United States Office of
Environmental Protection Research and Development
Agency Washington, DC 20460
EPA-600/R-93-045
March 1993
&EPA Identification and
Characterization of Five
Non-Traditional Source
Categories:
Catastrophic/Accidental
Releases, Vehicle Repair
Facilities, Recycling, Pesticide
Application, and Agricultural
Operations
Prepared for Office of Air Quality Planning and Standards
-------
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental Protection Agency, and
approved for publication. Approval does not signify that the contents necessarily
reflect the views and policy of the Agency, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
-------
EPA-600/R-93-045
March 1993
IDENTIFICATION AND CHARACTERIZATION OF FIVE NON-TRADITIONAL SOURCE
CATEGORIES: CATASTROPHIC/ACCIDENTAL RELEASES, VEHICLE REPAIR FACILITIES,
RECYCLING, PESTICIDE APPLICATION, AND AGRICULTURAL OPERATIONS
FINAL REPORT
Prepared by
Stanley Sleva
Joseph A. Pendola
John McCutcheon
Ken Jones
TRC Environmental Corporation
100 Europa Drive, Suite 150
Chapel Hill, NC 27514
and
Sharon L. Kersteter
Science Applications International Corporation
206 University Tower
3101 Petty Road
Durham, NC 27707
EPA Contract No. 68-D9-0173
Work Assignment Nos. 2/220 and 3/304
EPA Project Officer: E. Sue Kimbrough
Air and Energy Engineering Research Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
Prepared for:
U.S. Environmental Protection Agency U.S. Environmental Protection Agency
Office of Air Quality Planning and Standards Office of Research and Development
Research Triangle Park, NC 27711 Washington, DC 20460
-------
ABSTRACT
This report presents the results of work completed under Work Assignment Nos. 2/220 and
3/304 under EPA Contract No. 68-D9-0173. This work is part of EPA's program to identify and
characterize emissions sources not currently accounted for by either the existing AIRS or SIP
area source methodologies and to develop appropriate emissions estimation methodologies and
emission factors for a group of these source categories. 1 -ised on the results of the identification
and characterization portions of this research, five source categories were selected for
methodology and emission factor development: catastrophic/accidental releases, vehicle repair
facilities, recycling, pesticide application and agricultural operations. This report presents
emissions estimation methodologies and emission factor data for the selected source categories.
The discussions for each selected category include general background information,
emissions generation activities, pollutants emitted, sources of activity and pollutant data,
emissions estimation methodologies, issues to be considered and recommendations. The
information used in these discussions was derived from various sources including available
literature, industrial and trade association publications and contracts, experts on the category and
activity, and knowledgeable federal and state personnel.
CH-92-139
11
-------
TABLE OF CONTENTS
Section Page
Abstract ii
List of Figures ix
List of Tables x
List of Acronyms xii
Conversion Factors xiv
1.0 INTRODUCTION 1-1
1.1 Background 1-1
1.2 Purpose of Work Assignments 1-2
1.3 Contents 1-2
2.0 CATASTROPHIC/ACCIDENTAL RELEASES - RAIL CAR, TANK TRUCK,
AND INDUSTRIAL ACCIDENTS 2-1
2.1 Definition/Description of Category and Activity 2-1
2.1.1 Rail Car 2-2
2.1.2 Tank Truck 2-2
2.1.3 Industrial Facilities 2-3
2.2 Process Identification and Definition 2-3
2.2.1 Rail Car 2-3
2.2.2 Tank Truck 2-4
2.2.3 Industrial Facilities 2-4
2.3 Pollutants Emitted from Each Identified Source 2-4
2.4 Estimate of the Pollutant Levels 2-5
2.5 Point/Area Source Cutoff 2-6
2.6 Level of Detail of Source Activity Data Availability 2-6
2.7 Level of Detail Required by Users 2-8
2.8 Emission Factor Requirements 2-9
2.9 Regional, Seasonal or Temporal Characteristics 2-10
2.10 Urban or Rural Characteristics 2-10
2.11 Potential Methodology 2-10
2.12 References 2-13
3.0 VEHICLE REPAIR FACILITIES 3-1
3.1 Definition and Description of the Category and Activity 3-1
3.2 Process Identification and Definition 3-2
3.2.1 Maintenance 3-10
3.2.1.1 Antifreeze/Engine Coolants 3-10
3.2.1.2 Brake Fluids 3-11
3.2.1.3 Crankcase Oils 3-12
3.2.1.4 Lubricants and Silicones 3-12
3.2.1.5 Steering Fluids 3-14
3.2.1.6 Transmission Fluids 3-14
CH-92-139 ill
-------
TABLE OF CONTENTS (Continued)
Section
3.2.1.7 Windshield Washer Fluids ....................... 3~|*
3.2.2 Cleaning ......................................... 3"15
3.2.2.1 Brake Cleaners ............................... ^~15
3.2.2.2 Carburetor and Choke Cleaners ................... 3"J^
3.2.2.3 Engine/Parts Cleaners/Degreasers .................. 3"17
3.2.3 Specialty ......................................... 3'2()
3.2.3.1 Belt Dressings ............................... 3'20
o on
3.2.3.2 Engine Starting Fluids ......................... ->~zu
3.2.3.3 Tire Repair Products ........................... 3~21
3.2.3.4 Windshield Deicers ........................... 3'21
3.2.4 Additives ......................................... 3'22
3.2.4.1 Crankcase Additives ........................... 3'22
3.2.4.2 Fuel System Additives ......................... 3'22
3.2.4.3 Radiator Additives ............................ 3'23
3.2.4.4 Transmission Additives ......................... 3~24
3.3 Pollutants Emitted from Each Identified Process ................... 3-24
3.4 Estimate of the Pollutant Levels .............................. 3-28
3.5 Source Activity Data Availability ............................. 3-29
3.6 Level of Detail Required by Users ............................ 3-31
3.7 Regional, Seasonal or Other Temporal Characteristics ............... 3-32
3.8 Potential Methodology ..................................... 3-32
3.9 References ............................................. 3-34
4.0 RECYCLING ................................................. 4-1
4.1 Introduction ............................................. 4-1
4.2 Background ............................................ 4-2
4.3 Recycling Programs ........................................ 4-3
4.3.1 Emissions Resulting from Collection of Recyclable Materials ...... 4-6
4.3.1.1 Characterization ............................... 4-6
4.3.1.2 Quantification ................................ 4-6
4.3.2 Nonrecyclable Wastes ................................. 4-7
4.3.3 Emissions from Centralized Facilities ...................... 4-8
4.3.3.1 Characterization ............................... 4-8
4.3.3.2 Quantification ................................ 4-9
4.4 Metals Recycling ......................................... 4-10
4.4.1 Steel ............................................ 4-10
4.4.2 Detinning ......................................... 4-13
4.4.2.1 Air Classification and Magnetic Separation ........... 4-15
4.4.2.2 Chemical Detinning ..................... : ..... 4-16
4.4.2.3 Separation .................................. 4-16
4.4.2.4 Tin Removal ................................ 4-16
4.4.2.5 Air Emissions ............................... 4-17
CH-92-139
-------
TABLE OF CONTENTS (Continued)
Section Page
4.4.3 Iron and Steel Manufacturing 4-17
4.4.3.1 Basic Oxygen Process Furnace 4-18
4.4.3.2 Electric Arc Furnace 4-18
4.4.3.3 Air Emissions 4-20
4.4.4 Aluminum 4-21
4.4.4.1 Secondary Aluminum Production 4-23
4.4.4.2 Compaction/Baling 4-24
4.4.4.3 Crushing 4-26
4.4.4.4 Shredding 4-26
4.4.4.5 Scrap Drying/Delacquering 4-27
4.4.4.6 Smelting 4-27
4.4.4.7 Air Emissions 4-31
4.5 Paper Recycling 4-32
4.5.1 Primary Paper Recycling Technologies 4-34
4.5.1.1 Material Inspection and Storage 4-37
4.5.1.2 Conveyor Systems 4-40
4.5.1.3 Manual Sorting 4-40
4.5.1.4 Magnetic Separators 4-40
4.5.1.5 Trommel Screens 4-41
4.5.1.6 Pulper 4-41
4.5.1.7 Screening/Cleaning 4-42
4.5.1.8 Separators 4-42
4.5.1.9 Clarifier 4-44
4.5.1.10 Bleaching 4-44
4.5.1.11 Dewatering Equipment/Thickener 4-45
4.5.2 Air Emissions : 4-45
4.5.2.1 Characterization 4-45
4.5.2.2 Quantification 4-46
4.6 Glass Recycling 4-46
4.6.1 Glass Processing 4-49
4.6.1.1 Manual Sorting 4-50
4.6.1.2 Magnetic Separation 4-50
4.6.1.3 Velocity Trap/Air Classifier 4-52
4.6.1.4 Crusher/Grinder 4-52
4.6.1.5 Screening 4-53
4.6.1.6 Aluminum Separation 4-53
4.6.2 Air Emissions 4-54
4.7 Plastics Recycling 4-54
4.7.1 Processing 4-57
4.7.1.1 Manual Sorting 4-58
4.7.1.2 Shredding and Grinding 4-60
4.7.1.3 Washing 4-60
CH-92-139 V
-------
TABLE OF CONTENTS (Continued)
Section Pflge
4.7.1.4 Separation ~ „
A n i c TN_ .... 4-n.Z
4.7.1.5 Dnng
4.7.1.6 AI. num Separation
4.7.1.7 Extrusion
4.7.1.8 Air Emissions
4.7.2 Resin Specific ^recessing
4.7.2.1 Polyeuiylene Terephthalate (PET)
4.7.2.2 High-Density Polyethylene (HDPE)
4.7.2.3 Vinyl (Vx 4'70
4.7.2.4 Low-Di :y Polyethylene (LDPE) 4'71
4.7.2.5 Polypropylene (PP) 4'72
4.7.2.6 Polystyrene (PS) 4'72
4.7.2.7 Commingled Plastics 4'73
4.7.2.8 Air Emissions 4'74
4.8 Solvent Recycling 4'75
4.8.1 Category Definition and Description 4~75
4.8.2 Process Definition and Description 4-75
4.8.3 Pollutant and Activity Levels 4~77
4.8.4 Emission Factors and Available Literature --78
4.8.5 Potential for Addiaonal Data 4-80
4.9 Recycling Activity Summary 4-80
4.10 References 4-82
5.0 PESTICIDE APPLICATION 5-1
5.1 Background 5-1
5.2 Process Breakdown 5-5
5.2.1 User Categories 5-5
5.2.2 Formulations 5-6
5.2.3 Equipment 5-7
5.2.3.1 Dusters 5-8
5.2.3.2 Sprayers 5-8
5.2.4 Area to be Treated/Type of Application and Treatment 5-9
5.3 Pollutants Emitted 5-10
5.4 Estimate of Pollutant Levels 5-11
5.5 Source Activity Data Availability 5-12
5.5.1 Consumer 5-12
5.5.2 Agricultural 5-16
5.5.3 Commercial/Municipal/Industrial 5-17
5.6 Level of Detail Required by Users 5-18
5.6.1 Consumer 5-18
5.6.2 Agricultural 5-18
5.6.3 Commercial/Municipal/Industrial 5-19
CH-92-139 Vi
-------
TABLE OF CONTENTS (Continued)
Section Page
5.7 Emission Factors Available/Required 5-19
5.8 Regional, Seasonal and Other Temporal Characteristics 5-20
5.9 Potential Methodologies 5-20
5.9.1 Consumer 5-20
5.9.2 Agricultural 5-20
5.9.3 Commercial/Municipal/Industrial 5-22
5.10 References 5-24
6.0 AGRICULTURAL OPERATIONS 6-1
6.1 Background 6-1
6.2 Process Breakdown 6-1
6.2.1 Tilling 6-2
6.2.1.1 Crop 6-2
6.2.1.2 Soil Type/Site Characteristics 6-2
6.2.1.3 Equipment Type 6-3
6.2.2 Harvesting 6-3
6.2.2.1 Crop 6-4
6.2.2.2 Equipment 6-4
6.2.3 Wind Erosion 6-4
6.3 Pollutants Emitted 6-4
6.4 Estimate of Pollutant Levels 6-4
6.5 Source Activity Data Availability 6-6
6.6 Level of Detail Required by Users 6-6
6.6.1 Tilling 6r6
6.6.2 Harvesting 6-6
6.6.3 Wind Erosion 6-7
6.7 Emission Factors Available/Required 6-7
6.8 Regional, Seasonal and Other Temporal Characteristics 6-7
6.9 Potential Methodologies 6-7
6.9.1 Tilling 6-8
6.9.2 Harvesting 6-9
6.9.3 Wind Erosion 6-10
6.10 References 6-12
7.0 ISSUES AND RECOMMENDATIONS 7-1
7.1 Introduction 7-1
7.2 Catastrophic/Accidental Releases 7-1
7.3 Vehicle Repair Facilities 7-1
7.4 Recyling 7-2
CH-92-139 VU
-------
TABLE OF CONTENTS (Continued)
Section Page
7.5 Pesticide Application 7-3
7.6 Agricultural Operations 7-3
APPENDIX'A INDEX OF CODES A-l
APPENDIX B HYPOTHETICAL EXAMPLE OF AN NRC ACCIDENT REPORT B-l
CH-92-139
-------
LIST OF FIGURES
Number Page
4-1 Overview of Aluminum Recycling 4-25
4-2 Paper Recycling Process Flow 4-38
4-3 The Glass Recycling Process 4-51
4-4 Overview of Plastics Recycling Process With Inputs and Outputs 4-59
CH-92-139 IX
-------
LIST OF TABLES
VT v
Number
3-4
3-1 Formulation Profiles for Automotive Fluids Used in Vehicle Repair Facilities
3-2 \ latile Organic Compounds in Automotive Products Used in Vehicle Repair ^
Facilities
3-29
3-3 VOC Emission Factors for Automotive Products
4-4
4-1 Materials Recovery from Municipal Solid Waste, 1988
4-2 Typical Organic Components of Coatings Applied to Beverage Cans
4-3 Characterization Summary of Emissions from Recycling Processes for
Steel Product! n 4"21
A 99
4-4 Emission Factors for Steel Foundries H~^
4-5 Generation and Recycling of Aluminum Products in MSW 4-22
4-6 Typical Elemental Composition of Aluminum Scrap 4-23
4-7 Emissions Characterization Summary of Recycling Processes Secondary
Aluminum Operations 4-32
4-8 Particulate Emission Factors for Secondary Aluminum Operations 4-33
4-9 Generation Recycling of Paper and Paperboard in MSW, 1988 4-35
4-10 Specific Processes Associated with Wastepaper Categories 4-36
4-11 Deinking Chemicals 4-39
4-12 Emission Factors for Kraft Pulping 4-47
4-13 Generation and Recycling of Glass in MSW, 1988 4-48
4-14 Net U.S. Resin Sales of Commonly Recycled Thermoplastic Resins (1990) 4-55
4-15 Generation and Recycling of Plastics in MSW, 1988 4-56
4-16 Primary Feedstock Chemicals Used in Commonly Recycled
Thermoplastic Resins 4~65
CH-92-139
-------
LIST OF TABLES (Continued)
Number Page
4-17 Categories of Additives Used in Plastics, Use Concentrations, and Major
Polymer Applications (1987) 4-66
4-18 Emission Factors for Solvent Reclaiming 4-78
5-1 Per Capita Factors for Pesticide Emissions 5-13
5-2 Pesticide Emissions Estimates 5-14
CH-92-139 XI
-------
LIST OF ACRONYMS
ACGIH Amen. Conference of Governmental Industrial Hygienists
ADP Air-dried unbleached pulp
AFS AIRS Facility Subsystem
AIRS Aerometric Informat' >n Retrieval System
ASTM American Society for Testing and Materials
BLEVEs Boiling Liquid Expanding Vapor Explosions
CARB California Air Resources Board
CAS Chemical Abstract Service
CERCLA Comprehensive Environmental Response, Compensation and Liability Act
CHRIS Chemical Hazard Response Information System
CO carbon monoxide
DOT U.S. Department of Transportation
EPA U.S. Environmental Protection Agency
ERNS Emer ency Response and Notification System
FIFRA Federal Insecticide, Fungicide and Rodenticide Act
HTAHCAC Handbook of Toxic and Hazardous Chemicals and Carcinogens
HOPE high-density polyethylene
ITC International Trade Commission
JEIOG Joint Emission Inventory Oversight Group
LDPE low-density polyethylene
MRFs Material recovery facilities
MRI Mediamark Research Incorporated
MSW Municipal Solid Waste
NADB U.S. EPA, National Air Data Branch
NAPAP National Acid Precipitation Assessment Program
NEDS National Emissions Data System
NLM National Library of Medicine
NMR Neilson Marketing Research
NOX oxides of nitrogen
NRC National Response Center
PCV positive crankcase ventilation valve
PET polyethylene terephthalate
PM particulate matter
PM-10 particulate matter less than 10 jim in diameter
PP polypropylene
PS polystyrene
PVC polyvinyl chloride
RCRA Resources Conservation and Recovery Act
SAMI Selling Area Marketing Index
SARA SUPERFUND Amendments and Reauthorization Act of 1986
SCC source classification code
SERC State Emergency Response Commission
SIP State implementation plan
S02 sulfur dioxide
CH-92-I39
Xll
-------
SOCMI Synthetic and organic chemical manufacturing industry
SPI Society of the Plastics Industry
TLV Threshold Limit Values
TOG Total organics
TOXNET NLM's Toxicology Data Network
TPY tons per year
TRI Toxic Chemical Release Inventory
TRS total reduced sulfur
TSP total suspended particulate
TWA ACGIH's Time-Weighted Average
USCG U.S. Coast Guard
V vinyl
VOC volatile organic compound(s)
VMT vehicle miles traveled
CH-92-139 Xlll
-------
O WERSION FACTORS
To Convert From
To
Multiply By
Acre
Acre
Barrel (bbl)
Barrel (bbl) - petroleum*
Board foot
British thermal unit (Btu)
British thermal unit/hour (Btu/hr)
Centigrade
Cord
Cubic foot (ft3)
Cubic foot (ft3)
Cubic foot/minute (ftVmin)
Cubic yard (yd3)
Fahrenheit
Foot (ft)
Gallon (gal)
Inch (in)
Mile (mi)
Pound steam/hour** (Ib/hr)
Pound (Ib)
Pound/ton (Ib/ton)
Pound/square inch (psi)
Quart (qt)
Square foot (ft2)
Ton
Hectare (ha)
Square meter (m2)
Liter (1)
Gallon (gal)
Cubic meter (m3)
Gram/calorie (g/cal)
Watt(W)
Fahrenheit
Cubic meter (m3)
Cubic meter (m3)
Liter (1)
Cubic centimeter/second
(cmVsec)
Cubic meter (m3)
Centigrade
Meter (m)
Liter (1)
Centimeter (cm)
Kilometer (km)
British thermal unit/hour
(Btu/hr)
Kilogram (kg)
Gram/kilogram (g/kg)
Kilopascal (kPa)
Liter (1)
Square meter (m2)
Kilogram (kg)
2.471
4047
159
42
0.0024
251.98
0.293
(°C+32) 9/5
3.6224
0.0283
28.316
472.0
0.77
(°F-32) 5/9
0.3048
3.785
2.54
1.609
1400.0
0.45
0.496
6.894
0.946
0.0929
907.1
^42 gal/bbl is the standard as used in the oil industry. For other industries, diflc gallonstobl apply.
**Typical value based on common boiler design parameters. Value will vary de. ,ing upon steam temperature and
pressure.
CH-92-139
XIV
-------
SECTION 1.0
INTRODUCTION
1.1 BACKGROUND
Area source emissions of paniculate matter (PM or TSP), sulfur dioxide (SO2), oxides of
nitrogen (NOJ, reactive volatile organic compounds (VOC) and carbon monoxide (CO) are
estimated annually by the National Air Data Branch (NADB) of the U.S. Environmental
Protection Agency (EPA). Area sources are typically aggregations of individual sources that
are too small to be defined as point sources in a specific geographic area. Area sources usually
include all mobile sources and any stationary sources that are too small, difficult, or numerous
to be inventoried as point sources. The National Emissions Data System (NEDS) is the data
management and processing system that has historically been used to maintain these annual
emissions data. The statutory requirement for annual inventories defines an area source as an
anthropogenic mobile or stationary source that emits less than 100 tons per year (TPY) of TSP,
SO2, NOX or VOC, or 1,000 TPY of CO.
The original NEDS area source methodology and algorithms were developed in 1973 and 1974
using 1960 census data (e.g., population, housing, manufacturing). The NEDS methodology
has remained relatively unchanged over the past 17 years and forms the basis for the
Aerometric Information Retrieval System/Area and Mobile Source Subsystem (AIRS/AMS)
methods. The Joint Emissions Inventory Oversight Group (JEIOG) is currently updating and
revising emission estimation and allocation methods using more recent data.
While emissions sources included in current inventory methodologies do cover a large portion
of anthropogenic emissions, many small source categories are not included in the inventory.
Identification, characterization and inclusion of these categories and their emissions hi the
inventory will result in a more thorough and complete emissions inventory.
CH-92-139 1-1
-------
1.2 PURPOSE OF WORK ASSIGNMENT
The purpose of these work assignments is to more fully characterize the following five source
categories not currently accounted for in the NEDS area source and AIRS/AMS methodologies:
Catastrophic/Accidental Releases; Vehicle Repair Facilities; Recycling Processes; Farming
Operations; and Crop Dusting/Pesticide Application. To the extent that data and information
were available, the following topics are included in the categorization:
• Definition and description of the category and activity
• Process identification and definition
• Pollutants emitted from each identified process
• Estimate of the pollutant levels
• Source activity data availability
• Level of detail required by user
• Emission factors available/required for each identified process
• Regional, seasonal or other temporal characteristics
• Potential methodology
• Additional data requirements critical to methodology development
1.3 CONTENTS
Sections 2 through 6 of this report describe the characterizations of the five source categories.
Section 2 presents the results for catastrophic/accidental releases; Section 3 describes vehicle
repair facilities; Section 4 includes recycling processes; Section 5 includes farming operations and
Section 6 discusses crop dusting/pesticide application. An index of pollutant codes is provided
as Appendix A. Appendix B presents a sample National Response Center (NRC) accident report.
CH-92-139
-------
SECTION 2.0
CATASTROPHIC/ACCIDENTAL RELEASES - RAIL CAR, TANK TRUCK,
AND INDUSTRIAL ACCIDENTS
2.1 DEFINITION/DESCRIPTION OF CATEGORY AND ACTIVITY
Catastrophic releases, which often involve the release of large quantities of substances over a
very short period of time, potentially represent a significant portion of an area's total emissions.
However, these emissions are not represented in the current area source emissions inventory
methodology.
For this discussion, catastrophic/accidental releases refer to the unintentional and unexpected,
sudden release of pollutants to the atmosphere from rail cars, tank trucks, and industrial
facilities. Naturally occurring releases like the Mount St. Helens Volcanic eruption in 1980
are not covered in this definition. The accident or catastrophe may be caused by equipment
failure, roadway conditions, human error, or by natural conditions (i.e., hurricane, lightning,
earthquake, or flash flood).1 These two types of releases differ hi their severity. As defined
here, an accident is an unintentional or unexpected happening that is undesirable or unfortunate,
while a catastrophic event is a sudden and widespread calamitous event causing great damage
or hardship. Because accidental releases are considered not as severe as a catastrophic release,
minor accidental releases often go unreported. Examples of accidental releases are the
overloading of an underground storage tank and chemical spill resulting from a highway truck
accident. The Chernobyl disaster is an example of a catastrophic release.
Catastrophic releases from rail car, tank truck, and industrial accidents are usually chemical
spills, with or without combustion. The types and quantities of emissions depend on factors
such as the material released, remediation efforts, and weather conditions.
2-1
-------
2.1.1 RaU Car
According to recent statistics, about 80 million tons of hazardous materials are shipped
annually by rail in the United States.2 The majority of these shipments are in single tanks
permanently mounted on rail cars. Exceptions include multi-tank cars (the units are usually
ton containers), seamless steel cylinders (for very high-pressure service), and compartmented
tank cars in which each compartment is treated as a separate tank. The sizes of these will
range from a few hundred gallons hi the case of ;, 1-ton container to 45,000 gallons in so-
called jumbo tank cars. Since 1970, howeve- the capacity of new tank cars has been limited
to 34,500 gallons.
Rail cars are usually classified as pressure tank cars, non-pressure tank cars, cryogenic liquid
tank cars, or miscellaneous tank cars. Carbon steel is used to construct over 90 percent of the
tanks, with aluminum used for most of the remainder. Nickel or nickel alloy is found in acid
service, and there are a small number of stainless steel cars.3 Safeiy relief valves (and vents)
are required, unless otherwise specified. Tanks may be lined, insulated, and possibly fitted
with heating coils. Some may have special thermal protection to prevent Boiling Liquid
Expanding Vapor Explosions (BLEVES) or other explosions in the event of exposures to pool
fires or flame jets. To help prevent punctures from occurring during derailment, shelf couplers
and head shields are used.
In addition to bulk transportation, hazardous materials may be transported in small packages
(i.e., cylinders, drums, barrels, cans, bottles, and boxes). These containers are defined by the
U.S. Department of Transportation as having a capacity of less than 110 gallons or 1000
pounds. Packaged hazardous materials may be moved by truck, van, or boxcar.
2.1.2 Tank Truck
Tank trucks are usually tractor-serr jailer vehicles or smaller bobtail-type units. The tanks
themselves are typically constructed of steel or an aluminum alloy, but may also be constructed
of stainless steel, nickel and other materials. Capacities range from 3,000 to 10,000 gallons,
CH-92-139 2-2
-------
although slightly smaller and larger units are available. Interaodal tanks, tanks within a
protective rigid framework, one-ton tanks which are lifted on and off the transporting vehicle,
and large gas cylinder bundles are also commonly used for bulk transport by highway.
2.1.3 Industrial Facilities
A broad range of facilities may pose potential risks associated with the release of hazardous
materials. These facilities can include large refineries, chemical plants, and storage terminals;
more moderately sized industrial users, warehouses, and isolated storage tanks for water
treatment; and small quantity users/storage areas as may be found in high school and college
laboratories, florists, greenhouses, hardware and automotive stores, and paint stores.
2.2 PROCESS IDENTIFICATION AND DEFINITION
Air pollutants from catastrophic and accidental releases may enter the atmosphere through
evaporation of liquid releases, combustion of solid or liquid materials, or venting of gaseous
or particulate materials.
2.2.1 Rail Car
The release of hazardous materials from rail cars usually results from (1) collision or
derailment, which typically involves the largest spills or discharges; and (2) fitting or seal
leaks, relief valve leaks, and other releases associated with improper tightening of closures or
defective equipment. It is estimated that most releases occur as a result of this second
category.4 Results from rail car accidents, like accidents involving tank trucks, can range from
virtually no adverse consequences up to many deaths, depending on the materials involved and
the circumstances of the accident.
CH-92-139 2-3
-------
2.2.2 Tank Truck
Truck accidents on roadways, regardless of the cargo involved, are generally due to (1)
collisions with other vehicles; (2) collisions with fixed objects such as bridges or overpass
supports; or (3) loss of control and overturns due to excessive speed on curves. These four
events are most likely to result hi a release of large quantities of hazardous materials and are
predominately the result of human error. Smaller releases may arise due to defective or loose
valves, fittings or couplings; weld failures; and various other structural defects.l
2.2.3 Industrial Facilities
Releases from industrial fixed facilities may arise from storage tank or container ruptures or
leaks, piping ruptures or leaks, releases through safety and relief valves, fire-induced releases,
other equipment failures, malicious or deliberate actions, overfills and overflows of storage
tanks, human errors, open valves, failed loading hoses, or improper hose connections.1
Transfer areas include pipelines, pumps, valves, and control instrumentation needed to achieve
the movement of material within a facility. The loading/unloading area involves the most
handling operations and the largest potential for human error hi most facilities. Because the
greatest volume of materials are contained here, spills can be quite large.1
23 POLLUTANTS EMITTED FROM EACH IDENTIFIED SOURCE
The nature of catastrophic releases makes precisely describing the released materials difficult.
A material may be hi one form for storage or transportation but may form a different substance
when released. Appendix A is a compilation of common hazardous materials, from the
National Response Center, that could be subject to accidental release. Many of these
substances are included within EPA's List of Hazardous Substances, Section 302.4(a) of the
Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA). VOC
species emitted are dependent on the material released. VOC, NOX, and CO emissions are
CH-92-139 2-4
-------
possible if combustion takes place. Air toxics may also be emitted. Some examples of the
different types of materials and emissions are described in the following paragraphs.
In Chicago, a bulk storage tank of silicon tetrachloride developed a leak. The escaping liquid,
150,000 gallons, reacted with the moisture in the air and formed hydrogen chloride, resulting
in a dense, corrosive, choking plume that stretched 5-10 miles downwind.1
A train derailment transporting white phosphorus in Miamisburg, Ohio produced a white cloud
of toxic smoke that towered a thousand feet over the community and covered an area about
1 mile wide and 10-15 miles long.1
In Houston, a tank truck carrying liquefied anhydrous ammonia collided with a car and fell
from an elevated highway to a busy freeway. The truck exploded, releasing billowing clouds
of ammonia covering a three mile radius.1
2.4 ESTIMATE OF THE POLLUTANT LEVELS
Levels of pollutants vary widely from year to year and from area to area. Due to the nature
of catastrophic/accidental releases, it is very difficult to estimate annual emissions for any
particular hazardous material. Using national hazardous material databases, information on
various spills can be collected. For instance, using information from the Emergency Response
Notification System (ERNS), described in 2.6, estimates for the reported quantities of released
hazardous substances was obtained. In 1989 there was an estimated 219.8 million pounds of
catastrophic/accidental release of hazardous substances within the United States and its
territories.5 This number is low because it only covers reported occurrences. Employing a
methodology similar to that developed for oil spills, emission rates could be estimated,
provided that input data for the various factors in equations are available.6
Estimates on missing sources for an area emissions inventory could also be obtained by
collecting data on the total gallons or pounds of material released in a specific area. Using
some simplifying assumptions, such as 50 percent dispersion rate for particulate releases or
CH-92-139
2-5
-------
10 percent volatilization rate for liquids, rough emission estimates could be calculated from the
available data.
2.5 POINT/AREA SOURCE CUTOFF
Catastrophic releases are not specifically identified in current point or area source inventories.
The reason for this is that Source Classification Codes (SCC) codes do not exist for these
categories. Source Classification Codes are required for storing source and emissions data in
EPA's Aerometric Information Retrieval System (AIRS) Facility Subsystem (AFS), and in
states' computerized source files.7 To include such emissions hi an inventory, SCC codes
would need to be developed.
2.6 LEVEL OF DETAIL OF SOURCE ACTIVITY DATA AVAILABILITY
40 CFR Part 302.6 requires that releases of hazardous chemicals be reported to the National
Response Center (NRC). The NRC, operated by the U.S. Coast Guard (USCG) and EPA,
maintains a database on oil spills, hazardous materials, and other releases. Access to these data
is guaranteed by the Freedom of Information Act.8 Data reported for each accident include,
but are not restricted to, the following:9
• Date of release
• Material released
• Media affected (water, ah-, etc.)
• Mode (tram, ship, truck, etc.)
• Location
• Quantity released
Appendix B contains an example of an NRC accident report. The entries are fictitious and are
only presented fc sample purposes.
Agencies requesting information from the NRC should send written requests to the following
address:
CH-92-139 2-6
-------
National Response Center
U.S. Coast Guard Headquarters
Room 2611
2100 2nd Street S.W.
