the acid
baths or receptacles. Other emission control practices are water sprays and good work practices
in general.
Emission reductions of 99 percent and above can be obtained when fabric filters
are used to control slitting, paste mixing, and three-process operations. The use of scrubbers to
6-14
control emissions from paste mixing and grid casting operations, and at lead reclamation facilities,
can result in emissions reductions of 85 percent or better.
Many lead-acid battery manufacturing plants use central vacuum systems for
general housekeeping practices. However, these units may be subject to the New Source
Performance Standards (NSPS) for lead-acid battery manufacture as an “other lead emitting
source.” The industry typically uses fabric filters to control exhaust emissions from these vacuum
systems.
Fabric filters have become an accepted method for controlling emissions from grid
casting and lead reclamation. Also, since the original NSPS development project, two new lead
control techniques have been applied to various facilities manufacturing lead-acid batteries. These
are the use of cartridge collectors as primary control devices and the use of high efficiency
particulate air (HEPA) filters for secondary collection. Specifically, cartridge collectors and
HEPA filters can be used in grid casting, paste mixing, lead oxide manufacturing, the
three-process operation, or lead reclamation.
Table 6-4 presents lead emission factors for lead-acid battery manufacturing
operations and lead oxide production. The emission factors presented include lead and its
compounds, expressed as elemental lead. Controlled emission factors expressed in terms of lead
emissions per lead processed or production were not readily available. Therefore, the appropriate
control efficiency should be applied to the uncontrolled factors. Bag filters and scrubbers are the
most commonly used controls for lead acid batteries.24 Emissions data for lead-acid battery
manufacturing facilities, including grid casting, paste mixing, lead oxide manufacturing, three-
process operation, lead reclamation, and formation are presented in the EPA document Review of
New Source Performance Standards for Lead-Acid Battery Manufacture.165
6-15
TABLE 6-4. LEAD EMISSION FACTORS FOR LEAD-ACID BATTERY PRODUCTION
a
Emission factors are expressed in lb (kg) of lead emitted per 1000 batteries produced, except where noted.
b
Emission factors are expressed in lb (kg) of lead emitted per ton (Mg) of lead produced.
"---" means data are not available.
6.3 LEAD OXIDES IN PIGMENTS
Lead oxide is used primarily in the manufacture of lead-acid storage batteries (see
Section 6.2). It is also useful as a pigment in paints and ceramic glazes. The principal oxides of
lead include litharge, lead dioxide, and red lead. Black oxide, the most widely used form of lead
oxide, consists of a mixture of litharge and finely divided metallic lead. Red lead is a major lead
pigment. Other lead pigments include white lead, lead chromates, and leaded zinc oxides. Total
lead oxide production in the United States in 1995 was 68,013 tons, excluding lead oxide used in
batteries (61,700 Mg).167
Lead Oxides
Lead Monoxide--Most lead oxides and many of the major lead pigments are
derived from lead monoxide, in a form called litharge. There are four principal processes for
producing high-grade litharge:
6-17
TABLE 6-5. U.S. FACILITIES MANUFACTURING LEAD OXIDES IN PIGMENTS
Lead Oxides
Lead Monoxide
Admiral Chemical Co. Peabody, Massachussetts
ASARCO Incorporated Denver, Colorado
Eagle-Picher Industries, Inc., Electronics Division, Joplin, Missouri
Chemicals Department
Great Western Inorganics Golden, Colorado
Hammond Lead Products, Inc. Hammond, Indiana
Pottstown, Pennsylvania
Johnson Matthey, Inc., Aesar/Alfa Wardhill, Massachusetts
Micron Metals, Inc., Atlantic Equipment Engineers Division Bergenfield, New Jersey
Oxide & Chemical Corporation Brazil, Indiana
Lancaster, Ohio
Pacific Dunlap Columbus, Georgia
Quenell Enterprises, Inc., Daelco Division City of Commerce, California
Lead Dioxide
Aithaca Chemical Corporation Uniondale, New York
Eagle-Picher Industries, Inc., Electronics Division, Joplin, Missouri
Chemicals Department
Hammond Croton, Inc. South Plainfield, New Jersey
PSI Chemicals Division, Pluess & Staufer International, Inc. Stamford, Connecticut
Spectrum Chemical Manufacturing Corporation Gardena, California
Lead Pigments
Red Lead
Hammond Lead Products, Inc. Hammond, Indiana
Pottstown, Pennsylvania
Oxide & Chemical Corporation Brazil, Indiana
Spectrum Chemical Manufacturing Company Gardena, California
Robert I. Webber Co., Inc. City of Commerce, California
Stamford, Connecticut
White Lead
Hammond Lead Products, Inc., Halstab Division Hammond, Indiana
National Chemical Co., Inc. Chicago, Illinois
6-18
TABLE 6-5. U.S. FACILITES MANUFACTURING LEAD OXIDES IN PIGMENTS
(CONTINUED)
Lead Chromate
Aithaca Chemical Corporation Uniondale, New York
ALL-Chemic, Ltd. Fort Lee, New Jersey
Cookson Pigments, Inc. Newark, New Jersey
Engelhard Corporation, Pigments and Additives Division Louisville, Kentucky
Kikuchi Color & Chemicals Corp. U.S.A. Paterson, New Jersey
Mineral Pigments Corporation, Chemical Color Division Beltsville, Maryland
National Chemical Co., Inc. Chicago, Illinois
Spectrum Chemical Manufacturing Company Gardena, California
Wayne Pigment Corporation Milwaukee, Wisconsin
Lead Antimonate Yellow Pyrochlore
Ferro Corporation, Coatings, Colors & Electronic Materials Cleveland, Ohio
Group, Color Division
6-19
In all cases, the product must be cooled quickly to below 570EF (300EC) to avoid formation of
red lead.163
The Barton process is shown in Figure 6-3. Lead ingots are first melted and then
fed into a vessel or pot, where the molten lead is rapidly stirred and atomized into small droplets.
The droplets of molten lead are then oxidized by air drawn through the pot and conveyed to a
product recovery system, which typically consists of a settling chamber, cyclone, and baghouse.
In the ball mill process, shown in Figure 6-4, lead pigs or ingots are charged with
air into a ball mill. Oxidation is initiated by the heat generated by the tumbling lead ingots.
During milling, the lead oxide that forms on the surface of the ingots and fine particles of
unoxidized lead are broken off, forming a fine dust that is removed from the mill by a circulating
air stream. Air flow through the mill, the temperature of the charge, and the weight of the charge
are controlled to produce a specified ratio of lead oxide to finely divided metallic lead.
Centrifugal mills and/or cyclones are used to collect large particles, while the finer particles are
collected in a baghouse.
6-20
Lead
Gas
Feed
Melter Stream
Exit
6-21
Conveyer
(Product to Storage)
(SCC 3-01-035-54)
Red Lead--Red lead, also called minium, is used principally in ferrous metal
protective paints. The manufacture of red lead begins by charging litharge into a reverberatory
furnace held at 900 to 950EF (480 to 510EC). The litharge is oxidized until a specified amount of
lead monoxide is converted to Pb3O4. A typical red lead manufacturing plant will produce 30 tons
(27 Mg) of red lead per day.
White Lead--The commercial varieties of white lead include basic carbonate white
lead, basic sulfate white lead, and basic lead silicate. Manufacture of basic carbonate white lead is
based on the reaction of litharge with acetic acid. The product of this reaction is then reacted
with carbon dioxide to form lead carbonate, which is contained in a slurry and recovered by wet
filtration and drying. Other white leads are made either by a chemical or a fuming process. The
chemical process is like that described above except that other mineral dioxides are used in place
of carbon dioxide. The fuming process differs in that the product is collected in a baghouse rather
than by wet slurry filtration and drying.
The lead nitrate solution can be made using either lead monoxide or by reacting molten lead with
nitric acid.
Leaded Zinc Oxides--Leaded zinc oxides are used almost entirely as white
pigments for exterior oil-base paints. Leaded zinc oxides are produced either by smelting and
cofuming combinations of zinc and lead sulfide ores or by mechanically blending separately
6-23
prepared fractions of zinc oxide and basic lead sulfate. The first process involves heating the two
materials to produce a fume, which is cooled and collected in a baghouse.
6.3.3 Emissions
Lead Oxides
Lead Pigments
Red Lead--Collection of dust and fume emissions from the production of red lead
is an economic necessity. Consequently, particulate emissions are minimal. Particulate emissions
after a baghouse have been measured at 1.0 lb/ton (0.5 g/kg) product.163 Only lead monoxide and
oxygen go into the production of red lead, so most of the particulate emissions can be assumed to
be lead.
Data on emissions from the production of white lead pigments, leaded zinc oxides,
and chrome pigments are not available.
6-24
TABLE 6-6. CHARACTERISTICS OF UNCONTROLLED EXHAUST GAS FROM LEAD
OXIDE BALL MILL AND BARTON POT PROCESSES
a
Emissions are after a baghouse, which is considered process equipment.
production facilities are presented in Table 6-7. Collection efficiencies in excess of 99 percent are
generally considered achievable.
Lead emission factors found in the literature for the manufacture of lead oxides
and lead pigments are presented in Table 6-8. The emission factors for lead oxide production
were assigned an E rating because of high variabilities in test run results and nonisokinetic
sampling.
About 90 percent of the lead cable covering produced in the United States is on
lead-cured jacketed cables and 10 percent is on lead-sheathed cables.174 Approximately
7,000 tons of lead were consumed for lead cable sheathing production in 1996.175 Today, lead
sheathing is only being used on power cables with voltage levels generally greater than 10 kV.
6-25
TABLE 6-7. PERFORMANCE TEST RESULTS ON BAGHOUSES SERVING LEAD
OXIDE FACILITIES
6-26
TABLE 6-8. LEAD EMISSION FACTORS FOR MANUFACTURE OF LEAD OXIDE IN
PIGMENTS
Average Emission
Control Factor in lb/ton Emission
SCC Number Emission Source Device (kg/Mg)a Factor Rating
Lead Oxide Production
3-01-035-06 Barton pot None 4.40x10-1 E
(2.20x10-1)
3-01-035-07 Calciner None 1.40x101 E
(7.0)
Baghouse 5.00x10-2 E
(2.50x10-2)
Pigment Production
3-01-035-10 Red Lead None 9.00x10-1 B
(4.50x10-1)
3-01-035-15 White Lead None 5.50x10-1 B
(2.75x10-1)
3-01-035-20 Lead Chromate None 1.30x10-1 B
(6.50x10-2)
Source: Reference 12
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of oxide/pigment produced.
6-27
Extrusion rates for typical presses are 3,000 to 15,000 lb/hr (1.3 to 6.8 Mg/hr). A
lead melting kettle supplies lead to the press, which is heated either electrically or with a
combustion-type burner.
6.4.3 Emissions
The melting kettle is the only source of atmospheric lead emissions in lead
sheathing production. Fumes from these kettles are exhausted to the atmosphere. Table 6-9
presents uncontrolled lead emission factors for cable covering.
Cable sheath reliability and quality relate directly to the oxide content of the
sheath. Because of lead density, flotation of lead oxides from the melting and holding kettles used
to feed the extruder is possible. To minimize introduction of oxygen into the lead bath, modern
melting pots use pneumatically operated lids and splash prevention devices on the ingot loading
mechanism.176
Further control is provided by controlling the height of the overflow channel from
the melting pot to the holding pot by properly spacing the baffles to prevent oxide movement
along the direction of metal flow and bottom tapping of the holding pot.176
Emissions data from facilities with any type of emission controls are scarce or
unavailable. Also, the percentage of facilities having any type of controls in place is unknown.
6-28
TABLE 6-9. LEAD EMISSION FACTOR FOR LEAD CABLE COATING
Process/Emission Control Average Emission Factor Emission Factor Range Emission Factor
SCC Number Source Device lb/ton (kg/Mg)a lb/ton (kg/Mg)a Rating
3-04-040-01 Cable Covering None 5.00x10-1 --- C
(2.50x10-1)
To begin the process, raw materials are shipped to the manufacturing facility by
truck or rail and are stored in bins. Next, the raw materials are carefully weighed in the correct
proportions. The raw batch is then dry mixed and transferred to a hopper prior to being fed into
the smelting furnace. Although pot furnaces, hearth furnaces, and rotary furnaces have been used
to produce frit in batch operations, most frit is now produced in continuous smelting furnaces.
Depending on the application, frit smelting furnaces operate at temperatures of 1700E to 2700EF
(930E to 1480EC). If a continuous furnace is used, the mixed charge is fed by screw conveyor
directly into the furnace. Continuous furnaces operate at temperatures of 2000E to 2600EF
(1090E to 1430EC). When smelting is complete, the molten material is passed between
water-cooled metal rollers that limit the thickness of the material, and then it is quenched with a
water spray that shatters the material into small glass particles called frit.177
6-30
After quenching, the frit is milled by either wet or dry grinding. If the latter, the
frit is dried before grinding. Frit produced in continuous furnaces generally can be ground
without drying, and it is sometimes packaged for shipping without further processing. Wet
milling of frit is no longer common. However, if the frit is wet-milled, it can be charged directly
to the grinding mill without drying. Rotary dryers are the devices most commonly used for drying
frit. Drying tables and stationary dryers also have been used. After drying, magnetic separation
may be used to remove iron-bearing material. The frit is finely ground in a ball mill, into which
clays and other electrolytes may be added, and then the product is screened and stored. The frit
product then is transported to on-site ceramic manufacturing processes or is prepared for
shipping. In recent years, the electrostatic deposition spray method has become the preferred
method of applying frit glaze to surfaces. Frit that is to be applied in that manner is mixed during
the grinding step with an organic silicon encapsulating agent, rather than with clay and
electrolytes. Glaze application to ceramics is discussed in more detail in Section 6.6. Figure 6-5
presents a process flow diagram for frit manufacturing.177
6.5.2 Emissions
When frit containing lead oxides is being manufactured, lead emissions are created
by the frit smelting operation in the form of dust and fumes. These emissions consist primarily of
condensed lead oxide fumes that have volatilized from the molten charge.177
Lead emissions from the furnace can be minimized by careful control of the rate
and duration of raw material heating, to prevent volatilization of the more fusible charge
materials. Lead emissions from rotary furnaces also can be reduced with careful control of the
rotation speed, to prevent excessive dust carryover. Venturi scrubbers and fabric filters are the
devices most commonly used to control emissions from frit smelting furnaces, and fabric filters
are commonly used to control emissions from grinding operations. No information is available on
the type of emission controls used on quenching, drying, and materials handling and transfer
operations.177 Also, no lead emission factors for frit manufacturing were identified.