Washington, DC 20593
The NRC also operates a toll-free accident reporting service (1-800-424-8802).
Another source of information on catastrophic emissions is ERNS. ERNS is a national
computer database and retrieval system that is run by the EPA and supported by the USCG.
ERNS stores information on releases of oil and hazardous substances, and provides a direct
source of easily-accessible data that can be used to analyze spills and to support emergency
planning efforts by Federal, state, and local governments. The database contains the following
types of information:
• Material released
• Amount released
• Source of release
• Incident location
• Response actions taken
• Environmental medium into which the release occurred
Information from ERNS is made available to the public in periodic reports published by EPA's
Emergency Response Division. These reports can be obtained by calling the RCRA/Superfund
Hotline at 1-800-424-9346 (in the Washington, D.C. metropolitan area, call 1-202-382-3000).10
All states are required by CERCLA to have a State Emergency Response Commission (SERC).
It is the duty of the SERC to compile information on accidental/catastrophic releases occurring
within the state. However, the quality of the information varies from state to state, and much
of the information can be obtained from NRC or ERNS.11
CH-92-139
2-7
-------
A future source of information on accidental releases will be the Toxic Chemical Release
Inventory (TRI). TRI contains files on the annual estimate;! releases of toxic chemicals to the
environment from point sources complying with Title III of the SUPERFUND Amendments
and Reauthorization Act (SARA) of 1986. EPA collects the information and it becomes
accessible through the National Library of Medicine's (NLM) Toxicology Data Network
(TOXNET). Data submitted to EPA include names and addresses of facilities wHch
manufacture, process or otherwise use these chemicals, as well as amounts released to die
environment or transferred to waste sites.12 Beginning in 1992, a new section will be added
to the data form and database for r porting facilities to fill in amount of material released
accidentally.13
Contact the following source for further information about the TRI file and gaining access to
it:
TRI Representative
Specialized Information Services
National Library of Medicine
8600 Rockville Pike
Bethesda, MD 20894
Telephone (301) 496-6531
EPA also maintains the Emergency Planning and Community Right to Know Hot Line. This
service provides additional information about the requirements of Title III of SARA and
technical questions about TRI. The number of the hotline is 1-800-535-0202.
2.7 LEVEL OF DETAIL REQUIRED BY USERS
Catastrophic releases should be inventoried on an area wide or county basis. NRC and ERNS
contain area-specific release data (amount, type, remediation efforts, date of release, etc.) for
the nation. NRC reports could be generated for all re : ases occurring in a particular area. To
quantify catastrophic releases, the following information is required to estimate emissions:
CH-92-139 2-8
-------
Area covered by the spill
Quantity of spill
Type of material released
Time period of release
Meteorological conditions
Occurrence of combustion
Release site demographics characteristics
Media affected
Remediation efforts
The total number of releases occurring
2.8 EMISSION FACTOR REQUIREMENTS
The releases reported to the NRC and ERNS should be examined individually to determine the
volatility of material, and the effect of remediation and climate. Furthermore, the evaporative
loss needs to be calculated along with the emission factor for any fire that may be associated
with the release. Because there has been work toward developing a methodology for assessing
the emissions from structural fires14, that aspect is not covered in this report.
Evaporation losses for liquid spills can be calculated by the following steps:
• Determine the spill area and spill material
• Determine the elapsed time
• Calculate mass transfer coefficient
• Calculate evaporative exposure
• Determine volume fraction evaporated
• Calculate mass evaporated
CH-92-139
2-9
-------
Atmospheric emissions as a result ;~re can be calculated by the following steps:
• Determine burning velocity
• Determine spill area and spill material
• Determine elapsed time of fire
• Determine mass of fuel burned
• Determine mass of pollutant released
2.9 REGIONAL, SEASONAL OR TEMPORAL CHARACTERISTICS
Seasonal climate variations could affect the likelihood of a spill and volatilized emissions,
depending on regional or temporal conditions. Winter conditions in the northeast or west
increase the potential for vehicular accidental releases because of ice and snow accumulation.
Freezing temperatures would also decrease the volatilization of released material. In the
southwest, dry hot conditions could lead to greater evaporation losses from a spill.
2.10 URBAN OR RURAL CHARACTERISTICS
Point sources are just as likely to locate in rural as in urban areas. Therefore this probability
of releases occurring would be equal for either of them. However, studies on truck
transportation of hazardous substances have shown a higher probability of releases occurring
in urban road areas compared to interstate or state highways.15 Catastrophic or accidental
releases are likely to happen hi urban as well as rural areas.
2.11 POTENTIAL METHODOLOGY
Due to the wide variety of factors and circumstances inherently associated with
catastrophic/accidental releases, it is very difficult and resource intensive to accurately assess
emissions. There are several ways to estimate emissions from releases, each of which result
in estimates with varying degrees of uncertainty. The methodologies described in this section
CH-92-139 2-10
-------
cover current years. For releases from current years, two methods are proposed, although
multiple variations of these are also possible. Emission estimates for each method could be
based on a variation of the following general procedure, using data from databases containing
historical records of catastrophic/accidental releases.
Step 1 Determine the activity level from appropriate databases (i.e., the number of
releases, the pollutant and its physical state, and the amount of material released).
Step 2 Determine emissions by multiplying the activity indicator by an emission factor
(no emission factors are currently available), or determine emissions by use of
appropriate equations which account for variables such as liquid spill area, gas-
phase mass transfer coefficient, and volume and depth of the spill (these equations
also need to be developed).
Future projections on the number of catastrophic/accidental releases could be calculated by
applying statistical analysis to the number of yearly accidents over the past 20 years to obtain
a projection of the number of releases for a given year.
In the first method, emissions from accidental releases would be estimated using existing NRC,
ERNS, or state databases to obtain the type and amount of material released for any particular
geographic area. This method would require that each accidental release be treated separately:
emissions from each release would be calculated individually and then added together to
provide an estimate of the total released emissions.
In the second method, activity indicators (number and type of release) would also be obtained
from the NRC, ERNS, or state database. However, each release would not be treated
separately. Instead, the total amount of pollutant would be summed and multiplied by an
appropriate emission factor. The emission factor would be based on some gross assumptions
concerning the factors that affect the emissions. Because of the use of assumptions, the
emissions estimate for this method would have the highest level of uncertainty.
CH-92-139
2-11
-------
For future year emission estimates, probabilistic accident estimation is suggested. This
techniques involves historical data summarization, trend direction procedures, and possibly one-
to five-year forecasts.
CH-92-I39 2 I?
-------
2.12 REFERENCES
1. Handbook of Chemical Hazard Analysis Procedures. Federal Emergency Management
Agency, Technological Hazards Division, U.S. Department of Transportation, Office
of Hazardous Materials Transportation and U.S. Environmental Protection Agency,
Chemical Emergency Preparedness and Prevention Office, 1990.
2. Office of Technology Assessment. Transportation of Hazardous Materials: State and
Local Activities, OTA-SET-301, Washington, DC: U.S. Government Printing Office,
March 1986.
3. Wright, CJ. and P.J. Student. Understanding Railroad Tank Cars, Fire Command,
November 1985, pp. 18-21 and December 1985, pp. 36-41.
4. Harvey, A.E., P.C. Conlon, and T.S. Glickman. Statistical Trends in Railroad
Hazardous Materials Transportation Safety - 1978 to 1986, Publication R-640,
Association of American Railroads, Washington Systems Center, September 1987.
5. U.S. Environmental Protection Agency. Selected Data on Oil and Hazardous
Substances Release Notifications, Emergency Response Division Emergency Response
Notification System (ERNS). 1991.
6. Kersteter, S. et al. Identification and Characterization of Missing or Unaccounted for
Area Source Categories, EPA-600-R-92-006 (NTIS PB92-139377), Air and Energy
Engineering Research Laboratory, Research Triangle Park, NC, January 1992.
7. U.S. Environmental Protection Agency. PM-10 Emission Factor Listing Developed
by Technology Transfer with AIRS Source Classification Codes, EPA-450/4-89-022
(NTIS PB91-148411), Office of Air Quality Planning and Standards, Research
Triangle Park, NC, November 1989.
8. Personal Communication. Wallace, K., National Response Center, to Stanley Sleva,
Alliance Technologies Corporation, Chapel Hill, NC, September 20,1991. Information
from the database concerning spills.
9. Kohl, Jerome, L.A. Weaver III, and Linda Deal. Hazardous Waste Management for
Small Generators. Industrial Extension Service, College of Engineering, North
Carolina State University. April 15, 1990.
10. U.S. Environmental Protection Agency. The Emergency Response Notification System.
EPA 9360.0-21 (NTIS PB90-249715), Office of Emergency and Remedial Response,
August 1989.
CH-92-139
2-13
-------
11. I -onal Communication. Matheson, C., Chemical Emergency Preparation and
F Tition Office, U.S. Environmental Protection Agency, to Kenneth Jones, Alliance
Te Biologies Corporation, Chapel Hill, NC, March 24, 1992. Information on current
databases relating to catastrophic releases.
12. U.S. Department of Health and Human Services. TRI Toxic Chemical Release
Inventory National Library of Medicine Fact Sheet, Bethesda, MD, January 1992.
13. Personal Communication. Information Specialist, Emergency Planning and
Community Right to Know Hot Line, to Kenneth Jones, Alliance Technologies
Corporation, Chapel Hill, NC, June 3, 1992. Information on TRI Database.
14. U.S. Environmental Protection Agency. Procedures for Emission Inventory
Preparation, Volume III: Area Sources, EPA-450/4-81-026c (NTIS PB82-240128),
Office of Ah- Quality Pbnning and Standards, Research Triangle Park, NC, September
1981.
15. Abkowitz, M.D., A. Eiger, and S. Srinivasan. Assessing the Releases and Costs
Associated with Truck Transport of Hazardous Wastes, EPA Office of Solid Waste
NTIS PB-84-224468, 1984.
CH-92-139
2-14
-------
SECTION 3.0
VEHICLE REPAIR FACILITIES
3.1 DEFINITION AND DESCRIPTION OF THE CATEGORY AND ACTIVITY
Vehicle repair facilities are defined as locations which service or repair light-duty vehicles with
predominantly gasoline engines. This category includes the general service station or garage, as
well as facilities offering more specialized services (e.g., oil change, tune-up, muffler/exhaust
repair, radiator repair, etc.). This category does not include exterior-related services such as car
washing/detailing shops and paint and body repair shops. Many repair activities which generate
emissions are also performed by individual vehicle owners. These do-it-yourselfers (DIYers)
could account for a large percentage of the emissions related to this category. Due to the broad
scope of this category, several subcategories were identified. The following subcategories
represent the fluids or class of fluids identified as sources of emissions.
Maintenance
• Antifreeze/engine coolants
• Brake fluids
• Crankcase oils
• Lubricants & silicones
• Steering fluids
• Transmission fluids
• Windshield washer fluids
Cleaning
• Brake cleaners
• Carburetor and choke cleaners
• Engine/parts cleaners/degreasers
Specialty
• Belt dressings
• Engine starting fluids
• Tire repair products
• Windshield deicers
Additives
• Crankcase
• Fuel system
CH-92-139
3-1
-------
Radiator
Transmission
3.2 PROCESS IDENTIFICATION AND DEFINITION
Automotive repair products are used by professional mechanics and vehicle owners. VOC
emissions from automotive fluids are associated with draining, refil'ng, overfilling, or replacing
fluids and from running and standing losses. Vehicle repair facilities generate emissions through
the use of products containing solvents and aerosol propellants. Propellants are used to propel
aerosol products from containers, solubilize active ingredients, and serve as part of the diluting
system. Solvents solubilize the product ingredients and affect the evaporation rate of the product.
Many of these products are composed of volatile organic compound /OC). In addition, some
of the compounds in automotive fluids are considered hazardous, composed of toxic and ignitable
chemicals.
Some categories and product types were found to be more fully defined than others, particularly
with regard to the specificity of the terminology for various discrete product types and the
variability of formulations for a specific type of product. For example, the basic functional fluids
used in vehicles (antifreeze, brake fluid, transmission fluid, etc.) tend to have the same basic
formulation and principal ingredients. However, the term "carburetor cleaner" can apply to
products designed to be sprayed into the carburetor as well as buckets of solvent used to soak
partially-disassembled carburetors. There are also numerous other examples of multi-use
products, such as dressings, and other product categories such as lubricants, where descriptions
and designations may overlap. With the available information on product types and formulations,
it can be difficult to distinguish between formulations for distinct product types (i.e., products
with different intended applications) and different formulations for products intended for the same
basic use. In some cases, varying formulations may be due to differences in product form
(e.g., aerosol, liquid or solid), while some products in the same category may use different
ingredients for the same function (e.g., different solvents) or even operate on different basic
principles (solvent versus alkaline cleaning).
CH-92-139 3_2
-------
Almost without exception, the products discussed here are designed and labeled for use in general
automotive applications, which include cars, trucks and motorcycles. Specific products for trucks
or motorcycles are mentioned where they have been identified.
The formulation data presented in Table 3-1 and the following discussions are derived mainly
from product-specific and general formulations by product type listed in Clinical Toxicology of
Commercial Products.1 Except where another source is noted, all formulations summarized or
cited in this section were found in this reference. Wherever possible, distinctions have been
made between information from actual product formulations and general formulations compiled
by the authors, since in some cases the two sets of data did not agree. Some additional
information was also available in Household and Automotive Cleaners and Polishes,2 but most
of the formulations in this reference are from sources such as technical bulletins, and could not
be verified as being related to any actual product currently on the market.
Most automotive fluids contain varying combinations of additives such as oxidation inhibitors,
rust inhibitors, antiwear agents, detergents and dispersants, pour-point depressants, viscosity index
improvers and foam inhibitors. Oxidation inhibitors are generally organic compounds containing
sulfur, nitrogen and phosphorus, or alkyl phenols. Rust inhibitors are mildly polar organic acids
such as alkyl succinic or organic amines. Antiwear agents are composed of fatty acids, esters,
ketones, sulfur or sulfur dioxide mixtures, organic chlorine compounds (such as chlorinated wax),
organic sulfur compounds (such as sulfurized fats and sulfurized olefins), chlorine-sulfur
compounds, organic phosphorus compounds (such as tricresyl phosphate, thiophosphates and
phosphites) and organic lead compounds.3 Detergents and dispersants often make up 2 to
20 percent of automotive lubricants and are primarily composed of sulfonates, calcium/barium
salts of petroleum mahogany sulfonic acids, phosphonates, thiophosphonates and polymers
containing oxygen or nitrogen-bearing comonomers. Pour-point depressants are usually
polymethacrylates or polymers formed by condensation of wax with naphthalene or phenols.
Viscosity index improvers are linear polymers and foam inhibitors are methyl silicone polymers.3
CH-92-139
3-3
-------
TABLE 3-1. FORMULATION PROFI
VEHICLE REPAIR FAC
FOR AUTOMOTIVE FLUIDS USED IN
ES
Species Name
Percen
bv Weight
Species Name
Percent
by Weight
Antifreeze/Engine Coolants
Formulation 1
Ethylene glycol 95
Water 3
Soluble inhibitors/dyes 2
Formulation 2
Ethylene glycol 95.0
Water 2.5
Soluble inhibitors/dyes 2.5
Formulation 3
Ethylene glycol 95.0
Alkaline metal earths 2.5
Water 2.5
Brake Fluids
Formulation 1
Mixed polyglycol ethers 79
Polyalkylene glycol 20
Inhibitors 1
Formulation 2
M d polyglycol ethers 73
POJ> Jkylene elycol 26
Inhibitors ]
Formulation 3
Mixture of glycol ethers (diethylene glycol
monoethyl ether, triethylene glycol
monoethyl ether, triethylene glycol
monomethyl ether) 7.
Polypropylene glycol 20
Propylene or dipropylene glycol 10
Formulation 4
Poly-oxy-alkylene glycols, tri-glycol-ethers 1™
Crankcase Oils (no entries)
Lubricants
Formulation 1
Naphtha (aliphatic) 64.5
Oxygenated organic acids 20.0
Tricresyl phosphate (synthetic base) 10.0
Colloidal graphite dispersion in aliphatic
naphtha 5.0
Nonylphenoxy acetic acid 0.5
Formulation 2
Mineral oil 95
Additive, containing sulfur, chlorine, lead 5
Formulation 3
Mineral oil 99
Additives, containing methacrylate
copolymer 1
Formulation 4
Combined amount: Petroleum distillate,
2-butyl alcohol, glycerol mono-oleate,
1,1,1-trichloroethane 97.7
Carbon dioxide 2.3
Mineral oil 100
Formulation 6
Mineral spirits 70
Mineral oil 21
Petrolatum 6
Emulsifiers 3
Carbon dioxide (aerosol)
Formulation 7
Trichloroethane 94
Silicone fluid 4
Vegetable oil 2
Formulation 8
Mineral oil 50
Colloidal graphite dispersion in mineral oil 48
Sorbitan fatty acid ester 2
CH-92-139
(continued)
3-4
-------
TABLE 3-1. FORMULATION PROFILES FOR AUTOMOTIVE FLUIDS USED IN
VEHICLE REPAIR FACILITIES (Continued)
Species Name
Steering Fluids (no entries)
Transmission Fluids
Formulation 1
Mineral oil
Additive, containing zinc alkyl
dithiophosphate, boron, nitrogen
sulfur compounds
Formulation 2
Mineral oil
Percent
by Weight
92
and
8
91
Additive, containing polymer, dye, boron,
sulfur phosphorus compounds
Windshield Washer Fluids
Formulation 1
Methanol
Water
Formulation 2
Water
Methanol
Detergent/dye
Formulation 3
Methanol
Water
Ethylene glycol
Formulation 4
Methanol
Polyether alcohol surfactant
Formulation 5
Concentrate:
Methanol
Water
Mercapto ethoxylate
Premix:
Methanol
Water
Mercapto ethoxylate
CH-92-139
9
64
36
>59.97
40.00
<0.03
68
27
5
>95
1
>70
>10
<1
>40
>50
1-10
Species Name
Brake Cleaners
Formulation 1
Methanol
Formulation 2
Ethanol
Formulation 3
Isopropanol
Formulation 4
Aliphatic chlorinated solvents
Carburetor and Choke Cleaners
Formulation 1
Ethylene dichloride
Cresol
Butane
Formulation 2
Aliphatic hydrocarbons
n-Butane
Formulation 3
Cresol (o-,m-,p-)
Ethylene dichloride
n-Butane
Ethanol
Formulation 4
Toluene
Isomers of xylene
Methanol
Tetrahydrofurfuryl alcohol
Acetone
Formulation 5
Methylene chloride
o-Dichlorobenzene
Cresylic acid
Complex amines
Percent
by Weight
100
100
100
100
63
25
12
88
12
35
30
24
11
38.89
33.33
11.11
11.11
5.56
42.10
41.57
15.80
0.53
(continued)
3-5
-------
TABLE 3-1. FORMULATION PROFILES FOR AUTOMOTIVE FLUIDS USED IN
VEHICLE REPAIR FACILITIES (Continued)
Species Name
Percent
by Weight
Species Name
Percent
by Weight
Carburetor and Choke Cleaners, continued
Formulation 6
Xylol
Mixture of petroleum distillates
>50
>40
Formulation 7
Mineral oil >60
Combination: high molecular weight esters,
Carburetor and Choke Cleaners, continued
Formulation 15
Polybutene amine inhibitor
Mixed xylenes
Engine/Parts Cleaners/Degreasers
mixture of oxygenated unsaponifiable
hydrocarbons, alkyl aryl phosphate,
aromatic solvents
Formulation 8
Acetone
Aromatic hydrocarbons
Chlorinated hydrocarbons
Formulation 9
Aromatic hydrocarbons
Ketone
Formulation 10
Xylene
Methylene chloride
Orthodichlorobenzene
2-Butoxyethanol
Formulation 11
Chlorinated solvents
Cresols
Soaps
Formulation 12
Xylene
Acetone
Diacetone alcohol
Formulation 13
Aromatic hydrocarbons
Ketones
Formulation 14
Mixed xylenes
Diacetone alcohol
CH-92-139
>30
<50
<35
<25
71
29
37
15
10
5
>50
>20
1-10
35
35
12
71
29
64.7
32.4
Formulation 1
Is- .ropanol
Formulation 2
Kerosene
Formulation 3
Aromatic 150 solvent
Formulation 4
Mineral spirits
Formulation 5
Heavy aromatic naphtha
Formulation 6
Kerosene
Pine oil
Ethanolamine
Formulation 7
Kerosene
Perchloroethylene
Butyl cellosolve
Ethanolamine
Formulation 8
Kerosene
Butyl cellosolve
Formulation 9
Butyl cellosolve
(continued)
3-6
<30
<30
100
100
100
100
100
59.04
37.27
3.69
87.03
9.28
2.22
1.48
75
25
100
-------
TABLE 3-1. FORMULATION PROFILES FOR AUTOMOTIVE FLUIDS USED IN
VEHICLE REPAIR FACILITIES (Continued)
Species Name
Percent
by Weight
Species Name
Percent
by Weight
Engine/Parts Cleaners/Degreasers, continued
Formulation 10
Petroleum distillates 80
Pine oil 10
Ethoxylated linear alcohol 10
Formulation 11
Water 52
Petroleum distillates 40
Anionic surfactant 6
Sodium metasilicate 2
Formulation 12
Coal tar distillates <65
Aliphatic chlorinated solvents <40
Formulation 13
Petroleum distillates <90
Vegetable fatty acid soap >5
Synthetic wetting agents <5
Coupler <3
Formulation 14
Petroleum distillates 95
Nonionic surfactants 5
Formulation IS
Water 86
Anionic surfactant 6
Glycol ether 5
Alkaline detergent builders 3
Formulation 16
Petroleum hydrocarbon 93
Nonyl phenyl polyethylene glycol ether 7
Formulation 17
Petroleum distillates 70
Vegetable fatty acid soap >5
Synthetic wetting agents <5
Water <5
Coupler <4
Engine/Parts Cleaners/Degreasers, continued
Formulation 18
Aromatic hydrocarbons 78.2
Nonionic surface active agents 6.8
Formulation 19
Aliphatic chlorinated solvents 45-52
Phenolic compounds 16-19
Water 14-25
Vegetable fatty acid soap 12-14
Synthetic wetting agents <1
Soluble chromates 0.2
Belt Dressings
Formulation 1
Petroleum derived resins 42.5
Chlorinated solvent as methylene chloride 25.5
Petroleum distillate 17
Formulation 2
Combined amount: solid petroleum fraction
of an asphaltic nature, heavy bodied
mineral oil fraction of crude, and
unrefined wool grease 70
Petroleum distillates 30
Formulation 3
Combined amount: petroleum distillates,
solid petroleum fraction of an asphaltic
nature, heavy bodied mineral oil
fraction of crude, and unrefined wool
grease 75
Engine Starting Fluids
Formulation 1
Ethyl ether
100
CH-92-139
(continued)
3-7
-------
TABLE 3-1. FORMULATION PROFILES FOR AUTOMOTIVE FLUIDS USED IN
VEHICLE REPAIR FACILITIES (Continued)
Species Name
Percent
by Weight
Species Name
Percent
by Weight
Engine Starting Fluids, continued
Formulation 2
Ethyl ether >90
Combined amount: high molecular weight
esters, mixture of oxygenated
unsaponifiable hydrocarbons <1
Formulation 3
Unrefined ether 63
Aliphatic hydrocarbon 36
Mineral oil 1
Formulation 4
Unrefined ethyl ether 80-90
Tire Repair Products
Formulation 1
Combined amount: rubber solvent,
1,1,1-Trichloroethane 100
Formulation 2
Combined amount: rubber solvent,
1,1,1-Tricnloroethane 80
Formulation 3
Toluol >80
Windshield De-icers
Formulation 1
Water 50
Methanol 35
Ethylene glycol 15
Formulation 2
Methanol 45
Water 40
Ethylene glycol 15
Crankcase Additives
Formulation 1
Petroleum distillate <90
Alcohol >5
Ester >5
Crankcase Additives, continued
Formulation 2
Naphthenic oil 90
Mixture of solvents: 10
Butyl carbitol
Butyl cellosolve
Methyl isobutyl carbinol
Diacetone alcohol
Cyclohexanone
Formulation 3
Mineral oil >60
Combined amount: high molecular weight
esters, mixture of oxygenated
unsaponifiable hydrocarbons, alkyl aryl
phosphate >30
Fuel System Additives
Formulation 1
Methanol
Radiator Additives
Formulation 1
Water
Mineral oil
Surfactants and emulsifiers
Formulation 2
Oxalic acid
Clay
Nonionic surfactants
100
64-67
25-27
8-9
95
4
1
CH-92-139
(continued)
3-8
-------
TABLE 3-1. FORMULATION PROFILES FOR AUTOMOTIVE FLUIDS USED IN
VEHICLE REPAIR FACILITIES (Continued)
Species Name
Percent
by Weight
Species Name
Percent
by Weight
Radiator Additives, continued
Formulation 3
Sodium carbonate 95
Clay 4
Nonionic surfactants 1
Formulation 4
Water 84-85
Sodium citrate 7
Anionic and nonionic surfactants 5
Isopropyl alcohol 3-4
Formulation 5
Petroleum distillates 74
n-Butyl alcohol 18
Nonionic surfactants 8
Formulation 6
Mineral spirits >50
n-Butanol >20
Alkyl phenol ethoxylate >10
Radiator Additives, continued
Formulation 7
Water 78
Sodium citrate 10
Anionic and nonionic surfactants 7
Isopropyl alcohol 5
Transmission Additives
Formulation 1
Refined mineral oil 100
Formulation 2
Mineral oil >60
Combined amount: amine salt of an acid,
chlorinated hydrocarbons >30
CH-92-139
3-9
-------
3.2.1 Maintenance
3.2.1.1 Antifreeze/Engine Coolants
The automotive engine cooling system controls metal temperatures within safe limits by removing
excess heat generated by the engine. In liquid-cooled engines (which account for essentially all
motor vehicles currently in use), this is accomplished by circulating a fluid coolant through
channels in the engine block and then through the radiator to release the block-generated heat to
the atmosphere. The coolant temperature hi an engine varies from ambient to hot and then cools
again to ambient temperature. These cyclic temperature changes can affect the stability of
protective films at metal surfaces and can cause corrosion. Coolant typically consists of a
mixture of water and "antifreeze" product designed to depress the freezing point, elevate the
boiling point, and prevent corrosion of metal surfaces within the engine, water pump and other
parts of the liquid circulation system. .
The corrosion protection afforded by antifreeze is dependent on the inhibitor effectiveness, the
antifreeze concentration, and the quality of the water with which it is mixed. Various alcohols
and glycols are effective freezing point depressants for water. However, because glycols,
specifically ethylene glycol, raise the boiling point of water while alcohols lower it, alcohol
antifreezes are no longer recommended by vehicle manufacturers. A minimum ethylene glycol
concentration of 50 percent by volume is recommended to ensure freezing protection to -34°F
(-37°C) and boiling protection to 227°?* (108°C).
According to the American Society for Testing and Materials (ASTM), car manufacturers
recommend that the factory-filled coolant be used for one to two years because longer periods
would show appreciable loss of freezing protection, loss of inhibitor reserve, and rust in solution.5
Major antifreeze manufacturers recommend that their products be used for one year, preferably
being replaced with fresh antifreeze each fall. A 1981 survey of antifreeze concluded that
products packaged by original manufacturers accounted for 63 percent of total sales, secondary
packaging for consumer sales accounted for 22 percent, and commercial and bulk users
(i.e., service stations and repair facilities) accounted for 5.5 percent of the sales of engine coolant.
CH-92-139 3-10
-------
The remainder (less than 10 percent) consisted of sales to original equipment manufacturers and
the government.6
Generic components of antifreeze products include solvents, freezing point depressants, fluidifiers,
and corrosion inhibitors/alkaline preservers. In current formulations, ethylene glycol serves the
function of solvent, freezing point depressant and fluidifier. Concentrations of ethylene glycol
in current formulations are more than 90 percent and commonly around 95 percent. About
3 percent water is typically included as a fluidifier. Corrosion inhibitors/alkaline preservers
represent 2.5 to 4.5 percent of typical formulations and may include borax, caustic soda, sodium
mercaptobenzothiazole, arsenites, or nitrates.
Air emissions of ethylene glycol can occur as evaporation of leaked or improperly disposed of
coolant removed during servicing or regular replacement of spent coolant.
3.2.1.2 Brake Fluids
Brake fluid is used as a pneumatic fluid to deliver pressure from the master brake cylinder to
slave cylinders which apply brake shoes or pads to the drums or discs at each wheel. It also acts
as a lubricant for the brake cylinder and seals.
Automobile manufacturers recommend that brake fluid should be changed "as needed." Some
brake fluid manufacturers recommend that the brake fluid should be changed once a year, but to
change it properly, the wheel cylinder should be taken apart, the whole system should be flushed
with clean fluid, and the cylinder should be rebuilt. Due to the cost of this operation, it is
common practice to add only enough fluid to raise the level hi the master cylinder and replace
what is lost due to leakage.7 Thus, it is typical for brake fluid to be replaced only when major
brake system maintenance (replacement or rebuilding of master or slave cylinders) is performed.
The U.S. Department of Transportation (DOT) has set standards and designations for brake fluids.
DOT-2 is the designation for standard drum fluid. Fluids equally suited for both drum and disc
systems are labeled DOT-3. An even higher-rated fluid (DOT-4) is for heavy-duty disc
CH-92-139
3-11
-------
applications.7 Published formulations for brake fhaids are typically based on a mixture of
polyglycol ethers (70 to 80 per i), with the remainder being either polyalkylene glycol,
propylene glycol, polypropylene glycol or a combination of these glycols and a small amount of
additives (inhibitors, antioxidants or dyes).1 A DOT-5 designation has been created for silicone-
based brake fluids, which can prevent water absorption and provide a higher boiling point, but
which may damage brake seals.8 No published formulations have been located for silicone-based
brake fluids.
Brake fluids may volatilize when exposed to the atmosphere following leakage or servicing and
upon improper disposal.
3.2.1.3 Crankcase Oils
Crankcase oils are well-fractionated and refined cuts from paraffin-base, mixed base or
cycloparaffinic crude oils. The best grades of oils are derived from paraffinic or solvent-refiner
mixed base crudes. Crank case oils often contain one to two percent zincdithiophosphate or
terpene.
Emissions occur with refilling and replacing, and through leaks, improper disposal and standing
losses. These emissions are expected to be relatively low as compared to the other product
categories due to the low volatility of crankcase oils.
3.2.1.4 Lubricants and Silicones
Transmission and axle lubricants are generally well-refined heavy lubricating oils containing fihu-
strength improvers or extreme pressure additives. They may contain between 0.5 and 1.0 percent
phenolic and aromatic antioxidants. Antifriction bearing and chassis greases are usually derived
from medium and high viscosity, well-refined lubrication oils, gelled by the addition of metallic
soaps or other thickeners.3
CH-92-139 3-12
-------
Activities in this category are limited to lubrication or greasing. Lubrication is the application
of a substance of low viscosity between two adjacent solid surfaces (one of which is in motion)
to reduce friction, heat and wear between the surfaces.
A lubricating grease is a mixture of a mineral oil or oils with one or more soaps. The most
common soaps are those of sodium, calcium, barium, aluminum, lead, lithium, potassium and
zinc. Oils thickened with residuum, petrolatum or wax may be called greases. Some form of
graphite may be added. Greases range in consistency from thin liquids to solid blocks and in
color from transparent to black. Grease specifications are determined by the speed, load,
temperature, environment and metals in the desired application.3'9
Synthetic lubricants are any of a number of organic fluids having specialized and effective
properties that are required in cases where petroleum-derived lubricants are inadequate. Each
type has at least one property not found in conventional lubricants. The major types are
polyglycols (hydraulic and brake fluids), phosphate esters (fire-resistant), dibasic acid esters
(aircraft turbine engines), chlorofluorocarbons (aerospace), silicone oils and greases (electric
motors, antifriction bearings), silicate esters (heat transfer agents and hydraulic fluids), neopentyl
polyol esters (turbine engines) and polyphenyl ethers (excellent heat and oxidation resistance, but
poor low temperature performance).10
Specific automotive lubricant product types that do fall under the scope of this effort include
general-purpose, dry film-type and silicone-based lubricant formulations, as well as rust
preventive/remover, penetrant and nut-loosening products that often also function as lubricants.
Published formulations for these products typically contain either 90 to 100 percent mineral oil
or better than 65 percent mineral spirits or naphthas, with additional petroleum-base oils,
graphite-containing components and proprietary ingredients. Some of these products also include
chlorinated hydrocarbons, oxygenated organic acids and tricresol phosphate. There are a variety
of both liquid and spray formulations, with hydrocarbons frequently mentioned as a propellant.
One silicone lubricant spray is an exception to the mineral spirit/naphtha formulation mentioned
above, with the liquid portion consisting of 94 percent trichloroethane (this percentage excludes
the hydrocarbon propellant).
CH-92-139
3-13
-------
Air emissions from these types of products would include immediate or near-term volatilization
of propellants and lighter solvents upon application to exposed parts, followed by slower
evaporation of heavier constituents.
3.2.1.5 Steering Fluids
Information on steering fluids was not readily available. However, in most vehicles transmission
fluid may be used as a substitute.
3.2.1.6 Transmission Fluids
Tram, mission fluids are used to cool and lubricate the gears and housing of automatic
transmissions, and to protect against rust and corrosion of internal transmission parts. They are
also used in manual transmissions, transaxles and power steering systems, although some specific
makes of power steering systems are reported to require a specially-manufactured product.7'11
Published formulations consist of over 90 percent mineral oil with thf remainder a mixture of
primarily inorganic additives.1 It is recommended that the automatic transmission fluid and filter
be replaced every 24,000 miles or two years.8 Air emissions from transmission fluid may occur
upon leakage and disposal, and may be fairly gradual due to the low volati1 if mineral oil.
3.2.1.7 Windshield Washer Fluids
The primary components of windshield washer fluids are alcohols and water. The purpose of
alcohol in windshield washer fluid is to provide freeze protection for the fluid while in the
vehicle windshield water reservoir, to avoid freezing of the fluid on the windshield while in use,
and to assist in defrosting or deicing the exterior surface of the automotive windshield. The
product is typically used full strength in the winter and diluted 50 percent by volume with water
in the summer. The variability of use of windshield washer antifret precludes quantification
of its operational lifetime. The amount used is entirely dependent upon climatic conditions and
driver discretion. Some concentrated products are also labeled for direct use as windshield
cleaners to be applied by hand.
CH-92-139 3-14
-------
Methanol, or occasionally isopropanol, is the basic ingredient acting as freezing point depressant
in windshield washer fluid. A small volume of soluble inhibitors may be included (i.e., less than
1 percent potassium phosphate) with the remainder being water, which acts as a solvent.
Windshield washer antifreeze concentrates, generally requiring some dilution by the consumer,
are packaged in metal cans or plastic containers. Pre-mix solutions are ready-to-use solutions
requiring little or no dilution, and come in plastic containers. A 1974 survey of windshield
washer fluids sales showed that pre-mix accounted for about 87 percent of national windshield
washer sales volume while concentrates accounted for about 13 percent.12
A California Air Resources Board (CARB) shelf survey found pre-mix formulations with contents
of 23 to 40 percent VOC by weight. Concentrated formulations were found to range from 35
to 80 percent.13 Other published formulations of windshield washer antifreeze include 80 to
90 percent methanol for concentrates and 40 to 45 percent methanol for pre-mix. The balance
is water (more than 10 percent for concentrates and more than 50 percent for pre-mix) and
wetting agents and other additives such as mercapto ethoxylate, ammonia, or detergents (less than
1 percent). Some formulations using isopropanol are also mentioned briefly in the literature, but
no further information is available on this alternative approach.1'13
The methanol in windshield washer fluid is the primary agent that prevents freezing. Thus, the
percentage required varies with the temperatures that the vehicle is exposed to, which is a
function of the region and the season. A concentration of 35 percent methanol will prevent
freezing down to -25°F, and 10 percent methanol will prevent freezing down to 20°F.13
3.2.2 Cleaning
3.2.2.1 Brake Cleaners
Brake cleaners are liquid or aerosol products used during servicing to remove contaminants from
the mechanical and working surfaces of brakes. For conventional brakes, parts that can be
cleaned include drums, linings, shoes, cylinders and spring sets. On disc brakes, the caliper units,
CH-92-139
3-15
-------
pads, discs and relatea parts can be cleaned. The product is applied liberally and then wiped off
or allowed to air-dry.11
The major function of these products is to clean the desired parts without leaving any residue
which might interfere with brake function. Published formulations mention perchloroethylene
as the main ingredient of one brake cleaner and a liquid version consisting entirely of "aliphatic
chlorinated hydrocarbon" (which may also be perchloroethylene). The volatile portion of these
products will be released when ^ product is applied or shortly thereafter, with a smaller amount
gradually leaving any sludge-t. c material removed from the parts.
3.2.2.2 Carburetor and Choke Cleaners
Carburetor/chokc/fuel injection system cleaners include a variety of specialized products designed
for removal of dirt, gummy deposits, surface glaze and other contaminants from the exterior and
interior working parts and passages in these three types of engine parts. Although they are
labeled for single uses or in combinations (i.e., "carburetor cleaner," "choke cleaner,"
"carburetor/choke cleaner," "carburetor and fuel system cleaner," etc.), the published formulations
for these products are similar in that they consist entirely of various mixtures of VOCs. Other
components such as water or detergents are inappropriate since these products are sprayed
directly into the fuel/air system and any components that would leave deposits or condensation
in the system must be avoided.
Labels on these products give instructions for the different types of uses as follows. Heavy
spraying, soaking, and rinsing can be used for external cleaning of the carburetor linkages and
automatic choke as well as the outside of the carburetor itself. Internal cleaning of the carburetor
involves removi the air filter while the engine is running and spraying bursts of the product
on the carburetor valve and the throttle plate as well as down the carburetor throat. The engine
is revved to avoid stalling and to enhance air flow through the carburetor, which flushes loosened
deposits through the system and into the cylinders to be burned. The engine should be run until
it rum >othly after this procedure. In addition, these products can be used to clean the
posith .unkcase ventilation (PCV) valve. This procedure involves disconnecting the PCV
CH-92-139 3-16
-------
valve on the crankcase side, spraying into the exposed valve, allowing it to soak and then starting
the engine and repeating the spraying, after which the engine is stopped and the valve
reconnected.11 Procedures for using these products to clean fuel injectors have not been located.
Simpler products hi this category consist of a majority of aromatic hydrocarbons (over
65 percent) with one additional ingredient (alcohol or ketone). Many other formulations have
xylene as the largest-percentage component (35 to 65 percent) with alcohol or a combination of
hydrocarbon and chlorinated solvents, ranging from glycol ethers to methylene chloride,
orthodichlorobenzene, 2-butoxyethanol or diacetone alcohol and acetone. There are also some
products that do not follow this basic formulation, including one based on mineral oil
(65 percent) with the remainder a mixture of various organics (esters, hydrocarbons and solvents),
and another based on equal amounts of xylenes and polybutene amine inhibitor.
Direct use of these products on external working parts is expected to result in immediate and
disposal-type emissions similar to degreasers. Spraying into the carburetor will result in some
direct emissions, but the fate of these products as they pass through the engine is not
documented. If they have a significant effect on completeness of combustion, some components
may not be burned or other compounds of concern may be formed.
3.2.23 Engine/Parts Cleaners/Degreasers
Cleaning vehicle engines involves a variety of distinct cleaning functions and several different
types of products. For the purposes of this discussion, they will be divided into engine
cleaner/degreasers, which are generally for use on external surfaces, and parts cleaners and
related products which are used on internal surfaces and disassembled parts. For most of these
products, emissions will occur as the products are applied, allowed to soak and removed. Use
on a hot engine will encourage volatilization. In addition, components which are wiped off in
sludge form or rinsed off with water may continue to volatilize from those media over time.
Emissions from bucket-type carburetor cleaners would be an exception to this general pattern,
and may include volatilization of solvents carried out of the bucket by cleaned parts, gradual
evaporation through the water seal, and losses when the product is disposed of.
CH-92-139
3-17
-------
3.2.2.3.1 Engine Cleaners/Degreasers The general terms "engine or motor cleaner" and
"degreaser" refer to products designed to remove grease, grime, oil and other contaminants from
the external surfaces of engines and other mechanical parts. These products are generally used
prior to or as part of a maintenance procedure, to provide a clean work area, or to clean parts to
enhance their functioning. Engines and parts may also be cleaned for aesthetic purposes, as part
of overall vehicle detailing, and thus these products might also be considered detailing products
as well as maintenance and repair products.
These products may also be labeled as "engine shampoo," "motor wash," "engine scour," "grease
eater" or other similar names. It should be noted that the term "degreaser" can be somewhat
confusing in some contexts, since it is also used for organic solvent cleaners such as open-top
vapor degreasers, which are not a consumer product but pieces of capital equipment used by
industry and some large repair facilities to clean metal and other parts with specially formulated
chlorinated solvent vapors, sprays or baths. Industrial degreasers are addressed by EPA via other
regulatory programs.
Most of these products are aerosols or pump sprays which are sprayed on or foamed on a hot or
cold engine, allowed to soak for 10 or 15 minutes and removed with a water spray. The engine
is then started and allowed to idle for a period to ensure thorough drying. This process may be
repeated if necessary.
Almost all published formulations for engine cleaner/degreasers are predominantly petroleum
distillates/hydrocarbon solvent (80 to 95 percent), with additional volatile components such as
pine oil, alcohols, glycol ethen >. -id chlorinated solvents which sometimes constitute essentially
the rest of the product. Many products also include some surfactant, soap, wetting agent or water
(trace to 5 percent). One of these typical products is labeled specifically for "motorcycle
degreasing." There are some products designated "bulk" or "concentrated" which have lower
solvent contents and are designed to be reduced with hydrocarbon solvents such as kerosene (one
formulation cited a typical 1:9 dilution by volume).
CH-92-139 3-lg
-------
There are also some products labeled as automotive cleaner/degreasers which contain
considerably more water than the majority of these products (from 52 percent in a product also
containing 40 percent petroleum distillates, to 86 percent in a product with 5 percent glycol ether
and the remainder surfactants and detergent builders).1 Finally, there are some newer products
which are labeled as using d-limonene (a hydrocarbon chemical occurring in citrus oils and other
botanical sources) as a cleaning agent, and not containing the typical ingredients of the other
degreaser formulations previously discussed. These products are advertised as "environmentally
safe."11
3.2.2.3.2 Parts Cleaners Other products in this category include several separate types of "parts
cleaners." Depending on their formulations, these products may be used to remove grease and
oil, carbon and other baked-on surface coatings, other contaminants and even paints. One
product is a liquid that is brushed on small mechanical parts, and a similar product is an aerosol
made to be sprayed on small parts. A bucket-type, solvent-based product, often known as a
"carburetor cleaner," is formulated for immersing carburetors and other small disassembled parts.
(These are not to be confused with spray-type products discussed in the following subheading
which are also termed "carburetor cleaners" or "carburetor/choke cleaners.")
One published formulation for a brush-on parts cleaner includes over 60 percent petroleum
distillates, less than 25 percent chlorinated solvents, over 5 percent phenolic compounds and
additional soap and wetting agents. There are also several liquid degreaser formulations which
are similar to the typical aerosol/spray formulations previously described, but which apparently
could be used as brush-on cleaners or as fillers for spray bottles. One aerosol product intended
for cleaning motorcycle plugs, points and chains, contains only chlorinated hydrocarbons. These
appear to be more specialized, less common types of parts cleaners.
The bucket-type parts cleaners are generally di-phase (two layer) liquids which consist of a
combination of chlorinated and non-chlorinated hydrocarbon solvents, with cresols/cresylic acid,
water and soaps or other cleaning agents. The latter ingredients form a layer which floats on top
of the solvent, reducing evaporation.
CH-92-139
3-19
-------
There are also other liquid products designed for use in parts cleaning tanks and a variety of
tank/spray combinations which are usec commercial and industrial parts cleaning. The latter
typically involves a commercial rental agreement under which a vendor supplies both the
equipment and solvent, retrieving and reclaiming used solvent on a regular schedule. This type
of product is not c -red in this review, both because it is not detailed in the consumer/
commercial literature and because it is a basically different product from the other products
discussed. Only one published formulation which specified use in a parts-cleaning tank was
located, containing over 50 percent aliphatic chlorinated solvents, almost 20 percent phenolics
and the remainder water, soap and wetting agents.
3.2.3 Specialty
3.2.3.1 Belt Dressings
Belt dressings are aerosol or liquid products which are sprayed on engine drive belts to clean,
lubricate and protect them, as well as to reduce noise such as squealing from belt/wheel contact
points. Published formulations for aerosol products contain a combination of petroleum distillate
and methylene chloride (17 and 25 percent, respectively, in one product), with the remainder
consisting of "petroleum derived resins" or a combination of solid asphaltic petroleum fraction,
mineral oil and wool grease. The one published formulation for a liquid product consists of
30 percent petroleum distillates and the same asphaltic/mineral oil/wood grease combination. The
volatile ingredients will essentially evaporate upon use of the product.
3.23.2 Engine Starting Fluids
Engine starting fluids are aerosol products which are sprayed into the carburetor to assist in
starting engines which may be balky due to cold, dampness or undermaintenance. They typically
consist of a large proportion of ethyl ether (80 to over 90 percent) with the remainder being other
petroleum hydrocarbons. One published formulation contains only 63 percent ethyl ether, with
the remainder being aliphatic hydrocarbons. If used correctly, most of the product may be drawn
into the cylinders and combusted, but documentation of the fate of these products has not been
CH-92-139 3-20
-------
located. Two published formulations mentioned carbon dioxide as the propellant, but propellants
are otherwise not specified.
3.2.3.3 Tire Repair Products
Tire repair products that have been identified include tire cement, tire sealant and tire inflators.
Tire cements are used to glue in plugs and patches which are applied to tires or inner tubes.
Available formulations include a large solvent content consisting of a combination of "rubber
solvent" (probably naphtha) and 1,1,1-trichloroethane. These solvents would be emitted upon
use.
Separate sealant and inflator products were not found, but combination "puncture seal" products
have been located, consisting of an aerosol can with an attachment which fits a tire valve in the
place of the regular spray valve. These products are made to inflate and temporarily seal tires
with small punctures. When attached to a flat tire with a sufficiently small puncture, a sealant
compound and pressurized gas are introduced into the tire. The sealant fills the leaking hole and
the gas partially inflates the tire (to a pressure of about 20 psi). The vehicle should be driven
slowly for several miles to distribute the remainder of the sealant. At least some products
apparently use a hydrocarbon as the propellant/inflator gas, since the labels specify that the tire
will be rilled with an extremely flammable gas and care should be taken to avoid explosions on
discharge of the inflator gas.11 Only one formulation for a tire sealant was located, consisting
of unspecified quantities of urethane, toluene, isopropyl alcohol, isopropyl acetate, tergitol
(polyethylene glycol) and dichlorodifluoromethane (a chlorofluorocarbon which may no longer
be used in this application). Solvents and propellant/inflators from these products would be
emitted upon deflation of the repaired tire or during attempted inflation of a tire with too big a
hole for the product to seal.
3.2.3.4 Windshield Deicers
Windshield deicers are used to remove frost or ice from windshields. They come in squeeze
bottles or as manual or aerosol spray products. The active ingredient in most published
CH-92-139
3-21
-------
formulations is methanol, ranging from 35 to 70 percent, depending on the product (exclusive
of propellant). Additional ingredients include up to 50 percent water and up to 15 percent
ethylene glycol or a mixture of glycols. One published formulation uses isopropanol as the active
ingredient.
When sprayed on, the methanol soaks into the frozen material and rapidly lowers the melting
point of the ice to allow it to become a soft, slush-like mixture even at below-freezing
temperatures. This mixture is then removed with windshield wipers or a windshield-cleaning
tool.
3.2.4 Additives
3.2.4.1 Crankcase Additives
Motor flush/crankcase cleaner products are liquids which are added to crankcase oil just before
an oil change and circulated briefly through the crankcase to remove accumulated deposits prior
to draining and replacing the oil and filter. Published formulations consist of a dominant
hydrocarbon ("naphthenic oil" or petroleum distillates, about 90 percent), with the remainder
being a mixture of other solvents (such as glycol ethers and ketones, alcohol and esters and
sometimes a combination of five organic solvents). These more volatile ingredients are likely
to volatilize during removal and disposal of the old oil.
3.2.4.2 Fuel System Additives
Fuel system antifreeze includes products sold for two related uses: gas-line antifreeze and fuel
tank drier. The purpose of these products is to absorb condensation or accidentally-introduced
water from the gasoline in the fuel tank, fuel lines and carburetor. This can prevent freezing of
gas lines in cold weather, aid engine startup in freezing temperatures, help prevent stalling before
the engine warms up and also prevent corrosion of the fuel tank and system due to the presence
of water. The recommended concentration is 1 pint to 10 gallons of gasoline.
CH-92-I39 3-22
-------
Generic components of a gas-line antifreeze/fuel tank drier include solvents and freezing point
depressants. Published formulations consist almost exclusively of 100 percent methanol, which
functions both as the solvent and the freezing point depressant. Some other unverified
formulations include aliphatic alcohols, commonly methyl or isopropyl, with concentrations
ranging from 30 to 90 percent, and solvents, commonly toluene, acetone, xylene, and isopropanol
with concentrations ranging from 20 to 40 percent.
These products essentially become part of the fuel in the gas tank and are burned with the fuel.
There is some possibility that more-volatile ingredients could evaporate from the fuel into the
vapor space of the tank and then be preferentially emitted upon refueling. However, this has not
been documented and it is not clear that these products actually contain anything other than
methanol, which is less volatile than gasoline.
3.2.4.3 Radiator Additives
Radiator compounds and lubricants are products that are added to the vehicle's radiator fluid to
perform a variety of functions related to the components of the cooling system. These products
are different from the radiator cleaners discussed below in that they are meant to remain in the
engine until the next regular change of coolant. Specific types include stop-leak products (for
sealing small leaks in the radiator), anti-rust compounds (to stop or prevent corrosion in the
radiator and other cooling system parts) and water pump lubricants. An individual product can
often accomplish more than one of these functions. Several of these products appear to contain
no volatile compounds, consisting of water, mineral oil, sealers and detergent-type products.
Some other formulations contain compounds that may be of concern, including unspecified
percentages of aromatic hydrocarbons/petroleum distillates.
Volatile components of these products would be emitted upon application to the radiator or as
the coolant leaves the engine, either as leaks or upon waste disposal.
Radiator cleaners are products that are used on a one-time basis to clean the internal portions of
a vehicle's cooling system, removing sludge, rust and other deposits that may form in the system.
CH-92-139
3-23
-------
Also known as "radiator flush," they are liquids which are added to the cooling system (by
removing a small amount of coolant and replacing it with the product) and allowed to circulate
throughout the system for about 10 minutes prior to complete draining and replacement of the
coolant. These products are generally more concentrated than the radiator compounds discussed
previously, and contain ingrei its tha; would not be appropriate for longer-term use in the
cooling system
Published radiator cleaner formulations are divided between aqueous products which contain no
volatile or a small ^rcentage of isopropanol, and solvent-based products which can contain 80
to 90 percent volatile compounds (mostly mineral spirits/petroleum distillates). Volatile
components of these products would be emitted as the coolant is removed from the engine or
during proper or improper waste disposal.
3.2.4.4 Transmission Additives
Transmission additives include sealer/leak-stop products, conditioners, treatments and flush-type
products. Partial formulations have been located for all but the flush-type products, and indicate
that while some of these products consist largely of mineral oil, they may contain other petroleum
distillates, chlorinated hydrocarbons, and xylene, as well as phosphates, sulfonate and inorganics.
The more volatile ingredients may volatilize quickly upon leakage or disposal of the transmission
fluid, while the mineral oil will evaporate more slowly.
3.3 POLLUTANTS EMITTED FROM EACH IDENTIFIED PROCESS
Reviewing the available product formulation data for automotive products resulted in a large
database of compounds which have been mentioned as occurring hi specific product types. This
information is presented in Table 3-2. Table 3-2 provides a comprehensive overview of the
chemicals found in automotive consumer products which have been identified as being of concern
due to then- apparent volatility and either their potential to participate hi atmospheric
photochemical reactions or potential toxic/hazardous properties. Table 3-2 also provides the
Chemical Abstract Service (CAS) Registry Number and the American Conference of
CH-92-139 3-24
-------
TABLE3-2. VOLATILE ORGANIC COMPOUNDS IN AUTOMOTIVE PRODUCTS USED IN VEHICLE REPAIR FACILITIES
PRODUCT COMPONENTS
Acetone . x x% ^ " ^ ^\v -^x xs> ^
Butyl Cellosolye
Chlorinated Attirriatic Hydrocarbon
Chlorinated Hydrocarbons
Odorinated Solvents
Cresol
Cyclohexanone
^j Diacetone Alcohol
^ Dichlorodifluoromethane -' , ' x
*-n Ethanol
Ethyl Ether v v : ' ," 'V
Ethyl Ether of Diethylene Glycol
Ethyl Ether of Ethylene Glycol
Ethylene Bichloride
Ethylene Glycol
Formaldehyde
Glycol Ether
Graphite in Aliphatic Naphtha
Graphite in Mineral Oils
Hydrocarbons
Hydrocarbon Radicals
Isopropanol
Isopropyl Acetate
Kerosene
Ketones
Methanol
Maintenance
A B C L S T W
x1* * v ^ "^ x '
X
\\N xV xxvC: ^xs y ^ \^"*f ?"lv
s X1* vS*" •"* v •
, -.,„ x
x^ * " ' ^V _
^ -> , _ :,-^;
X
5J^ v\^ s' •«* ™ "* s'
X ,* X
X ~r~ ' X " >?V
X
" T '-x's^
xr;;;\< '.-t^;
S-S'NX"''' " -^
X
: X~ ^
X
X K X X
X
X
X
X
X
X X
X
Cleaning
B C E
X!""V3t' '
, X ,^X
^" \['^X
~rt!T?t''^A* •
"x"t'"" ""
X
t ' ^
X X _
*"""" s-'
\J" x-V ^
X
"^ ;- - ^
xt^ - > -^ p
x
'Y , ' * x
"'XX
s
XX
S s
XX
V (^ p
s% - x - " •
Speciality
B E T W
X
X
X
X
X X
X
X
Additives
C F R T
X
X
X
X
X
X
X X
X
X X
X
X
X
CAS
67641
85687
71410
111762
1319773
108941
123422
75718
64175
60297
107062
107211
50000
67630
108214
8008206
67561
CAA
X
X
X
X
X
X
ACGIH
1780
22
100
238
4950
1880
1210
40
127
0.21
**
985
1040
262
HTAHCAC
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Continued
-------
LO
I
TABLE 3-2. VOLATILE ORGANIC COMPOUNDS IN AUTOMOTIVE PRODUCTS USED IN VEHICLE REPAIR FACILITIES (Continued)
Maintenance Cleaning Speciality Additives
PRODUCT COMPONENTS ; ABCLSTW BCE BETW CFMT CAS CAA ACGIH HTAHCAC
Methyl Ethyl ICetone Peroxide
Methyl Isobtityl Carbinol
Methylene Chloride
Mineral Spirits
Morpholine
NaphthenicOil < "' ""
N-Butyl Alcohol
Orthodiclorobettasne
Perchloroethylene
Petroleum Diia!ktes "" f" " '"p*;""1" y---^-
Petroleum Hydrocarbons
Petroleum Oils -" ~'v s*
Petroleum Solvents
Pine Oil """ "" ""'•"'
Polyethylene Glycol
Polypropylene GlyfcoJ s 0%
Propane
PropySene Glycol
Rubber Solvents
Toluene
Trichloroethane
Tricresyl Phosphate
Urethan
Xvlerie , s
•^
X" • X
X
x ":""' ''T!";
M "*""" "x ' v""T-"'f*
X X
'i'-l-;J'\', x' ' "" 7>~m
•^f-x-^" "
T">1T- ^ 5"";
X
• X' '
, ,
X
•*£• ^
f ^ - r
X
'"" !x T -
'sv -7
""'jrC']
X
' ^""x 'x-"-
-x.
ff-y^ ^i
,.. ^.^>,
•;•<- r*r^"'
?r"r\?«?r
X
•'"" S'C «" ,-
*'(
..*• x"x
X
X
r
X
X
X
X
X
X
X
X
X
X
X
X XX
X
X
1338234
108112
75092
8030305
110918
71363
9550!
127184
8002059
8002093
25322683
25322694
74986
57566
108883
71556
78308
51796
1110207
X
X
X
X
X
X
LS
104
174
71
152
339
890
377
1910
O.I
434
X
X
X
X
X
X
X
X
X
X
X
X
Note: Descriptions of data items on this table are provided on the following page
-------
NOTES FOR TABLE 3-2
Maintenance
A. Antifreeze/engine coolants
B. Brake fluids
C. Crankcase oils
L. Lubricants & silicones
S. Steering fluids
T. Transmission fluids
W. Windshield washer fluids
Cleaning
B. Brake cleaners
C. Carburetor and choke cleaners
E. Engine/parts cleaners/degreasers
Specialty
B. Belt dressings
E. Engine starting fluids
T. Tire repair products
W. Windshield deicers
Additives
C. Crankcase
F. Fuel line
R. Radiator
T. Transmission
CAS: Chemical Abstract Service Registry number
CAA: These chemicals are listed in the 1990 Clean Air Act Amendments (Title ffl,
Sec. 301) as hazardous air pollutants
ACGIH: American Conference of Governmental Industrial Hygienists, Time-Weighted
Average (TWA) limits in mg/m3 of air
HTAHCAC: These chemicals are listed in the Handbook of Toxic and Hazardous Chemicals
and Carcinogens
See references and further discussion in text.
CH-92-139
3-27
-------
Governmental Industrial Hygienists' ^CGffl) Time-Weighted Average (TWA) workplace air
concentration standard for the liste mpounds. An "X" indicates whether the compound
appears on the list of IIAPs in Title ffl of the CAAA and/or in the Handbook of Toxic and
Hazardous Chemicals and Carcinogens (HTAHCAC).14
ACGIH Threshold Limit Values (TLV) refer to airborne concentrations of instances and
represent conditions under which it is believed that nearly all workers may be repeatedly exposed
without adverse effect The TWA is the weighted average concentration for a normal 8 ti~"-
workday and a 40 houi workweek to which nearly all workers may be repeatedly ex j
without adverse effect. TWAs permit excursions above the TLV provided they are compensated
by equivalent excursions below the TLV-TWA during the workday.15
The Handbook of Toxic and Hazardous Chemicals and Carcinogens is a document which
includes EPA Priority Toxic Pollutants, substances with standards adopted by ACGIH, all
sub 'ances considered in the National Institute for Oc: jpational Safety and Health's Standards
Completion Program, a nost of the chemicals classified by EPA as hazardous wastes or
hazardous substances.14 ine Handbook also includes chemicals which are listed as carcinogens,
compounds with dangerous properties, and compounds of concern hi industrial/workplace settings.
3.4 ESTIMATE OF THE POLLUTANT LEVELS
AP-42 contains national evaporative emissions and pe~ capita emission factors for commercial/
consumer solvent use.16 The only automotive pr ts categorized however, is windshield
washing. The windshield washing per capita emission factor listed is 0.63 Ib/yr. Use of this
factor and assuming an annual growth rate of 1.8 percent results hi a VOC emissions national
total of 81,900 TPY for calendar year 1990. Other estimates of VOC emissions from the use of
consumer products have been reported in References 17 and 18. National VOC estimates for
solvents used hi automotive repair hi 1986 are 37,143 tons per year.17 In a study of New York
State emissions, the total annual tons of VOC for 49 consumer product categories is estimate
as 26.979.19 Of this total, 2,766 tons are attributed to the following seven automotive categories:
auto antifreeze, carburetor and choke cleaners, brake cleaners, engine degreasers, engine starting
CH-92-139 3-28
-------
fluids, lubricants and silicones, and windshield deicers. In addition to these data, the California
Air Resources Board has an extensive program underway to reduce VOC emission from
consumer products. This effort includes data on average annual day VOC emissions from aerosol
consumer products in California.20 For the category automotive and industrial consumer products,
CARB estimates a total of 3.96 VOC tons per day of propellant emissions and 27.37 tons per day
of solvent emissions for a combined total of 31.33 tons per day.
Automotive product emissions may be apportioned on the basis of automobile-related activity.17
There were approximately 135,671,000 automobiles and light-duty trucks registered in the United
States in 1986. Per-vehicle emission factors were derived by dividing total VOC emissions by
this number. National 1986 VOC emissions and per-vehicle emission factors are listed in
Table 3-3.
TABLE 3-3. VOC EMISSION FACTORS FOR AUTOMOTIVE PRODUCTS16
VOC Product
Carburetor and Choke Cleaners
Brake Cleaners
Engine Degreasers
Engine Starting Fluid
Nation VOC
Emissions
(tons/year)
13,093
9,824
5,192
9,034
LB/YR VOC
Per Vehicle
Registered
0.193
0.145
0.077
0.133
LB/YR Per
Capita
0.109
0.082
0.043
0.075
3.5 SOURCE ACTIVITY DATA AVADLABDLITY
The CAAA require EPA to prepare a report to Congress on VOC in consumer and commercial
products and to promulgate regulations that would reduce VOC emissions from these products.
EPA is currently working on the automotive consumer products portion of this report, which will
be published in November, 1993. The Office of Air Quality Planning and Standards is
developing a survey of consumer product manufacturers nationwide. This will eventually provide
a comprehensive inventory of VOC in consumer and commercial products and activities. The
following reports include information on comprehensive inventories of VOC from consumer and
commercial products.
CH-92-139
3-29
-------
Photochemically Reactive Organic Compounds Emissions from Consumer and
Commercial Products19
Compilation and Speciation of National Emissions Factor for Consumer/Commercial
Solvent Use"
Analysis of Regulatory Alternatives for Controlling Volatile Organic Compounds (VOC)
Emissions from Consumer and Commercial Products in the New York City Metropolitan
Area (NYCMA)21
Expansion of the New York Study: Evaluation of VOC Emission Reduction Alternatives
from Selected Consumer and Commercial Products22
Marketing data for automotive repair products, as well as many other categories, may be obtained
from Mediamark Research Incorporated (MRI) and Simmons Market Research Bureau. However,
these sources are based on consumer surveys of brands that the consumers report using and not
on actual sales data.18 Therefore it may not be an accurate representation of vehicle repair
facilities' use of automotive fluids.