6-31
Figure 6-5. Process Flow Diagram for Frit Manufacturing
6-32
6.6 CERAMICS AND GLAZES
Basic carbonate white lead [2PbCO3CPb(OH)2] has been the preferred leaded glaze
used in ceramic manufacture for hundreds of years. White lead has varied applications in
whiteware glazes, particularly for fine china and commercial artware. White lead has a small
particle size and lower particle density, making it capable of suspending a glaze without the
presence of clays or organic binders. However, white lead and other lead oxides are more soluble
than other forms of lead, and because the lead leaches out over time, they are being phased out by
the ceramic industry.14
The ceramics industry is addressing this solubility problem by adding lead to glaze
in frit form. The frit is a ground mixture of two or more compounds. For example, lead
monosilcate (PbOC0.67SiO2), which is considered one of the most economical methods for
introducing lead into a glaze, contains 85 percent PbO and 15 percent SiO2. The frit form
desolubilizes and detoxifies the lead compounds. The frit also allows the glazes to be fired at
lower temperatures and creates a more uniform glaze. The fritted glaze usually includes clay or
organic binders, which ensure that the glaze adheres to the ceramic and does not dust off prior to
firing.14 Frits are usually manufactured by frit manufacturers rather than ceramic manufacturers.
(See Section 6.3 for a list of frit manufacturers.)
Since the 1970s, attention has been focused on the use of lead glazes in china
dishes and the tendency for lead from the glaze to leach into food. This tendency toward
leachability depends upon several factors, including glaze composition, firing conditions, pH
(e.g., orange, tomato juices, vinegar), temperature, and physical state of food (liquid, moist),
duration of food contact.
6-33
The following presents a brief history of the regulatory drivers influencing lead
reduction in ceramics. The U.S. Food and Drug Administration (FDA) set informal guidelines in
1971 for levels of lead leaching from ceramic products. These levels were tightened in 1979.
They are now being further reduced because new information shows that lead can pose health
hazards. The guideline levels for lead leaching from ceramic waste are being reduced as follows:
C From 7.0 to 3.0 ppm for plates, saucers, and other flatware;
C From 5.0 to 2.0 ppm for small hollowware, such as cereal bowls (but not
cups and mugs);
C From 2.5 to 1.0 ppm for large (greater than 1.1 liters) hollowware such as
bowls (but not pitchers).180
These guideline levels for ceramics are expected to reduce lead emissions from
ceramic manufacturers. However, the leaded glaze content of certain non-food ceramic products
(such as tiles) is not expected to be affected. A list of ceramicware manufacturers in the United
States is presented in Table 6-10; a list of ceramic tile manufacturers in the United States is
presented in Table 6-11.
6-34
TABLE 6-10. MANUFACTURERS OF CERAMICWARE
Facility Location
Bennington Potters, Inc Bennington, VT
Buffalo China, Inc.a Buffalo, NY
Burden China Co., Inc. El Monte, CA
Ebaz Systems, Inc. Williamsburg, VA
Frankoma Potterya Sapulpa, OK
Haeger Potteries, Inc.a Dundee, IL
Homer Laughlin China Co. Newell, WV
Innovative Ceramic Corporation East Liverpool, OH
Kingwood Ceramic, Inc. East Palestine, OH
Lenox Inc.b Pomona, NJ
Kinston, NC
Mayer China Co. Beaver Falls, PA
Nelson McCoy Ceramic Co. Roseville, OH
Pewabic Pottery Detroit, MI
Sterling China Co.c Wellsville, OH
Syracuse China Corporation Syracuse, NY
6-35
TABLE 6-11. DECORATIVE CERAMIC TILE MANUFACTURERS
Facility Location
Acme Brick Co. Fort Worth, TX
American Olean Tile Co., Inc.a/Dal-Tile Lansdale, PA
Corporationb
Dal-Tile Corporation Dallas Texas
Florida Tileb Lakeland, FL
Monarch Tileb Florence, AL
American Marazzib Sunnyvale, TX
Bennington Potters, Inc. Bennington, VT
Lone Star Ceramics Co. Dallas, TX
Mannington Ceramic Tile, Inc. Lexington, NC
Metropolitan Ceramics, Inc. Canton, OH
Pewabic Pottery Detroit, MI
Stark Ceramics, Inc.c East Canton, OH
Winburn Tile Manufacturing Co. Little Rock, AR
a
Listed in the 1992 TRI under SIC code 3253 (Ceramic Wall and Floor Tile) with reported lead compound
emissions of 2 lb/yr. Source Reference 159.
b
Source: Reference 184
c
Listed in the 1992 TRI under SIC code 3251 (Brick and Structural Clay Tile). Source Reference 159.
6-36
TABLE 6-12. MANUFACTURERS OF ENAMELS FOR STOVE AND RANGE USE
Facility Location
A.O. Smith, Protective Coatings Division Florence, KY
Randolph Products Co. Carlstadt, NJ
Schenectady Chemicals Schenectady, NY
Ferro Corporation, Frit Division Cleveland, OH
Chit-Vit Corporation Urbana, OH
Sterling Group Sewickley, PA
Prior to glaze application, the frit and other glaze materials are ground in a ball mill
until they reach a particular size distribution that will permit uniform application, but not so fine
that the lead exceeds solubility standards.14
Dipping is an older process for glaze application, and is generally used only on
shapes that are not conducive to spraying. Flat surfaces (such as wall tile) can be glazed using a
waterfall technique--passing the tiles under a thin falling sheet of glaze.14
6-37
6.6.2 Emissions
When leaded glazes are used, lead is emitted during the glaze spraying phase. One
uncontrolled emission factor for lead measured from a spray booth stack during ceramic glaze
spraying is presented in Table 6-13. The glaze being used during this test contained 28.3 weight
percent lead monosilicate. The test was conducted using combined EPA Methods 5 and 12
sampling trains.184 Although no lead emission factors were identified for other steps in the
ceramic process, lead emissions can also occur during the firing of glazes.185 Two emission
control options frequently used at ceramic kilns are (1) the limestone gravel-bed filter, and (2) dry
scrubbing.185
Because of the special properties that lead imparts to ceramic glazes, it will
continue to be used in the ceramic industry. However, work is continuing in the United States to
identify ways to lower the lead solubilities of commercial ceramic frits.14
6-38
TABLE 6-13. LEAD EMISSION FACTOR FOR CERAMIC/GLAZE APPLICATION
Facility Location
American Piezo Ceramics, Inc. Mackeyville, PA
Bullen Ultrasonics, Inc. Eaton, OH
Cerac Inc. Milwaukee, WI
Channel Products, Inc. Chesterland, OH
Channel Technologies, Inc. Santa Barbara, CA
Edo Corp., Electro Ceramic Divisiona Salt Lake City, UT
Enprotech Corporation Pittsburgh, PA
Hoechst CeramTec North America, Inc. Mansfield, MA
International Transducer, Inc. Santa Barbara, CA
Materials Research & Analysis (MRA) North Adams, MA
Laboratories, Inc.
Motorola, Inc. Ceramics Productsa Albuquerque, NM
NTK Technical Ceramics Springfield, NJ
Mesa, AZ
Piezo Kinetics, Inc. Bellefonte, PA
Radio Materials Corporation Attica, IN
Tam Ceramics, Inc. Niagara Falls, NY
Ultran Labs, Inc. State College, PA
Ultrasonic Powders, Inc. South Plainfield, NJ
Vernitron Corp., Piezoelectric Division Cleveland, OH
a
Listed in the 1992 TRI under SIC code 3679 (Electronic Components, NEC). Source: Reference 159.
6-40
Process Description
Emissions
Lead emissions are expected to occur during PZT manufacture, handling of raw
materials, casting, and ceramic firing. Because these PZT ceramics require no glazing, lead
emissions are expected to be much lower than those from manufacture of ceramics and decorative
tiles. No lead emission factors were identified for PZT ceramic manufacturers.
The following categories (in decreasing order of lead usage) are the most
significant sources of lead emissions in the miscellaneous lead products group: ammunition, type
metal, and other metallic lead products (including bearing metals, and pipe and sheet lead). Since
1992, U.S. can manufacturers no longer use lead solder. Also, the EPA has recently proposed a
regulation under the Toxic Substances Control Act to prohibit the manufacture of lead-containing
fishing sinkers.187 Therefore, neither can solder nor fishing sinkers are included as miscellaneous
lead products in this section. Also, information on abrasive grain processing is included in this
section. Available information indicates that this process is likely to emit metals (including lead)
as constituents of the feed material.
6-41
Figure 6-6. Multilayer Ceramic Capacitor Manufacturing Process
6-42
6.7.1 Ammunition
Emissions
A lead emission factor for ammunition production is presented in Table 6-15. The
emission factor represents a manufacturing scenario where little or no air pollution control
equipment was used. Lead emissions from ammunition manufacturing are controlled by fabric
filters, wet scrubbers and/or cyclone separators, depending on the manufacturing situation.188
Lead type has been used primarily in the letterpress segment of the printing
industry. However, in the late 1980s, the printing industry started phasing out the use of lead
type. The use of lead type has decreased in the last few years, but still continues to be used at
some facilities. Lead typemaking processes are classified according to the methods of producing
the final product: linotype, monotype, and stereotype. Because type metal is recycled many times
before it is spent, the quantity of type metal actually processed in a particular year can not be
calculated.
6-43
TABLE 6-15. LEAD EMISSION FACTORS FOR MISCELLANEOUS LEAD PRODUCTS
Emission
Factor
Average Emission Range in
SCC Factor lb/ton Emission
Number Process/Emission Source Control Device in lb/ton (kg/Mg) (kg/Mg) Factor Rating Reference
3-04-051-01 Ammunition None <1.0 --- C 57,174
(<5.0x10-1)
3-04-051-02 Bearing Metals None Negligible --- C 57,174
3-04-051-03 Other Metallic Lead Processes None 1.5 --- C 57,174
(7.5x10-1)
3-05-035-05 Abrasive Grain Wet Scrubber 4.4x10-3 --- E 190
Processing/Washing/Drying (2.2x10-3)
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All type metal is an alloy consisting mainly of lead and much smaller amounts of
antimony and tin. Each constituent provides a desired metallurgical characteristic for a slug (a
solid bar with raised letters in a line) or other form of type-casting. Lead constitutes 60 to 85
percent of the type metal because it has a low melting point. Antimony lends hardness to the alloy
and minimizes contraction as the metal cools. The antimony expands as the slug solidifies,
providing a clear type face. Tin gives both strength and fluidity to the type metal and provides a
smooth and even surface to the slug.
Emissions174
The melting pot is the major source of emissions in type metal production.
Melting the dirty recycled type metal, contaminated with printing ink, paper, and other impurities,
generates smoke that contains hydrocarbons as well as lead particulates. Only small quantities of
particulates are created by the oxidation of lead after the meltdown because of the protection
afforded by the layer of dross on the metal surface. Limited test data indicate that lead may
comprise as much as 35 percent of the total amount of PM emitted.191,192 Table 6-16 presents lead
emission factors for type metal production.
The transferring and pouring of the molten metal into the molds may produce
fuming because of surface oxidation of the metal. The trimming and finishing operations emit lead
particles. However, the particles are typically large in size and tend to settle out in the vicinity of
the trimming saws and finishing equipment.
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TABLE 6-16. LEAD EMISSION FACTOR FOR TYPE METAL PRODUCTION
a
Emission factor is expressed in lb (kg) of pollutant emitted per ton (Mg) of lead processed.
b
The emission factor is an industry average. Typical control devices utilized by the industry are cyclones, wet
scrubbers, fabric filters, and electrostatic precipitators, which may be used in various combinations.
The most frequently controlled sources at hot metal printing facilities are the main
melting pots and drossing areas. Linotype melting pots and finishing equipment do not require
emission controls when they are operated properly. Emission control devices in current use
include wet scrubbers, baghouses, and electrostatic precipitators. These can be used in various
combinations. During drossing, the enclosure doors are opened and pot emissions may enter the
plant atmosphere unless vented to a control device or to the outside.
Lead is also consumed and emitted in the manufacture of other metallic lead
products such as bearing metals, caulking lead, pipe and sheet lead, casting metals, solder, and
terne metal. Lead is also used for galvanizing, annealing, and plating. Approximately 68,100 tons
of lead were consumed in the manufacturing operations of these metallic lead products in 1991.193
Process Description
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and engines. In the manufacturing of other metallic lead products, lead is usually processed by
melting and casting, followed by mechanical forming operations.
Emissions
Abrasive grain manufacturers produce materials for use by bonded and coated
abrasive product manufacturers during production of abrasive products.
Process Description190
The most commonly used abrasive materials for abrasive grain manufacturing are
silicon carbide and aluminum oxides. These synthetic materials account for as much as 80 to
90 percent of the abrasive grains produced domestically. Other materials used for abrasive grains
are cubic boron nitride (CBN), synthetic diamonds, and several naturally occurring minerals such
as garnet and emery. The use of garnet as an abrasive grain is decreasing. CBN is used for
machining the hardest steels to precise forms and finishes. The largest application of synthetic
diamonds has been in wheels for grinding carbides and ceramics. Natural diamonds are used
primarily in diamond-tipped drill bits and saw blades for cutting or shaping rock, concrete,
grinding wheels, glass, quartz, gems, and high-speed tool steels. Other naturally occurring
abrasive materials (including garnet, emery, silica sand, and quartz) are used in finishing wood,
leather, rubber, plastics, glass, and softer metals.
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amount of sawdust is added to the mix to increase its porosity so that the CO formed during the
process can escape freely. Common salt is added to the mix to promote the carbon-silicon
reaction and remove impurities in the sand and coke. During the heating period, the furnace core
reaches approximately 4,000EF (2,200EC), at which point a large portion of the load crystallizes.
At the end of the run, the furnace contains a core of loosely knit silicon carbide crystals
surrounded by unreacted or partially reacted raw materials. The silicon carbide crystals are
removed to begin processing into abrasive grains.