Sales volume data may be obtained from Nielsen Marketing Research (NMR) and the Selling
Area Marketing Index (SAMI). NMR uses electronic checkout scanner data, while SAMI is
based on warehouse withdrawal data. Although neither of these services provide data for the
non-retail sector of the market, a possible source for such information may be Technomics,
Incorporated in Chicago. Technomics reportedly estimates institutional usage of products from
surveys of major buyers.18
Data on automotive fluid use can be derived from vehicular use data, such as those provided by
references 23 and 24. In addition, statistics on the total number of registered vehicles by county
are available from state Department of Motor Vehicle records. In 1990, approximately
143,550,000 passenger cars were registered in the United States.24 Total 1990 vehicle miles
traveled (VMT) for cars, hi millions of vehicle-miles, were ! 51,370, for buses 5,728, and 616,831
for trucks.24
CH-92-139 3-30
-------
It is also necessary to determine usage rates for each automotive fluid per automobile. Simmons
Market Research Bureau, Inc. reports that 34.4 percent of the U.S. population changes radiator
coolant during any one-year period.25 Two to four gallons of coolant are used per application.24
The quantity of fluid used per application depends on the type of fluid. One and a half to three
quarts of windshield washer fluid is used per application; product labels specify one pint of gas-
line antifreeze per application.26 For the 1 to 15 percent of car owners using gas-line antifreeze,
gas-line antifreeze may be applied once every 8 to 10 gallons, 2 to 4 fill-ups or 1,000 miles.24
Alternatively, total usage can be calculated at a national level and then scaled to a per capita
level. C.H. Kline reported 1.72 million gallons of gas-line antifreeze used or sold in 1981,
extrapolating from 1974 data and assuming a two percent annual growth rate.27 Similarly, C.H.
Kline reported 18.4 million gallons of windshield washer fluid sold in 1981.27 In 1988, Simmons
reported that 86,698,000 gallons of antifreeze and 26,788,000 cans of gasoline additives had been
purchased by consumers in the United States during the preceding year. Simmons also reported
that 102,353,000 quarts of crankcase oil had been purchased during the preceding six months.28
Specific data on use of the other automotive repair fluids are not readily available.
Emissions per volume of automotive fluid must be determined from field experiments, since few
emission factors have yet been developed. EPA's AP-42 provides a per capita emission factor
estimate for VOC derived from windshield washing fluid.16
3.6 LEVEL OF DETAIL REQUIRED BY USERS
The following data items are needed by users to estimate emissions from the use of automotive
products during vehicle repair.
• County, state or other geographic area information: number of registered vehicles and
population
• Emissions per volume of fluid used by fluid type
• Fluid use per vehicle by fluid type
• Service stations per geographic area
CH-92-139
3-31
-------
• Vehicles serviced per station
• Class of vehicle serviced
3.7 REGIONAL, SEASONAL OR OTHER TEMPORAL CHARACTERISTICS
Two of the product categories considered, windshield deicers and fuel system additives, are
predominantly used in the winter and are therefore of less concern than the other categories, since
winter is not an ozone season. Antifreeze is somewhat of a misnomer due to its alternative use
as an antiboil agent. Because of this, engine coolants will show regional variation based on
climatic differences, as well as a seasonal inclination toward summer and winter. All of the
product categories will be used principally during the standard business week in accordance with
the hours of operation for the repair facilities.
3.8 POTENTIAL METHODOLOGY
Emissions from automotive vehicle repair and maintenance activities can be estimated using
several different methodologies. Three methods for estimating emissions are presented here. The
procedure in Method I calculates total annual emissions for individual automotive products based
on automotive product sales. Method n estimates are based on the number of registered vehicles
per specified location (state, county, or region). Method in suggests a procedure for estimating
emissions by automotive fluid and vehicle class.
Method 1
• Compile a list of all the automotive repair products and their manufacturers.
• Determine sales volumes for each automotive repair product per area.
• Conduct laboratory testing, use existing emission factors to "generalize" VOC content
by product assuming 100 percent volatilization, and determine emissions from each
automotive product.
• Calculate total annual emissions for each automotive product by multiplying the
appropriate emission factor by the annual product sales for the area.
CH-92-139 3-32
-------
Method 2
• Compile a list of all the automotive repair products and their manufacturers.
• Determine sales volumes for each automotive repair product per area.
• Determine the number of vehicles registered in each area.
• Conduct laboratory testing or use existing VOC per-vehicle emission factors to
determine automotive product emissions from each automobile in the area.
• Calculate total annual emissions for each area. Multiply per-vehicle emission factors
by the number of registered vehicles in each area.
Method 3
• Determine the number of service stations per area.
• Determine the number of vehicles serviced by vehicle class.
• Determine the amount of fluid used per vehicle, by fluid type and vehicle class.
• Develop emission factors through field studies to determine emissions per unit volume
of fluid used broken down by fluid type.
• Compute pollutant emissions per area broken down by fluid type and vehicle class by
multiplying the number of vehicles serviced by the appropriate emission factors.
CH-92-139
3-33
-------
3.9 REFERENCES
1. Gosselin, Robert E., Roger P. Smith and Harold G. Hodge. Clinical Toxicology of
Commercial Products (Fifth Edition). Williams & Wilkins, Baltimore, MD. 1984.
2. Flick, Ernest W. Household and Automotive Cleaners and Polishes (Third Edition).
Noyes Publications, Park Ridge, NJ. 1986.
3. Kirk-Othmer Encyclopedia of Chemical Technology, Third edition. John Wiley and
Sons, New York, NY, 1981.
4. Kallgren, R.W. "Antifreezes" in Kirk-Othmer Ency^. -pedia of Chemical Technology,
Volume 2. John Wiley and Sons, New York. 1963.
5. Engine Coolant Testing. American Society for Testing and Materials, Philadelphia, PA.
1989.
6. 1981 Ethylene Glycol Base Antifreeze Survey. Chemical Specialists Manufacturing
Association, Washington, D.C. 1982.
7. Murray, Spence, el al. Basic Chassis, Suspension and Brakes (No. 4). Petersen
Publishing Company, Los Angeles, CA. 1977.
8. Spaniola, Mike. The Complete Consumer Car Guide. McGraw-Hill Book Company,
New York, NY. 1987.
9. Gressner, H. The Condensed Chemical Dictionary, Van Nostrand Remhold Company
Incorporated, New York, NY, 1981.
10. Chemical and Process Technology Encyclopedia. McGraw-Hill, Incorporated, New
York, NY, 1974.
11. Shelf Survey of Automotive Products. Western Auto Store, Chapel Hill, NC.
Conducted by Alliance Technologies Corporation, Chapel Hill, NC. September 1991.
12. Multi-Client Survey, Gas-line Antifreeze, Windshield Washer Antifreeze. Charles H.
Kline and Company, Fairfield, NJ. 1975.
13. Technical Support Document for A Proposed Regulation to Reduce Volatile Organic
Compound Emissions from Consumer Products. State of California Air Resources
Board, Solvents Control Section, Sacramento, CA. August 1990.
14. Sittig, Marshall. Handbook of Toxic and Hazardous Chemicals and Carcinogens,
Second Edition. Noyles Publi tions, Park Ridge, NJ. 1985.
CH-92-139 3-34
-------
15. Threshold Limit Values and Biological Exposure Indices for 1989-1990. American
Conference of Governmental Industrial Hygienists. 1989.
16. U.S. Environmental Protection Agency. Compilation of Air Pollutant Emission Factors,
Fourth Edition and Supplements, AP-42,, Research Triangle Park, NC, September 1985
through September 1991.
17. U.S. Environmental Protection Agency. Compilation and Speciation of National
Emission Factors for Consumer/Commercial Solvent Use. Information Compiled to
Support Urban Air Toxics Assessment Studies, EPA-450/2-89-008 (NTIS PB89-207203),
Research Triangle Park, NC. April 1989.
18. Memorandum from Ron Ryan, Alliance Technologies Corporation, to Bruce Moore and
Al Vervaert, U.S. Environmental Protection Agency, Office of Air Quality Planning and
Standards, Research Triangle Park, NC. Issues for consumer products inventory
protocol. September 28, 1990.
19. U.S. Environmental Protection Agency. Photochemically Reactive Organic Compound
Emissions from Consumer and Commercial Products. EPA-902/4-86-001 (NTIS PB88-
216940), Region 2 Office, New York, NY. November 1986.
20. Letter and Attachments from Andrew P. Delao, California Air Resources Board to
Randy Strait, Alliance Technologies Corporation. Consumer Product Emission Estimate
Methodologies. November 9, 1989. Section 3-6 Solvent Use - Aerosol Consumer
Products and Section 4-1, Pesticide Application-Aerosol Consumer Product Pesticides.
21. Pacific Environmental Services. Analysis of Regulatory Alternatives for Controlling
Volatile Organic Compounds (VOC) Emissions from Consumer and Commercial
Products in the New York City Metropolitan Area (NYCMA). Reston, VA, 1989.
22. Pacific Environmental Services. Expansion of the New York Study: Evaluation of VOC
Emission Reduction Alternatives from Selected Consumer and Commercial Products,
February 1990.
23. Skinner, S.K and T.P. Dungan. National Transportation Statistics Annual Report, DOT-
TSC-RSPA-90-2, U.S. Department of Transportation, Transportation Systems Center,
Cambridge, MA, 1990.
24. Highway Statistics 1990. FHWA-PL-91-003, U.S. Department of Transportation,
Federal Highway Administration, Washington, DC, 1990.
25. Simmons Market Research Bureau, Inc. 1978/1979 Selective Markets and the Media
Reaching Them -- Automotive Marketing, Volume 24, New York, NY, 1978.
26. Chemical Specialties Manufacturing Association. Ethylene Glycol Base Antifreeze
Surveys, Washington, DC, 1982.
CH-92-139
3-35
-------
27. C.H. Kline and Company. Multi-c ent Survey, Gas-line Antifreeze Windshield Washer
Antifreeze, Fairfield, NJ, 1975.
28. Simmons Market Research Bureau, Inc. Study of Media and Markets, New York, NY,
1988.
CH-92-I39
-------
SECTION 4.0
RECYCLING
4.1 INTRODUCTION
Recycling may be defined as the reclamation of materials from waste. For purposes of this
report, the definition includes all activities or processes related to the recycling effort, beginning
with the removal of material from the waste stream and extending to the point where recycled
material is essentially identical to products derived from virgin materials or may be acceptable
as a substitute for virgin materials. This distinction is made to concentrate on the air emissions
which are attributable to recycling processes up to the identified point. In reporting emissions
however, care is needed to ensure that emissions associated with a recycling process are not
double counted. For example vehicle emissions resulting from the collection of recyclable
materials should be reported as part of a mobile source inventory and not as part of a recycling
emissions inventory. Air emissions data are currently available from several information sources,
such as AP-421 and EPA's Aerometric Information Retrieval System (AIRS), for a number of
manufacturing processes which incorporate recycled materials. This section presents findings
from research on the air emissions generated during recycling processes involving five materials:
paper, plastic, glass, metals from Municipal Solid Waste (MSW) and solvents. Recycling of the
first four materials involves one or more energy intensive steps. Emissions resulting from
associated energy production however, are not addressed as part of this section. This section
focuses on emissions from actual recycling processes.
The fifth category of materials researched for air emissions resulting from recycling was solvents.
Unlike the other four recyclable material categories in this study which originate hi homes or
commercial establishments, spent solvents are generated primarily by industry. As the point of
origination and the recycling path of spent solvents are significantly different from the other
materials, the findings on this subject are presented separately.
A limited amount of statistical information is provided to describe the extent of recycling
activities. Sections of the recycling industry are experiencing rapid changes. As evidence of this
CH-92-139
4-1
-------
change, pertinent historical data are provided along with projections. The flow of recyclable
material is traced from the post-consumer waste stream through the production of materials
suitable for secondary markets. Descriptions of the various collection and sorting methods are
provided, followed by a detailed description of material-specific processing activities.
Information which considers potential to emit air contaminants is presented for each of the four
materials in the study.
4.2 BACKGROUND
Historically, recycling has been practiced primarily by the manufacturing sector to reduce waste
stream volumes, the resulting disposal costs, and also as a means of cost recovery by selling
scrap materials. Recycling of post-consumer wastes was primarily limited to paper and rags until
the 1970s. The environmental movement was partially responsible for educating the general
population on the potential benefits of recycling, but markets for recycled materials remained
limited. One of the driving forces behind an increased interest hi recycling is the dwindling
number of available landfills in the more densely populated areas of the United States. The
Municipal Solid Waste Landfill Survey conducted by EPA projects that the number of landfills
is expected to decrease from approximately 5500 in 1988 to about 1000 in 2013.2
The amount of MSW generated hi 1988 was 180 million tons. MSW amounts are expected to
rise to 200 million tons by 1995, and to 216 million tons by 2000.
Three disposal methods are used for MSW: landfilling, incineration, and recycling. Incineration
and recycling are becoming increasr .y popular. In 1984, 85 percent of MSW was disposed of
in landfills, 5 percent was incinerated, and 10 percent was recycled. Statistics from 1988 show
the incineration and recycling proportions to have grown to 14.2 and 13.1 percent, respectively,
with 72.7 percent disposed of hi landfills.
In 1986, 17 million tons of material were recycled, a 13 percent increase over the 1984 level.
This amount is primarily due to voluntary efforts. However, most states have adopted recycling
initiatives with recycling targets of 15 percent or higher. EPA has set a national recycling goal
CH-92-139 4-2
-------
of 25 percent of the MSW by 1995. It is estimated that 63 percent of MSW generated in 1988
was recyclable. Further, disposal of these materials accounted for 68 percent of landfill volume.
Recycling of post-consumer wastes will be an important factor in extending landfill lifetimes.
The paths followed by post-consumer paper, plastic, glass and metals are initially quite similar,
originating in homes and businesses and eventually arriving at resource recovery facilities. Table
4-1 presents statistics on the recovery of paper, plastic, metals, and steel from MSW in 1988.
Recovery rates (by weight) for these materials in this study range from a high of 31.7 percent
for aluminum to a low of 1.1 percent for plastic. The largest percentage of the ferrous metals
category consists of "white goods," or household appliances, such as refrigerators, clothes
washers, etc. The next largest ferrous metals subcategory represents steel containers, including
cans. Overall, rigid containers (i.e., bottles and cans) represent a considerable portion of the
MSW weight. Glass is the most common material used in container manufacturing, representing
64 percent of the MSW rigid container weight. Other materials with respective MSW weight
compositions are plastic (17 percent), steel (15 percent), and aluminum (4 percent).
The percentage of aluminum recycled from rigid containers was 53 percent hi 1988.
Corresponding percentages for other materials recycled from rigid containers were steel (15
percent), glass (15 percent), and plastic (6 percent).
4.3 RECYCLING PROGRAMS
The passage of the Resource Recovery and Conservation Act (RCRA) hi 1976 placed the
management of municipal solid waste (MSW) on state and local governments. Several strategies
have been developed in response to the need to reduce the volume of post-consumer wastes
which are landfilled. Recycling is a key element of many of these plans.
CH-92-139
4-3
-------
TABLE 4-1. MATERIALS RECOVERY FROM MUNICIPAL SOLID WASTE, 1988
Weight
Generated
(in Millions
of Tons)
Paper and Paperboard 71.8
Glass 12.5
Metals
Ferrous 11.6
Aluminum 2.5
Other Nonferrous 1.1
Total Metals 15.3
Plastics 14.4
Rubber and Leather 4.6
Textiles 3.9
Wood 6.5
Other 3.1
Total Nonfood
Product Wastes 132.1
Other Wastes
Food Wastes 13.2
Yard Wastes 31.6
Miscellaneous
Inorganic Wastes 2.7
Total Other Wastes 47.5
Total MSW 179.5
Weight
Recovered
(in Millions
of Tons)
18.4
1.5
0.7
0.8
0.7
2.2
0.2
0.1
0.0
0.0
0.7
23.1
0.0
0.5
0.0
0.5
23.6
Percent
Recovered
of Each
Material
25.6
12.0
6.0
32.0
63.6
14.4
1.4
2.2
0.0
0.0
22.6
17.5
0.0
1.6
0.0
1.1
13.2
Discards
(in Millions
of Tons j
53.4
1 )
10.9
1.7
0.4
13.1
14.2
4.5
3.9
6.5
3.1
109.0
13.2
31.1
2.7
47.0
155.9
Source: Reference 2.
CH-92-139
4-4
-------
A number of recycling programs have been developed, both voluntary and mandatory. The type
of program selected for a given area depends on a number of factors. Considerations include
population density, current disposal methods, availability of funds, and marketability of recycled
materials. The role of the consumer in a recycling program may also vary widely. A brief
description of the more common programs follows in order of increasing consumer participation.
Two recycling program types require no consumer participation. For some solid waste facilities
employing incinerators, recycling activity is limited to the removal of large ferrous-bearing items
after incineration for sale to scrap dealers. Other facilities equipped with incinerators have front-
end processing; materials to be recycled are removed from the waste stream prior to incineration.
Removal of glass and metal components of the MSW stream prior to incineration has proven to
be beneficial in the operation of the incinerator and associated equipment as it reduces downtime
and produces a higher heat content for the remaining refuse.
Some programs allow recyclable materials to be commingled, with final separation to be
performed at a central facility. For such programs, a separate pickup may be required as standard
refuse vehicles may not be designed to store the commingled materials. Other mandatory
recycling programs require that recyclables be separated by material type prior to curbside
pickup. Specially designed trucks are equipped with bins to accept the material types. Refuse
workers maintain the material type integrity by placing materials hi the appropriate bins.
Many volunteer programs allow consumers to transport separated materials to a drop-off location
during designated hours/days using their vehicles. Receptacles are provided for each material
collected by the program. Volunteers are responsible for inserting materials in appropriate bins.
Other voluntary programs provide curbside pickup of specified materials either in conjunction
with the normal municipal refuse pickup or in a second pickup.
A number of states have implemented legislation requiring deposit on certain beverage containers.
Consumers may retrieve their deposit upon returning the containers to specified return centers,
often at the place of purchase.
CH-92-139
4-5
-------
One final option allows consumers to receive payment for recyclable materials brought to
redemption centers. Payment to consumers is based on the weight and quality of the material
being turned in, as opposed to the number of containers returned, which is the basis of the
deposit system.
4.3.1 Emissions Resulting from Collection of Recyclable Materials
4.3.1.1 Characterization
Several criteria pollutants would be released by vehicles involved in the collection and
transportation of recyclable materials. Carbon monoxide, nitrogen dioxide, paniculate matter and
volatile organic compounds (VOCs) are emitted by vehicles. As noted in the introduction,
however, such emissions should not be counted as part of an agency's recycling emissions
inventory. Their proper place is the mobile source inventory.
4.3.1.2 Quantification
When assessing emissions quantities, factors to be considered would include the type of recycling
program and the extent of public participation. Many curbside recycling programs attempt to
minimize additional vehicle (and manpower requirements by performing collection of recyclable
materials concurrently with non-recyclables. Given that many municipalities perform weekly
refuse collection, vehicle miles travelled (VMT) by refuse collection vehicles should represent
a negligible portion of total vehicle miles travelled in most areas.
Those programs which require a second pickup would result in additional vehicle miles travelled
during collection. Some municipalities have gone from weekly pickup of MSW to biweekly
alternating pickups of both MSW and recyclable materials. This approach was designed to
minimize additional VMT. For prc ns resulting in increased VMT, emissions may be
estimated by obtaining the VMT attnoutable to recycling and other vehicle information.
Emission factors may then be obtained from AP-42, Volume H1
CH-92-139 4-6
-------
Volunteer programs which involve dropoff centers would also result in an increase of vehicle
emissions. Again, emissions quantification could be difficult as some individuals may make a
separate trip while others may combine a number of activities with the dropoff. However, the
number of vehicles involved in transporting the recyclable materials to the drop-off center would
be much higher than for curbside pickup programs.
Possible approaches to quantifying vehicular emissions for programs involving drop-off centers
could include assumptions or gathering actual data on both the level of participation and mean
distance between the residence and the drop-off center. Information should also be obtained
regarding vehicle types, models and ages to develop emission factors.
4.3.2 Nonrecyclable Wastes
Regardless of the type of recycling program, the result of waste segregation produces one or
more reclaimed materials, and remaining wastes which require disposal by landfilling or
incineration.
Incineration achieves significant waste volume reductions, lending to increased landfill lifetimes.
As of 1988, nearly 160 municipal waste combustion facilities were on-line, accounting for
approximately 320 incinerators.3 Air emissions resulting from waste combustion must be
addressed along with potential problems associated with the disposal of incinerator ash.
Over 95 percent of the municipal combustors brought on-line since 1980 have heat recovery
boilers. These facilities represent 78 percent of the total incinerator capacity of 68,000 tons/day.3
Although energy is "recovered" at some facilities, incineration is not considered to be a recycling
process for the purposes of this report.
CH-92-139
4-7
-------
4.3.3 Emissions from Centralized Facilities
4.3.3.1 Characterization
Many recycling programs utilize a central facility for separation of recyclable materials. Two
types of facilities have been developed: waste processing and material recovery. Waste
processing facilities (WPFs) recover materials from raw MSW. Material recovery facilities
(MRFs) perform final sorting of commingled recyclables. WPFs are more expensive to construct
and are not widely used.
Automated systems are often employed in separating waste types in either of these facility types.
A number of different processes may be employed to remove materials from the waste stream.
Upon arriving at a processing facility, collection vehicles usually dump their contents on a tipping
floor. Equipment, such as a front-end loader, is used to transfer the materials to a conveyor
system. The waste moves between one or more stations within the facility where specific
components are targeted for removal from the total stream. The waste is treated by a number
of processes to achieve material-specific segregation. Some recyclables may also be subjected
to compaction and/or baling prior to shipping.
The waste is exposed by breaking open plastic trash bags and other containers, and spreading the
waste in a manner acceptable for the subsequent processing steps. Magnetic forces are often
applied to the waste to remove ferrous-bearing items, such as steel cans. Other metals, such as
aluminum, may be removed through the use of rare earth magnets or electrostatic separators. The
latter method induces a charge on waste materials passing beneath. Materials capable of holding
this induced charge are removed from the stream and are diverted for additional processing.
Air classification systems are used to separate waste items by density. Waste is exposed to a
stream of high velocity air which removes the lighter fractions of the waste stream, such as loose
papers and plastic items. Heavier components, such as glass containers, settle put of the air
stream and are passed to the next processing station.
CH-92-139 4-8
-------
A number of facilities may use manual extraction of specific materials from the waste in place
of any or all of the aforementioned mechanical means. This is more common in smaller scale
facilities.
The methods of separation used by a given facility depend on a number of factors, including
waste stream composition, throughput rates, worker's wages, health and safety considerations,
alternate disposal methods, and secondary market material specifications and prices.
4.3.3.2 Quantification
Airborne paniculate concentrations are likely to be high in the tipping floor area.4 Particulates
are generated by the waste handling activities. One potential source of particulate matter may
consist of waste paper in MSW which contacts the tipping floor, usually an indoor concrete pad.
The pad surface's roughness abrades the paper when the waste is moved by equipment, such as
a front-end loader. Additional dust could be created by waste abraded by the conveyor system,
or by waste/waste contact. Tipping floors are often located in a structure which is not fully
enclosed during operation. Doors are open to allow collection vehicles ingress and egress. This
may allow particulate matter to escape the structure as fugitive emissions. Some tipping floors
operate under negative pressure to reduce odors and fugitive emissions.
Air classification systems can produce particulate matter. Any fines in the waste stream reaching
this stage may be separated from remaining waste by the air stream. A baghouse is often used
to control emissions from this process. The composition of the fugitives would depend on the
waste components and would be expected to be highly variable. Information on the
characterization of particulate matter arising from this activity was not readily available.
Further, quantification of emissions may also prove difficult. The nature of activities in the
structure containing the tipping floor may prevent attempts to measure the amount of dust
escaping from the structure. Installation of a fan and baghouse could minimize dust and
associated fugitives.
CH-92-139
4-9
-------
After separation and consolidation, p> plastic, glass, and metals are all subject to a unique
series of additional processes in prej ion for sale in the secondary market. The pathway
followed by each material will be presented separately.
4.4 METALS RECYCLING
This category may be divided into ferrous and nonferrous metals. Ferrous metals are partially
or wholly composed of iron and are attracted by magnetic forces. Nonferrous metals include
copper, lead, tin, zinc, brass, bronze, and aluminum.
Ferrous metal wastes comprised 11.6 million tons (76 percent) of the total metals waste in MSW
in 1988.2 Aluminum waste accounted for 2.5 million tons (16 percent), and other nonferrous
metal waste contributed 1.1 million tons (7 percent). Of these three categories, recovery rates
are lowest for ferrous metals (iron and steel) at 5.8 percent, rising to 31.7 percent for aluminum,
and are highest for other nonferrous metals at 65.1 percent.
Several fractions of the nonferrous metals have high scrap value. Excluding aluminum, these
metals only comprise around 1 percent of total MSW. This low composition has hindered efforts
to recover these metals from MSW. Out of ten facilities designed to recover nonferrous
fractions, a majority have abandoned the effort.5
Ferrous metals and aluminum accounted for more than 90 percent of the metals in MSW in 1988,
therefore, research efforts focussed on recycling of these components.
4.4.1 Steel
Large household appliances, known as "white goods" or durables, and steel cans are the two
largest categories of steel in MSW. White goods are usually collected separately from other
MSW and are sent to automobile processing facilities for shredding.6 Due to the different
recovery path for these items, reclamation of steel from white goods was not investigated.
CH-92-139 4-10
-------
Steel cans may be constructed in a number of different ways and may include other materials.
Bimetal cans are constructed of three components; a steel body with a seam and two aluminum
end pieces. Cans may be constructed of steel components with the inner surfaces having been
plated with tin, a chemically stable metal used to prevent reaction between the steel and the
container contents. While this type of can is typically referred to as a "tin" can, the actual tin
content is only about one percent of the total container weight, having been applied by
electroplating. Other materials, such as epoxies and rosin esters, may be used in place of tin to
line steel cans.
Three piece cans require the use of sealing compounds, such as synthetic rubber, between the end
caps and can body, and also along the seam.
Two piece steel cans are a relatively new development, eliminating the seam. These cans are
distinguishable from three piece cans not only by the lack of a seam, but also by the presence
of a rounded edge between the can base and body. The only sealing required is between the top
and can body, reducing the amount of sealing compound per container.
Organic materials may be applied to cans as components of interior and exterior coatings. Primer
coatings are applied to the exterior of the can and may include epoxy, epoxy ester, acrylic vinyl,
and polyester resin. Overvarnish coatings are the final application, and may contain polyesters,
alkyds, and acrylics. Wide ranges of solvents are used in the coating process. Table 4-2 lists
some of the organic compounds used hi the coating and sealing of beverage cans. Many of the
same compounds would be used for cans designed to contain products other than beverages.
Paper labels are affixed to cans by glue. Many recycling programs require that the labels be
removed from cans, and that the interior be washed. However, some residual paper and glue may
remain on the can exterior, and product residuals may also be found on interior surfaces.
CH-92-139
4-11
-------
TABLE 4-2. TYPICAL ORGANIC COMPONENTS OF COATINGS
APPLIED TO BEVERAGE CANS
Interior Base Coat
Butadienes
Rosin esters
Phenolics
Epoxies
Vinyls
Organosols
Overvamish Coat
Polyesters
Alkyds
Acrylics
Primer (size) Coat
Epoxy
Epoxy ester
Acrylic vinyl
Polyester resin
Solvents (used for interior and exterior base coats, overvarmsh, and size coats)
Mineral spirits Ethylene glycol monoethyl ether acetate
Xylene n-Butanol
Toluene Isopropanol
Dicatone alcohol Butyl carbinol
Methyl iso-butyl ketone Paraffins
Methyl ethyl ketone Propylene oxide
Isophorone Resityl oxide
Solvesso 100 and 150 (TM) Aliphatic petroleum hydrocarbons
Ethylene glycol monobutyl ether Di-isobutyl ketone
Ethylene glycol monoethyl ether Di-methyl formamide
Ethanol Nitropropane
Cyclohexanone
End Sealing Compound
Synthetic rubber
Source: Reference 7.
CH-92-139 4-12
-------
Construction of the steel can has introduced sealing and coating compounds, and in the case of
the bimetal can, different metals. Organic coatings may account for 1.8 percent of the container
weight.8 Residual waste may be present on the can interior. Each of these may be considered
as contaminants with regard to recycling processes.
Scrap dealers will purchase only recycled materials fitting their specifications, such as accepting
only cleaned cans stripped of label materials. The scrap will then be subject to additional
processing, such as compaction and/or baling, in preparation for the secondary market.
Reclaimed steel may be marketed to three industries: iron/steel, detinning, and copper precipitate.
The copper industry uses scrap steel to act as a precipitate in extracting copper. This process is
not considered to be recycling in the context of this report and will not be covered.
The iron/steel and detinning industries have differing specifications for materials to be purchased.
For example, less dense bales of scrap allow for more efficient removal of tin at detinning
facilities. Iron/steel mills, however, prefer more dense scrap bales to minimize material handling.
4.4.2 Detinning
The detinning industry purchases scrap for purposes of recovering the tin content and, as a direct
result, increasing the quality of the steel scrap. Detinned steel stock demands a higher price in
the secondary market. The steel industry considers tin to be a contaminant, which when present
in sufficient quantity, results in inferior product quality. Tin is removed from these materials
through a chemical process called detinning. Detinning significantly lowers the amount of tin
in the scrap and allows for increased usage.
A limited number of detinning facilities operate in this country. In 1968, 15 facilities were in
operation, but by 1990, the number had decreased to around 6. In 1986, approximately 550,000
tons of tinplate scrap were detinned, yielding 1,250 tons of tin.6 It should be noted that a portion
of the stock which was detinned was scrap from container manufacturing facilities. An example
CH-92-139
4-13
-------
of such scrap would be tinplate sheet stock remaining after can tops and/or bases had been
punched out.
A number of factors can affect the viability of this industry. Detinning is ultimately tied to
activities within the steel container industry. The container market share for steel containers has
experienced change in the last 15 years. In 1976, 46 pounds of tin cans were produced per
capita; however, by 1983, this amount had dropped to 26 pounds.5 Recently, the steel industry
has been promoting the use and recyclability of steel cans to regain market share. The recycling
rate for steel cans (including tinplate cans) has been increasing, from a level of nearly 18 percent
in 19899 to 34 percent in 1991.10
Further, the amount of tin per container has decreased due to technological changes. Tin content
is currently at a level of around 0.4 percent of the container weight. The price of both scrap steel
and tin are critical to profitability of detinning operations. A weakening in either or both the
scrap steel and tin markets could result in a decrease in the number of detinning operations.
Transportation costs are significant for detinning. As a result, these facilities tend to be located
near th ir source, populated areas with a high level of recycling activities or near steel mills.
Industry wide detinning capacities are likely to increase in response to the number of state and
local recycling initiatives, assuming favorable market conditions as previously discussed.
Detinned scrap steel stock is sold to the iron and steel industry. Information on this market is
presented in the section on steel recycling.
The detinning industry is the only significant domestic source of tin metal in the United States.11
The sources of tin are clean tinplate scrap and tin-coated food and beverage cans. This section
describes each of the steps involved hi the overall process and the potential associated hazards.
The detinning process includes the following steps:
• Unloading of ferrous metal scrap
• Shredding
CH-92-139 4-14
-------
' Air classification and magnetic separation
• Chemical detinning
• Separation
• Tin removal
The detinning and separation steps take place at all detinning facilities whereas other steps are
not always required. The process at most detinning facilities is continuous, operating 24 hours
per day, 5 days per week, although some older facilities use a batch process.
Continuous processes are more commonly utilized due to higher efficiencies and are present in
most modern detinning facilities.
Tin cans must be shredded for two reasons. First, shredding loosens and separates most
contaminants such as paper, glue, lacquer, plastic, and organics (food residues or dirt) from
the cans. Shredding also separates aluminum ends from the bi-metal food and beverage cans.
This step allows contaminants to be removed from the cans during subsequent magnetic
separation and air classification. Second, shredding exposes a greater area of the tin cans to the
tin-removing chemicals used. The area exposed may be up to one square acre per ton of tin
cans.12
Shredding may result in airborne paniculate matter. Other materials may be released by this
process, such as contents of aerosol spray cans, and cans containing residual paints, solvents,
fuels and cleaning compounds. In 1976, aerosol and paint cans accounted for 2.7 percent and
3.2 percent of total can shipments.8 While recycling programs frequently do not permit many
of these containers, they may arrive at a shredder from a facility which used magnetic separation
to segregate the steel scrap.
4.4.2.1 Air Classification and Magnetic Separation
After tin cans have been shredded, a conveyor system carries the cans to the air classification and
magnetic separation step. In this step, most contaminants in the scrap (paper, glue, lacquer,
CH-92-139
4-15
-------
organics, aluminum, etc.) are removed. These contaminants, depending upon their properties,
either fall (aluminum scrap not picked up by the magnetic separators), or are blown (less dense
material pulled hi by the air classifier) into disposal containers. While the tin cans remain
attached to the magnet, the contaminants are transported to landfills for disposal. Industry
sources have reported that the combination of shredding, magnetic separation, and air
classification removes 98 percent of non-metallic contaminants and 99 percent of the aluminum.13
4.4.2.2 Chemical Detinning
After tin cans have passed through the shredder, magnetic separator, and air classifier, they are
considered clean and have a large surface area exposed to increase the efficiency of the chemical
detinning step. The actual detinning is accomplished by treating cans with a hot alkaline
solution, usually caustic soda (sodium hydroxide), containing an oxidizing agent to dissolve the
tin and precipitate it as sodium stannate.11 This step would also remove any contaminants
remaining on the scrap (e.g., paints). The cans are placed in the detinning solution either through
the- use of steel baskets lowered into solution tanks (typical of batch processes) or a tube-like
device that works like a screw conveyor.14 The scrap works its way through the chemicals and
into a wash. The screw conveyor is popular because it is a continuous process.
4.4.2.3 Separation
The detinned feedstock (cans) is separated from the detinning solution through the use of rinse
trommels (a cylindrical rotating screen). The cans are rinsed with hot water that is recycled into
the detinning tanks. The residual tin remaining on the surface of the detinned scrap is usually
less than 0.06 percent.14 The detinned scrap is baled and sold to iron and steel manufacturers for
use in new products.
4.4.2.4 Tin Removal
Tin remaining in the detinning solution is removed through an electropla' process which
utilizes electricity to turn the sodium stannate back into tin metal.14 The tin *, then melted off
CH-92-139 4-16
-------
the plates and cast into ingots that are sold. In older detinning plants, process residues, the spent
caustic soda, and "detinner's mud" are recovered and used by other industries, while any rinse
water is treated and reused.
Detinning also leads to recovery of aluminum and lead. For every ton of cans, the following
yield may be typical: 5 pounds of tin, 34 pounds of aluminum, and 9 pounds of lead.15
In newer facilities, the spent caustic soda is also recycled through the system. The "detinner's
mud," sludge that results from this process, is usually sold to tin smelters as a low-grade ore.16
4.4.2.5 Air Emissions
Modern detinning facilities produce small amounts of ammonia during the reduction of sodium
nitrate. Process heating decreases the time required for detinning. The heat energy may be
derived from the combustion of a number of fuels. Emissions associated with these facilities are
produced by fuel combustion.17 Such emissions, however, should already be reported in emission
inventories.
4.43 Iron and Steel Manufacturing
The iron and steel manufacturing industries in the United States utilize two types of furnaces, the
basic oxygen furnace and the electric arc furnace. The basic oxygen furnace produces about 60
percent of the steel in the United States, utilizing an average of 30 percent scrap while the
electric arc furnace produces about 40 percent of the steel, using virtually 100 percent scrap.18
The steps used to introduce ferrous metal scrap into each of the furnaces, at which point the scrap
may be mixed with virgin materials, are slightly different for each type of furnace and will be
discussed separately. Despite the differences in the charging steps, the equipment used and the
ferrous scrap being charged to each of the furnaces are comparable.
CH-92-139
4-17
-------
4.4.3.1 Basic Oxygen Process Furnace
A basic oxygen process furnace is a large open-mouthed vessel lined with a refractory material.
The furnace is mounted on trunnions that allow it to be rotated 360° in either direction. A typical
vessel can be 12 to 14 feet across and 20 to 30 feet high. The basic oxygen furnace receives a
charge composed of scrap and molten iron (produced in a blast furnace using iron ore and other
materials) and converts it into molten steel. Steel is produced by introducing a jet of high purity
oxygen into the furnace which oxidizes the carbon and the silicon in the molten iron, removes
these oxidized products, and produces heat which melts the scrap.19 The oxygen is injected into
fr furnace at supersonic velocities (Mach 2) through a water-cooled, copper tipped lance.20
Emissions including metallic oxides, particles of slag, carbon monoxide, and fluoride are typically
released from this process, however, the feedstock is composed primarily of virgin materials (at
least 70 percent molten iron).20
The process steps to charge the basic oxygen furnace with ferrous metal scrap include loading
the charge box and charging the furnace.
The ferrous metal scrap usually arrives at the facility's scrap yard in railroad cars. In the scrap
yard, the scrap is transferred to the charge box (a container) by means of an overhead crane and
electromagnet which are operated by a worker. The charge boxes are moved by special railed
cars from the scrap yard into the charging aisle for the furnace.19 The movement of the ailed
cars is controlled by workers at an operating panel.
When the furnace is ready to be charged, it is tilted toward the charging aisle, the charge box is
lifted by mechanical means, and its contents deposited into the vessel.19 Workers remotely
control this equipment from an operating panel.
4.4.3.2 Electric Arc Furnace
Electric arc furnaces consist of a refractory-lined, cylindrical vessel made of heavy welded plates,
a bowl-shaped hearth, and a dome-shaped roof. Three graphite or carbon electrodes are mounted
CH-92-139 4-18
-------
on a superstructure located above the furnace and can be lowered and raised through holes in the
furnace roof. The electrodes convey the energy for melting the scrap charge. There are water-
cooled bladders located at the holes in the furnace roof which cool the electrodes and also
minimize the gap between the openings in the roof and the electrodes in order to reduce
emissions, noise, heat losses and electrode oxidation. When the electrodes are raised, the furnace
roof can be swung aside allowing charge materials to be deposited in the furnace. Any alloying
agents that are required are added through the side or slag door of the furnace. Alloying agents
used in the electric arc furnace include ferromanganese, ferrochrome, high carbon chrome, nickel,
molybdenum oxide, aluminum, manganese-silicon, and others.20 Charging of the furnace is easily
accomplished in just a few minutes. The furnace is usually mounted on curved rocker trunnions.
Hydraulic cylinders or an electromechanical means are utilized for tilting the furnace.21
Like the basic oxygen furnace, the process steps to charge the electric arc furnace with ferrous
metal scrap include loading the charge bucket and charging the furnace.
Ferrous metal scrap is usually removed from railroad cars by a crane equipped with an
electromagnet. The crane places the scrap into a drop-bottom (clam-shell type) charge bucket.
The charge bucket is filled to a specified weight. The weight is checked on a scale having a
digital display that is visible to the crane operator.21 The charge bucket may be mounted on an
overhead track system or attached to a crane.
Once the charge bucket has been filled with the specified weight of ferrous scrap, it is moved
by the overhead track system or by a crane to the electric arc furnace. The furnace roof is swung
open and the charge of scrap is deposited into the furnace. Charging the furnace in this manner
results in uncontrolled emissions in most plants. During the charging process, the scrap must be
introduced properly so that the refractory (lining of the furnace) is not damaged. When pieces
of scrap remain above the parting line of the furnace roof (bezel ring), these pieces must be
relocated so that the roof can be set in place. This relocation can be accomplished with the use
of the charge bucket or some other large mass of metal suspended from the crane. Each of these
actions are controlled remotely by operators at an operating panel and/or by the crane operator.21
CH-92-139
4-19
-------
At some facilities, the charge may be deposited directly into the furnace from the incoming
transport by an electromagnet mounted on a crane. At facilities with smaller furnaces that do
not have a removable roof, the charge is deposited in the furnace through doors.20
4.4.3.3 Air Emissions
For steel recycling, only those processes unique to or altered by the use of scrap steel which
result in air emissions are addressed. Such emissions, however, are reported in the current
inventories. The major source of emissions attributable to the recycling of steel is melting. Once
this process is complete, the emissions resulting from the remaining processes are independent
of the origin of the feedstock.
Melting processes include: (1) charging; (2) melting; (3) backcharging, or the addition of more
feedstock or alloys; (4) refining, when the carbon level is adjusted; (5) oxygen lancing, to adjust
the batch chemistry and loosen slag; (6) slag removal; and (7) drawing off the molten metal
into a ladle or molds.
4.4.3,3.1 Characterization Contaminants such as paper labels, lacquer, glue, inks, and organics
may be found in varying quantities in scrap purchased by iron and steel mills. Charging the
furnace with this scrap may produce emissions of particulate matter, carbon monoxide, and
hydrocarbon vapors. Lead, cadmium and other heavy metals may be present in pigments used
in printed labels.6 Inks used in coating cans may contain compounds which result in air
contaminants when burned off during charging. Some of the compounds found hi lithowhite ink
include titanium dioxide, manganese naphthenate, drying alkyd, and aliphatic hydrocarbon
solvent.22
Table 4-3 presents an emissions characterization summary for steel industry processes involving
reclaimed steel. The range of pollutants is dependent on the type of contaminants within the
scrap.
CH-92-139 4-20
-------
TABLE 4-3. CHARACTERIZATION SUMMARY OF EMISSIONS FROM
RECYCLING PROCESSES FOR STEEL PRODUCTION
Activity/Process Emissions
Scrap preparation Hydrocarbons (degreasing process), smoke, organics,
CO (heating process)
Charging, melting, refining, Particulates, CO, organics, SO2, NOX, chlorides,
lancing, slag removal fluorides
Source: Reference 1.
4.4.3.3.2 Quantification The quantity of air emissions released during steel production is
dependent on the following parameters: percent of scrap in the charge; type and amount of
contaminants in the scrap; and furnace type.
AP-42 Volume I contains emission factors for processes involved with steel production using the
three main furnace types: basic oxygen, electric arc, and open hearth. Table 4-4, extracted from
AP-42, presents a range of emission factors for particulate emissions for melting. The low end
of the range would be appropriate for clean scrap, such as rejects from an iron or steel mill. The
upper end of this range would provide a better estimate of emissions where the scrap has a high
level of contaminants, such as post-consumer tin cans.
Scrap purchased from detinning facilities should produce lower air emissions. Many
contaminants, including paints, coatings, and residuals, are removed by the caustic solution.
4.4.4 Aluminum
Aluminum has numerous applications that may ultimately contribute to the MSW recyclable mix.
Architectural uses include siding, window frames, awnings/canopies, and heating and ventilation.
CH-92-139
4-21
-------
TABLE 4-4. EMISSION FACTORS FOR STEEL FOUNDRIES'
Participates" Nitrogen Oxides
Process
Melting
Electric arcblC
Open hearth4"
Open hearth oxygen lancedfl8
Electric induction11
kg/Mg
6.5 (2 to 20)
5.5 (1 to 10)
5 (4 to 5.5)
0.05
Ib/ton kg/Mg
13 (4 to 40) 0.1
11 (2 to 20) 0.005
10 (8 to 11)
0.1
Ib/ton
0.2
0.01
-
-
Reference 1.
b Expressed as units per unit weight of metal processed. If the scrap metal is very dirty or oily, or if increased oxygen
lancing is employed, the emission factor should be chosen from the high side of the factor range.
c Electrostatic precipitator, 92-98 percent control efficiency; baghouse (fabric filter), 98-99 percent control efficiency;
venturi scrubber, 94-98 percent control efficiency.
d Electrostatic precipitator, 95-98.5 percent control efficiency; baghouse, 99.9 percent control efficiency; venturi
scrubber, 96-99 percent control efficiency.
e Electrostatic precipitator, 95-98 percent control efficiency; baghouse, 99 percent control efficiency; venturi scrubber,
95-98 percent control efficiency.
' Usually not controlled.
It is also used in the food and beverage industry in the form of cans, foils and closures.
Table 4-5 presents a breakdown of aluminum waste from MSW. The elemental composition of
recyclable material varies depending on the general type of material considered. Table 4-6 lists
elements, with the exception of aluminum, which are present in different types of aluminum
scrap.
TABLE 4-5. GENERATION AND RECYCLING OF ALUMINUM PRODUCTS IN
MSW
Product Category
Weight Weight
Generated Recovered Percent Discards
(hi thousand tons) (in thousand tons) Recovered (in thousands tons)
Major Appliances
Furniture and Furnishings
Miscellaneous Durables
Miscellaneous Non-Durables
Beverage Cans
Other Cans
Foil and Closures
Total
107
89
280
240
1,439
67
324
2,546
0
0
0
0
791 55
0
16 5
807 32
107
89
280
240
648
67'
308
1,739
Source: Reference 23.
CH-92-139
4-22
-------
TABLE 4-6. TYPICAL ELEMENTAL COMPOSITION OF ALUMINUM SCRAP
Source
Used Beverage Containers
(directly reclaimed)
Municipal
(mostly UBC)
Automotive
(automobile shredder residue)
Element Percent
Silicon Iron Copper Manganese
0.2 0.6 0.15 0.9
0.8 0.5 2.4 0.6
5.0 0.8 1.3 0.3
Magnesium
1.1/1.3
0.1
0.1
Zinc
2.0
0.6
Source: Reference 24.
Aluminum used-beverage containers (UBC) constitute between 95 and 98 percent of all aluminum
recycled from MSW. Aluminum UBCs, like containers made from ferrous metals, include either
waterborne or solvent-borne surface coatings. Coatings are typically applied to both interior and
exterior surfaces to isolate the can's contents from the metal body, improve appearance, protect
lithography, and increase can mobility during the filling processes.19 Together with inks and
pigments used in exterior labeling, coatings contribute a variety of organic and inorganic
chemicals to the recyclable material. Organic components typically used in surface coatings are
similar to those used on steel cans as presented in Table 4-2.
4.4.4.1 Secondary Aluminum Production
Secondary aluminum production from scrap aluminum began shortly before World War I and has
grown at a constant rate since World War n. The technology of aluminum recycling has
remained essentially the same throughout the years, with changes primarily found in the method
of casting ingots and the introduction of emission control devices.
Recyclable MSW aluminum can be obtained from several sources. A major source of aluminum
is used aluminum beverage cans obtained from retailers who collect cans in states with deposit
laws. Retailers presort the cans and usually sell them to a scrap dealer or directly to a secondary
aluminum processor. Aluminum collected from municipal recycling programs can be a mixture
of UBC, other aluminum cans, foil, and closures, though most is UBC.24 Scrap dealers also
CH-92-139
4-23
-------
purchase aluminum in many forms directly from individuals, usually on a weight basis.
Depending on the purchaser of the recycled aluminum, the scrap dealer may or may not separate
or sort the various forms of aluminum. Large beverage can manufacturers like ALCOA and
Reynolds require separated aluminum. Finally, it is possible to recover and recycle aluminum
from incinerated MSW. However, the available information indicated that this source of
recyclable aluminum is not considered significant.
Aside from separation/sorting, the processing steps are similar for all forms of aluminum. The
recycling process described below emphasizes UBCs since they comprise the majority of
aluminum cycled from MSW.
The actual process of aluminum recycling consists of several steps. If the scrap aluminum is to
be transported over a long distance to the reclamation facility (secondary smelter), or if economic
factors are a concern, the aluminum can be densified in order to reduce the volume of the scrap.
Densification (compaction) is followed by shredding, which is then followed by a series of steps
occurring at the secondary smelter. These include scrap drying or delacquering, smelting, and
casting. Figure 4-1 presents an overview of the general aluminum recycling steps.
4.4.4.2 Compaction/Baling
Sorted aluminum may be compacted hi order to reduce the volume of scrap prior to being
transported to the secondary smelter. Aluminum UBC typically arrives at the compactor in the
form of loose, flattened cans. The "loose flats" are unloaded from the truck onto the floor, and
with the use of a forklift or front-end loader, are loaded into high density balers. Balers are of
two types, either vertical (loaded on the top) or horizontal (loaded on one side). These machines
compact the aluminum into bales generally weighing 700 to 1,200 pounds each.25-26 Alternatively,
the aluminum can be compacted into 35-pound biscuits which are packaged into 2,500-pound
bundles.25
CH-92-139 4-24
-------
Scrap
Aluminum
—
Compacting/
doling
Bales or^
Crushing
1
V
Delacquering
Air Emissions
Containing Volatile
Organic Compounds
Bundles"
Shredded Aluminum
"Clean"
Aluminum
Fluxing Agents
Demagging Agents
Alloys
i
Smelting
Dross, Slag, Air and
Water Emissions
Molten
Aluminum
Water
Casting/
Cooling
f
Shredding and
Magnetic
Separation
Water Containing Oil,
Grease, and Aluminum
Crucible
Magnetics
(Fe)
Ingots
^ / Molten
^*1 Aluminum
Figure 4-1. Overview of aluminum recycling.
-------
The exact size of the bales or the choice between baling or biscuiting depends on economic
factors (which form is less expensive to produce and transport) as well as operational limits ize
of machinery, etc.) of both the facility producing the compacted aluminum and the customer
buying it. As a final step, the bales or bundles are loaded by crane or forklift onto a truck or rail
car.
4.4.4.3 Crushing
A hammer mill is used to break up compacted or baled aluminum is broken up prior to
processing. The aluminum is placed on a conveyor belt using a forklift or a crane with grapples
(claws). The conveyor belt feeds the aluminum into the hammer mill which breaks the aluminum
into fist-size pieces.27 Further shredding is required by some facilities.
4.4.4.4 Shredding
Whether the . iuminum is transported to the secondary smelter in the form of bales, bundles, or
as loose flats, it must be shredded into smaller pieces prior to smelting. Shredding permits
removal of any remaining iron by magnetic separation and allows more efficient cleaning and
melting of the aluminum.
In preparation for shredding, aluminum is loaded into a hopper by either a forklift or a front-end
loader. The hopper can be fed directly or the aluminum can be pushed onto a conveyor belt
(recessed into the floor) which then feeds the hopper. The hopper in turn feeds a steady flow
of aluminum to a second conveyor belt. The aluminum travels along the conveyor belt, up an
incline, to a conical-shaped weigh hopper with a door at the bottom. The weight of the
aluminum within the weigh hopper is computer-monitored. When a pre-detennined weight is
attained, the conveyor belt feeding the weigh hopper is stopped and the door at the bottom is
opened. The aluminum is then loaded onto another conveyor belt which feeds the shredding
machinery. The weigh hopper discharges the aluminum onto the conveyor belt at a constant rate.
CH-92-139 4-26
-------
Within the shredding machine, the aluminum is sheared and cut into smaller pieces. The exact
size of these pieces varies depending on the specifications of the machinery and the size desired
by the customer purchasing the shredded aluminum. The shearing and cutting is performed by
rotating blades, or by grinding action. Both methods involve high speed machinery. The
shredded aluminum is then blown into the back of a trailer for transport to the secondary smelter.
4.4.4.5 Scrap Drying/Delacquering
Before aluminum scrap can be melted for remanufacture, any impurities such as paints, coatings,
container residues, or other contaminants must be removed. Impurities/contaminants are removed
during a drying or delacquering phase. Drying is the general process of removing contaminants
from the aluminum through heating. The scrap aluminum is heated in a gas- or oil-fired rotary
furnace until the contaminants are burned off.
Drying is referred to as delacquering when recycling UBC. In this process, the shredded UBC
is loaded onto a conveyor belt which feeds the delacquering kiln. The kiln is situated on a slight
angle and rotates to allow the shredded UBC to travel, by gravity, through the kiln. As the paint
and coatings burn off the aluminum, additional heat is produced which may be captured or
reintroduced to the kiln. This produces a greater fuel efficiency in the kiln as well as more
complete combustion of contaminants released from the aluminum.
The aluminum leaving the delacquering kiln is considered "clean", free of any paints, coatings,
or residues. Aluminum is gravity fed from the delacquering kiln onto a conveyor belt moving
toward the smelting furnace.
4.4.4.6 Smelting
Generally, two types of charge furnaces are used in secondary aluminum smelting; reverberatory
and rotary. Reverberatory furnaces are used for most medium to large secondary aluminum
smelting operations.27 These furnaces typically range in capacity from approximately 10 tons to
90 tons, operate by a continuous feed method, and can be either gas- or oil-fired. A charge well
CH-92-139
4-27
-------
is usually used to introduce pieces of iaiirninum below the liquid level of the already melted
aluminum within the reverberatory furnace. The introduction of uuminum below the liquid level
has two main advantages. First, fumes produced can be captured much more efficiently by using
a submerged hood. Also, oxidation of aluminum is greatly reduced as the fresh molten aluminum
surface is located below the molten aluminum/air interface. Oxidation of aluminum yields less
aluminum product.
Rotary furnaces usually operate by a batch-type method. These furnaces have a relatively low
capacity and are unsuitable for the addition of alloys and production of a homogeneous product.
Thus, most rotary furnaces are used by smaller facilities that produce aluminum for use in
products wheiu the composition of the aluminum is not specific. Advantages of the rotary
furnace include a controlled pouring rate and mechanical mixing action. Should an emergency
arise during the pouring of molten aluminum, it is much easier to stop the flow from a rotary
furnace than a reverberatory furnace.
For melting small quantities of aluminum (up to 1000 pounds), crucible or pot-type furnaces are
used extensively. Most crucibles are made of silicon carbide or a similar refractory material.27
While aluminum is in its molten form, several different processes can be performed depending
upon the scrap aluminum's characteristics and the desired composition of the recycled aluminum.
These processes include the addition of fluxing or alloying agents, the removal of excess
magnesium, and the removal of dross or slag which forms on the top of the molten aluminum.
4.4.4.6.1 Additives Fluxing agents are usually added to the furnace along with scrap. The
addition of fluxing agents reduces losses of aluminum and removes extraneous contaminants.
As aluminum reaches the molten stage, the fluxing agents react with leftover contaminants (inks,
coatings, etc.) to form insoluble materials which float to the top of the melt. The accumulation
of the flux (and contaminants) on top of the melt produces a layer on the surface known as slag.
This layer reduces any losses of aluminum exposed to the surface due to oxidation. A flux may
contain any one or combination of sodium chloride, potassium chloride, calcium chloride, calcium
CH-92-139 4-28
-------
fluoride, aluminum fluoride, or cryolite. A typical composition of a flux may be 47.5 percent
sodium chloride, 47.5 percent potassium chloride, and 5 percent sodium fluoaluminate (cryolite).27
Alloys may also be added to the molten aluminum in order to achieve the desired composition
of the recycled aluminum. Typical alloying agents include copper, silicon, manganese,
magnesium, and zinc. Generally, in the case of UBC, aluminum is recycled for the purpose of
producing new beverage cans. This end use obviates the need to add alloys as the aluminum
already possesses its desired composition.
4.4.4.6.2 Demagging The covers of used beverage cans possess a higher concentration of
magnesium than the rest of the can.28 Therefore, it is necessary to remove some of the
magnesium in order to produce a desirable, homogeneous aluminum metal product. Demagging
is the process of removing excess magnesium from the aluminum. The process uses chlorine or
chlorinating agents (i.e., anhydrous aluminum chloride) or aluminum fluoride to react with the
magnesium from the melt.29
Demagging through the use of chlorine is performed by introducing elemental chlorine gas, under
pressure, through tubes at the bottom of the molten aluminum. As the chlorine bubbles upward
it combines with the magnesium to form magnesium chloride. As the magnesium becomes
scarce in the melt, aluminum chloride, a volatile compound, begins to form as fumes. Wet
scrubbers are frequently used as an emission control method. Contaminated wastewater from the
scrubbers may contain suspended solids, chlorides, and heavy metals.29
Fluoride may also be used for demagging in a process similar to chlorine demagging.
Magnesium fluoride is produced which rises to the surface and combines with the flux on top
of the melt. Gaseous fluorides and fluoride dusts are emitted from this process. . Fluoride
emissions may be controlled by either wet or dry methods. Dry methods produce a solid waste
and wet methods produce both wastewater and solid waste. Other wastewater will have similar
properties to that produced in chlorine demagging, with the exception of fluorides being present
instead of chlorides.
CH-92-139
4-29
-------
4,4.4.6.3 Skimming Skimming is the procedure by which the dross (layer of oxidized aluminum)
and/or slag (layer of flux and contaminant) are removed from the top of the molten aluminum.
Cooled slag and dross are removed and stored for shipment to either a residue processor or
recycler, or to be discarded (i.e., landfilled).
4.4.4.6.4 Pollution Control Methods Emissions from the charge furnace can be controlled
through the use of a scrubber or a scrubber-baghouse combination. If a charge well is employed
and the aluminum scrap is introduced to the melt below the liquid level, a partially submerged
hood may be installed. This increases the efficiency of emissions captured. The partially
submerged hood is located above the charging area and below the liquid level, therefore
emissions are captured prior to their dissipation into the air.
In a wet scrubber, the hot furnace gases are spray quenched with water. This produces steam
which, in the case of chlorine demagging, reacts with the aluminum chloride to produce hydrated
aluminum oxide and hydrochloric acid. These compounds are removed by the scrubber.
A coated baghouse may be used to increase the removal of emissions such as acid gases. In the
coated baghouse, fabric filters are coated with a material which neutralizes acid gases from
demagging and removes fines from loading and storage areas in one step. As the coating
materi, becomes saturated or dirty, it is removed and a new batch of material is applied to the
fabric filters. The baghouse may also be connected to hoods which extend over possible sources
of dusts such as the loading and storage areas. Although most aluminum dust produced in these
areas would be composed of large particles and settle almost immediately, these additional hoods
may further reduce the presence of fine paniculate.
Afterburners may also be used to reduce hydrocarbon emissions. These afterburners may be
attached to the drying and/or delacquering kiln as well as the charge furnace. Temperatures used
are on the order of 1500°F, which provides complete combustion and virtually no hydrocarbon
emissions. However, due to the burning of fuel, nitric oxide and nitrogen dioxide may be
produced.27
CH-92-139 4-30
-------
4.4.4.7 Air Emissions
4.4.4.7.1 Characterization As the paint and coatings burn during the delacquering/drying
process, organic contaminants may be released due to incomplete combustion of the various
compounds which make up these layers (see Table 4-2). Any one or combination of these
chemical compounds may be present in the emissions from delacquering due to incomplete
combustion. Also, lead, cadmium (a carcinogen) and other heavy metals may be present in
paniculate form in the emissions.30 Wet scrubbers are usually employed to control emissions.
Dry scrubbers are not favored due to the possible buildup of fines which can result in explosions.
Air emissions generated during smelting are typically controlled using submerged hoods
connected to an air pollution control system. During the demagging process, hydrated aluminum
oxide, hydrochloric acid, volatile aluminum chloride, magnesium fluoride, gaseous fluorides, or
fluoride dusts can be formed. Table 4-7 presents processes and related emissions for the
recycling of aluminum.
Afterburners are sometimes used to control hydrocarbon emissions. Afterburners are typically
connected to both the delacquering and smelting furnaces. These can generate nitric oxide and
nitrogen dioxide emissions.
4.4.4.7.2 Quantification Table 4-8 contains emission factors obtained from AP-42 for secondary
aluminum production processes. Many contaminants are removed from aluminum scrap by the
delacquering/drying process. Remaining contaminants are removed or driven off during smelting,
resulting in air emissions. Emissions resulting from primary versus secondary processing vary
and are difficult to compare directly.30
CH-92-139
4-31
-------
TABLE 4-7. EMISSIONS CHARACTERIZATION SUMMARY OF RECYCLING
PROCESSES' SECONDARY ALUMINUM OPERATIONS
Activity/Process
Emissions
Crushing/screening
Shredding/classifying
Baling
Burning/drying
Hot dross processing
Sweating furnace
Smelting/refining
(using chlorine or fluorine)
Metallic and nonmetallic paniculate
Metallic and nonmetallic particulate
Dirt, alumina dust
Wide range of pollutants, including particulate
matter, VOCs (chlorides, fluorides, sulfur oxides,
oxidized alumina fines)
Dust
Products of incomplete combustion of rubber, oil
and grease, plastics, paint, cardboard, paper, fumes
from oxidation of magnesium and zinc
contaminants
Chlorine, fluorine, HC1, metal chlorides of Zn,
Mg, Al, aluminum oxide, others (depending on
scrap composition)
Source: Reference 1
4.5
PAPER RECYCLING
Paper is made from wood fibers, cotton, and other materials. Both hardwood and softwoods are
used in a variety of paper and paperboard products. There are two primary paper manufacturing
methods, mechanical and chemical. Mechanical papers are made from wood that has been
physically reduced to fibers. Chemical papers are made using caustic soda, sodium sulfate, and
various sulfides to reduce wood to fibers. In 1980, roughly 20 percent of the papers
manufactured hi the United States were mechanical papers and more than 50 percent were
chemical.31 Mechanical and chemical manufacturing techniques are chosen depending on the
CH-92-139
4-32
-------
TABLE 4-8. PARTICIPATE EMISSION FACTORS FOR
SECONDARY ALUMINUM OPERATIONS'
Uncontrolled Baghouse
Operation kg/Mg Ib/ton kg/Mg Ib/ton
Sweating furnaceb 7.25 14.5 1.65 3.3
Smelting
Crucible furnace6 0.95 1.9
Reverberatory furnace0 2.15 4.3 0.65d 1.3d
Chlorine demagging6
Electrostatic
Precipitator Emission
kg/Mg Ib/ton rating
C
C
0.65 1.3 B
* Reference 1. Emission factors for sweating and smelting furnaces expressed as units per unit weight of metal processed. For chlorine demagging, emission factor
is kg/Mg (Ib/ton) of chlorine used.
b Based on averages of two source tests.
c Uncontrolled, based on average of ten source tests. Standard deviation of uncontrolled emission factor is 1.75 kg/Mg (3.5 Ib/ton), that of controlled factor is 0.15
kg/Mg (0.3 Ib/ton).
d This factor may be lower if a coated baghouse is used.
' Based on average of ten source tests. Standard deviation of uncontrolled emission factor is 215 kg/Mg (430 Ib/ton); of controlled factor, 18 kg/Mg (36 Ib/ton).
-------
quality requirements of the end product. The remainder of paper manufactured is recycled
(25 percent) and additives (5 percent).
In addition to fiber, paper consists of numerous coatings, sizing agents, and colorants. In 1980,
these additives constituted 3.5 percent of the components in paper made in the United States.31
Coatings, used to make the paper strong and smooth, include clay, titanium oxide, calcium
carbonate, zinc sulfide, talc, and synthetic silicates. Sizing agents make the paper water resistant
and include rosin, hydrochemical and natural waxes, starches, glues, and cellulose derivatives.
Colorants are primarily made of a wide range of inorganic elements. The most commonly used
pigments are carbon black (black) and titanium oxide (white).
Inks are the other primary constituents of the paper. Inks consist of pigment and vehicle.
Carbon-derived black pigments are the most common. Titanium oxide, zinc sulfide, and zinc
oxide are also used in pigments. The vehicle is not actually applied to the paper as is the
pigment, however, vehicle residues may remain in the paper. Printing vehicles include a variety
of oils, waxes, and solvents. Letterpress and lithographic inks, which are commonly used on
newsprint, use mineral oil, resin, and solvent vehicles. Xerographic, uv-cured, and laser printing
inks use solvent, acrylic, and polyester-based vehicles.32 Flexographic inks have wide
applications and are gaining in popularity. These inks use numerous solvents as the printing
vehicle.