Fused aluminum oxide is produced in pot-type electric arc furnaces with capacities
of several tons. Before processing, bauxite, the crude raw material, is calcined at about 1,740EF
(950EC) to remove both free and combined water. The bauxite is then mixed with ground coke
(about 3 percent) and iron borings (about 2 percent). An electric current is applied and the
intense heat, on the order of 3,700EF (2,000EC), melts the bauxite and reduces the impurities that
settle to the bottom of the furnace. As the fusion process continues, more bauxite mixture is
added until the furnace is full. The furnace is then emptied and the outer impure layer is stripped
off. The core of aluminum oxide is then removed to be processed into abrasive grains.
Figure 6-7 presents a process flow diagram for abrasive grain processing.
Abrasive grains for both bonded and coated abrasive products are made by graded crushing and
close sizing of either natural or synthetic abrasives. Raw abrasive materials first are crushed by
primary crushers and then reduced by jaw crushers to manageable size, approximately
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Figure 6-7. Flow Diagram for Abrasive Grain Processes
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0.75 inches (in) (19 millimeters [mm]). Final crushing is usually accomplished with roll crushers
that break up the small pieces into a usable range of sizes. The crushed abrasive grains are then
separated into specific grade sizes by passing them over a series of screens. If necessary, the
grains are washed in classifiers to remove slimes, dried, and passed through magnetic separators
to remove iron-bearing material before they are again closely sized on screens. This careful sizing
is necessary to prevent contamination of grades by coarser grains. Sizes finer than 250 grit
(0.10 mm) are separated by hydraulic flotation and sedimentation or by air classification.
Emissions 190
The primary emissions from abrasive grain processing consist of PM and PM10
from the crushing, screening, classifying, and drying operations. PM is also emitted from
materials handling and transfer operations. Table 6-15 presents a lead emission factor developed
from the results of a metals analysis conducted on a rotary dryer controlled by a wet scrubber in
an abrasive grain processing facility.
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emissions. However, it is assumed that other conventional devices such as scrubbers and
electrostatic precipitators can be used to control PM emissions from abrasives grain and products
manufacturing.
A small fraction of the total lead produced is transformed into solder. Lead
content in solder can range from 0 to over 50 percent. Industrial trends are showing an increased
demand for lead-free solder, partially in response to the June 1988 amendments to the Safe
Drinking Water Act, which set limits of 0.02 percent lead in solders and fluxes and 8 percent lead
in pipe and fittings used in public water supply systems and facilities connected to them. Lead
used in soldered food and soft drink cans declined steadily through the 1980s. As of November
1991, cans made with lead-containing solder were no longer manufactured in the United States.195
Lead and tin pigs are melted and blended in a kettle. The alloy is cast into billets in
the slug molds and put into a press, where it is hydraulically extruded at 15,000 psi through holes
1/2 inch in diameter. The solder is wire-spooled and put through a drawing machine to produce
threads of varying diameters. After extrusion, wire stock can go to the rolling mills (rather than
being spooled), where it is formed into a solder ribbon from which washers are stamped.197
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Paste solder is produced by alloying various amounts of tin and lead or silver or
lead oxide. The alloy is put into a powder form by centrifuging or spraying. The solder powder
is mixed with a vehicle (water-based or other solvents plus additional ingredients).197
6.8.3 Emissions
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TABLE 6-17. LEAD EMISSION FACTOR FOR SOLDER MANUFACTURING FACILITIES
a
Emission factors are expressed in lb (kg) of lead emitted per ton (Mg) of materials processed.
A flow diagram for a typical electroplating process for the coating of parts other
than printed circuit boards is presented in Figure 6-8. Prior to plating, the parts undergo a series
of pretreatment steps to smooth the surface of the part and to remove any surface soil, grease, or
oil. Pretreatment steps include polishing, grinding, and/or degreasing of the part to prepare for
plating. The part being plated is rinsed after each step in the process to prevent carry-over of
solution that may contaminate the baths used in successive process steps.
Polishing and grinding are performed to smooth the surface of the part.
Degreasing is performed either by dipping the part in organic solvents or by vapor degreasing the
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TABLE 6-18. LEAD ELECTROPLATING MANUFACTURERS
Company Location
CP Chemicals Inc. Fort Lee, NJ
CuTech Inc. Hatfield, PA
Enthone-OMI Inc. New Haven, CT
GSP Metals & Chemicals Corp. Los Angeles, CA
General Chemical Corp. Parsippany, NJ
Harstan Div., Chemtech Industries Inc. St. Louis, MO
JacksonLea, A Unit of Jason Inc. Conover, NC
LeaRonal Inc. Freeport, NY
MacDermid Inc. Waterbury, CT
Maclee Chemical Co., Inc. Chicago, IL
McGean-Rohco Inc. Cleveland, OH
Pitt Metals & Chemicals Inc. McDonald, PA
Quin-Tec Inc. Warren, MI
Shipley Co., Inc. Newton, MA
Taskem Inc. Brooklyn Heights, OH
Technic Inc. Pawtucket, RI
Transene Co., Inc. Rowley, MA
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Figure 6-8. General Electroplating Process Flow Diagram
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part using organic solvents. The exact pretreatment steps used depend upon the amount of soil,
grease, or oil on the parts. Following pretreatment, the parts are transferred to the plating tank.
In lead plating, the part(s) is placed in a tank and connected into the electrical
circuit as the cathode. If small parts are to be plated, the parts are first placed in a plating barrel
or on a plating rack. The plating barrel or plating rack is then placed in the tank and connected
into the electrical circuit. As current is applied, lead ions in solution are drawn to the negatively
charged cathode where they undergo reduction, resulting in the deposition of lead onto the part.
The efficiency of the plating bath is based on the amount of current that is consumed in the
deposition reaction versus the amount of current that is consumed by other side reactions.
Following plating, the part is thoroughly rinsed. Post-treatment of the part may be
necessary.
The American Electronics Association (AEA) advises that a major reason that
tin/lead solder is used is because it is a conductive material that bonds aggressively. The low
melting point of tin/lead solder is often preferred because of the reduced probability of thermal
shock to soldered assemblies during high speed soldering operations. In addition to its ability to
bond aggressively at a relatively low temperature, tin/lead solder has other advantageous physical
properties, including: good wicking tendencies, i.e., the tendency to produce strong bonds by
traveling up the holes to mount components to some printed circuit boards; pliancy to resist
breakage from vibration; and good electrical conductivity.
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Manufacturing circuit boards involves the application of tin/lead solder to maintain
the circuit boards' solderability by protecting the copper boards from oxidizing. The oldest
manufacturing technique employs the application of tin/lead plating to the circuit board. This
process begins with a copper clad circuit board--a laminate such as fiberglass or epoxy that has
been coated with copper on one or both sides. Tin/lead solder is used as a protective pattern of
“etch resist,” which is deposited on the copper surface, and the unwanted copper is etched away.
This technique produces a copper clad circuit pattern protected by tin/lead plating.
Both tin/lead plating and hot air leveling are presently in use in the electronics
manufacturing industry; however, a comparison of the frequency of use of each process is not
available.
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Surface mount assembly and through-hole assembly are two technologies used to
attach electrical components to the circuit boards. With surface mount technology, components
are attached directly to the circuit boards without drilling or punching holes. Without holes, the
components can be densely packed on the board, thereby reducing the size of the board. Texas
Instruments cites a 40 percent reduction in size of the printed circuit board assembly over
through-hole technology when surface mount technology is used. With through-hole technology,
the leads of the electrical components are placed in holes that have been drilled in the circuit
board. Usually, the circuit board is soldered on the side from which the leads protrude.201
6.9.3 Emissions
Lead emissions potentially occur from the plating stage of the electroplating
process. However, these emissions are estimated to be low.
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• Hydrous tribasic lead sulfate (3PbO@PbSO4H2O),
These lead-containing stabilizers are used primarily in polyvinyl chloride (PVC), vinyl chloride
copolymers, and PVC blends.204 PVC is generally regarded as one of the most versatile of
polymers because of its compatibility with many other materials, such as plasticizers, fillers, and
other polymers. A list of manufacturers of heat stabilizers containing lead is presented in
Table 6-19.
Demand for lead stabilizers in plastics increased steadily during the 1980s due to
increased demand for PVC products related to construction activity.206 Since that time, demand
has remained relatively stable. In the 1992 Toxic Release Inventory, there were 53 facilities
reporting lead and lead compound emissions from the manufacture of resins and plastics.159 These
facilities are listed in Table 6-20 and probably represent some of the major lead-stabilized resin
and plastic manufacturers in the United States.
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TABLE 6-19. MANUFACTURERS OF HEAT STABILIZERS CONTAINING LEADa
Facility Location
Akzo Chemical Division New Brunswick, NJ
Hammond Lead Products, Halsted Division Hammond, IN
Mooney Chemicals, Inc. Cleveland, OH
M-R-S Chemicals Inc. Maryland Heights, MO
Synthetic Products Co. Cleveland, OH
RT Vanderbilt Co., Inc. Norwalk, CT
a
Includes dibasic lead phthalate, dibasic lead phosphite, and tribasic lead sulphate.
Due to increasing pressure from state and federal agencies, U.S. manufacturers of
heavy-metal heat stabilizers (including lead) are focusing research and development on finding an
acceptable alternative. Some of these replacement heat stabilizers under development include
magnesium-zinc, barium-zinc, and tin stabilizers.208
Lead stabilizer production can be a highly variable process because many of the
stabilizers are custom-blended for specific applications. Probably the most commonly used lead
stabilizer is tribasic lead sulfate, a fine white powder that is made by boiling aqueous suspensions
of lead oxide and lead sulfate. The anhydrous compound decomposes at 1,643EF (895EC). The
addition of 2 to 7 percent tribasic lead sulfate to flexible and rigid PVC provides efficient, long-
term, economical heat stability.209
Addition of the heat stabilizer additives occurs as part of the overall production of
the formulated PVC resins. Formulation of the resin normally uses a blender system and,
depending upon the particular PVC product, may be a batch or continuous operation.
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TABLE 6-20. MANUFACTURERS OF RESINS AND PLASTICS REPORTING LEAD AND
LEAD COMPOUND EMISSIONS IN THE
1992 TOXIC CHEMICALS RELEASE INVENTORY
Facility Location
SIC 2821: Plastics Materials and Resins
Ampacet Corporation Deridder, LA
BF Goodrich Company, Geovinyl Division Pedricktown, NJ
BF Goodrich Company Louisville, KY
Avon Lake, OH
North American Plastics Inc. Madison, MS
Prairie, MS
Synergistics Inc. Howell Township, NJ
Union Carbide Chemicals and Plastics Texas City, TX
Vista Chemical Company, Polymers Division Aberdeen, MS
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TABLE 6-20. MANUFACTURERS OF RESINS AND PLASTICS REPORTING LEAD AND
LEAD COMPOUND EMISSIONS IN THE 1992 TOXIC CHEMICALS RELEASE
INVENTORY (CONTINUED)
Facility Location
Manner Plastic Materials Inc. Rancho Dominguez, CA
Pantasote Inc., Plastic & Materials, Vinyl Compounds Passaic, NJ
Plastics Color Chip Inc. Asheboro, NC
PMS Consolidated Somerset, NJ
Elk Grove Village, IL
Saint Peters, MO
Reed Plastics Corporation, Sandoz Holden, MA
Grand Prairie, TX
Spectra Polymer Company Inc. Ashburnham, MA
Teknor Color Company Henderson, KY
Teknor Apex Company Pawtucket, RI
Vista Performance Polymers Mansfield, MA
Jeffersontown, KY
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TABLE 6-21. POLYVINYL CHLORIDE MANUFACTURERS IN THE UNITED STATES
Capacity
Facility Location (millions of lb)
Borden Chemicals and Plastics Geismar, LA 500
Partnership Illiopolis, IL 350
CertainTeed Corporation Lake Charles, LA 260
Formosa Plastics Corporation U.S.A. Baton Rouge, LA 865
Delaware City, DE 130
Point Comfort, TX 1,050
The BFGoodrich Company, BFGoodrich Avon Lake, OH 300
Chemical Group Deer Park, TX 325
Henry, IL 60
Louisville, KY 400
Pedricktown, NJ 370
Georgia Gulf Corporation Delaware City, DE 150
Plaquemine, NJ 840
The Goodyear Tire & Rubber Company, Niagara Falls, NY 115
General Products Division
Keysor-Century Corporation Saugus, CA 60
Occidental Chemical Corporation, Baton Rouge, LA 450
Polymers & Plastics, Vinyls Division Burlington, NJ (south) 150
Pottstown, PA 250
Pasadena, TX 1,400
Shintech Incorporated Freeport, TX 2,400
Union Carbide Corporation, Solvents & Texas City, TX 140
Coatings Materials Division
Vista Chemical Company, Olefins & Aberdeen, MS 440
Vinyl Division Oklahoma City, OK 400
Vygen Corporation Ashatbula, OH 125
Westlake PVC Corporation Pensacola, FL 200
Total 12,030
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The primary process used to manufacture lead-stabilized PVC in the United Sates
is suspension polymerization. In this process, the vinyl chloride monomer is finely dispersed in
water with vigorous agitation. At this point, monomer-soluble initiators and lead stabilizers in
suspension are used. The particular sequence of stabilizer addition depends upon the processing
method to be used (e.g., calendaring, extrusion, injection molding). The molecular weight of the
PVC can be controlled by varying the temperature, where the molecular weight increases as the
temperature increases.206
6.10.2 Emissions
No information is available for the specific types of emission control devices used
to control lead emissions resulting from production of lead stabilizers or lead-containing PVC
products. One potential source of lead emissions is materials handling, especially since lead
stabilizers are used in powder form. Lead emissions may occur when lead stabilizers are added to
the PVC resins during formulation and prior to processing the PVC resin.
Lead emissions may also be present during subsequent phases: drying, extruding,
molding, grinding, weighing, packaging. However, emissions from these sources are expected to
be minimal since temperatures necessary to volatilize significant quantities of lead compounds
would thermally destroy the resin and other organic constituents.
No emission factors are published for this process, and no test data are available to
allow calculation of an emission factor.
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Plants are usually located near the job site, so they are concentrated in areas with an extensive
highway and road network.210 Additional information on the location of individual hot-mix
asphalt facilities can be obtained by contacting the National Asphalt Pavement Association in
College Park, Maryland.
There are three types of hot-mix asphalt plants operating in the United States:
batch-mix, continuous-mix, and drum-mix. Batch-mix and continuous-mix plants separate the
aggregate drying process from the mixing of aggregate with asphalt cement. Drum-mix plants
combine these two processes. Production capacities for all three types of plants range from 40 to
600 tons (36 to 544 Mg) of hot mix per hour. Almost all plants in operation are of either the
batch-mix or drum-mix type. Less than 0.5 percent of operating hot-mix plants are of the
continuous-mix design.211
Aggregate, the basic raw material of hot-mix asphalt, consists of any hard, inert
mineral material. Aggregate typically comprises between 90 and 95 percent by weight of the
asphalt mixture. Because aggregate provides most of the load-bearing properties of a pavement,
the performance of the pavement depends on selection of the proper aggregate.
Asphalt cement is used as the binding agent for aggregate. It prevents moisture
from penetrating the aggregate and acts as a cushioning agent. Typically, asphalt cement
constitutes 4 to 6 percent by weight of a hot-mix asphalt mixture.210 Asphalt cement is obtained
from the distillation of crude oil. It is classified into grades under one of three systems. The most
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commonly used system classifies asphalt cement based on its viscosity at 140EF (60EC). The
more viscous the asphalt cement, the higher its numerical rating.
The asphalt cement grade selected for different hot-mix asphalts depends on the
type of pavement, climate, and type and amount of traffic expected. Generally, asphalt pavement
bearing heavy traffic in warm climates requires a harder asphalt cement than pavement subject to
either light traffic or cold climate conditions.
The primary processes of a typical batch-mix hot-mix asphalt facility are illustrated
in Figure 6-9.211 The moisture content of the stockpiled aggregate at the plant usually ranges
from 3 to 5 percent. The moisture content of recycled hot-mix asphalt typically ranges from 2 to
3 percent. The different sizes of aggregate are typically transported by front-end loader to
separate cold-feed bins and metered onto a feeder conveyor belt through gates at the bottom of
the bins. The aggregate is screened before it is fed to the dryer to keep oversize material out of
the mix.
The screened aggregate is then fed to a rotating dryer with a burner at its lower
(discharge) end that is fired with fuel oil, natural gas, or propane. In the production of hot-mix
asphalt, the majority of lead emissions can be expected from the rotating dryer. The dryer
removes moisture from the aggregate and heats the aggregate to the proper mix temperature.
Lead emissions occur primarily from fuel combustion. Aggregate temperature at the discharge
end of the dryer is about 300EF (149EC). The amount of aggregate that a dryer can heat depends
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6-67
Figure 6-9. General Process Flow Diagram for Batch-Mix Asphalt Paving Plants
Vibrating screens segregate the heated aggregate into bins according to size. A
weigh hopper meters the desired amount of the various sizes of aggregate into a pugmill mixer.
The pugmill typically mixes the aggregate for 15 seconds before hot asphalt cement from a heated
tank is sprayed into the pugmill. The pugmill thoroughly mixes the aggregate and hot asphalt
cement for 25 to 60 seconds. The finished hot-mix asphalt is either loaded directly into trucks or
held in insulated and/or heated storage silos. Depending on the production specifications, the
temperature of the hot-mix asphalt product mix can range from 225 to 350EF (107 to 177EC) at
the end of the production process.
Drum-mix plants dry the aggregate and mix it with the asphalt cement in the same
drum, eliminating the need for the extra conveyor belt, hot bins and screens, weigh hopper, and
pugmill of batch-mix plants. The drum of a drum-mix plant is much like the dryer of a batch
plant, but it typically has more flights than do batch dryers to increase veiling of the aggregate and
to improve overall heat transfer. The burner in a drum-mix plant emits a much bushier flame than
does the burner in a batch plant. The bushier flame is designed to provide earlier and greater
exposure of the virgin aggregate to the heat of the flame. This design also protects the asphalt
cement, which is injected away from the direct heat of the flame.210
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Figure 6-10. General Process Flow Diagram for Drum-Mix Asphalt Paving Plants
Of the 3,600 active hot-mix asphalt plants in the United States, approximately
2,300 are batch-mix plants, 1,000 are parallel-flow drum-mix plants, and 300 are counterflow
drum-mix plants. About 85 percent of plants being constructed today are of the counterflow
drum-mix design; batch-mix plants and parallel-flow drum-mix plants account for 10 percent and
5 percent respectively.211
Emissions of lead from hot-mix asphalt plants most likely occur because of fuel
combustion in the aggregate rotary dryers, but some emissions from the aggregate during the
drying process are possible. These emissions are most often controlled by wet scrubbers or
baghouses.211
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6.11.3 Emissions
Emissions from hot-mix asphalt plants were reexamined recently for the purpose of
updating the information contained in the EPA's Compilation of Air Pollutant Emission Factors,
commonly referred to as AP-42. Representative batch-mix and drum-mix plants (both parallel
and counterflow) were selected for testing. Emissions from hot-oil heaters used to warm stored
asphalt concrete were also evaluated. Lead emissions from hot-mix plants can result from fuel
combustion, aggregate mixing and drying, and asphalt heating. The only lead emissions found
from these tests were from the drying process. These lead emission factors are provided in
Tables 6-22 and 6-23.212
Leaded house paints were common up until the mid-1950s. In 1971, the
Lead-Based Paint Poisoning Prevention Act prohibited the use of paints containing more than
1 percent lead by weight in the nonvolatile portion of liquid paints or in the dried film on all
interior and exterior surfaces accessible to children in residential structures. In 1972, the FDA
ordered a reduction of the lead content of paints used in and around households to 0.5 percent in
1973 and 0.06 percent in 1975. Further legislation in 1976 required the Department of Housing
and Urban Development to prohibit lead-based paint in residential structures built or rehabilitated
with federal assistance. Also, the Department of Health, Education, and Welfare banned lead
paints from cooking and eating utensils, and the Consumer Products Safety Commission
prohibited lead paints on toys and furniture. As a result, the use of white lead in paints for these
consumer applications has plummeted in recent years.213
Although the use of lead paint has dramatically decreased in these consumer
products, leaded paint is still used in certain applications. The major uses of lead-based paints
today are as metal primers in automobile refinishing, as anti-corrosive undercoating in the
automobile industry, for public works applications (such as bridges and roads), as traffic paint, in
art materials, and in marine applications (such as boats and buoys).213,217
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TABLE 6-22. LEAD EMISSION FACTORS FOR BATCH-MIX HOT-MIX ASPHALT PLANTS
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of waste incinerated.
FF = Fabric Filter.
TABLE 6-23. LEAD EMISSION FACTOR FOR DRUM-MIX HOT-MIX ASPHALT PLANTS
a
Emission factors are expressed in lb (kg) of pollutant emitted per ton (Mg) of hot mix asphalt produced.
FF = Fabric Filter.
The future trend for the paint industry is to identify substitutes for the lead
compounds currently being used. However, there is no perfect substitute that can impart all of
the properties of lead, which include color, brightness, cost effectiveness, insolubility, opacity,
nonbleeding in solvents, and durability. At present, substitutes of acceptable quality exist for only
some of these uses.217 The major current uses of lead-based paints are discussed briefly below.
Because lead enhances the corrosion protection and durability of surface coatings,
products such as paints and primers containing lead are frequently used to coat autobody surfaces
and in automobile refinishing shops.218 White-basic lead silicochromate is used in the
electrodeposition of water-based coatings for the automotive industry. Its use in this application
has increased because of its capability to be tinted to a variety of colors.213
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Industrial Applications
Red lead is used as a rust-inhibitive pigment in paints for structural steel, such as
bridges and support beams.213 Basic lead silicochromate, which can be thinned with either solvent
or water, is also used for its excellent anti-corrosive properties in industrial and maintenance
paints.13 The use of lead as an anti-corrosive in steel primers is decreasing because of
containment costs required for application/removal. In certain applications, titanium oxide (TiO2)
is being substituted for lead.217
Lead chromates are added to paints because they are inexpensive and provide
durability in exterior applications. Chrome orange is used in machinery finishes, such as farm
equipment and trucks. Chrome yellow is used in traffic paints--for highway stripes and markings,
as well as curb markings, guard railings, and crosswalks. The pigment constitutes 25 percent of
the total weight of the paint.213 In 1990, about 40 million pounds of lead chromate were produced
in the United States, and an additional 8 million pounds were imported.219
Artists Paints
Oil colors contain large amounts of pigment, ranging from 30 percent for toners to
as high as 80 percent with dense pigments such as white leads.213
Marine Coatings
Anti-corrosive coatings are also used for marine applications, such as ship hulls,
buoys, and offshore towers. Red lead has been used extensively for this purpose; however, zinc
dust has largely replaced red lead. Basic lead silicochromate is also being used for corrosion
protection.213
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6.12.2 Process Description
For some of the categories discussed above, paint is applied using a surface
coating operation (such as automobiles, farm machinery, buoys, boats). For other categories, the
paint is applied (either by spraying or brushing) directly on the structure or item once it has been
erected (such as bridges, beams, marine towers, curbs, roads). Because the variety of applications
is so diverse, detailed process descriptions are not included in this document.
Spraying operations are normally performed in a spray booth using one of the
following spray application methods: air atomization; airless atomization; air-assisted airless;
high-volume, low pressure (HVLP); and electrostatic methods. All of these techniques are used
in automobile refinishing. Air atomization is also used to apply traffic markings.220
Dip coating involves briefly immersing the substrate in a tank containing a bath of
paint. The object is slowly removed from the tank allowing excess paint to drain back into the
tank. Flow coating is used on articles which cannot be dipped due to their buoyancy. In this
operation, the coating material is fed through overhead nozzles, distributing the paint in a steady
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stream over the article to be coated. Excess paint is allowed to drain from the coated object and
is then recycled.220
6.12.3 Emissions
No specific emission factors for lead were identified for any of the paint
application source categories.
Various materials and explosives are regularly destroyed at ordnance disposal sites
within military facilities. These facilities use open burn/open detonation (OB/OD) treatment
processes to eliminate the hazardous properties of reactive waste munitions. As materials are
combusted or exploded during the OB/OD treatment processes, chemical byproducts of
incomplete combustion are emitted into the atmosphere.
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6.13.2 Emissions
Lead is emitted from the firing of small arms ammunition with lead projectiles
and/or lead primers, but the explosive charge does not contribute to lead emissions.
Indoor shooting ranges may expose firing personnel to lead during indoor shooting
practices and qualification exercises. OSHA regulations may apply to indoor range situations.
Ventilation systems at indoor shooting ranges should be designed with enough air flow from the
firing line toward the target area to effectively remove the airborne lead generated during firing of
conventional ammunition. New bullet traps are also available to reduce lead exposure generated
from trap impact.
Lead emissions from small arms can be reduced by using different ammunition
types and/or special leadfree primers. The Department of Defense and ammunition manufacturers
are undertaking an R&D effort to develop lead free ammunition. Zinc bismuth, tungsten, nickel
and plastic (among other items) are being considered as potential alternatives. None are currently
available for widespread use and most are being considered for practice ammunition only. No
emission factors were available for indoor shooting activities.223
Table 6-24 presents lead emission factors for various categories of propellants. All
emission factors are in gram emitted per gram of material burned or detonated. Each type of
propellant represents a fairly different material. TNT represents a specific type of explosive. The
double-based and composite-based propellants are nitroglycerin- and nitrocellulose-based
6-78
TABLE 6-24. UNCONTROLLED LEAD EMISSION FACTORS FOR EOD ACTIVITIES
Lead is used as a pigment for rubber products that require color differentiation or
for aesthetic appeal. Some uses of lead as a pigment in rubber products include white wall tires
and markings on sporting goods such as basketballs.225 Sometimes lead chromates are used as
pigments when bright yellow or orange colors are desired.226 Recent interest has developed in
eliminating the use of lead-based pigments. However, lead pigments have several desirable
qualities that are difficult to match, including heat and light stability, and low formulation and
processing costs.226
According to the Department of Commerce, 1,650 tons (1,500 Mg) of lead were
consumed by the rubber industry in 1990, with about 10 percent used for pigments. The majority
of this lead was consumed in manufacturing lead sheathed hosing and for making molds for the
6-80
TABLE 6-25. END USES OF RUBBER THAT MAY CONTAIN LEAD
manufacturing process.225 Table 6-26 lists rubber product manufacturing facilities reporting lead
and lead compound emissions in the 1992 Toxic Release Inventory.
6-81
TABLE 6-26. RUBBER PRODUCT MANUFACTURING FACILITIES IN THE
UNITED STATES REPORTING LEAD AND LEAD COMPOUND EMISSIONS IN 1992
UNDER SARA 313
Facility Location
SIC 3069: Fabricated Rubber Products
Ashtabula Rubber Company Ashtabula, OH
Elastochem Inc. Chardon, OH
Goodyear Tire & Rubber Company Norfolk, NE
Kennedy Company, Inc. Scottsboro, AL
Mach-I Compounding Macedonia, OH
Polymerics Inc. Cuyahoga Falls, OH
Rhein Chemie Corporation Trenton, NJ
6-82
6.14.2 Emissions
Although no emission factors for lead from rubber manufacturing were identified
in the literature, lead emissions from this process are expected during the materials handling stage
(especially since the additives are in particulate form) and while the additives are being combined
with the monomers, catalysts, and other compounds during the polymerization step.
6-83
SECTION 7.0
EMISSIONS OF LEAD AND LEAD COMPOUNDS FROM MOBILE SOURCES
7.1 GENERAL
Elemental lead and lead alloys are used in the manufacture and operation of
vehicles. For example, lead is used in connecting electrical components, and antimonial lead is
used in bearings. The positive plate grids in automobile batteries are made of an alloy of lead,
antimony, tin, arsenic, and copper. Lead is also an anticorrosive additive in automobile paint
primers. Combining lead and tin produces an alloy referred to as turn or turnplate, which is used
to make corrosion-resistant gas tanks. 229 Lead is also an additive in automotive plastics and is
included in ceramic electrical components. Despite this widespread use of lead in vehicles, the
largest source of lead emissions from vehicles is from fuel combustion.
Lead has been used in motor gasoline since the 1920s to boost octane and provide
lubrication for intake and exhaust valves. The lead compounds function by decomposing in the
combustion cycle to form metal oxide particles. The particles interrupt the hydrocarbon chain
branching reactions that cause rapid combustion, known as “knock.” Lead anti-knock
compounds foiled 1970 catalytic converter technologies developed to reduce hydrocarbon, carbon
monoxide, and nitrogen oxide emissions. This led to the development of lead-free fuel in the early
1970s.230
The 1970 Clean Air legislation permitted the regulation of fuel additives,
established a schedule for reducing lead additives, and required automobile manufacturers to
design and construct vehicles that could run on low-lead and unleaded fuel. The phase-down of
leaded gasoline in highway motor vehicles began in 1973. Section 211(n) of the CAA prohibits
7-1
the manufacture of highway engines requiring leaded gasoline after 1992. In January 1992,
remaining lead additives used in fuels were banned for use in on-road vehicles in California. The
final deadline for the abolition of all lead-containing highway vehicle fuels was December 31,
1995.