4.5.1 Primary Paper Recycli , Technologies
Plants that recycle wastepaper from MSW receive it from commercial collectors, wastepaper
dealers, or directly from municipal collection programs. Table 4-9 presents an overview of the
status of paper recycling. Once paper has arrived at the facility it is inspected and passed
through a series of sorting stages (i.e., magnets, trommel screens, manual sorting) that remove
gross contaminants. Next the paper is pulped and the pulp is cleaned, deinked, and bleached.
Technology used in wastepaper recycling plants varies depending on the paper grades accepted,
as shown in Table 4-10. Facilities generating pulp for use in low-grade products (e.g., brown
paper bags and cardboard) use no deinking and little bleaching. Pulp used in higher-grade
CH-92-139 4-34
-------
TABLE 4-9. GENERATION AND RECYCLING OF PAPER AND PAPERBOARD
IN MSW, 1988
Weight
Generated (in
Millions of
Tons)
Nondurable Goods
Newspapers
Books and Magazines
Office Papers
Commercial Printing
Tissue Paper and Towels
Paper Plates and Cups
Other Nonpackaging Paper*
Total Paper and Paperboard
Nondurable Goods
Containers and Packaging
Corrugated Boxes
Milk Cartons
Folding Cartons
Other Paperboard Packaging
Bags and Sacks
Wrapping Papers
Other Paper Packaging
Total Paper and Paperboard
Containers and Packaging
Total Paper and Paperboard
13.3
5.3
7.3
4.1
3.0
0.7
5.2
38.9
23.1
0.5
4.4
0.3
2.9
0.1
1.5
32.9
71.8
Weight
Recovered (in
Millions of
Tons)
4.4
0.7
1.6
0.6
Neg.
Neg.
Neg.
7.4
10.5
Neg.
0.3
Neg.
0.2
Neg.
Neg.
11.0
18.4
Percent
Recycled
33.3
13.2
22.5
14.6
Neg.
Neg.
Neg.
18.9
45.4
Neg.
7.7
Neg.
7.0
Neg.
Neg.
33.5
25.6
Discards (in
Millions of
Tons)
8.9
4.6
5.7
3.5
Neg.
Neg.
Neg.
31.5
12.6
Neg.
4.1
Neg.
2.7
Neg.
Neg.
21.9
53.4
•Includes tissue in disposable diapers, paper in games and novelties, posters, tags, cards, etc.
Neg. = Negligible.
Source: Reference 23.
CH-92-139
4-35
-------
TABLE 4-10.
SPECIFIC PROCESSES ASSOCIATED WITH
WASTEPAPER CATEGORIES
Wastepaper Category
Process
Finished Products
Pulp substitutes
Deinking grade paper
Newspaper
Mixed papers
Corrugated
Pulping
Pulping
Screening
Cleaning
Deinking
Pulping
Screening
Cleaning
Deinking
Pulping
Screening
Cleaning
Pulping
Screening
Cleaning
Fine paper
Tissue
Tissue
Fine paper
Newsprint
Folding cartons
Packing
Packaging
Molded products
Corrugating medium
Linerboard
Kraft towels
Source: Reference 33.
products must undergo more involved cleaning processes. Most facilities include some
combination and configuration of the following types of steps and equipment.
• Material Inspection and Storage
• Conveyors
• Manual Sorting
• Magnetic Separators
• Trommel Screens
• Pulper
• Screens/Cleaners
CH-92-139
4-36
-------
• Separation
Flotation
Washing
• Clarification
• Bleaching
• Dewaterer/Thickener
• Effluent Treatment
• Sludge Disposal
Figure 4-2 depicts the generalized process flow of a paper recycling plant.
A number of chemical additives are vital to the processing of wastepaper. Table 4-11 lists
chemical additives used in the deinking process. These chemicals are added at many points
throughout the system, depending upon the technology used and the degree of pulp quality
required for endproducts. Chemical additives remaining in washwater and sludge are handled
by on site wastewater and sludge treatment systems. Many contaminants are found in the
wastepaper stream that must be removed manually or by screens or filters throughout the process.
4.5.1.1 Material Inspection and Storage
Wastepaper must be carefully inspected for quality before it can be used as a pulp supply. Aged
or water-damaged papers are often discolored, which limits their use in high quality end products.
Levels of contaminants, aging, and water damage must all be evaluated when the wastepaper
arrives at the recycling facility. With current technology, roughly 70 percent of the mixed
wastepaper that enters a facility can be used for recycled paper.34 Twenty to 30 percent must be
discarded, usually landfilled or incinerated. The inspection and storage area is generally arranged
much like the tipping floor of a materials recovery facility. Trucks deliver loads of loose or
baled wastepaper and dump them on a concrete receiving floor. Paper is stored in piles or in
concrete bins or compartments. Bucket-loaders and forklifts are used to move the .paper around
the facility.
CH-92-139
4-37
-------
00
fwastepaper Jj
^^ Inspection ,
^" and Storage "1
t
^ Manual ,
^ Sorting 1
t
Pallets Paper Discards
Paper Discards
Large Contaminants
^ Magnetic ^
^ Separator "•
t
Paper Clips
Staples
Other Steel
_ Terr
** Scr
\
ninal
een
n
Glass
Rocks
Sand
i ^ Pulper T^
1 t *
Wire
Wood
Paper
Plastic
Rags
Coarse ^
Screen ^
t
Plastic
Rubberbands
Staples
Glue
Dirt
Flotation ^
* Separator ™
t
Ink
Rber
Fine ^
* Screen J^
». Washer ^> Bleacher
t *
Plastic
Glue
Waxes
\
r
Clanlier
Sludge:
Coatings
Inks
Fiber
Process Chemicals
Treated
Effluent
Coatings
Inks
Fiber
Process Chemicals
Figure 4-2. Paper recycling process flow.
-------
TABLE 4-11. DEINKING CHEMICALS
Deinking Chemical
Sodium Hydroxide
Sodium Silicates
Sodium Carbonate
Sodium or Potassium
Nonionic Surfactants
Solvents
Hydrophilic
Polymers
Fatty Acid Soap
Hydrogen Peroxide
Sodium Hydrosulfite
Chlorine
Structure/Formula
NaOH
Na^iOj
(hydrated)
NajCO3
(NaPO3)n, n=15
Hexametaphosphate
Na5P3010
Tripolyphosphate
Tetrasodium
pyrophosphate
Ethoxylated linear
alcohol
Ethoxylated alkyl
phenols
C,-C14 aliphatic
saturated hydrocarbons
CH2CHC=OOH(Na)n
Polyacrylates
CH3(CH)16COOH
Stearic acid
HA
NajSA
CLjOCl
Function
Fiber swelling
Ink breakup
Saponification
Ink dispersion
Wetting
Peptization
Ink dispersion
Alkalinity ledger and
buffering
Peroxide stabilization
Alkalinity
Buffering
Water softening
Metal ion sequestrant
Ink dispersion
Buffering
Alkalinity
Detergency
Peptization
Ink dispersion
Wetting
Emulsification
Solubilizing
Ink Removal
Ink softening
Solvation
Ink dispersion
Antiredeposition
Ink flotation acid
Bleach
Bleach
Bleach
Dosage (% of Fiber)
3-5
3-5
3-5
0.2-1.0
0.2-2.0
0.5-2.0
0.1-0.5
0.1-0.5
0.5-5.0
1.0
0.5-1.0
0.2-1.0
Source: Reference 35
CH-92-139
4-39
-------
4.5.1.2 Conveyor Systems
Conveyor belts frequently are used at the beginning of many paper recycling facilities as part of
the sorting arrangement and to feed wastepaper to the pulper. Specialized conveyors are
sometimes engineered to turn paper over or spread recyclables to a uniform depth to assist
manual sorters.36 In many facilities, conveyors are mounted at or below floor level on the tipping
floor so that material may be pushed directly onto the belt.
4.5.1.3 Manual Sorting
Unless a consistently high quality wastepaper stream is available (i.e., in-plant scrap), most plants
perform some degree of sorting prior to pulping. Sorting wastepaper by quality, color, or grade
is essentially a manual operation. The wastepaper stream is usually sorted as it passes workers
on a conveyor belt. Both positive and negative sorting techniques are used. Negative sorting
is the removal of contaminants from the recyclable stream. Negative sorting is marginally
effective because sorters inevitably allow some contaminants to pass their station. Positive
sorting removes the desired grade of paper from the mixed paper stream and results in lower
contaminant levels. The Garden State Paper Company in Garfield, New Jersev uses both systems
to sort different paper grades.37
Elevated sorting platforms and sunken conveyors are common design features at paper processing
facilities. This reduces the number of times recyclables must be handled. Increasingly, plant
designs place sorting stations directly over conveyor belts and/or processing equipment. This
arrangement is efficient because it allows workers to drop sorted papers or waste into chutes that
carry it to further processing.
4.5.1.4 Magnetic Separators
Magnetic separators are used in some wastepaper processing facilities to separate ferrous metals
from highly-contaminated papers. In general, magnetic separators in paper plants employ a
suspended magnet to remove ferrous metals from a conveyor belt passing beneath it.38 Separated
CH-92-139 4-40
-------
material is then dropped into a bin for disposal. Metal contaminants commonly include paper
clips, staples, and wire.
4.5.1.5 Trommel Screens
Trommels are inclined screen cylinders that are used to sort fine materials (i.e., glass fragments)
from the wastepaper stream. Wastepaper is fed in one end of a rotating trommel screen by a
conveyor and discharged to a conveyor or storage container at the other end. Fine material that
falls through the trommel screen is collected by a trough that lines the outside of the screen and
diverted to a conveyor or storage container.
4.5.1.6 Pulper
After undergoing some combination of the sorting steps discussed, wastepaper is passed to the
pulper. The pulper is the initial recycling step for most wastepaper recycling systems. Its
function is to "fiberize" the paper and to break-down contaminants with a minimum amount of
fiber degradation. The pulper is basically a large mixing vat that contains spinning paddles or
blades that chum the paper in a water-based slurry. Wastepaper bales that have been broken
apart are evenly fed to open pulping vats manually or by a conveyor belt. Some pulpers use
metal rotors and discs to grind fibers, while others rely on fiber-to-fiber contact to break down
the paper. Heated water (generally below 150 degrees Fahrenheit) and caustic chemicals, such
as sodium hydroxide, are added to assist in the pulping process. The pH of pulper slurry is
raised to between 10 and 12. The alkalinity swells fibers releasing inks into suspension. It also
hydrolizes ink vehicles and binders. Some screening of large contaminants takes place as the
pulp is drained from the pulper. From the pulper the pulp slurry, or "stock," is carried by pipes
to subsequent process steps.
Recently, high-consistency pulpers have gained popularity. These pulpers rely on a higher fiber
concentration (roughly 15 percent) to break down the paper. High fiber concentrations are
obtained by using less water. This method reduces the amount of chemicals and energy required.
CH-92-139
4-41
-------
This method also permits larger contaminant particles to remain unbroken in the pulp, which
facilitates subsequent flotation separation.
4.5.1.7 Screening/Cleaning
Most plants include a number of screening/cleaning steps throughout the system. Screens varying
in coarseness are used to remove a range of progressively finer contaminants. Rotors are often
used to press pulp through the screens.
4.5.1.8 Separators
Separation is the step that removes the ink from the pulp. Flotation and washing are the primary
deinking technologies used. Historically, flotation systems have been popular in Europe and
washing systems have been common in the United States. At present, the flotation method is
growing in popularity in the United States. Deinking systems separate ink by either floating large
ink particles to the surface of the pulp or washing dissolved inks from the pulp. Both techniques
generate ink-laden sludge in the form of a froth or wastewater. Most systems pass liquid wastes
to the clarifier to remove ink, fiber, and other contaminants from the water.
4.5.1.8.1 Flotation Separators Flotation systems float inks to the top of the pulp slurry and then
skim them from the surface. Small ink particles are agglomerated into larger clusters that are
floated to the surface using dispersed and some dissolved air that is injected into the bottom of
the flotation tank. The ink clusters attach themselves to the air bubbles and are floated to the
surface. The resulting inky foam is mechanically skimmed from the surface of the slurry. The
ink foam is usually dewatered prior to disposal.
For flotation to work effectively, ink must be stabilized as insoluble particles. Fatty acids aie
added to the pulp to form calcium soaps that act as stabilizers.39 Fatty acid soaps (surfactants)
and ethoxylates are commonly used along with calcium chloride, which assists in converting the
fatty acid into insoluble soap. Typical concentrations are approximately 80 pounds of surfactant
per ton of dry pulp produced.40 In addition, clay enhances the process of ink removal, so it is
CH-92-139 4-42
-------
frequently added to flotation systems. This has created a potential demand for some heavily-
coated magazine paper grades.
4.5.1.8.2 Washing Separators Washing separation systems operate by dispersing ink into tiny
particles that can be washed from the pulp. Surfactants are necessary to stabilize the ink in
solution and make it hydrophilic. Classes of alkylphenol ethoxylates and linear alcohol
ethoxylates are commonly used as dispersants in washing systems.39 Water is clarified and added
to the pulp slurry before it enters the washer. There are a variety of washing systems available,
and the most common types of washers are described below.41
Sidehill screens are basically inclined troughs lined with a screen. Pulp
released at the top of the screen gradually tumbles to the bottom under its own
weight. Water passes from the fiber and through the screen into a collection
tank below. This equipment is generally an open-air arrangement.
Gravity deckers use spinning horizontal screen drums that accept a coating of
pulp slurry. Water drains to the center of the drum and is removed. The pulp
cake is scraped off as it dries.
Inclined screw extractors use a screw to pull the pulp slurry up through an
inclined screen cylinder. Water drains away as the pulp rises in the cylinder.
Vacuum filters draw water from the slurry by sucking the pulp against screens.
Screw Presses extract water from the slurry by compacting the pulp in an
enclosed chamber using a large screw. Water is forced from the pulp through
perforations in the chamber walls.
All of these types of equipment are enclosed systems, except for the sidehill screen. Wastewater
is drawn from the pulp and usually sent to the clarifier for treatment. Using clean water for
washing is not practical for environmental reasons because of the required water volumes and
CH-92-139
4-43
-------
in terms of ch; ical use.41 For these reasons, recycled wastewater streams are commonly used
throughout the washing system. If necessary, pulp passes from the separation stage to a
bleaching stage.
4.5.1.9 Clarifier
Process water is commonly treated and reused to conserve process chemicals. Water removed
from washing and flotation is d:scharged to the clarifier where ink and other contaminants are
removed. The clarified liquid is then recycled throughout the process to dilute the pulp. Most
paper facilities pass unclarified water backward through the process. Cleaner water passes from
the final washing stage to earlier and dirtier stages. The water is drained when it reaches the first
washer and is then sent to the clarifier, treated, and recycled. A large percentage of liquid and
solid plant effluents and emissions is generated at the clarifier.
Most clarifiers are designed as large vats or tanks; some are enclosed. A filter is often the first
clarification stage, intended to reduce the loss of fiber and remove large contaminants. During
washing, dispersants break the inks into tiny particles. Clarification reverses this process by
adding flocculants to reagglomerate the ink into larger particles that can then be floated or settled
and removed. Low-molecular weight cationic liquid polymers and high- molecular-weight
anionic polymers are used as flocculants depending on the wastewater makeup.39 Dissolved air
flotation is generally used to float the flocculated particles to the surface of the clarifier. The
flocced particles are skimmed from the surface by a scoop mechanism that slowly rotates on an
axis in the middle of the tank. A sediment sump draws heavy material from the bottom of the
tank. Skimmed material and sludge are usually thickened and incinerated or landfilled.
Wastewater is recycled through the plant or treated and released.
4.5.1.10 Bleaching
Once the deinking process has removed ink particles from the pulp, bleaching may be necessary
to attain necessary brightness requirements for certain endproducts. A majority of paper
recycling plants bleach the fibers to improve their brightness. Bleaching is accomplished by
CH-92-139 4-44
-------
adding bleaching agents to pulp before it enters a screw mixer. The fiber and bleach mixture is
often allowed to soak and react in a holding tank or tower after mixing. The entire bleach
process is usually enclosed. Water flowing from the reaction is clarified and reused or released
to the plant's effluent control system.
Chlorine-based bleaches, such as hypochlorite, are commonly used throughout the paper industry.
A 1987 survey by U.S. EPA Region V of paper mills revealed that 12 out of 14 deinking
facilities surveyed used chlorine bleaching.42 Concerns surrounding the use of chlorine-based
bleaching agents have spurred the use of alternative bleaching agents. Hydrosulfite, peroxide,
and oxygen-based bleaches are frequently used as alternatives when lower-quality brightness
levels are acceptable.
4.5.1.11 Dewatering Equipment/Thickener
Some deinking facilities are directly connected to papermaking mills, allowing the bleached pulp
to be sent directly to the paper mills. Sometimes, pulp must be stored or transported before
being used in paper production. To reduce the volume and weight of the pulp, it is processed
through a dewaterer. There are numerous dewaterer designs using screens, screws, presses, and
vacuum systems to draw water from the pulp.
4.5.2 Air Emissions
No information specifically pertaining to air emissions from pulping of recycled paper was
available in AP-42 or AIRS. AP-42 Volume I contains data on the characterization of and
emission factors for chemical wood pulping. This information is discussed in this section
because reclaimed paper would be subject to the same or similar processes.
4.5.2.1 Characterization
Chlorophenols, chloroform, chloroethylene, chlorobenzene, methylene chloride, and carbon
tetrachloride may be emitted during or after the bleaching process. The recovery furnace, lime
CH-92-139
4-45
-------
kiln, and smelt dissolving tank emit particulate matter composed primarily of sodium salts with
some calcium salts from the lime kiln. A number of reduced sulfur compounds are emitted,
including hydrogen sulfide, methyl mercaptan, dimethyl sulfide and dimethyl disulfide. Sulfur
dioxide emissions result from the oxidation of reduced sulfur compounds in the recovery furnace.
Carbon dioxide and nitrogen oxides are also emitted by the recovery furnace. Boilers used to
provide heat and energy may also be a source of a number of the above pollutants, depending
on the fuel being fired.
The pulping and papermaking processes produce significant amounts of wastewater. Many
compounds found in wastewater may become airborne after release to treatment ponds.
4.5.2.2 Quantification
Table 4-12 contains emission factors from AP-42 for Kraft pulping. As stated earlier, emissions
data for facilities using strictly reclaimed paper as a source of pulp were not discovered during
this project. As a result, quantification of emissions for this scenario is not available at this time.
The use of recycled paper is expected to increase significantly in the near future. One study
shows a 53 percent increase in consumption by mills in the U.S. and Canada by 1995.43
4.6 GLASS RECYCLING
Post-consumer glass can be classified into functional groups depending on the forming method
used. Three groups, container glass (bottles and jars), flat glass (window glass, plate glass, float
glass, tempered glass, and laminated glass), and pressed and blown glass (ornamental glass and
stemware) constitute virtually all of glass produced.44 As of 1988,6.9 percent (12.5 million tons)
of all MSW generated in the United States consisted of glass products, 92 percent of which was
container glass, as shown in Table 4-13.
CH-92-139 4-46
-------
TABLE 4-12. EMISSION FACTORS FOR KRAFT PULPING"
EMISSION FACTOR RATING: A
Source
Digester relief and blow tank
Brown stock washer
Multiple effect evaporator
Recovery boiler and direct
evaporator
Noncontact recovery boiler
without direct contact
evaporator
Smelt dissolving tank
Lime kiln
Turpentine condenser
Miscellaneous"
Type of control
Untreated"
Untreated"
Untreated"
Untreated11
Venturi
scrubber'
ESP
Auxiliary
scrubber
Untreated
ESP
Untreated
Mesh pad
Scrubber
Untreated
Scrubber or ESP
Untreated
Untreated
Particulates
kg/Mg
_
.
-
90
24
1
1.5-7.51
115
1
3.5
0.5
0.1
28
0.25
-
-
Ib/ton
.
.
-
180
48
2
3-15"
230
2
7
1
0.2
56
0.5
-
-
Sulfur dioxide (SO,)
kg/Mg
.
.
-
3.5
3.5
3.5
-
-
0.1
0.1
-
0.15
-
-
-
Ib/ton
_
.
7
7
7
-
-
0.2
0.2
-
0.15
-
-
-
Carbon monoxide (CO)
kg/Mg
_
-
5.5
5.5
5.5
5.5
5.5
_
-
-
0.05
0.05
-
-
Ib/ton
_
.
11
11
11
11
11
_
-
-
0.1
0.1
-
-
Hydrogen sulfide (Sm)
kg/Mg
0.02
0.01
0.55
6°
6'
6'
(f
0.05"
0.05h
0.1J
O.I1
0.1'
0.25m
0.25™
0.005
-
Ib/ton
0.03
0.02
1.1
12'
12e
12'
12e
0.1"
0.1"
0.2'
0.2J
0.2'
0.5m
0.5™
0.01
-
RSH, RSR, RSSR (Sm)
kg/Mg
0.6
0.2C
0.05
1.5"
1.5'
1.5'
1.5e
-
-
0.15*
O.l*
0.151
o.r
o.r
0.25
0.25
Ib/ton
1.2
0.4C
0.1
y
y
3"
3'
-
-
o.*
0.3"
0.3>
0.2™
0.2m
0.5
0.5
Reference!. Factors expressed in unit weight of air dried unbleached pulp (ADP). RSH = Methyl mercaptan. RSR = Dimethyl sulfide. RSSR = Dimethyl disulfide. ESP = Electrostatic precipitator.
Dash = No data.
If noncondensible gases from these sources are vented to lime kiln, recovery furnace or equivalent, the reduced sulfur compounds are destroyed.
Apply with system using condensate as washing medium. When using fresh water, emissions are 0.5 (0.1).
Apply when cyclonic scrubber or cascade evaporator is used to direct contact evaporation, with no further controls.
Usually reduced by 50 percent with black liquor oxidation and can be cut 95-99 percent when oxidation is completed and recovery furnace is operated optimally.
Apply when venturi scrubber is used for direct contact evaporation, with no further controls.
Use 7.5 (15) when auxiliary scrubber follows venturi scrubber, and 1.5 (3) when it follows ESP.
Apply when recovery furnace is operated optimally to control total reduced sulfur (TRS) compounds.
Usually reduced to 0.01 g/kg (0.02 Ib/ton) ADP when water low in sulfides is used in smelt dissolving tank and associated scrubber.
Usually reduced to 0.015 g/kg (0.03 Ib/ton) ADP with efficient mud washing, optimal kiln operation and added caustic in scrubbing water. With only efficient mud washing and optimal process
control, TRS compounds reduced to 0.05 g/kg (0.08 Ib/ton) ADP.
Includes knotter vents, brownstock seal tanks, etc. When black liquor oxidation is included, emissions are 0.3 (0.6).
-------
TABLE 4-13. GENERATION AND RECYCLING OF GLASS IN MSW, 1988
Product Category
Durable Goods*
Containers and Packaging
Beer and Soft Drink Bottles
Wine and Liquor Bottles
Food and Other Bottles and Jars
Total Glass Containers
Total Glass
Weight
Generated
(in
Millions
of Tons)
1.2
5.4
2.0
3.9
11.3
12.5
Weight
Recovered
(in
Millions
of Tons)
Neg.
1.1
0.1
0.3
1.5
1.5
Percent
Recovered
Neg.
20.0
5.0
7.7
13.3
12.0
Discards
(in Millions
of Tons)
1.2
4.3
1.9
3.6
9.8
11.0
•Glass as a component of appliances, furniture, consumer electronics, etc.
Neg. = Negligible.
Source: Reference 23.
Nearly 100 percent of the glass recycled from MSW was container glass. Because of the
intended longevity of the product, plate glass does not provide a consistent market for recyclers
and little is recycled. Pressed and blown glass is also generally formed into items considered to
;-. "durable goods." Because of the variety of methods used in its production, as well as the
variety of raw materials used to produce it, pressed and blown glass is also seldom recycled.
The most common types of glass are soda-lime, borosilicate, lead silicate, and opal.
Approximately 77 percent of all glass manufactured is soda-lime glass. Glass food and beverage
containers ore manufactured exclusively from this glass type. Borosilicate glass, a common
example of which is Pyrex (produced by Owens-Coming Glassware), comprises approximately
11 percent of all glass produced. Lead silicate and opal glass comprise five percent and seven
percent, respectively, of glass produced.44 Other less common glass types are produced on a
smaller scale for numerous markets; the production and rec\ oig of these glass types can be
considered negligible due to the low production volumes.
CH-92-139
4-48
-------
Soda-lime glass is used exclusively in the production of food and beverage containers because
of the ease and efficiency with which it is produced. Three colors of soda-lime glass, clear
(flint), green, and amber, are commonly produced and recycled. Green and amber glass are
produced by adding minerals such as chromium trioxide, iron oxide, and cupric oxide for green
glass and sodium sulfide for amber glass to a flint batch.45 Recyclers generally segregate by
color because clear glass can be used in any batch, whereas colored glass is generally used to
produce recycled products in a specific color.
Borosilicate glass is used commonly in industry as well as in the commercial market. The
formula for each type of borosilicate is so precise that cullet from different sources it not
generally mixed, resulting in limited recycling potential. Lead silicate and opal glass constitute
a minor portion of the glass industry. Because both glass types are considered to be "durable,"
very little is thrown away and therefore very little is recycled.44
4.6.1 Glass Processing
The basic method used to recycle glass waste varies only slightly nationwide.46 In general, when
separated glass arrives at a processing facility the following steps occur:
• Manual sorting
• Mechanical sorting
• Crushing and grinding
• Mechanical removal of metal, plastics, and any other small foreign materials
• Segregation of cullet by size and shipment to a manufacturer
Depending on the grade of cullet and its expected market, it may be rinsed with water following
the above steps.
While numerous variations of this process are employed, approximately 90 to 95 percent of the
glass processing facilities in the United States employ these methods.46 Very few technologically
CH-92-139
4-49
-------
advanced separation methods are used, primarily because the price and profits associated with
cullet are so low that most compares cannot afford expensive machinery.
The following sections discuss the most conventional process used to produce glass cullet.
Figure 4-3 presents a schematic diagram of a typical glass recycling process.
Although the steps outlined below are used consistently in glass recycling facilities, the order that
the steps are applied varies from facility to facility. For example, one facility may magnetically
separate the waste before crushing, while another may do so after crushing. Others may use
magnets before and after crushing. The operators of a facility rely upon trial and error to
determine the most effective means of producing cullet for their facility. No single method has
been proven to work most effectively under all circumstances.
4.6.1.1 Manual Sorting
When glass arrives at a p ocessing facility, it has usually been pre-sorted by color. At the
processing facility, it is first emptied into a surge hopper which deposits the glass onto a
conveyor belt. Generally, a facility will process different colored glass on different belts or at
different times.47 The glass passes along the conveyor where workers remove any large debris
such as stones, brandies, or other non-glass material.46 Most facilities process glass at a rate that
requires only two or three sorters per conveyor.
4.6.1.2 Magnetic Separation
Magnetic separation of ferrous material typically follows hand sorting. The most common type
of magnet used to remove ferrous waste is the cross-conveyor magnet.48 Magnets are suspended
over the conveyor belt at heights inversely proportional to the force of the magnets. A belt
system, arranged perpendicular to the conveyor, surrounds the magnets and moves the attracte-'
ferrous material off to the side. After the ferrous material moves over the edge of the conveyu
and out of the magnetic field, it drops or is scraped into a waste chute.49
CH-92-139 4-50
-------
Post-Consumer
Glass
Waste
Bins
^ Surge
Hopper
^ Manual ^ Magnetic ^ Air
Sorting Separator Classifier
Wood
Stones
Plastic
Cardboard
1
i
Ferr
Met
1
ous Plastic
als Styrofoam
Aluminum
Cardboard
r
f-
-------
Other types of magnets, such as drum magnets and pulley magnets, are occasionally used in this
step. Drum magnets are encased within a revolving drum located over the conveyor. When
ferrous metals are attracted to the magnet, they adhere to the drum surface, which rotates out of
the magnetic field and into a waste bin. Pulley magnets are located at the end of a conveyor.
When material passes over the end, non-ferrous material is carried onto another conveyor.
Ferrous material adheres to the conveyor until it passes out of the magnetic field and into a waste
bin.
4.6.1.3 Velocity Trap/Air Classifier
After the glass material is passed through the magnetic separator, it is often passed through some
type of air classifier or bag vacuum to remove the lighter organic material, paper, plastic, and
styrofoam. A bag vacuum is simply a powerful vacuum or series of vacuums (up to 150) placed
over the conveyor belts. Air is passed through a chute and bag system, similar to a common
household vacuum. The chute is placed over the conveyor and the dust and fines are pulled up.
The bags are semi-porous so air passes through but particulates do not. This system effectively
removes the lighter material while allowing the heavier glass to remain on the conveyor.46
In a less common method, glass is passed across a vibrating screen. An upward air flow blows
the light material away from the heavier glass. A similar system of air classification passes glass
into a vertically oriented, hollow cylinder. The cylinder has a constant upward wind current that
lifts the lighter material out but allows the heavier objects to fall.50
4.6.1.4 Crusher/Grinder
After the glass is separated from the extraneous waste, it is ready to be crushed. Two types of
crushers are commonly used. Many glass recycling facilities use impact crushers to produce
cullet.47 In . ..s process, a conveyor deposits the glass into an inclined chute where the force of
gravity breaks it against transverse steel rods or chains. The broken glass and debris is then
deposited back onto a conveyor belt.
CH-92-139 4-52
-------
The second commonly used machine is a jaw crusher, which consists of two vertical steel plates
into which glass is deposited. Initially, one of the two plates is positioned at an angle to form
a housing to catch the glass. When glass is loaded, the two plates actively grind it into cullet,
which is then redeposited onto a conveyor.48 This technique is also commonly used to process
glass into powder, but very few facilities powder glass.47
4.6.1.5 Screening
After glass is crushed, a conveyor moves it onto a vibrating screen or series of screens, which
allow smaller glass shards to pass through to the next stage of the recycling process. The larger
pieces, accompanied by any plastic and aluminum bottle caps, are conveyed back to the sorters
or magnetic separators for reprocessing. Cullet that has not been crushed to a specified size
passes through the separators and crushers until it meets the size specifications of the facility.47
This process may be repeated three or four times before the cullet is crushed to an acceptable
size. Most container manufacturers (one of the less stringent markets for cullet) require the cullet
to be crushed to pieces smaller than 6 millimeters.51
4.6.1.6 Aluminum Separation
After being passed through each of the aforementioned processes, cullet may still contain waste
aluminum. Most processing facilities use an electrostatic or eddy-current magnet to remove the
aluminum after crushing and screening.48 In both electrostatic and eddy-current separators, the
process stream is charged by a high-voltage ion source. The charged material is then passed over
the edge of a conveyor onto a rotating, electrically grounded drum. Highly conductive material
(aluminum) rapidly dissipates its charge to the drum and falls into a waste bin. Non-conductive
material (glass) remains adhered to the drum's surface for a greater distance and falls onto
another conveyor.7
CH-92-139
4-53
-------
4.6.2 Air Emissions
Paniculate is generated during crushing and grinding operations. Some facilities use air scrubbers
to cleanse the air.7 No information was readily available on the frequency of scrubber use for
this process. Many individual processes contribute to the amount of glass dust in the air, but the
airborne levels in recycling plants are difficult to quantify. No negative environmental effects
have been attributed to glass recycling.50
4.7 PLASTICS RECYCLING
Plastics are broadly classified by their polymer structure as either thermoplastic or thermoset
resins. Thermoplastics are recycled because they can be melted and reformed, while the cross-
linked polymers of thermoset resins cannot. Table 4-14 lists U.S. sales figures, in pounds, of the
six commonly recycled thermoplastic resins for 1990.