The lead levels in leaded gasoline have been gradually reduced from the industrial
average of 2.5 g lead/gal (0.66 g/L) leaded gasoline in the 1970s to 0.0002 g lead/gal
(5.283x10 -5 g/L) unleaded gasoline in 1991 (see Table 7-1). Since 1982, the majority of gasoline
fuel sold for motor vehicles is lead-free. Currently, less than 1 percent of gasoline motor vehicle
fuel is leaded (see Table 7-2). As of 1995, only one gasoline refinery continues to produce
gasoline with lead additives.231 The fuel that currently has the greatest lead content is aviation
gasoline (2 to 4 g lead/gal [0.528 to 1.057 g/L]). The petroleum industry may continue to make
and market gasoline produced with lead additives for non motor vehicle uses, including use as fuel
in aircraft, racing cars, and non-road engines such as farm equipment engines and marine
engines.231 Diesel fuel is assumed to contain quantities of lead that are insignificant compared to
gasoline fuel.17,158
The two most common lead anti-knock additives are tetraethyl lead (TEL) and
tetramethyl lead (TML). TEL and TML, both high in octane, lubricate intake and exhaust valves
and help reduce engine knock.230 In 1990, 93 percent of highway fuel lead additives were TEL,
and the remaining 7 percent were TML. The composition and properties of TEL and TML are
shown in Table 7-3.
The manufacture of TEL and TML compounds for use in gasoline was
discontinued in the United States in May 1991.232 The plants that manufactured alkylated lead
compounds have been dismantled.232,233,234 However, TEL is still manufactured in Canada and
Europe and imported by a few companies in the United States to produce leaded gasoline.232,235,236
7-2
TABLE 7-1. LEAD CONTENT OF MOTOR VEHICLE FUELS
7-3
TABLE 7-2. FUEL SALES
The blend of TEL and TML used in motor vehicle fuel depends upon the grade of
gasoline being produced. For regular gasolines (i.e., below about 93 RON [research octane
number for all distillate fractions of the gasoline]), TEL is usually the preferred anti-knock
additive. For premium gasolines where elevating RON is important, TEL is normally preferred
for lead concentrations below 1.514 g lead/gal (0.40 g/L). Above this level, mixtures of TEL and
TML may be more beneficial. For premium gasolines where MON (motor octane number--a
guide to the anti-knock performance of a fuel under relatively severe driving conditions) is
important, mixtures of TEL and TML are again likely to produce the best results. For premium
gasolines where R100EC (research octane number of the fraction of gasoline distilled up to
100EC) is important, TML, or mixtures of TML with TEL, are likely to be most beneficial.230
7-4
TABLE 7-3. COMPOSITION AND PROPERTIES OF TEL AND TML
TEL TML
COMPOSITION, WT %
Lead Alkyl 61.5 50.8
1,2-dibromoethane 17.9 17.9
1,2-dichloroethane 18.8 18.8
Dye, diluent, inhibitor, etc. 1.8 12.5
Lead content, wt% 39.39 39.39
PROPERTIES
Specific Gravity, 20E/4EC 1.6 1.58
Vapor pressure @ 20E C mbar 67 87
Boiling point of lead alkyl, EC 200 110
(decomposes)
chamber. These lead deposits can flake off and cause valve burning by holding valves off their
seats, thus allowing the hot combustion gases to escape past the valves. During combustion, lead
and halogenated additives combine to form lead halides that are exhausted from the engine.230
Of the different aviation fuels currently in use, only aviation gasoline contains lead
as an anti-knock compound. Jet kerosene and JP-4 do not contain lead additives. Aviation
gasoline is used in reciprocating piston-engine aircraft and is therefore more prevalent in civil
aviation and general commercial aviation. There are two grades of aviation gasoline: low-lead,
which has a lead concentration of 2 g lead/gal (0.528 g/L) aviation gasoline, and high-lead, which
has a lead concentration of 4 g lead/gal (1.057 g/L) aviation gasoline. Only TEL is used in
leaded aircraft fuel.239
Due to the economics of producing leaded gasoline, fewer refineries and blending
facilities are producing it. This has caused the Federal Aviation Administration and the General
Aviation Manufacturer's Association to begin a cooperative research program to develop an
7-5
unleaded gasoline for aircraft. The two organizations have set a goal to develop an American
Standard for Testing and Material (ASTM) specification for unleaded gasoline for aircraft by
1995 and the goal of eliminating the use of leaded gasoline in aircraft by 1998.240
Although Section 211(n) of the CAA does not require a lead phase-down of
aviation fuels, the aircraft fuel industry is currently developing standards for unleaded aviation
gasoline, but continues to rely on leaded fuels.
Refiners began producing unleaded gasoline in the early 1970s for automobiles
equipped with catalytic converters. As a result of the 1990 CAA amendments, lead additives in
gasoline were replaced by high-octane hydrocarbon fractions with properties suitable for gasoline
blending. Straight-run refinery products, for example, have comparatively low-octane numbers.
On the other hand, aromatics, isoparaffins, and olefins produced from catalytic cracking and
reforming processes have much higher octane numbers. Adjusting the relative amount of these
hydrocarbon fractions results in gasolines with different octane numbers.241 Still, a trace amount
of lead remains in unleaded gasoline. This lead is picked up as it passes through refinery
processes and fuel distribution systems that had previously contained leaded gasoline. These
trace amounts may not exceed 0.05 grams of lead per gallon. At this level, catalytic control
devices are still protected.231
Calculated TML evaporative profiles are two orders of magnitude greater than
TEL profiles because the vapor pressure of TML (23 mm Hg at 68EF) is two orders of magnitude
higher than that of TEL (0.2 mm Hg at 68EF). The difference between TML and TEL varies
relative to ambient temperatures, with lower temperatures producing the greatest differences.
7-6
The TML weight fraction can be applied to leaded gasoline throughput to estimate
TML emissions. The TML emission factor can be adjusted for different ambient temperatures, as
noted in the following equation:
1289.8 900
1.321 x 100.60 & %
T % 219 T % 233
TMLgas =
1289.8 900
6900 % 1.015 x 100.60 & %
T % 219 T % 233
where: TMLgas = TML vapor phase fraction (mass TML emitted/mass leaded
gasoline throughput)
T = Temperature (EC)
Similarly, the TEL weight fraction can be applied to leaded gasoline throughput to
estimate TEL emissions. To adjust TEL emission factors for different ambient temperatures, the
following equation can be used:
1789.6 900
1.934 x 101.451 & %
T % 195 T % 233
TELgas +
1789.6 900
6200 % 1.563 x 101.451 & %
T % 195 T % 233
where: TELgas = TEL vapor phase fraction (mass TEL emitted/mass leaded gasoline
throughput)
T = Temperature (EC)
TEL emissions from the distribution of aviation fuel can be estimated using the following
equation:
1789.6 1115.86
79.25 x 100.914 & %
T % 195 T % 228
TELavgas =
1789.6 1115.86
6900 & 62.35 x 100.914 & %
T % 195 T % 228
7-7
where: TELavgas = TEL vapor phase fraction (mass TEL emitted/mass leaded
aviation gasoline throughput)
T = Temperature (EC)
In general, most TEL and TML evaporative emissions from leaded fuel distribution
are relatively small. In 1990, 5 percent of highway fuel sold in the United States was leaded.
Given that the lead concentration of leaded fuel used in the EPA study (0.85 g/gal), and the lead
concentrations in current unleaded fuels (0.0003 g/gal) are approximately three orders of
magnitude different, and given that the quantity of fuel distributed is approximately two orders of
magnitude different, total evaporative emissions from fuel distribution should be less for unleaded
than for leaded fuel. By the end of 1995, the lead content of all motor vehicle fuels will be
reduced to zero, making the highway fuel distribution category a negligible source.
Vehicles designed and operated on leaded gasoline exhaust 75 percent of the lead
in the fuel. For catalytically equipped vehicles operating on unleaded gasoline, 40 percent of the
lead burned is emitted into the atmosphere. Lead is retained in the catalyst (45 percent),
crankcase oil (25 percent), combustion chamber, and the rest of the exhaust system
(30 percent).242,243
Rf
Ecf ' Lf x x Ff
100
7-8
For a more precise estimate of mobile combustion emissions, use of the EPA/ Office of Mobile
Sources (OMS) PART5 Mobile Emission Model is recommended. The reader is cautioned that
modeling results are only estimates, not actual emissions, and have the potential for being over or
under estimated.
Presently, there are no emission factors to characterize lead emissions from aircraft
fuel combustion. The equation used to characterize motor vehicle emissions may be used, but will
probably lead to an underestimation of emissions because of differences in engine design, exhaust
system configurations, and operation.
Several studies have shown that lead from atmospheric deposition can be
reintrained by vehicles as road dust.244-248 This section provides estimation procedures for this
source derived from a U.S. EPA report entitled Estimating and Controlling Fugitive Lead
Emissions from Industrial Sources.249
Open dust fugitive emissions from paved roads depend upon the loose surface
material and traffic characteristics of the road. These emissions have been determined to vary
directly in proportion to the surface material loading and silt content of the road. The surface
material loading is the amount of loose dust on the road surface and is measured in units of mass
of material per unit area. (Surface material loading for a specific road is typically expressed in
units of mass per unit length of road.) The silt content is the percentage of silt (i.e., particles less
than or equal to 75 microns in diameter) in the loose surface dust. Some typical values for silt
loading on industrial paved roads are presented in Table 7-4. Other factors that affect industrial
paved road fugitive emissions include the volume of traffic, number of traffic lanes, average
vehicle weight, and the degree to which vehicles travel on nearby unpaved areas (thereby allowing
more dust to be deposited on the paved road). This last factor is known as the industrial
7-9
TABLE 7-4. INDUSTRIAL PAVED ROAD SILT LOADINGS
a
The data presented in this table are based on an EPA-sponsored sampling and analysis program, for which the number
of samples specified in the table were collected at the specified number of sites.
augmentation factor and ranges in value from 1.0 to 7.0. Higher values indicate greater fugitive
dust emissions. Typical values for this factor are found in Table 7-5.
The magnitude of fugitive lead emissions (or emissions of any other substance)
may be estimated by direct proportion with the percent by weight of lead (or substance of
concern) in the silt fraction. Because of variations from location to location, site-specific data
should be used for all of the above-mentioned factors whenever possible.
The fugitive lead emission factor for industrial paved roads in units of kilograms
per vehicle kilometer traveled (kg/VKT), or pounds per vehicle mile traveled (lb/VMT), can be
determined by the following modified equation for total suspended particulate emissions:
0.7
C 4 s L W
E = 0.22 I (kg/VKT)
100 n 10 280 2.7
0.7
C 4 s L W
E = 0.22 I (lb/VMT)
100 n 10 1,000 3
7-10
TABLE 7-5. TYPICAL VALUES FOR PAVED ROAD INDUSTRIAL AUGMENTATION
FACTOR (I)
Ia Conditions
1.0 Travel on paved roads only
3.5 Travel on paved roads with unpaved shoulders--20 percent of vehicles travel with one
set of wheels on shoulder
7.0 Traffic enters from unpaved roads
To estimate lead emissions from paved road dust, the developed emission factors should be
applied to local VMT data.
Fugitive dust emissions from unpaved roads, like paved road fugitive emissions,
are directly proportional to the silt content of the surface material. In addition, fugitive lead
emissions can be estimated by direct proportion with the lead content in the silt fraction. Unpaved
road fugitive dust emissions are also proportional to the mean vehicle speed, mean vehicle weight,
and mean number of wheels. Fugitive emissions from unpaved roads are also affected by the
rainfall frequency. For particles under 30 microns in diameter, a particle size multiplier must also
be included in the computation of emissions. However, for total suspended particulate emissions,
which is the concern here, the value of this factor is assumed to be unity, and it may be dropped
from the equation.
7-11
The fugitive lead emission factor for unpaved roads per unit of vehicle distance
traveled can be estimated by the following modified equation for total suspended particulates:
C s S W 0.7
w 0.5
(365 & p)
E = (1.7) (kg/VKT)
100 12 48 2.7 4 365
C s S W 0.7
w 0.5
(365 & p)
E = (5.9) (lb/VMT)
100 12 30 3 4 365
Measured silt values for a number of industries are given in Table 7-6. The number
of wet days per year, p, for the geographical area of interest should be determined from local
climatic data. As with paved road fugitive dust emission factors, the use of site-specific data is
strongly encouraged.
To estimate lead emissions from unpaved road dust, the developed emission
factors should be applied to local VMT data.
7-12
TABLE 7-6. TYPICAL SILT CONTENT VALUES OF SURFACE MATERIAL ON
INDUSTRIAL AND RURAL UNPAVED ROADS
The EPA has published reference methods for measuring lead in ambient air and
lead contained in stack gas emissions. EPA Reference Method for the Determination of Lead in
Suspended Particulate Matter Collected from Ambient Air was first published in the Federal
Register on October 5, 1978, and was last revised on July 1, 1987. 250 The EPA has also
published Method 12 and draft Method 29 for measuring lead in stack gases. Method 12 was
first published in the Federal Register on January 14, 1980 and last revised on
November 14, 1990 and is used to sample for only total inorganic lead in stack gases. 251 Draft
Method 29 was first published in the Federal Register on July 17, 1991 as part of the boiler and
industrial furnace regulations and is used to sample for total inorganic and organic lead and other
metals in stack gases. EPA Method 29 was finalized on April 25, 1996 and is included in
Appendix A of 40 CFR Part 60.
Sections 8.1 and 8.2 of this report summarize the field sampling procedures for
measuring lead in ambient air and stack gases, respectively. Section 8.3 describes the different
analytical techniques used to analyze and measure the amount of lead collected in ambient air
and stack gas samples.
8-1
Figure 8-1. Components of a High-Volume Ambient Air Sampler for Lead
8-2
shelter equipped with a roof. Ambient air is drawn under the roof of the shelter through a
pre-weighed glass-fiber filter. Figure 8-2 shows a simplified diagram of the air flow through a
high-volume sampler located in a shelter. 253 The high-volume sampler should be operated for
24 hours at an average flow rate of 1.7 cubic meters per minute (m 3/min). The primary and
secondary national ambient air quality standards for lead are 1.5 micrograms per cubic meter
(µg/m3) averaged over a calendar quarter. For determining compliance with the primary and
secondary national ambient air quality standards for lead, at least one 24-hour sample must be
collected every six days except during periods or seasons exempted by the Regional EPA
Administrator.254
After sampling, the filter is removed and sent to a laboratory for analysis. The
filter is weighed several times until a constant weight is measured and then the filter is digested
in an acid solution and analyzed for total lead content either by atomic absorption
spectrophotometry (AAS) or inductively coupled plasma emission spectroscopy (ICP). The
typical range in the amount of lead collected by use of this method is 0.07 to 7.5 µg/m 3 assuming
an upper linear range of analysis of 15 micrograms per milliliter (µg/mL) and an air volume of
2,400 cubic meters (m3).
The major advantage to the high-volume lead sampling method is the low
detection limit that can be achieved (i.e., 0.07 to 7.5 µg lead/m 3). Another advantage is that the
ambient air sample is collected over a 24-hour period, which encompasses all types of weather
conditions, particularly temperature changes, and the range of emission source activities that
occur throughout a 24-hour period.
One disadvantage of the high-volume sampling method is that it was designed for
sampling only total inorganic lead compounds in suspended PM. Inorganic lead cannot be
speciated and most organic lead compounds cannot be detected. A second disadvantage is that
the high-volume method is very dependent on meteorological conditions. Any change in wind
speed or direction and any amount of precipitation can influence the sample results. To interpret
the effects of weather conditions on the sample results, meteorological data must be recorded
during the sampling period.
8-3
Figure 8-2. Air Flow through a High-Volume Sampler in a Shelter
8-4
8.2 STATIONARY SOURCE SAMPLING METHODS
Two methods are available for sampling stack gas concentrations of lead: EPA
Method 12 and EPA Method 29.251,252 Method 12 is used to sample for only total inorganic lead.
EPA Method 29 is used to sample for total inorganic and organic lead and other metals in a
stack. These two methods are described on the following pages.
Method 12 (also called a multi-metals train) can be used to sample PM and total
inorganic lead (i.e., elemental lead and inorganic lead compounds) isokinetically from stack
gases. A diagram of the Method 12 sampling train is shown in Figure 8-3. Particulate lead is
collected through a glass nozzle and probe onto a glass-fiber filter and in a dilute nitric acid
solution in the impingers. The nozzle and probe are washed with dilute nitric acid and the wash,
filter, and impinger solution are sent to a laboratory, where they are digested in an acid solution
and analyzed for total lead content by AAS or ICP.
The exact run time and volume samples vary from source to source depending on
the required detection limit. Typically, Method 12 sampling is conducted for 2 hours to sample
approximately 2.55 m3 of stack gas. The lower range of detection for this method is 25 µg of
total lead. The upper range can be extended considerably by diluting the sample prior to analysis.
The major advantage to Method 12 is that the method was designed to sample for
inorganic lead compounds from a wide variety of industrial processes, and the method has been
validated. The stack gas stream is sampled isokinetically, which provides an accurate emission
rate. Method 12 is also extremely flexible. The length of sample runs and the sample volume
collected can be adjusted depending on the expected concentration of the stack gas stream. The
disadvantage is that Method 12 cannot be used to speciate inorganic lead compounds or to
sample for organic lead compounds.
8-5
Figure 8-3. Method 12 Sampling Train
8-6
8.2.2 EPA Method 29 - Determination of Metals Emissions from Stationary Sources
EPA Method 29 can be used to sample PM and total inorganic and organic lead
compounds isokinetically from stack gases. The Method 29 sampling train is a modified EPA
reference Method 5 sampling train and is shown in Figure 8-4.
The exact run time and volume sampled varies from source to source depending
on the required detection limit. Typically, the Method 29 train is run for 2 hours and samples
approximately 2.55 m3 of stack gas. The lower range of detection for this method is 25 µg of
total lead. The upper range can be extended considerably by diluting the sample prior to analysis.
8-7
Figure 8-4. Method 29 Sampling Train
8-8
8.3 ANALYTICAL TECHNIQUES FOR THE MEASUREMENT OF LEAD
The most common technique for measuring total lead in air samples is
spectroscopy. The two spectroscopic techniques used most by environmental laboratories are
AAS and ICP. AAS is the most common method used to measure total lead. The advantages to
AAS are that the method is simple, rapid, and applicable to a large number of metals. Samples
other than drinking water must be acid-digested prior to analysis. Two types of AAS methods
for measuring total lead are direct aspiration (flame) and graphite furnace.
The second most common technique for measuring total lead in air samples is
ICP, which allows simultaneous, or sequential, determination of several metals in a sample
during a single analytical measurement. Air samples must be acid-digested prior to analysis.
Method 7420 specifies the procedure for analyzing air samples for total lead using
direct-aspiration (flame) AAS. 256 In direct-aspiration (flame) AAS, a sample is aspirated and
atomized in an air/acetylene flame. A light beam from a hollow cathode lamp whose cathode is
made of the element being measured is directed through the flame into a monochromator, and
onto a detector that measures the amount of light absorbed. Absorption depends upon the
presence of free, unexcited ground-state atoms in the flame. Because the wavelength of the light
beam is characteristic of only the element being measured, the light energy absorbed by the flame
is a measure of the concentration of that element in the sample. The detection limit for lead is
100 micrograms per liter (µg/L). The optimum concentration ranges are from 1,000 to 20,000 µg
per sample. If direct-aspiration (flame) AAS techniques do not provide adequate sensitivity,
graphite furnace techniques can be used.
8-9
8.3.2 Graphite Furnace Atomic Absorption Spectroscopy
Method 7421 specifies the procedure for analyzing air samples for total lead using
graphite furnace AAS.257 The principle of graphite furnace AAS is essentially the same as for
direct-aspiration (flame) AAS, except a furnace rather than a flame is used to atomize the sample.
In graphite furnace AAS, a representative aliquot of a sample is placed in a graphite tube in the
furnace, evaporated to dryness, charred, and atomized. The radiation from a given excited
element is passed through the vapor containing ground-state atoms of that element. The intensity
of the transmitted radiation decreases in proportion to the amount of the ground-state element in
the vapor. The metal's atoms to be measured are placed in the beam of radiation by increasing
the temperature of the furnace, thereby causing the injected specimen to be volatized. A
monochromator isolates the characteristic radiation from the hollow cathode lamp or
electrodeless discharge lamp, and a photosensitive device measures the attenuated transmitted
radiation. The detection limit for lead is 1.0 µg/L. The optimum concentration ranges are from
5 to 100 µg per sample.
The major advantage of this technique is that it affords extremely low detection
limits. It is the easiest technique to perform on relatively clean samples. Because this technique
is so sensitive, however, interferences can be a problem; finding the optimum combination of
digestion, heating times, temperatures, and matrix modifiers can be difficult for complex
matrices.
Method 6010A specifies the procedures for analyzing air samples for total lead
using ICP.258 The ICP method measures element-emitted light by optical spectrometry. The
sample is nebulized and the resulting aerosol is transported to the plasma torch, where excitation
occurs. Characteristic atomic-line emission spectra are produced by radio-frequency inductively
coupled plasma. The spectra are dispersed by a grating spectrometer, and the intensities of the
lines are monitored by photomultiplier tubes. The photocurrents from the photomultiplier tubes
8-10
are processed and controlled by a computer. The detection limit for lead is 42 µg/L. The
optimum concentration range varies with the make and model of the instrument used.
8-11
SECTION 9.0
REFERENCES
9-1
12. U.S. EPA. Compilation of Air Pollutant Emission Factors, 5th ed. (AP-42), Vol. I:
Stationary Point and Area Sources, Section 12.16: Lead Oxide and Pigment
Production. Research Triangle Park, North Carolina: U.S. Environmental Protection
Agency, Office of Air Quality Planning and Standards, 1995. p. 12.16-1.
13. American Chemical Society. Chemcyclopedia 1995, Volume 1. Washington, D.C.:
American Chemical Society, 1995. p. 139.
14. Nordyke, J.S. Lead in the World of Ceramics. Columbus, Ohio: American Ceramic
Society, 1984.
15. Sax, N. Dangerous Properties of Industrial Materials, 1993.
16. Woodbury, W.D. Annual Report 1992, Lead. Washington, D.C.: U.S. Department
of Interior, Bureau of Mines, October 1993.
17. OECD. Risk Reduction Monograph No. 1: Lead. Paris, France: Environment
Directorate, Organization for Economic Co-operation and Development, 1993.
18. U.S. EPA. Control Techniques for Lead Air Emissions, Unpublished Draft.
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency,
Office of Air Quality Planning and Standards, Emission Standards Division, 1990.
19. Woodbury, W.D. Annual Report 1990, Lead. Washington, D.C.: Bureau of Mines,
U.S. Department of the Interior, U.S. Government Printing Office, April 1992.
20. U.S. EPA. Compilation of Air Pollutant Emission Factors, 5th ed. (AP-42), Vol. I:
Stationary Point and Area Sources, Section. Section 12.6: Primary Lead Smelting.
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency,
Office of Air Quality Planning and Standards, 1995.
21. U.S. EPA. Secondary Lead Smelting Background Information Document for
Proposed Standards, Volume 1. EPA-450/R-94-024a. Research Triangle Park,
North Carolina: U.S. Environmental Protection Agency, Office of Air Quality
Planning and Standards, June 1994. pp. 2-1 to 2-36.
22. U.S. EPA. Assessment of the Controllability of Condensible Emissions.
EPA-600/8-90-075. Research Triangle Park, North Carolina: U.S. Environmental
Protection Agency, Air and Energy Engineering Research Laboratory, October 1990.
23. U.S. EPA. Compilation of Air Pollutant Emission Factors, 4th ed. (AP-42), Vol. I:
Stationary Point and Area Sources, Supplements A, B, and C. Research Triangle
Park, North Carolina: U.S. Environmental Protection Agency, Office of Air Quality
Planning and Standards, 1985.
24. Weinberg, David. Letter to Dennis Beauregard, EPA. Comments on draft report,
Locating and Estimating Air Emissions of Lead and Lead Compounds
(August 15, 1996).
9-2
25. Hall, R.M. and J.L. Gittleman. Control Technology for Metal Reclamation
Industries at Sanders Lead Company Inc. CT-202-11a. Cincinnati, Ohio:
U.S. Department of Health and Human Services, Engineering Control Technology
Branch, Division of Physical Sciences and Engineering, NIOSH, July 1993. pp. 1-8.
26. U.S. EPA. Secondary Lead Smelting Background Information Document for
Proposed Standards., Volume 1. EPA-450/R-94-024a. Research Triangle Park,
North Carolina: U.S. Environmental Protection Agency, Office of Air Quality
Planning and Standards, June 1994. pp. 3-1 to 3-13.
27. U.S. EPA. Primary Copper Smelters. National Emission Standards for Hazardous
Air Pollutants (NESHAP), Final Summary Report. ESD Project No. 91/61.