In the late 1980s, the Society of the Plastics Industry (SPI) voluntarily devised and implemented
a system of seven codes to facilitate the identification and separation of common thermoplastic
resins used in packaging applications. The symbols usually appear on the bottoms of containers
and other disposable plastic items. The symbol consists of three arrows arranged head to tail in
a triangular shape. The number appearing in the center of the triangle identifies the resin type.
The common resins with their respective number identifiers are: (1) polyethylene terephthalate;
(2) high density poi iiylene; (3) vinyl; (4) low density polyethylene; (5) polypropylene; and
(6) polystyrene. A "7" appearing within the symbol indicates "other" and may include mixtures
or layers of resins.
Table 4-15 lists the various plastic goods recycled in 1988 and their contributions to recycling
of plastics hi general. At present, containers made from polyethylene terephthalate (PET) and
high-density polyethylene (HDPE) are the only post-consumer plastics being recycled in
significant quantities. These resins comprised one-half, or 0.1 million tons, of the plastic
CH-92-139 4-54
-------
TABLE 4-14. NET U.S. RESIN SALES OF COMMONLY RECYCLED
THERMOPLASTIC RESINS (1990)
Type
Million Lbs.
Example Products
Low-density Polyethylene (LDPE) 10,859
Polyvinyl Chloride (PVC)
Polypropylene (PP)
Polystyrene (PS)
Polyethylene Terephthalate (PET)
9,297
High-density Polyethylene (HOPE) 8,505
8,132
5,137
2,139
Garbage bags
Coated paper
Clear film
Wire coatings
Construction pipe
Blister packs
Food wrap
Cooking oil bottles
Floor tiles
Milk and detergent bottles
Heavy-duty films
Wire and cable insulation
Yogurt and margarine tubs
Fishing nets
Drinking straws
Auto fenders
Auto battery cases
Disposable foam dishes and cups
Egg cartons
Cassette tape cases
Foam insulation
Soft drink bottles
Synthetic textiles
X-ray and photographic film
Magnetic tape
Source: Reference 2, 52
CH-92-139
4-55
-------
TABLE 4-15. GENERATION AND RECYCLING OF PLASTICS IN MSW, 1988
Product Category
Durable Goods'8'
Nondurable Goods
Plastic Plates and Cups
Clothing and Footwear
Disposable Diapers(a)
Other Misc. Nondurables(b)
Weight
Generated
(in Millions
of Tons)
4.1
0.4
0.2
0.3
3.8
Weight
Recovered
(in Millions
of tons)
<0.1
Neg.
Neg.
Neg.
Neg.
Percent
Recovered
1.5
Neg.
Neg.
Neg.
Neg.
Discards
in (Millions
of tons)
4.1
0.4
0.2
0.3
3.8
Total Plastics
Nondurable Goods 4.6
Containers and Packaging
Soft Drink Bottles 0.4
Milk Bottles 0.4
Other Containers 1.7
Bags and Sacks 0.8
Wraps 1.1
Other Plastic Packaging 1.2
Total Plastics
Containers and Packaging 5.6
Neg.
0.1
Neg.
Neg.
Neg.
Neg.
Neg.
0.1
Neg.
21.0
<1.0
Neg.
Neg
Neg.
Neg.
1.6
4.6
0.3
0.4
1.7
0.8
1.1
1.2
5.5
Total Plastics
14.4
0.2
1.1
14.3
(a) Appliances, toys, furniture, etc.
(b)Does not include non-plastic materials in diapers.
Neg. = Negligible.
Source: Reference 23.
CH-92-139
4-56
-------
recycled in 1988. Both resins are recycled at high rates because of their substantial use in
packaging. Most PET is used to manufacture carbonated beverage containers, twenty-one percent
of which were recycled in 1988. The high recycling rate is due to elevated collection levels in
states with bottle bill legislation. HDPE is also used in base cups for PET bottles. HDPE is
easily recyclable and is considered a resin of choice for numerous applications. However, less
than one percent of HDPE milk bottles produced are currently recycled.
Limitations of collection systems and other factors have hindered reclamation of the other coded
resins, which include: low-density polyethylene (LDPE), vinyl (V), polypropylene (PP),
polystyrene (PS), and others. These resins appear in a range of products from building materials
and luggage to egg cartons and garbage bags. In 1990, these resins together represented more
than 34 billion pounds of potentially recyclable plastics, 8.9 billion pounds of which were used
in packaging.52
Reclamation facilities acquire recyclable resins from various recycling programs. The resins are
purchased as single resins (homogeneous) or mixed resins (heterogeneous). In general, recyclable
plastics are separated into pure resin streams before being used as supplements to virgin
feedstocks; The need for separation is primarily due to differences in melt characteristics.
Commingled plastics recycling represents the significant exception to this rule. This technology
allows a mixed stream of plastic wastes to be manufactured into dense products such as plastic
lumber for outdoor applications.
4.7.1 Processing
This section presents an overview of the general processing steps to reclaim plastics, details resin-
specific processes, and describes commingled resin processing.
Plastics reclamation systems vary widely depending upon the type of raw materials processed,
the degree of processing, and the specific technology used. Regardless of the materials accepted
at a reclamation facility, or the physical condition of the waste, plastics are generally processed
using some combination of the following steps:
CH-92-139
4-57
-------
• Manual sorting
Shredding and grinding
Washing
Separation (air classification, flotation, hydrocyclone)
• Drying
• Aluminum separation
• Extrusion
This section describes the general technologies associated with these steps. Reclamation of soft
drink bottles, the most frequently recycled plastic product, generally follows the described
process. Soft drink bottles are composed of three resins (PET, HDPE, PP), aluminum, and a
paper label. Figure 4-4 presents an overview of a plastics recycling system with process inputs
and outputs.
Due to their large volume, more and more plastics arrive at processing centers either shredded,
in bales, or some in other compacted form. A hydraulic bale breaker can be used to break bales
apart. So * facilities prefer to receive unaltered containers because of unique sorting and
separation ..sthods. At this point, the plastics are fed onto a conveyor or into a bin on the
processing line and reclamation begins.
4.7.1.1 Manual Sorting
The first processing step performed at a plastics recycling facility is hand sorting, except in cases
where plastics are received preshredded. Since few reliable automated sorting technologies exist
for separating plastics, most facilities integrate some type of hand sorting into their system.
Recyclers that accept a heterogenous resin stream may employ hand sorting as the primary
method of resin separation. Any necessary separation by color must also be done by hand.
Facilities accepting pre-sorted or homogeneous plastics may also use hand sorting to guarantee
the quality of the material stream.
CH-92-139 4-58
-------
Post-Consumer
Plastics
f-
Ln
VO
A ^
J ^
Manual
Sorting
1
Discards
Shredder
Possible Air
Classification
Plastic Fines
Paper Labels
Water
Detergent
Heated
Washer
and Rinse
Adhesives
Waste Water
Plastic Fines
Paper Labels
Separation Media
Hydrocyclone
Separator
Flotation Media
Flotation
Separator
Metals
Plastic Fines
Paper Labels
Discard Plastics
Flotation Media
Separation Media
Waste Water
120-150° C Air
1
Water Vapor
Additives
\
\
\
Aluminum
Volatiles
CO2 ,CO
Used Filter
Plastic Scrap
Water Vapor
Filtered Contaminants
Water
I.
Cyclone
Dryer
^>
Air
Dryer
-^
Aluminum
Separator
^>
Extruded
-^
Cooling Bath
^f Pellets
Water
Figure 4-4. Overview of plastics recycling process with inputs and outputs.
-------
4.7.1.2 Shredding and Grinding
Most processors of post-consumer plastic waste convert the raw plastic waste into a stream of
plastic flakes of uniform size (1/4 to 1/2 inch on a side) that can be accepted by subsequent
cleaning and separation equipment. Plastics are generally "flaked" using one of a large variety
of grinders, shredders, or granulators currently available. These machines cut or shear the
plastics with blades or sharp rotors. Shredding allows caps, labels, HDPE base cups, security
closure rings, and other impurities to be separated from the bulk of the container during washing
and automated separation. For processes requiring smaller particles, a second grinding stage may
be employed after initial shredding.
Plasucs are fed to the shredder or grinder by a gravity feed or conveyor system. Conveyor
systems provide a more even introduction of material and allow for the material to be visually
and magnetically inspected before processing.53 Shredding and grinding are performed by a
series of blades or rotating drums that either chop the plastic or draw it and tear it against a
sharpened surface. When flakes are reduced to the target dimensions, they either fall through a
screen or are blown from the shredder/grinder to transport ducts.
Some recently developed grinding systems, such as one designed by Herbold Granulators U.S.A.,
processes film scrap (i.e., plastic bags and sheeting) and other particularly duty plastic waste
streams using a wet grinding method.54 This technology uses a stream of water to wash film
scrap as it is carried past cutting knives. The water not only washes impurities from the plastic
flakes, but it also minimizes temperatures in the grinder chamber.
4.7.13 Washing
Once plastics have been shredded or ground, they are transferred to either a washing or
separation process. Washing methods vary depending on the type of plastic being cleaned, the
degree of contamination, and the specific machinery being used. However, most systems consist
of a water bath, a mechanical or air agitator, and possibly a solvent rinse. To facilitate the
CH-92-139 4-60
-------
removal of labels and other impurities, washing usually occurs after the plastics have been
shredded. Certain systems under development do some washing prior to shredding.54
As mentioned previously, washing is usually done in a water bath. Most facilities heat wash
water to a temperature that effectively dissolves label adhesives and other contaminants.
Temperatures can be as high as 160°F. In some cases, a mild caustic detergent is added to
remove labels and kill bacteria. These detergents can be effective in concentrations as low as
1 percent. A vinyl recycling operation in Akron, OH, operated by BF Goodrich uses a one
percent solution of Electrosol automatic dishwasher detergent agitated in hot water.55 Mechanical
paddles or air streams are used to accelerate cleaning. Washed plastics are frequently rinsed in
one or more water rinse steps.
4.7.1.4 Separation
Separation is done to obtain a clean, single-resin feed material. One of three methods is typically
used (i.e., air classification, flotation, and hydrocyclone). In facilities using hydrocyclone or
flotation tank systems to separate mixed resins, plastic containers must first be reduced to a
single-resin chip or flake that can be skimmed from the surface or scraped from the bottom of
a flotation tank.
4.7.1.4.1 Air Classification Air classification systems separate wastes using an air stream. This
technology can be used to isolate a lightweight target material by removing it from the waste
stream, or to remove lightweight impurities from a heavier resin. For example, polystyrene or
plastic film wastes are often separated from heavier contaminants using air classification.
4.7.1.4.2 Flotation Flotation is an effective means of separation because of differences in resin
densities. Flotation can also be used to separate contaminants from the target resin. Most
flotation systems use water as the separation medium. A stream of mixed plastics is added to
the flotation tank. Lighter fractions, polyethylene film for example, can be mechanically
skimmed from the water surface, and heavier components scraped from the bottom. Solutions
such as calcium nitrate can be used to adjust the specific gravities of the flotation bath to separate
CH-92-139
4-61
-------
the target material from the contaminant.55 In some cases, a surfactant may also be added in low
concentrations to prevent plastic flakes from adhering to the equipment or to each other.
Since materials separation represents one of the greatest hurdles to recycling the large variety of
resins being manufactured, separation technology is constantly under development. Research is
underlay at Rochester Polytechnic Institute on a flotation system that uses a heated chemical
bath to dissolve and separate mixed resins.56 A batch of mixed resins is heated to the melting
point of the most unstable resin. The molten resin is then removed from the bath. The bath
temperature is raised to the next lowest melting point, and that resin removed. The process
continues until all recoverable resins are isolated. This method requires a solvent filtration and
recirculation system to process a waste stream consisting of solvents and various wastes.
4.7.1.4.3 Hydrocyclone Hydrocyclone technology, adapted from the mining industry, has
recently been successfully applied to MSW handling. The equipment is essentially a centrifuge
that separates plastic wastes and contaminants based on their specific gravities. Air, water, or
oil is used to enhance the separation process. The separation medium can be filtered and reused.
The fluid requirements are generally less than for flotation separation systems.
4.7.1.5 Drying
It is necessary to dry the cleaned plastic flakes before they are extruded into pellets or packaged
for shipping. In the case of PET reprocessing, elevated water content in the resin can lower
maximum processing temperatures, increasing the potential for decomposition during extrusion.57
Cyclone driers are often used initially to dewater plastics. This is followed by some type of air
drying system. Flakes dry as they pass under a stream of hot air on a conveyor. Air hopper
dryers are also used. Heated air streams in the range of 120°C to 160°C range are common to
most drying systems. Some systems also incorporate industrial dehumidifiers.
CH-92-139 4-62
-------
4.7.1.6 Aluminum Separation
Most PET reprocessing systems grind PET bottles together with aluminum caps and safety rings.
The aluminum fragments must be removed from the plastic flakes to less than 100 ppm.
Aluminum removal is commonly accomplished with an electrostatic separator. This technology
utilizes a roller or disc to which an external electron field is applied. As the material stream
contacts the charged roller, conductive materials quickly lose their charge and fall from the roller.
Less conductive materials, such as PET, lose their charge more slowly, are pinned to the roller,
and are dropped into a separate bin. A second system utilizes a combination of rare earth
magnets and steel poles to create a magnetic field which can pull aluminum contaminants from
the plastic stream.58
4.7.1.7 Extrusion
The form and composition of recycled resins required by endproduct processors varies widely.
Plastics scrap processors commonly supply cleaned or separated resins in either a flake or pellet
form depending on the needs of the buyer. While plastic flake can be added directly to virgin
feedstocks, extruded pellets are generally preferred for the following reasons: 1) pellet extrusion
involves additional filtration that results in a higher quality endproduct; 2) necessary
compounding agents can be added during extrusion; and 3) extruded pellets can be tailored to
match the size, density, and composition of virgin feedstocks to which they are to be added.
Typical extruder designs include a screw-shaped mechanism that uses friction to heat and melt
the feedstock of recycled plastic flakes in a closed chamber. The plastic is softened and
compounded with additives as it passes through the chamber.57 The literature indicates that as
the flakes or granules melt, they fuse together, trapping air and possible chemical degradation
products. Such gases must be forced from the melt before it reaches a mold or pelletizer. Once
pellets have been formed, they are commonly cooled in a recirculated water bath.
To improve the flexibility of recycled resins and the quality of endproducts, a range of
compounds can be added to homogeneous, as well as heterogeneous, resin streams. These
CH-92-139
4-63
-------
ac 'es represent many of the same compounds that are added to virgin feedstocks, including
cu.^atibilizers, impact modifiers, colorants, and antioxidants. Tables 4-16 and 4-17 list additives
used in commonly recycled plastics.
4.7.1.8 Air Emissions
Dust is frequently cited as a significant problem associated with shredding and grinding plastics.
Most operations incorporate some form of air filtration to minimize dust. In addition, a number
of shredders/grinders have been introduced in recent years that operate at slower speeds, greatly
reducing the amount of fines and dust generated.59 In one study of dust levels in a plastics
reclamation facility (Vermont Republic Industries), Vermont Department of Health inspectors
measured concentrations of plastic dust in the vicinity of a PVC grinding operation that were
below allowable levels for nuisance dusts.60
Heating plastics beyond resin-specific degradation and oxidation temperatures will result in resin
degradation and air emissions. While oxidation may occur at normal process temperatures,
degradation is usually the result of improper resin handling or equipment malfunction and misuse.
It should be noted that many of the emissions from plastic melting are similar to those associated
with the processing of virgin feedstock. Degradation and oxidation products from heated and
melted plastics have been studied extensively, particularly as they pertain to the use of plastics
in incinerators.
One study of Quantum Chemical Corporation,61 evaluating the use of post-consumer HOPE in
molding applications, used changes in melt temperatures to confirm that some resin degradation
had occurred during reprocessing. This research also identified elevated smoke levels during the
heating of some reprocessed resins. Smoke is believed to be generated by volatilized soap
residues and other contaminants. This is a particular concern when extruders become jammed
or clogged, causing temperatures to rise beyond the temperatures of thermal decomposition.
CH-92-139 4-64
-------
TABLE 4-16.
PRIMARY FEEDSTOCK CHEMICALS USED IN
COMMONLY RECYCLED THERMOPLASTIC RESINS
Resin
Feedstock Chemicals
Low-density polyethylene
Polyvinyl Chloride
High-density polyethylene
Polypropylene
Polystyrene
Polyethylene terephthalate
Butane
1-Butane
Ethylene
Octane
Propane
Vinyl acetate
Acetylene
Acrylic esters
Acrylonitrile
Butadiene
Cety vinyl ether
Chlorotrifluoroethylene
Divinylbenzene
Ethylene
Methacrylic esters
Propylene
Vinyl chloride
Vinyidene chloride
Butane
Ethylene
Polypropylene
Ethylene
Propylene
Acrylonitrile
Acrylamide
Acrylic acid
Alkyl esters
Aromatic acids
Benzene
Methacrylic acid
Methyl acrylate
N-vinyl-z-pyrolidone
Styrene
Vinyl chloride
Dimethyl terephthalate
Ethylene glycol
Terephthalic acid
Titanium oxide
Triaryl phosphites
Phenolic compounds
Sources: References 2, 62, 63.
CH-92-139
4-65
-------
TABLE 4-17. CATEGORIES OF ADDITIVES USED IN PLASTICS, USE CONCENTRATIONS, AND MAJOR
POLYMER APPLICAflONS (1987)
Additive
Additive Concentration
in Plastic Products00
(Ib additive/100 Ib resin)
Largest Polymer Markets
Fillers
Inorganics
Minerals
Calcium carbonate
Kaolin & other
Talc
Mica
Other minerals
Other inorganic
Natural
High, 10-50
PVC
Plasticizers
High, 20-60
PVC
^>
I
Phthalates
Dioctyl (OOP)
Diisodecyl
Diethyl
Dimethyl
Others
Epoxidized oils
Soya oil
Others
Phosphates
Polymerics
Dialkyl adipates
Trimellates
Others
Oleates
Palitates
Stearates
Reinforcing Agents
Fiberglass Cellulose
Asbestos Carbon
Flame Retardants
Additive Flame Retardants Others
High, 10-40
High, 10-20
Various
Various
Aluminum trihydrate
Phosphorous compounds
Antimony oxide
Bromine compounds
Chlorinated compounds
Boron compounds
Reactive Flame Retardants
Epoxy reactive
Polyester
Urethanes
Polycarbonate
Others
(continued)
-------
TABLE 4-17.
CATEGORIES OF ADDITIVES USED IN PLASTICS, USE CONCENTRATIONS, AND MAJOR
POLYMER APPLICATIONS (1987) (Continued)
Additive
Additive Concentration
in Plastic Products00
Ob additive/100 Ib resin)
Largest Polymer Markets
•e-
Colorants
Inorganics
Titanium dioxide
Iron oxides
Cadmium
Chrome yellows (includes lead)
Molybdate orange
Others
Organic pigments
Carbon black Others
Phthalo blues
Organic reds
Organic yellows
Phthalo greens
Others
Dyes
Nigrosines
Oil solubles
Anthroquinones
Low, 1-2
Numerous
Impact modifiers
Acrylics
MBS
ABS
Lubricants
Metallic stearates
Fatty acid amides
Petroleum waxes
Heat stabilizers
Barium-cadmium
Tin
Lead
High, 10-20
PVC
CPE
Ethylene-vinyl acetate copolymers
Others
Fatty acid esters
Polyethylene waxes
Calcium-zinc
Antimony
Low,
PVC, PS
Moderate, 1-5
PVC
(continued)
-------
TABLE 4-17. CATEGORIES OF ADDITIVES USED IN PLASTICS, USE CONCENTRATIONS, AND MAJOR
POLYMER APPLICATIONS (1987) (Continued)
Additive
Additive Concentration
in Plastic Products""
(Ib additive/100 Ib resin)
Free radical initiators0"
Antioxidants
Hindred phenols
Others
Chemical blowing agents
Azodicarbonides High temperature CBS's
Oxbissulfonylhydrazide Inorganic
Antimicrobial agents
Antistatic agents
o> Quaternary ammonium compounds Fatty acid ester derivatives
co
Fatty acid amides & amines
Phosphate esters
Others
UV stabilizers
Benzotriazoles
Benzophenes
Salicylate esters
Cyanoacrylates
Malonates
Benzilidenes
Others
Catalysts(c)
Others
Low, <1
Low, <1
Moderate, 1-5
Low, <1
Low, <1
Low,
Low,
Low,
Largest Polymer Markets
LrrE, PS, PVC, PE
PS
PVC.PP, PS
PVC, PE
PVC
PE, PP, PS, PVC
Numerous
'"'Estimates refer to concentrations in those products where the additive is
""'Includes organic peroxides only, as reported by source.
'''Includes urethane catalysts only, as reported by source.
Source: Reference 2.
-------
Emissions collection and treatment systems are employed on extruders throughout the industry
to collect released gases. Incineration, fixed carbon-bed adsorbers, electrostatic precipitators,
distilling equipment, and fractionalizers can all be used effectively to control air emissions.
The degradation of some resins, (e.g., PVC) can result in the formation of acidic byproducts.
These emissions can be neutralized using the appropriate neutralizing agents. Innovative Plastic
Products Incorporated (IPPI) of Greensboro, GA sprays a sodium hydroxide mist to neutralize
elevated hydrochloric acid levels.64
4.7.2 Resin Specific Processing
Process methods in plastics reclamation vary depending upon the type of resin being processed.
Reclamation process steps for the seven post-consumer plastics defined previously generally
incorporate some combination of the technologies discussed above; Some resins may require
distinctive process technologies. These resin-specific issues are discussed below.
4.7.2.1 Polyethylene Terephthalate (PET)
Polyethylene terephthalate is currently the most recycled resin in the United States. Reclaimed
PET is used as either a pelletized feedstock supplement for mold applications or as an extruded
fiber. The fiber is used in such products as carpeting and clothing insulation.
PET is liable to degrade if overheated above 300°C. It should not be held above temperatures
approaching 300°C for longer than a few seconds. In addition PET will degrade more readily
if it is not thoroughly dried before processing.57
PET vapor and paniculate emissions are expected to be released during pellet extrusion.62
However, the PET polymer is chemically stable except for the release of carbon dioxide, and it
is generally considered to be free of toxic byproducts.
CH-92-139
4-69
-------
4.7.2.2 High-Density Polyethylene (HDPE)
High-density polyethylene is currently used as a recycled feedstock supplement for a wide variety
of products ranging from oil and detergent bottles to extruded piping and other thick-walled
items. HDPE is considered to be a nontoxic compound. It is used extensively in packaging and
medical industries, as well as in the manufacture of pipe to carry potable water.
HDPE can be extruded between 170°C and 220°C57 and decomposes at roughly 400°C.65 When
ignited, polyethylene burns easily with a very smoky flame.57
Vapor emissions from pelletizing operations may consist of ethylene, polyethylene polymer fines,
and smoke. Extruder vents have been found to release 0.63 kg of volatile organic compounds/Mg
of product processed.62 This release consisted primarily of steam and air, with 0.05 percent by
volume of cyclohexane. Significant oxidation byproducts of HDPE at 150°C are water, carbon
dioxide, carbon monoxide, and acids.65 In addition a variety of additives and solvents
(e.g., chromium oxide and cyckhexane) may be released.
4.7.23 Vinyl (V)
PVC is the primary post-consumer vinyl currently being recycled and showing potential to
produce significant volumes of reclaimed scrap. Post-consumer PVC appears in bottles of
cooking oil and water, as well as perishable food shrink wrap. Recycled PVC is used as a
feedstock supplement in pipe, siding, and other building materials.
Although electronic and flotation separation systems are sometimes used to sort PVC containers,
most sorting is done manually. PVC processing plants generally incorporate the basic process
steps indicated hi Figure 4-4. Due to the similar densities of PVC and PET, separating them
remain a technical challenge. More sophisticated separation systems are under development that
involv. e use of flotation baths adjusted to specific gravities, and X-ray and other electron;c
sorting ^ystems.55'66
CH-92-139 4-70
-------
EPA's Industrial Process Profiles for the Plastics Industry describes poly vinyl chloride as
chemically inert and nontoxic.62 The release of residual vinyl chloride monomer, a human
carcinogen, is sometimes cited as a concern when reprocessing PVC. However, industry sources
generally believe that the tightly-bound PVC yields little monomer during reheating.67 Maximum
extrusion processing temperatures are around 170°C. The polymer will degrade rapidly if
processed slowly at temperatures well above 170°C. Hydrochloric acid is produced during
processing due to the release of chlorine. All metal surfaces designed to contact melted PVC
should resist strong acids. Solvents commonly used with vinyl include cyclohexane,
dichloroethane, and nitrobenzene.57
The use of cadmium and lead in PVC has long produced health concerns. Both are being
replaced by safer alternatives, but recovered scrap may still contain heavy metals. PVC-coated
wire scrap, traditionally compounded with lead additives, represents a significant source of
contamination in plastics waste.
4.7.2.4 Low-Density Polyethylene (LDPE)
Low-density polyethylene is used primarily in bags and other film applications. Due to its
flexibility, it is a desirable reclamation feedstock. It is particularly beneficial when used as a
matrix resin in the manufacture of commingled plastic products (see below).
The processing of LDPE is similar to the steps indicated in Figure 4-4 except that a wet grinder
may be used. LDPE can be extruded between 120°C and 160°C. LDPE oxidizes at 150°C and
decomposes at roughly 400°C.
Significant oxidation byproducts of LDPE are water, carbon dioxide, carbon monoxide, and
acids.65 The manufacture of virgin polyethylene requires the use of ethylene, considered to be
highly explosive, but little or no unreacted ethylene should remain in recycled LDPE. Additional
process and exposure information is similar to that listed for HDPE.
CH-92-139 4-71
-------
4.7.2.5 Polypropylene (PP)
Polypropylene is used in a variety of products from drinking straws to battery cases. Its high
decomposition temperatures make it a desirable resin for commingled plastics products. PP can
be extruded without decomposition below 240°C. Thermal stability of PP in the absence of
oxygen is high.57
Degradation gases produced between 360°C and 400°C include primarily pentane, propylene, and
methane, with increasing amounts of 2,4-dimethyl-l-heptene at higher temperatures. Additional
byproducts include ethane, propane, isobutylene 2-methylpentane, and 4-methylheptane.
Significant oxidation byproducts of PP at 150°C are water, carbon dioxide, carbon monoxide, and
acids.65
4.7.2.6 Polystyrene (PS)
Polystyrene finds applications hi both rigid and expanded foam forms. Rigid PS appears in
durable products such as furniture and appliances, while the foam form is used in plates, cups,
and egg cartons. Foam products have been the focus of considerable environmental criticism due
to the release of chlorofluorocarbon blowing agents during manufacture. However, in 1988, the
U.S. food packaging industry voluntarily discontinued the use of CFCs in their products.
PS reclamation includes standard shredding, washing, drying, and extrusion processes. Due to
the low de :,;ty of expanded PS, air classification is commonly employed to segregate it from
the rest of the waste stream. It is sometimes necessary to density or degasify bulky PS waste
prior to pelletizing. Specialized equipment is available to crush and compress PS waste; other
systems use high temperatures to release gases and density the expanded foam. PS can be
extruded between 150°C and 220°C. It will ignite and decompose between 245°C and 300°C
depending upon the percentage of oxygen present.57
Between roughly 110°C and the ignition temperature (including the range of standard densifying
and extrusion temperatures), polystyrene absorbs oxygen while releasing carbon monoxide, carbon
CH-92-139 4-72
-------
dioxide, acetone, and benzaldehyde. As temperatures approach 280°C, degradation products
include approximately 40 percent styrene monomer. Other releases include fillers and
compounding agents, including tetramer, toluene, and carbon monoxide.68 Jerry Johnson of the
Polystyrene Packaging Council estimates that styrene monomer emissions usually measure less
than 2 ppm during extrusion.69 A variety of solvents can be used to dissolve polystyrene,
including a number of chlorinated and non-chlorinated hydrocarbons.
4.7.2.7 Commingled Plastics
Commingled plastics recycling offers a relatively simple and flexible reprocessing alternative to
sorting and cleaning mixed plastics. While most municipal solid waste programs that collect
plastics for recycling concentrate their efforts on one or two resins, the opportunity to collect
large quantities of multi-resin waste exists. However, separating the growing variety of plastics
hi the waste stream represents a significant technical challenge.
A number of ventures have successfully applied extruder and compression mold technology to
the reprocessing of unsorted, mixed plastics into dense products such as lumber, automobile
curbstops, and playground equipment. Generally, higher solid contaminant levels and decreased
tensile strengths restrict this process to the manufacture of thick-walled endproducts.
There are several commingled plastics processing systems currently used in the United States.
Most facilities use extruder technology that incorporates the same basic features discussed in
4.7.1.7. These systems are generally capable of handling a wide range of unsorted and uncleaned
scrap. Most systems require the waste stream to be shredded to provide a more uniform
feedstock. Most systems also use one segregated resin, preferably polyethylene, as a base or
matrix to which the unsorted, even rigid, scrap is added as filler.
Since commingled recycling systems simultaneously melt a combination of resins, it is difficult
to ensure that none of the resins is heated beyond its degradation temperature, releasing thermal
degradation products. Thermal degradation temperatures vary depending upon the feedstock
resins. Although it is difficult to precisely control feedstock components when utilizing a mixed
CH-92-139
4-73
-------
waste stream, it is important to carefully maintain process temperatures within the range of
material decomposition temperatures.
Doty reports the generation of hydrochloric acid from chlorine released while melting PVC scrap
in commingled plastics processing.64 In one instance, gases severely corroded stainless steel ab-
ducts. The plant no longer processes PVC due to these emissions. The plant is equipped to
collect vapors or dust particles released during processing. Vapors are collected using vacuum
hoods and are separated and disposed of in a gas washer. The system includes cross-current
water spray chambers, pH meters that trigger an automated sodium hydroxide spray, a
conductivity meter that triggers water recirculation to activated carbon adsorption reactors, and
flocculation and filtration equipment.
4.7.2.8 Air Emissions
Generally, reclamation of plastics takes place hi fully enclosed processing facilities equipped with
emission and effluent control devices. Emissions hazards in plastics processing can result from
residues in the recyclable plastics, chemicals used during reclamation, fugitive particulates
generated during processing, organic chemicals absorbed in the plastic resins, and the degradation
of plastic resins themselves.
Concern is often raised about the potential release of chemical compounds from plastics during
processing. Actual polymer degradation can occur during extrusion and thermal oxidation of
resins can occur during both drying and extrusion. While degradation is usually the result of
improper resin handling or equipment malfunction, oxidation may occur at normal process
temperatures.
Thermal oxidation byproducts include carbon monoxide, carbon dioxide, acids, peroxides, esters,
and aldehydes. Degradation byproducts can encompass a number of toxic and carcinogenic
chemicals including hydrochloric acid and vinyl chloride (from PVC) and styrene (from
polystyrene). Other chemicals that can be released during processing include additives
(chromium oxide) and solvents (cyclohexane and dichloroethane). Heavy metals including
CH-92-139 4-74
-------
cadmium and lead are being phased out in materials such as PVC, but may still be present in
existing scrap.
Control technologies are used widely to prevent significant emissions from plastics drying and
extrusion operations. Extruders may have shut-off devices that are triggered when normal
operating temperatures are exceeded. Facilities are also equipped with systems to monitor, filter,
neutralize, and/or vent emissions that are produced.