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency,
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35. U.S. EPA. Compilation of Air Pollutant Emission Factors, 5th ed. (AP-42), Vol. I:
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9-4
48. California Air Resources Board. U.S. Pipe and Foundry Co. Stack Emission Tests of
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70. Suprenant, N.F., R.R. Hall, K.T. McGregor, and A.S. Werner. Emissions Assessment
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80. U.S. EPA. Compilation of Air Pollutant Emission Factors, 5th ed. (AP-42), Vol. I:
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91. Timber Association of California (TAC). Source Emission Testing of the
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114. U.S. EPA. Compilation of Air Pollutant Emission Factors, 5th ed. (AP-42), Vol. I:
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9-13
152. Smook, G.A. Handbook for Pulp and Paper Technologists. Atlanta, Georgia:
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244. Chamberlain, A.C. Fallout of Lead and Uptake by Crops. Atmospheric
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256. U.S. EPA. Test Methods for Evaluating Solid Waste, 3rd ed., Volume 1A:
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9-22
APPENDIX A
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
3-03-010-02 Primary Lead Smelting Blast Furnace None 1.0x10-4 lb/ton U
(5.0x10-5 kg/Mg)
Baghouse 6.7x10-2 lb/ton E
(3.4x10-2 kg/Mg)
Spray Tower/FF 1.7x10-2 lb/ton U
(8.5x10-3 kg/Mg)
3-03-010-04 Primary Lead Smelting Ore Crushing None 3.0x10-1 lb/ton U
(1.5x10-1 kg/Mg)
Baghouse 2.0x10-3 lb/ton E
(1.0x10-3 kg/Mg)
3-03-010-25 Primary Lead Smelting Sinter Machine Leakage ESP/Scrubber 3.2x10-2 lb/ton E
(1.6x10-2 kg/Mg)
3-03-010-28 Primary Lead Smelting Tetrahedrite Drier Baghouse 6.0x10-4 lb/ton E
(3.0x10-4 kg/Mg)
A-1
3-03-010-29 Primary Lead Smelting Sinter Machine (weak gas) ESP/Scrubber 1.9x10-2 lb/ton E
(9.5x10-3 kg/Mg)
3-03-010-32 Primary Lead Smelting Ore Screening Baghouse 2.0x10-3 lb/ton E
(1.0x10-3 kg/Mg)
3-04-004-03 Secondary Lead Smelting Blast Furnace (Cupola) None 1.04x102 lb/ton C
(5.2x101 kg/Mg)
Wet Scrubber/FF/ 2.9x10-1 C
Cyclone/Settling (1.5x10-1)
Chamber/Demister
3-04-004-04 Secondary Lead Smelting Rotary Sweating Furnace None --- E
-2
Baghouse 2.8x10 lb/ton D
(1.4x10-2 kg/Mg)
TABLE A-1. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
3-04-004-04 Secondary Lead Smelting Baghouse/scrubber 1.9x10-2 lb/ton D
(continued) (9.5x10-3 kg/Mg)
3-04-004-13 Secondary Lead Smelting Smelting Furnace Fugitives None --- E
Baghouse 1.2x10-2 lb/ton U
(6.0x10-3 kg/Mg)
3-04-004-02 Secondary Lead Smelting Reverberatory Furnace None 6.5x101 lb/ton C
(3.3x10-1 kg/Mg)
3-04-004-26 Secondary Lead Smelting Kettle Refining None 1.0x10-2 lb/ton C
(6.0x10-3 kg/Mg)
3-04-004-14 Secondary Lead Smelting Kettle Refining Fugitives None 6.00x10-4 lb/ton E
(3.00x10-4 kg/Mg)
Afterburner/FF/ 2.4 lb/ton
Venturi Scrubber/ (1.2 kg/Mg)
Demister
3-04-004-09 Secondary Lead Smelting Casting None 1.0x10-2 lb/ton C
A-2
(5.0x10-3 kg/Mg)
3-04-004-25 Secondary Lead Smelting Casting Fugitives None 7.0x10-4 lb/ton E
(3.5x10-4 kg/Mg)
3-03-005-03 Primary Copper Converter None 2.70x10-1 lb/ton C
Smelting Facilities (0.135 kg/Mg)
3-04-002-42 Secondary Copper Reverberatory Furnace [charge None 5.0 lb/ton B
Smelting Facilities with other alloy (7%)] (2.5 kg/Mg)
3-04-002-43 Secondary Copper Reverberatory Furnace [charge None 5.0x101 lb/ton B
Smelting Facilities with high lead (58%)] (2.5x101 kg/Mg)
3-04-002-44 Secondary Copper Reverberatory Furnace (charge None 1.32x101 lb/ton B
Smelting Facilities with red/yellow brass) (6.6 kg/Mg)
3-04-002-xx Secondary Copper Secondary Copper - smelting Baghouse 1.00x10-3 lb/ton B
Smelting Facilities (5.00x10-4 kg/Mg)
TABLE A-1. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
3-04-001-09 Secondary Aluminum Burning/Drying Venturi Scrubber 4.36x10-3 lb/ton U
Production (2.18x10-3 kg/Mg)
Baghouse 1.04x10-5 lb/ton U
(5.18x10-6 kg/Mg)
Multiple Cyclones 2.16x10-2 lb/ton U
(1.08x10-2 kg/Mg)
3-04-001-14 Secondary Aluminum Reverberatory Furnace Baghouse 1.4x10-3 lb/ton D
Production (7.0x10-4 kg/Mg)
3-04-003-01 Iron and Steel Iron Foundry - Cupola None --- B
Foundries
Afterburner/ 1.56x10-3 lb/ton U
Venturi Scrubber (7.80x10-4 kg/Mg)
Baghouse 2.67x10-3 lb/ton U
(1.34x10-3 kg/Mg)
3-04-003-02 Iron and Steel Iron Foundry - Reverberatory None --- B
A-3
Foundries Furnace
3-04-003-03 Iron and Steel Iron Foundry - Electric None --- B
Foundries Induction Furnace
3-04-003-20 Iron and Steel Iron Foundry - Casting Afterburner/ 4.80x10-3 lb/ton U
Foundries Venturi Scrubber (2.40x10-3 kg/Mg)
3-03-031-01 Leadbearing Ore Lead Ore (5.1% Pb content) None 3.00x10-1 lb/ton B
Crushing & Grinding (1.50x10-1 kg/Mg)
3-03-031-02 Leadbearing Ore Zinc Ore (0.2% Pb content) None 1.20x10-2 lb/ton B
Crushing & Grinding (6.00x10-3 kg/Mg)
3-03-031-03 Leadbearing Ore Copper Ore (0.2% Pb content) None 1.20x10-2 lb/ton B
Crushing & Grinding (6.00x10-3 kg/Mg)
3-03-031-04 Leadbearing Ore Lead-Zinc Ore (2.0% Pb None 1.20x10-1 lb/ton B
Crushing & Grinding content) (6.00x10-2 kg/Mg)
TABLE A-1. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
3-03-031-05 Leadbearing Ore Copper-Lead Ore (2.0% Pb None 1.20x10-1 lb/ton B
Crushing & Grinding content) (6.00x10-2 kg/Mg)
3-03-031-06 Leadbearing Ore Copper-Zinc Ore (0.2% Pb None 1.20x10-2 lb/ton B
Crushing & Grinding content) (6.00x10-3 kg/Mg)
3-03-031-07 Leadbearing Ore Copper-Lead-Zinc Ore None 1.20x10-1 lb/ton B
Crushing & Grinding (2.0% Pb content) (6.00x10-2 kg/Mg)
A21-04- Residential Coal Bituminous/ Subbituminous None 2.00x10-2 lb/ton U
002-000 Combustion Coal - All Combustor Types (1.00x10-2 kg/Mg)
A21-04- Residential Coal Anthracite Coal - All None 1.60x10-2 lb/ton U
001-000 Combustion Combustor Types (8.00x10-3 kg/Mg)
A21-04- Residential Distillate Distillate (No. 2 oil) None 2.2x10-4 lb/MMBtu U
004-000 Oil-fired Furnaces Oil-fired Furnaces (9.5x10-14 kg/Joule)
1-01-009-01 Wood Waste-fired Utility Wood Waste-fired Boiler None 2.90x10-3 lb/ton D
Boilers (Bark-fired) (1.45x10-3 kg/Mg)
1-01-009-02 Wood Waste-fired Utility Wood Waste-fired Boiler ESP 1.60x10-5 lb/ton D
A-4
1-01-009-03 Wood Waste-fired Utility Wood Waste-fired Boiler ESP 1.10x10-3 lb/ton D
Boilers (Wood-fired) (5.50x10-4 kg/Mg)
Multiple Cyclone without 3.10x10-4 lb/ton D
Flyash Reinjection (1.55x10-4 kg/Mg)
None 2.9x10-3 lb/ton U
(1.45x10-3 kg/Mg)
TABLE A-1. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
1-01-009-03 Wood Waste-fired Utility Limestone Injection, 4.49x10-6 lb/MMBtub U
Boilers (continued) Thermal de-NOx with (1.93x10-15 kg/Joule)
Ammonia Injection, Water
Treatment, Multi-Cyclone,
Fabric Collector
1-02-009-01 Wood Waste-fired Wood Waste-fired Boiler ESP - Medium Efficiency 1.50x10-6 lb/MMBtu U
Industrial Boilers (Bark-fired, >50,000 lb steam) (6.46x10-16 kg/Joule)
None 2.90x10-3 lb/ton D
(1.45x10-3 kg/Mg)
1-02-009-02 Wood Waste-fired Wood Waste-fired Boiler Multiple Cyclone with 3.20x10-4 lb/ton D
Industrial Boilers (Wood/Bark-fired, >50,000 lb Flyash Reinjection (1.60x10-4 kg/Mg)
steam)
ESP 1.60x10-5 lb/ton D
(8.00x10-6 kg/Mg)
Scrubber 3.50x10-4 lb/ton D
(1.75x10-4 kg/Mg)
A-5
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
1-02-009-03 Wood Waste-fired Wood Waste-fired Boiler Multiple Cyclone without 2.25x10-6 lb/MMBtu U
(continued) Industrial Boilers (Wood-fired, >50,000 lb Flyash Reinjection/ESP - (9.70x10-16 kg/Joule)
steam) Medium Efficiency
1-02-009-04 Wood Waste-fired Wood Waste-fired Boiler None 2.90x10-3 lb/ton D
Industrial Boilers (Bark-fired, <50,000 lb steam) (1.45x10-3 kg/Mg)
1-02-009-05 Wood Waste-fired Wood Waste-fired Boiler Multiple Cyclone with 3.20x10-4 lb/ton D
Industrial Boilers (Wood/Bark-fired, <50,000 lb Flyash Reinjection (1.60x10-4 kg/Mg)
steam)
ESP 1.60x10-5 lb/ton D
(8.00x10-6 kg/Mg)
Scrubber 3.50x10-4 lb/ton D
(1.75x10-4 kg/Mg)
Multiple Cyclone without 3.20x10-4 lb/ton D
Flash Reinjection (1.60x10-4 kg/Mg)
1-02-009-06 Wood Waste-fired Wood Waste-fired Boiler Multiple Cyclone without 3.10x10-4 lb/ton D
Industrial Boilers (Wood-fired, <50,000 lb Flyash Reinjection (1.55x10-4 kg/Mg)
A-6
steam)
ESP 1.10x10-3 lb/ton D
(5.50x10-4 kg/Mg)
Scrubber 1.14x10-5 lb/MMBtu U
(4.91x10-15 kg/Joule)
1-03-009-01 Wood Waste-fired Wood/Bark-fired Boiler (Bark- None 2.90x10-3 lb/ton D
Comm/Instit. Boilers fired) (1.45x10-3 kg/Mg)
1-01-006-04 Natural Gas Utility Boiler Natural Gas Boilers Overfire Air and Flue Gas 2.71x10-4 lb/ton E
Recirculation
1-01-006-04 Gas-fired Utility Boiler Gas Fired Boiler None .37 lb/trillion BTU U
1-03-009-02 Wood Waste-fired Wood/Bark-fired Boiler Multiple Cyclone with 3.20x10-4 lb/ton D
Comm/Instit. Boilers (Wood/Bark-fired) Flyash Reinjection (1.60x10-4 kg/Mg)
TABLE A-1. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
1-03-009-02 Wood Waste-fired Scrubber 3.50x10-4 lb/ton D
Comm/Instit. Boilers (1.75x10-4 kg/Mg)
(continued)
ESP 1.60x10-5 lb/ton D
(8.00x10-6 kg/Mg)
Multiple Cyclone without 3.20x10-4 lb/ton D
Flyash Reinjection (1.60x10-4 kg/Mg)
1-03-009-03 Wood Waste-fired Wood/Bark-fired Boiler Multiple Cyclone without 3.10x10-4 lb/ton D
Comm/Instit. Boilers (Wood-fired) Flyash Reinjection (1.55x10-4 kg/Mg)
ESP 1.10x10-3 lb/ton D
(5.50x10-4 kg/Mg)
1-01-001-02 Coal-fired Utility Boilers Anthracite Coal Travelling None 8.90x10-3 lb/ton E
Grate Overfeed Stoker (4.45x10-3 kg/Mg)
1-01-002-01 Coal-fired Utility Boilers Bituminous Coal: Pulverized: None 5.07x10-4 lb/MMBtu E
Wet Bottom (2.18x10-13 kg/Joule)
A-7
1-01-002-02 Coal-fired Utility Boilers Bituminous Coal: Pulverized: None 5.07x10-4 lb/MMBtu E
Dry Bottom (2.18x10-13 kg/Joule)
ESP,FF or venturi scrubber 4.20x10-4(lb/ton) A
2.10x10-4 kg/Mg)
1-01-002-03 Coal-fired Utility Boilers Bituminous Coal: Cyclone None 5.07x10-4 lb/MMBtu E
Furnace (2.18x10-13 kg/Joule)
ESP,FF or venturi scrubber 4.20x10-4(lb/ton) A
2.10x10-4 kg/Mg)
1-01-002-04 Coal-fired Utility Boilers Bituminous Coal: Spreader None 5.07x10-4 lb/MMBtu E
Stoker (2.18x10-13 kg/Joule)
1-01-002-05 Coal-fired Utility Boilers Bituminous Coal: Travelling None 5.07x10-4 lb/MMBtu E
Grate (Overfeed) Stoker (2.18x10-13 kg/Joule)
TABLE A-1. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
1-01-002-21 Coal-fired Utility Boilers Subbituminous Coal: None 5.07x10-4 lb/MMBtu E
Pulverized: Wet Bottom (2.18x10-13 kg/Joule)
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
1-02-002-03 Coal-fired Industrial ESP,FF or venturi scrubber 4.20x10-4(lb/ton) A
Boilers (continued) 2.10x10-4 kg/Mg)
1-02-002-04 Coal-fired Industrial Bituminous Coal Spreader None 5.07x10-4 lb/MMBtu E
Boilers Stoker (2.18x10-13 kg/Joule)
1-02-002-05 Coal-fired Industrial Bituminous Coal Overfeed None 5.07x10-4 lb/MMBtu E
Boilers Stoker (2.18x10-13 kg/Joule)
1-02-002-06 Coal-fired Industrial Bituminous Coal Underfeed None 2.24x10-1 lb/ton U
Boilers Stoker (1.12x10-1 kg/Mg)
1-02-002-13 Coal-fired Industrial Bituminous Coal Wet Slurry None 9.89x10-3 lb/ton U
Boilers (4.95x10-3 kg/Mg)
1-01-002-21 Coal-fired Industrial Subbituminous Coal: None 5.07x10-4 lb/MMBtu E
Boilers Pulverized: Wet Bottom (2.18x10-13 kg/Joule)
1-01-002-22 Coal-fired Industrial Subbituminous Coal: None 5.07x10-4 lb/MMBtu E
Boilers Pulverized: Dry Bottom (2.18x10-13 kg/Joule)
ESP,FF or venturi scrubber 4.20x10-4(lb/ton) A
A-9
2.10x10-4 kg/Mg)
1-01-002-23 Coal-fired Industrial Subbituminous Coal: Cyclone None 5.07x10-4 lb/MMBtu E
Boilers Furnace (2.18x10-13 kg/Joule)
ESP,FF or venturi scrubber 4.20x10-4(lb/ton) A
2.10x10-4 kg/Mg)
1-01-002-24 Coal-fired Industrial Subbituminous Coal: Spreader None 5.07x10-4 lb/MMBtu E
Boilers Stoker (2.18x10-13 kg/Joule)
1-01-002-25 Coal-fired Industrial Subbituminous Coal: None 5.07x10-4 lb/MMBtu E
Boilers Travelling Grate (Overfeed) (2.18x10-13 kg/Joule)
Stoker
1-03-001-02 Coal-fired Anthracite Coal Travelling None 8.90x10-3 lb/ton E
Comm/Inst. Boilers Grate (Overfeed) Stoker (4.45x10-3 kg/Mg)
TABLE A-1. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
1-03-002-08 Coal-fired Bituminous Coal Underfeed Multiple Cyclone without 1.21x10-3 lb/ton U
Comm/Inst. Boilers Stoker Flyash Reinjection (6.05x10-4 kg/Mg)
1-03-002-03 Coal-fired Bituminous Coal Cyclone None 5.07x10-4 lb/MMBtu E
Comm/Inst. Boilers Furnace (2.18x10-13 kg/Joule)
ESP,FF or venturi scrubber 4.20x10-4(lb/ton) A
2.10x10-4 kg/Mg)
1-03-002-05 Coal-fired Bituminous Coal Pulverized: None 5.07x10-4 lb/MMBtu E
Comm/Inst. Boilers Wet Bottom (2.18x10-13 kg/Joule)
1-03-002-06 Coal-fired Bituminous Coal Pulverized None 5.07x10-4 lb/MMBtu E
Comm/Inst. Boilers Coal: Dry Bottom (2.18x10-13 kg/Joule)
ESP,FF or venturi scrubber 4.20x10-4(lb/ton) A
2.10x10-4 kg/Mg)
1-03-002-07 Coal-fired Bituminous Coal Overfeed None 5.07x10-4 lb/MMBtu E
Comm/Inst. Boilers Stoker (2.18x10-13 kg/Joule)
1-03-002-09 Coal-fired Bituminous Coal Spreader None 5.07x10-4 lb/MMBtu E
A-10
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
1-03-002-25 Coal-fired Subbituminous Coal: None 5.07x10-4 lb/MMBtu E
Comm/Inst. Boilers Travelling Grate (Overfeed) (2.18x10-13 kg/Joule)
Stoker
1-01-004-01 Oil-fired Residual Oil-fired Boiler: None 1.00x10-5 lb/MMBtu E
Utility Boilers No. 6 Oil, Normal Firing (4.33x10-15 kg/Joule)
Flue Gas Recirculation 2.17x10-5 lb/MMBtu U
(9.35x10-15 kg/Joule)
1-01-004-04 Oil-fired Residual Oil-fired Boiler: None 1.00x10-5 lb/MMBtu E
Utility Boilers No. 6 Oil, Tangential Firing (4.33x10-15 kg/Joule)
1-01-004-05 Oil-fired Residual Oil-fired Boiler: None 1.60x10-5 lb/MMBtu U
Utility Boilers No. 5 Oil, Normal Firing (6.89x10-15 kg/Joule)
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
1-05-001-13 Waste Oil-fired Waste Oil Air Atomized None 50x L lb/1000 gal D
Industrial Boilers Burner (6.0 x L kg/kL)
1-01-013-02 Waste Oil-fired Waste Oil None 1.68 lb/1000 gal U
Comm/Inst Boilers (2.01x10-1 kg/kL)
1-05-002-13 Waste Oil-fired Waste Oil Air Atomized None 50x L lb/1000 gal D
Comm/Inst Boilers Burner (6.0 x L1 kg/kL)
1-01-012-01 Solid Waste-fired Solid Waste None 2.65x10-1 lb/ton U
Utility Boilers (1.33x10-1 kg/Mg)
ESP 1.24x10-4 lb/MMBtu C
(5.34x10-14 kg/Joule)
Spray Dryer/Absorber/ESP <2.66x10-4 lb/ton U
(<1.33x10-4 kg/Mg)
1-02-012-02 Miscellaneous Solid Waste Refuse-derived None 1.30x10-1 lb/ton U
Industrial Boilers Fuel (6.50x10-2 kg/Mg)
5-01-001-01 Municipal Waste Starved-Air: Multiple- None 1.20x10-1 lb/ton U
A-12
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
5-01-001-04 Municipal Waste Mass Burn: Refractory Wall None 2.13x10-1 lb/ton A
Combustion Sources Combustor (1.07x10-1 kg/Mg)
Spray Dryer/FF 2.61x10-4 lb/ton A
(1.31x10-4 kg/Mg)
Spray Dryer/ESP 9.15x10-4 lb/ton A
(4.58x10-4 kg/Mg)
Dry Sorbent Injection/FF 2.97x10-4 lb/ton C
(1.49x10-4 kg/Mg)
Dry Sorbent Injection/ESP 2.90x10-3 lb/ton E
(1.45x10-3 kg/Mg)
ESP 3.00x10-3 lb/ton A
(1.50x10-3 kg/Mg)
5-01-001-05 Municipal Waste Mass Burn: Waterwall None 2.13x10-1 lb/ton A
Combustion Sources Combustor (1.07x10-1 kg/Mg)
Spray Dryer/FF 2.61x10-4 lb/ton A
A-13
(1.31x10-4 kg/Mg)
Spray Dryer/ESP 9.15x10-4 lb/ton A
(4.58x10-4 kg/Mg)
Dry Sorbent Injection/FF 2.97x10-4 lb/ton C
(1.49x10-4 kg/Mg)
Dry Sorbent Injection/ESP 2.90x10-3 lb/ton E
(1.45x10-3 kg/Mg)
ESP 3.00x10-3 lb/ton A
(1.50x10-3 kg/Mg)
5-01-001-06 Municipal Waste Mass Burn: Rotary Waterwall None 2.13x10-1 lb/ton A
Combustion Sources Combustor (1.07x10-1 kg/Mg)
Spray Dryer/FF 2.61x10-4 lb/ton A
(1.31x10-4 kg/Mg)
TABLE A-1. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
5-01-001-06 Municipal Waste Spray Dryer/ESP 9.15x10-4 lb/ton A
Combustion Sources (4.58x10-4 kg/Mg)
(continued)
Dry Sorbent Injection/FF 2.97x10-4 lb/ton C
(1.49x10-4 kg/Mg)
Dry Sorbent Injection/ESP 2.90x10-3 lb/ton E
(1.45x10-3 kg/Mg)
ESP 3.00x10-3 lb/ton A
(1.50x10-3 kg/Mg)
5-01-001-07 Municipal Waste Modular Excess Air Combustor None 2.13x10-1 lb/ton A
Combustion Sources (1.07x10-1 kg/Mg)
Spray Dryer/FF 2.61x10-4 lb/ton A
(1.31x10-4 kg/Mg)
Spray Dryer/ESP 9.15x10-4 lb/ton A
(4.58x10-4 kg/Mg)
A-14
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
5-01-005-15 Sewage Sludge Venturi Scrubber 1.80x10-3 lb/ton E
Incinerator Sources (9.00x10-4 kg/Mg)
(continued)
Venturi Scrubber/Wet ESP 1.80x10-4 lb/ton E
(9.00x10-5 kg/Mg)
Venturi Scrubber/ 6.00x10-2 lb/ton B
Impingement-type Wet (3.00x10-2 kg/Mg)
Scrubber
Venturi Scrubber/ 1.00x10-1 lb/ton E
Impingement-type Wet (5.00x10-2 kg/Mg)
Scrubber/Afterburner
Impingement-type Wet 4.00x10-2 lb/ton E
Scrubber (2.0x10-2 kg/Mg)
Single Cyclone/Venturi 2.20x10-2 lb/ton E
Scrubber/Impingement (1.10x10-2 kg/Mg)
Scrubber
A-15
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
5-01-005-05 Medical Waste Other Incineration None 7.28x10-2 lb/ton B
Combustion Sources Pathological/ (3.64x10-2 kg/Mg)
Controlled Air
5-01-005-05 Medical Waste Other Incineration Pathological Wet Scrubber - High 6.98x10-2 lb/ton E
Combustion Sources Efficiency (3.49x10-2 kg/Mg)
Wet Scrubber - Medium 1.60x10-3 lb/ton E
Efficiency/FF (8.00x10-4 kg/Mg)
FF 9.92x10-5 lb/ton E
(4.96x10-5 kg/Mg)
Spray Dryer/ FF 1.89x10-4 lb/ton E
(9.45x10-5 kg/Mg)
Spray Dryer/Carbon 7.38x10-5 lb/ton E
Injection/FF (3.69x10-5 kg/Mg)
Dry Sorbent Injection/ ESP 4.70x10-3 lb/ton E
(2.35x10-3 kg/Mg)
A-16
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
5-02-005-05 Medical Waste Wet Scrubber - High 6.98x10-2 lb/ton E
Combustion Sources Efficiency (3.49x10-2 kg/Mg)
(continued)
Wet Scrubber - Medium 1.60x10-3 lb/ton E
Efficiency/FF (8.00x10-4 kg/Mg)
Spray Dryer/FF 1.89x10-4 lb/ton E
(9.45x10-5 kg/Mg)
Spray Dryer/Carbon 7.38x10-5 lb/ton E
Injection/FF (3.69x10-5 kg/Mg)
Dry Sorbent Injection/ESP 4.70x10-3 lb/ton E
(2.35x10-3 kg/Mg)
Dry Sorbent 9.27x10-5 lb/ton E
Injection/Carbon (4.64x10-5 kg/Mg)
Injection/FF
Dry Sorbent Injection/FF 6.25x10-5 lb/ton E
(3.12x101 kg/Mg)
A-17
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
3-15-021-01 Crematories Crematory Stack None 4.10x10-8 lb/body U
(1.86x10-8 kg/body)
3-07-001-04 Kraft Process Recovery Direct Contact Evaporator ESP, ESP/Wet Scrubber 9.5x101 lb/106 ton D
Furnaces & Smelt Kraft Recovery Furnace (4.8x101 kg/106 Mg)
Dissolving Tanks
3-07-001-10 Kraft Process Recovery Nondirect Contact Evaporator ESP, ESP/Wet Scrubber 1.2x102 lb/106 ton D
Furnaces & Smelt Kraft Recovery Furnace (5.9x101 kg/106 Mg)
Dissolving Tanks
3-07-001-05 Kraft Process Recovery Smelt Dissolving Tank Demister, Venturi Scrubber 2.3x101 lb/106 ton D
Furnaces & Smelt (1.2x101 kg/106 Mg)
Dissolving Tanks
3-07-001-06 Lime Kilns Lime Kiln None 1.09x10-4 lb/ton U
(5.44x10-5 kg/Mg)
Scrubber 1.41x104 lb/ton D
(7.07x103 kg/Mg)
3-07-002-22 Sulfite Process Recovery Sulfite Recovery Furnace None 1.70x101 lb/106 ton D
A-18
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
3-05-006-22 Portland Cement ESP 7.10x10-4 lb/ton D
Manufacturing (continued) (3.55x10-4 kg/Mg)
3-05-006-23 Portland Cement Dry Process Preheater/ FF 7.50x10-5 lb/ton D
Manufacturing Precalcinator Kiln (3.75x10-5 kg/Mg)
ESP 7.10x10-4 lb/ton D
(3.55x10-4 kg/Mg)
3-05-007-06 Portland Cement Wet Process Kilns ESP 7.10x10-4 lb/ton D
Manufacturing (3.55x10-4 kg/Mg)
FF 7.50x10-5 lb/ton D
(3.75x10-5 kg/Mg)
None 1.00x10-1 lb/ton U
(5.00x10-2 kg/Mg)
3-05-007-17 Portland Cement Wet Process Clinker Grinding None 2.00x10-2 lb/ton U
Manufacturing (1.00x10-2 kg/Mg)
3-05-014 Processed and Blown Glass All Processes None 5 lb/ton (2.5 kg/Mg) B
A-19
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
3-04-005-09 Lead-acid Three-process Operation None --- B
Battery Production
FF 3.77x10-1 lb/1000 batteries U
(1.71x10-1 kg/1000
batteries)
3-04-005-10 Lead-acid Lead Reclaiming Furnace None --- B
Battery Production
Scrubber 1.01x10-1 lb/1000 batteries U
(5.05x10-2 kg/1000
batteries)
3-04-005-11 Lead-acid Small Parts Casting None 1.00x10-1 lb/1000 batteries C
Battery Production (4.60x10-2 kg/1000
batteries)
3-04-005-12 Lead-acid Formation None ---
Battery Production
3-04-040-01 Lead Cable Coating Cable Covering None 5.00x10-1 lb/ton C
A-20
(2.50x10-1 kg/Mg)
3-09-060-01 Ceramic/Glaze Application Ceramic Glaze Spraying - None 3.0 lb/ton B
Spray Booth (1.5 kg/Mg)
3-04-051-01 Miscellaneous Lead Ammunition None <1.0 lb/ton C
Products (<5.0x10-1 kg/Mg)
3-04-051-02 Miscellaneous Lead Bearing Metals None Negligible C
Products
3-04-051-03 Miscellaneous Lead Other Metallic Lead Processes None 1.5 lb/ton C
Products (7.5x10-1 kg/Mg)
3-05-035-05 Miscellaneous Lead Abrasive Grain Wet Scrubber 4.4x10-3 lb/ton E
Products Processing/Washing/Drying (2.2x10-3 kg/Mg)
3-06-001-01 Miscellaneous Lead Type Metal Production/ Industry Average 2.5x10-1 lb/ton C
Products Remelting (Cyclones, FF, ESP, or (1.3x10-1 kg/Mg)
Wet Scrubber)
TABLE A-1. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
3-04-004-14 Miscellaneous Lead Lead Melting Pot Afterburner/ Scrubber 4.6x10-2 lb/ton D
Products (2.3x10-2 kg/Mg)
3-05-002-01 Batch-Mix Hot-Mix Rotary Dryer FF 7.4x10-7 lb/ton D
Asphalt Plants (3.7x10-7 kg/Mg)
Wet Scrubber - Medium 3.10x10-6 lb/ton U
Efficiency (1.55x10-6 kg/Mg)
Wet Scrubber - Medium 1.03x10-6 lb/ton U
Efficiency/Single Cyclone (5.15x10-7 kg/Mg)
Single Cyclone/Baghouse 2.00x10-6 lb/ton U
(1.00x10-6 kg/Mg)
Multiple Cyclone without 2.08x10-7 lb/ton U
Fly Ash (1.04x10-7 kg/Mg)
Reinjection/Baghouse
None 4.0 lb/ton U
(2.0 kg/Mg)
A-21
Emission Factor
SCC/AMS Control English Factor
Code Description Emission Source Device (Metric) Rating
EOD Activities 20-mm High-explosive None 1.8x10-3 lb emitted/lb U
Incendiary Cartridges treated
(1.8x10-3 g emitted/g
treated)
EOD Activities 40-mm High-explosive None 1.3x10-3 lb emitted/lb U
Cartridges treated
(1.3x10-3 g emitted/g
treated)
EOD Activities M18A1 Claymore None 5.3x10-7 lb emitted/lb U
Antipersonnel Mine treated
(5.3x10-7 g emitted/g
treated)
EOD Activities T45E7 Adapter-booster None 7.7x10-4 lb emitted/lb U
treated
(7.7x10-4 g emitted/g
treated)
EOD Activities PBAN-Ammonium Perchlorate None 2.2x10-6 lb emitted/lb U
A-22
Propellant treated
(2.2x10-6 g emitted/g
treated)
EOD Activities CTPB-Ammonium Perchlorate None 2.3x10-6 lb emitted/lb U
Propellant treated
(2.3x10-6 g emitted/g
treated)
EOD Activities PEG/PBAN None 1.0x10-6 lb emitted/lb U
treated
(1.0x10-6 g emitted/g
treated)