Both carbon dioxide and acids are generated from thermal oxidation of plastics during drying and
extrusion. The quantities of these chemicals released from reclamation facilities have not been
characterized.
4.8 SOLVENT RECYCLING
4.8.1 Category Definition and Description
Solvent recycling may take place in many forms. The ultimate goal is to make further use of
the solvent material after it has been contaminated or modified by its initial use. Many firms
participate in solvent recycling activities because of the economic incentive. A recycling program
may reduce the cost of purchasing new raw materials and reduce the amount of waste generated.
Reduction of waste results in decreased disposal costs and less exposure to liability associated
with off-site shipments.70
4.8.2 Process Definition and Description
Solvents may be recycled on-site or sent to a commercial off-site facility. On-site recycling
operations may be performed with in-house staff or a commercial recycler may set up and
operate fixed or mobile recycling equipment on the generators property. Commercial operations
most often use distillation for solvent recovery, although solvent extraction is also commonly
used. Many commercial operations accept solvent waste to be burned for heat recovery, although
this is not universally considered to be a form of recycling. Another alternative is participation
CH-92-139 4-75
-------
in a waste-exchange program; however, relatively pure uniform wastes are typically more easily
transferred through waste exchange programs than mixed wastes.70
Because of economies of scale, it may be more cost effective for very small quantity generators
to make use of off-site recycling. However, a 1988 study of the economics of solvent recycling
equipment showed that on-site solvent recycling is feasible, even for small-scale waste generators.
Using the most conservative available assumptions, the study showed that an investment in small
scale recycling should pay for itself in less than two years. In many circumstances, the
investment will pay for itself in less than one year.71
On-site recycling has the following advantages over off-site recycling.
• Less waste leaving the facility and hence reduced liability and cost of transporting waste
off-site
• Owner's control over reclaimed solvent's purity
• Reduced paperwork and reporting in the form of manifesting
• Potential lower unit cost for reclaimed solvent
Off-site recycling has the following advantages over on-site recycling.
• Reduce capital for recycling equipment and possible cost of operator training
• Reduced operating costs
• Fewer liabilities for worker health and potential events associated with improper
operation of solvent recovery equipment such as fires, explosions, leaks, and spills.
Most recycling and solvent recovery operations involve employing similar technologies in varying
sequences. The design of the recovery system must be considered on a case-by-case basis,
accounting for material properties, purity requirements, process capacity, worker health and
safety, and economics. Solvent recycling occurs across a wide variety of industries. Some
examples of well known and common formalized recycling practices are listed below.70
CH-92-139 4-76
-------
• Recovery, by adsorption, of mixed solvents used for fabric coating
• Recovery of acetone from cellulose acetate spinning using water scrubbing and
adsorption, and subsequent recycling within this process
• Recovery of diluent in solvent refining of oil using vaporization and recompression
• Recovery of hexane in vegetable oil extraction
• Recovery of furfural in butadiene purification
• Batch recovery, by evaporation and condensation, of perchloroethylene in dry cleaning
• Distillation for recovery of mixed solvents (typically ethyl alcohol and triethylamine) in
antibiotic and pharmaceutical manufacture
Less formalized recycling which does not require special equipment is also being implemented
through use of more passive measures such as process modifications and changes in handling
procedures. Many firms have implemented these changes in procedures because of economic
incentives.
4.8.3 Pollutant and Activity Levels
Although it is known that the majority of recycling emissions are likely to be VOC, actual levels
of recycling emissions are difficult to document. Because procedural changes made to implement
recycling often do not require a permit, a considerable amount of recycling occurs which is not
publically documented or reported. The additional emissions resulting from such recycling
activities when integrated with a process operation may be negligible or zero. For example, at
a paint manufacturing plant, the waste cleaning solvent from each solvent-based paint batch is
collected individually and stored. When the same type of paint is produced again, the waste
cleaning solvent from the previous batch is used instead of new solvent. The paint manufacturing
facility reduced waste solvent by 98.4 percent with essentially no increase in emissions.72
CH-92-139 4-77
-------
4.8.4 Emission Factors and Available Literature
The emissions associated with recycling activities do not appear to be well documented in readily
available literature. Section 4.7 of AP-421 provides documentation of paniculate and VOC
emission factors for waste solvent reclamation. Table 4-18 provides these emission factor data
as they are tabulated in AP-42. A review of the references for this AP-42 section indicates that
all of the supporting references are dated in the 1970s. As a result, the applicability of these data
to current recycling operations is questionable.
TABLE 4-18. EMISSION FACTORS FOR SOLVENT RECLAIMING11
EMISSION FACTOR RATING: D
Source
Storage tank ventb
Condenser vent
Incinerator stack0
Incinerator stack
Criteria pollutant
Volatile organics
Volatile organics
Volatile organics
Particulates
Emission factor
Ib/ton
0.02
(0.004-0.09)
3.30
(0.52-8.34)
0.02
1.44
(1.1-2.0)
average
kg/MT
0.01
(0.002-0.04)
1.65
(0.26-4.17)
0.01
0.72
(0.55-1.0)
Fugitive emissions
Spillage0 Volatile organics
Loading Volatile organics
Leaks Volatile organics
Open sources Volatile organics
0.20
0.72
(0.00024-1.42)
NA
NA
0.10
0.36
(0.00012-0.71)
NA
NA
• Reference 1. Data obtained from state air pollution c r.trol agencies and presurvey sampling. All emission factors are for uncontrolled process
equipment, except those for the incinerator stack. Avt age factors are derived from the range of data points available. Factors for these sources
are given in terms of pounds per ton and kilograms per metric tons of reclaimed solvent. Ranges in parentheses.
b Storage tank is of fixed roof design.
c Only one value available.
NA - not available.
CH-92-139
4-78
-------
The U.S. EPA has published a number of control technology guidance documents associated with
some of the individual industry processes previously listed including fabric coating, vegetable oil
production, dry cleaning operations, and the synthetic and organic chemical manufacturing
industry (SOCMI). While these documents provide recommended or required emission rates,
industry specific emission factors associated with recycling practices of specific industries are not
provided.
The Industrial Technology Division of the EPA has been conducting a study of the solvent
recycling industry as a result of findings that the quantity of hazardous wastes discharged by the
recycling industry to publicly-owned treatment works is unknown.73 Information-gathering efforts
for this study have shown that not all solvent recyclers are RCRA-permitted facilities and that
generators of spent solvents are shipping wastes to these unpermitted facilities. Approximately
eighty percent of the recycling industry achieves zero discharge of solvent waste in wastewater
due to the practices of contract hauling off-site, fuel blending, and incineration. Of those
facilities which discharge wastes, only half treat the wastewater.
The U.S. Department of Energy has created a Chlorinated Solvent Substitution Program to
minimize hazardous wastes by identifying recycle/recovery techniques for proposed substitute
solvents.74 This program has gathered information to support a preliminary screening of
potentially feasible solvent recycling technologies and has performed some distillation tests on
subject solvents. The distillation of testing has shown that for commercial grade solvents,
distillation can accomplish recovery of key components, but not necessarily in the percentages
reported by the manufacturer. The program has also identified some emerging membrane
technologies such as pervaporation that may be feasible for some solvents. The program has
recommended extensive literature review for promising technologies; further laboratory
investigation; contact with vendors, researchers, and industrial experts; and creation of pilot
recycling units.
CH-92-139 4-79
-------
4.8.5 Potential for Additional Data
It is very possible that local and state agencies possess a considerable amount of data concerning
emissions resulting from solvent recycling activities. A review of permits for specific solvent
recycling industries such as those previously listed r ay yield data which would allow calculation
of process emission factors. Similarly, this information should also be available for those
industries which specialize in commercial waste recycling.
4.9 RECYCLING ACTIVITY SUMMARY
Due to the number of recycling initiatives a: icderal, state and local levels, recycling materials
from MSW will increase significantly. It is estimated that over 3,000 curbside pickup programs
are currently in operation in the United States; this number is expected to increase rapidly.
Collecting and sorting materials cause air emissions during handling and transportation. The
suggested methodology u.» address vehicular pollution has been presented. Emissions from
centralized processing facilities are not well documented and could represent an area requiring
additional effort.
Of the four materials recovered from MSW covered in this section, plastics are undergoing the
most rapid change. The recovery rates are increasing significantly due to the plastics industry's
expanded recycling efforts and historically low recovery rates for this type of material. Further,
several recovery processes are being developed to facilitate economical recovery of plastics.
The number of facilities which could potentially use recovered resins is estimated to be 14,000
in the top 10 states.75 Data on emissions resulting from using reclaimed resins are not readily
available and may prove difficult to derive due to the variety of resins and mixtures, facilities,
and respective source configurations. The following two methods used in conjunction may be
useful in developing the needed data. Reviewing state air permit files may provide some
preliminary inform^aon, and an industry survey requesting detailed in. -mation on control
devices, operating procedures, material throughput, and associated data c aid supplement data
from state files.
CH-92-139 4-80
-------
Recycling rates of paper, steel and aluminum will also increase. However, the process
technologies for recovery of these materials are generally well established. Research is being
conducted in a number of areas to improve the recovery process. The improvements may be in
a number of different areas, including cost reduction, lower environmental impacts, or increased
material yields. Emissions data are available in AP-42 and AIRS for steel and aluminum
recycling processes. Specific information concerning paper recycling process emissions is not
readily available. An industry survey and air permit file search may also prove to be a viable
approach in developing this information.
CH-92-139
4-81
-------
4.10 REFERENCES
1. U.S. Environmental Protection Agency. Compilation of Air Pollutant Emission Factors,
AP-42, Volumes I and II. Fourth Edition and Supplements. September 1985 through
September 1991.
2. U.S. Environmental Protection Agency. Methods to Manage and Control Plastic Wastes,
Report to Congress. EPA/530/SW-89-051 (NTIS PB90-163106). Office of Solid Waste.
February 1990.
3. Radian Corporation. Database of Existing Municipal Waste Combustion Studies.
Database maintained for the U.S. Environmental Protection Agency. Supplied by Ruth
Mead, Radian Corporation. Research Triangle Park, NC. 1989.
4. STC. A Technical and Economic Evaluation of the Project in Baltimore, MD.
Volume n. Prepared for the Environmental Protection Agency by Systems Technology
Corporation, Xenia, OH. 1979.
5. Bernheisel, J.F. Introduction to Material and Markets. Waste Age. Vol. 19, No. 4.
April 1988.
6. U.S. Congress. Facing America's Trash: What Next for Municipal Solid Waste, Office
of Technology Assessment. U.S. Government Printing Office, Washington, DC. OTA-
O-424. 1989.
7. U.S. Environmental Protection Agency. A Technical, Environmental, and Economic
E aation of the Glass Recovery Plant at Franklin, Ohio. EPA/SW- 146c (NTIS PB272-
0: ,. Prepared by Systems Technology Corporation. Solid Waste Management
Programs. 1977.
8. Alter, Harvey et al. The Recovery of Magnetic Metals from Municipal Solid Waste.
National Center for Resource Recovery. 1977.
9. Misner, M. Six Months of Recyclable Prices Show Market Instability. Waste Age
22(9):36-44. 1991.
10. Resource Recycling. At Press Tune. May 1992. Volume XI, No. 5.
11. Kirk-Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 23 p41
John Wiley & Sons, New York, NY. 1983.
12. Bailey, J. Personal communication between Alliance Technologies Corporation and
Jerry Bailey of Proler International Corporation on July 31, 1991.
CH-92-139 4-82
-------
13. Process Engineering. Recycling domestic waste: a processing challenge. Spring:
44-45.
14. Watson,!. A Force in Detinning. Resource Recycling. January/February: 18. 1989.
15. Kinsey, R. Ferrous metal recovery: keying processes to problems, markets. Solid Waste
Management, 23(5): 48-52. 1980.
16. Queens College. Development and Pilot Test of an Intensive Municipal Solid Waste
Recycling System for The Town of East Hampton, N.Y. Center for the Biology of
Natural Systems, Queens College, Flushing, NY. Submitted to NYS Energy Research
and Development Authority. 1988.
17. Ziegler, R.C. et al. Environmental Impacts of Virgin and Recycled Steel and Aluminum.
Prepared by Calspan Corp. EPA/530/SW-117c (NTIS PB253-487). 1976.
18. The Recycling Magnet (A Quarterly Publication of the Steel Can Recycling Institute).
Fall 1990.
19. Goodwin, Don R. Beverage Can Surface Coating Industry - Background Information
for Proposed Standards. Draft EIS. EPA-450/3-80-036a (NTIS PB81-113904).
September 1980.
20. U.S. Environmental Protection Agency. Development Document for Effluent Limitations
Guidelines and Standards for Iron and Steel Manufacturing, Point Source Category,
Volume III, Final. EPA-440/1-82-024 (NTIS PB82-240441). 1982.
21. U.S. Environmental Protection Agency. Electric Arc Furnaces and Argon-Oxygen
Decarburization Vessels in Steel Industry - Background Information for Proposed
Revisions to Standards. Office of Air Quality Planning and Standards.
EPA-450/3-82-020a (NTIS PB84-120641). July 1983.
22. Kirk-Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 13, p. 383.
John Wiley & Sons, New York, NY. 1981.
23. Kaldjian, P. Characterization of Municipal Solid Waste in the United States, EPA-
530/SW-90-042(NTISPB90-215112). Prepared by Franklin Associates, Ltd. For U.S.
Environmental Protection Agency, Municipal Solid Waste Program. 1990.
24. Henstock, M.E. Design for Readability. The Institute of Metals. 1988.
25. Vandevender, J. Personal communication between Alliance Technologies Corporation
and John Vandevender of the Aluminum Company of America (ALCOA) of Knoxville,
TN on August 2, 1991.
CH-92-139
4-83
-------
26. Brown, G. Personal communication between Alliance Technologies Corporation and
Gene Brown of Maine Beverage Container Service, Inc. of Portland, ME on August 13,
1991.
27. Brookman, E.T. Screening Study on Feasibility of Standards of Performance for
Secondary Aluminum Manufacturing. EPA-450/3-79-037a (NTIS PB80-132954). 1978.
28. Copperthite, G. Rigid Container Recycling Status and Impact on the Rigid Container
Industry. U.S. Department of Commerce Office of Metals and Commodities Iron and
Steel Division Basic Industrial Sector. 1989.
29. U.S. Environmental Protection Agency. Development Document for Effluent
Limitations Guidelines and Standards for the Nonferrous Metals Manufacturing Point
Source Category. Volume 2. Washington, DC. EPA/440/1-89/019.2 (NTIS PB90-
181975). May 1989.
30. Visalli, J.R. The Similarity of Environmental Impacts from All Methods of Managing
Solid Wastes. New York State Energy Research and Development Authority. Albany,
NY. 1989.
31. Kirk-Othmer Encyclopedia of Chemical Technology. Third Edition, Volume 16, p. 769.
John Wiley & Sons. New York, NY. 1981.
32. Carr, W. New trends in deinking technology. Tappi Journal. February: 127-132. 1991.
33. Broeren, L. New technology, economic benefits give boost to secondary fiber use. Pulp
& Paper. 63(ll):69-74. 1989.
34. Patrick, K. Legislation pushing paper industry despite limited recycling know how.
Pulp & Paper. 64(9): 161-163. 1990.
35. Amoth, A.J. Lee, Jr., and R. Seamons. Anaerobic Treatment of Secondary Fiber Mill
Effluents. Technical Association of Pulp and Paper Industry, Atlanta, GA.
Environmental Conference. 1991.
36. Egosi, N. and E. Romeo. Meeting high expectations through MRF design. Solid Waste
& Power. June:48-53. 1991.
37. Andrews, W. Contaminant removal, timely use vital to quality ONP fiber yield Pulp
& Paper. 64(9): 126-127. 1990.
38. Morgan, D. Everything you never knew about magnetic separation Waste Aee
18(7): 110-112. 1987. ' 5
CH-92-139 4-84
-------
39. Schriver, K. Mill chemistry must be considered before making deink line decision.
Pulp & Paper. 64(9): 76-79. 1990.
40. Basta, N., K. Gilges, and S. Ushio. Recycling everything: Part 3, paper recycling's new
look. Chemical Engineering. 98(3):46-48F. 1991.
41. Horacek, R. Recycling of Papermaking Fibers. Technical Association of The Pulp and
Paper Industry, Inc., Secondary Fiber Pulping Committee of the Pulp Manufacture
Division, Atlanta, GA. 1983.
42. Barney, J. Summary of Dioxin Data for Paper Mill Sludges. U.S. Environmental
Protection Agency, Region 5. 1987.
43. Tannazzi, Fred D., and Richard Strauss. Changing Markets for Recycled Paper.
Resource Recycling. Vol. XI, No. 4. April 1992.
44. Spinosa, E.D., D.T. Hooie, and R.B.Bennett. Summary Report on Emissions From The
Glass Manufacturing Industry. Prepared by Battelle Columbus Labs. EPA-600/2-79-101
(NTIS PB299-202). April 1979.
45. Kirk-Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 11, p. 845.
John Wiley & Sons, New York, NY. 1980.
46. Hecht, R. Personal communication between Alliance Technologies Corporation and
Roger Hecht, Vice President, Bassichis Company on July 31, 1991.
47. Apotheker, S. Personal communication between Alliance Technologies Corporation and
Steve Apotheker, Journalist, Resource Recycling Magazine on August 14, 1991.
48. Boxell, B. Personal communication between Alliance Technologies Corporation and Bill
Boxell, Corporate Process Manager, Foster-Forkes, Inc. on August 28, 1991.
49. Kirk-Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 14, p. 716.
John Wiley & Sons, New York, NY. 1981.
50. Huls, J. and T. Archer. Resource Recovery from Plastic and Glass Wastes. EPA-600/2-
81-123 (NTIS PB81-223471). Prepared by Municipal Environmental Research
Laboratory. 1981.
51. ASTM. Standard Specification for Waste Glass As a Raw Material for The Manufacture
of Glass Containers, Designation E 708-79. 1988.
52. Modern Plastics. Resin sales rise to 61.5 billion Ib (1990 resin sales-and markets
summary). January:! 13. 1991.
CH-92-139 4-85
-------
53. Dumas, S. Personal communication between Alliance Technologies Corporation and
Susan Dumas of Herbold Equipment, Sutton, MA on July 26, 1991.
54. Modern Plastics. Wet granulation cleans up film scrap in complete recycling system.
May: 17. 1988.
55. Summers, J. W., B. K. Mikofalvy, G. V. Wooton, and W. A. Sell. Recycling Vinyl
Packaging Materials from the City of Akron Municipal Wastes. BF Goodrich, Geon
Vinyl Division. Presented to the Society of Plastics Engineers, ANTEC. 1990.
56. Heath, G. Personal communication between Alliance Technologies Corporation and
George Heath of Chem Systems, Inc. of Tarrytown, NY on November 29, 1990.
57. Brydson, J. A. Handbook for Plastics Processors. Heinemann Newnes. Oxford,
England. 1990.
58. Koch, P. E. and M. Ross. Separation of PET and Aluminum. Pennsylvania State
University at Erie, Behrend College. Presented to the Society of Plastics Engineers,
ANTEC. 1990.
59. Modern Plastics. Granulators Are Coming Into The Mainstream... At Affordable Prices.
Novembers 1. 1987
60. Satink, F. Personal communication between Alliance Technologies Corporation and
Fred Satink of the Vermont Department of Health on July 29, 1991.
61. Gibbs, M. L. An Evaluation of Post-Consumer Recycled High Density Polyethylenes in
Various Mold Applications. Quantum Chemical Corporation. Presented to the Society
of Plastics Engineers, ANTEC. 1990.
62. Radian Corporation. Industrial Process Profiles for Environmental Use. Chapter 10,
The Plastics and Resins Production Industry. EPA-600/2-85-085 (NTIS PB85-245280).
1985.
63. Enviro Control Inc. Engineering Control Technology Assessment for the Plastic and
Resin Industry. Prepared for U.S. Department of Health, Education, and Welfare by
Enviro Control, Inc., Rockville, MD. 1978.
64. Doty, B. Personal communication between Alliance Technologies Corporation and
Brian Doty, Plant Manager, Innovative Plastic Products, Inc. Greensboro GA on July
29, 1991.
65. Allen, N. Degradation and Stabilization of Polyolefins. Applied Science Publishers.
London and New York, NY. 1983.
66. Monks, R. New reclaim methods target PVC. Plastics Technology. May:31. 1990.
CH-92-139 4-86
-------
67. Carroll, W. Personal communication between Alliance Technologies Corporation and
William Carroll, President, of OxyChem on July 29, 1991.
68. Brighton, C., A.G. Pritchard, and G.A. Skinner. Styrene Polymers: Technology and
Environmental Aspects. Applied Science Publishers, Ltd. London. 1979.
69. Johnson, J. Personal communication between Alliance Technologies Corporation and
Jerry Johnson of the Polystyrene Packaging Council on July 29, 1991.
70. Guide to Solvent Waste Reduction Alternatives - Final Report. Alternative Technology
and Policy Development Section, Toxic Substances Control Division, California
Department of Health Services. October 10, 1986.
71. Schwartz, S. Solid Waste Reduction Alternatives Symposia Conference Proceedings.
"Recycling and Incineration of Hazardous Waste Solvents: Economic and Policy
Aspects." University of California, Davis. October 1986.
72. The Reduction of Solvent Wastes in the Electronics Industry - Waste Reduction Grant
Program. State of California Department of Health Services, Toxic Substances Control
Division. June 1988.
73. Anderson, D. et al. Preliminary Data Summary for the Solvent Recycling Industry.
EPA-440/1-89-102 (NTIS PB90-126467). Washington, DC. September 1989.
74. Solvent Recycle/Recovery Phase I Final Report. U.S. Department of Energy, Idaho
Operations Office. September 1990.
75. Finelli, Anton J. Secondary Materials Markets: A Primer. Solid Waste and Power.
Vol. IV, No. 4. August 1990. pp. 48-56. 1990.
CH-92-139 4-87
-------
SECTION 5.0
PESTICIDE APPLICATION
5.1 BACKGROUND
Under the Federal Insecticide, Fungicide and Rodenticide Act (FIFRA), a pesticide (or economic
poison) includes any substance or mixture of substances intended for preventing, destroying,
repelling or mitigating any pest, and any substance or mixture of substances intended for use as
a plant regulator, defoliant or desiccant. The general category of pesticide can be further defined
by the following terms which identify the target of the pesticide.
• Acaricide (miticide) - used to control plant-feeding mites (acarids)
• Algicide - used to control algae
• Aphicide - used to control aphids (plant lice)
• Avicide - used to control pest birds
• Bactericide - used to control bacteria
• Biocide - when absorbed by eating, drinking, breathing or other means in relatively
small quantities, may cause illness or death, or even retardation of growth or shortening
of life
• Fungicide - used to protect against fungi
• Gameticide - used to prevent pollination
• Herbicide - used to control weeds
• Insecticide - used to control insects
• Larvicide - used to kill insect larvae
• Molluscicide - used to control slugs and snails (mollusks)
• Nematicide - used to control nematodes
• Ovicide - used to kill eggs of insects and mites
• Piscicide - used to control fish
• Predacide - used to control vertebrates
• Rodenticide - used to control rodents (rats, mice, etc.) and related animals (such as
rabbits)
• Slimicide - used to control slime and molds
CH-92-139 5-1
-------
Of the total pesticides currently used in the United States, approximately 60 percent are
herbicides, 25 to 30 percent are insecticic and 10 to 15 percent are fungicides.1
Several additional terms are used to describe the actions or purposes, rather than the target, of
certain pesticides.2
• Defoliant - a preparation intended for causing leaves to drop from crop plants such as
cotton, soybeans or tomatoes, usually to facilitate harvest
• Fumigant - a substance or mixture of substances which produce gas, vapor, fume or
smoke intended to destroy insects, bacteria or rodents
• Plant growth regulator - a preparation which, in minute amounts, alters the behavior of
ornamental or crop plants or the produce thereof through physiological (hormonal) rather
than physical action
• Repellant - a material used primarily for the control of insects, birds and other
vertebrates
Pesticides fall into three basic chemical categories: synthetics, nonsynthetics (petroleum
products) and inorganics. Formulations are commonly made by combining synthetic materials
with various petroleum products. The synthetic pest-killing compounds in such formulations are
labeled as active ingredients; the petroleum product solvents acting as carriers or diluents for the
active ingredients are labeled inert. Pesticides are regulated primarily on the basis of active
ingredients.2 (The terms active and inert hi this application refer to lexicological action in
pesticides and are not to be contused with the common use of these terms to indicate
photochemical activity.3)
Carriers are inert materials added to a technical (or, economic) poison to facilitate later dilution
to field strength hi simple blending equipment. (A technical poison or technical material is
defined as the pesticide chemical in pure form, usually 95 to 100 percent active ingredient, as
it is manufactured by a chemical company prior to being formulated into wettable powders, dusts,
emulsifiable concentrates, granules, etc.) Certain kaolin clays, attapulgites, diatomites and several
highly-absorbent synthetic pigments are used as carriers. Diluents are material liquids or solids
CH-92-139 5-2
-------
serving to dilute the technical material to field strength for adequate plant coverage, maximum
effectiveness and economy. They may be used directly with technical materials to dilute to field
strength sprays or dusts, but usually are blended with wettable powders and dust concentrates
previously prepared with carriers. The most widely used solid diluents are kaolin clays,
pyrophyllites and talcs, although attapulgites and diatomites, local clays, limestone products and
other minerals are also used. Although solid carriers and diluents are generally considered to be
inert, certain attapulgites, kaolin clays and diatomites aid in increasing toxic effectiveness,
probably due to physical properties which induce starvation, desiccation and abrasion. Most
formulations of dusts and sprays contain from 80 to 99 percent carrier-diluent.2
Adjuvants are materials which are added to a pesticide mixture in the spray tank to improve
mixing and application or enhance pesticide performance. An adjuvant customizes the
formulation to meet specific needs or to compensate for local conditions. By using the proper
adjuvant, it is often possible to use certain chemical pesticides in a tank mixture that otherwise
would present compatibility problems. (A tank mix is a mixture of two or more pesticides in the
spray tank at the time of application. Non-compatibility of the ingredients can be a problem.)
The term includes such materials as buffers, defoaming agents, spreaders, stickers, surfactants and
others, as defined below (these definitions are taken from Reference 2). Often, a single adjuvant
will accomplish more than one adjuvant function, such as a spreader-sticker, spreader-sticker-drift
retardant, etc.
• Acidifiers - acids that can be added to spray mixtures to neutralize alkaline solutions and
lower pH
• Attractants - food or bait, such as sugar, molasses, protein hydrolates or insect
pheromones, which attract specific pests. Attractants allow pesticides to be applied to
localized parts of the treatment area
• Buffers - substances capable of changing the pH of a water solution to a prescribed level
• Correctives (safeners) - substances which prevent objectionable changes when two or
more substances must be mixed which otherwise would not be compatible
• Defoaming agents (foam suppressants) - materials which eliminate the foam produced
in the spray tank from the action of the hydraulic or mechanical agitators
CH-92-139 5-3
-------
Deposition aids - adjuva- iat improve the ability of pesticide sprays to reach surfaces
in the treatment area. I ent types of products can be used with differing effects,
such as drift control agen^ ihat affect droplet size
Dispersants - materials that reduce the cohesiveness of like particles, either solid or
liquid. Dispersing and suspending agents are added during the preparation of
emulsifiable and wettable powders to facilitate dispersion and suspension of the
ingredients
Emulsifiers - surface-active substances which stabilize (reduce the tendency to separate)
a suspension of droplets of one liquid in another liquid which otherwise would not mix
with the first one
Extenders - chemicals that enhance the effectiveness or effective life of a pesticide.
Some extenders function by screening out ultraviolet light that decomposes many
pesticides; others slow down pesticide volatilization
Foaming adjuvants - surface-active substances that form a fast-draining foam to provide
maximum contact of the spray with the plant surface, to insulate the surface and to
reduce rate of evaporation. Used to enhance herbicide action, reduce drift of sprays and
mark spray swath widths
Penetrants - wetting agents, oils or oil concentrates that enhance the ability of a liquid
to enter into pores of a substrate, to penetrate the surface
Spray colorants - dyes that can be added to the spray tank so an applicator can see the
areas that have been treated
Spreader-sticker - a mixture of surfactant and latex or other adhesive sticker
Stickers (adhesives) - substances such as latex or other adhesives that improve pesticide
attachment to sprayed surfaces. They protect pesticides from washing off due to rainfall,
heavy dew or irrigation, and help prevent pesticide loss from wind or leaf abrasion
Surfactants - surface-active agents, also know as spreaders (film extenders) or wetting
agents. They enhance spray coverage by reducing the surface tension of spray droplets
and can be either nonionic, anionic or cationic
Thickeners (suspending agents) - materials which make spray mixtures more viscous.
IT - are often required as drift control agents with certain herbicides. They are used
to r; event settling out and hard packing of pesticide chemicals in water systems
Viscosity adjuvants - materials which stabilize herbicide sprays by increasing droplet
size, reducing off-target movement (drift) of spray particles
CH-92-139 5-4
-------
5.2 PROCESS BREAKDOWN
The "process breakdown" depends on several factors including the user, the pesticide formulation,
the type of equipment, the crop or area to be treated, and the application and treatment. These
factors are discussed in more detail below. These factors are often closely inter-related and not
easily separated from one another. For example, while the formulation of the pesticide helps to
determine the type of equipment to be used, the type of equipment available determines the type
of formulation that can be used. The specific pest to be controlled determines the type of
pesticides used. Particular pesticides may not be available in all formulations.
5.2.1 User Categories
Pesticide application may be broken down into several user categories: consumer, agricultural,
commercial, municipal and industrial. Consumer application refers to individual home and
garden pesticide use. These products are generally applied as sprays or baits and include
disinfectants, fungicides, insecticides, molluscicides, rodenticides, herbicides and repellents.
Agricultural pesticide application refers to farm chemical usage, other than fertilizers, for soil and
site preparation, pest control and harvesting aids. Agricultural pesticides can be applied in a
variety of formulations (sprays, dusts, pellets, fogs, etc.) from the ground or from the air (aerial
application).
Commercial pesticide application includes professional treatment of homes, buildings and lawns
for fleas, cockroaches, termites, nematodes, crabgrass etc. Municipal pesticide application refers
to governmental use of pesticides for mosquito control, roadsides, aquatic pests, etc., and includes
both ground and aerial applications. Industrial application refers to use for power line and gas
line right-of-ways, etc.
Approximately 68 to 75 percent of pesticides used in the United States are applied to agricultural
lands, both cropland and pasture.1'4 Of the remaining 32 to 25 percent, 8 to 17 percent is used
used privately for home and garden pests, and the remaining 24 to 8 percent, are used for
industrial, commercial and governmental purposes.1
CH-92-139 5-5
-------
The essentials of good pesticide application are correct timing of application; proper chemicals
and rates; and proper equipment, correctly used.5
5.2.2 Formulations
A single active ingredient is often sold in several different formulations. In choosing the
formulation for a particular use, the user must consider the following: the plant, animal or
surface to be protected; application machinery available and best suited for the job; hazard of
drift and runoff; safety to applicator, helpers and other humans and pets likely to be exposed;
habits or growth patterns of the pest; cost; and type of environment in which the application must
be made (agricultural, aquatic, etc.). These formulations and their descriptions are listed below:2
Emulsifiable Concentrate - A liquid formulation containing the active ingredient, one
or more solvents and an emulsifier which allows mixing with water. Little agitation is
required
Solution - Used for those active ingredients which dissolve readily in water. The
formulation is a liquid and usually consists of the active ingredient and additives. When
mixed with water, a solution will not settle out or separate
Flowable - A liquid formulation consisting of finely ground active ingredient suspended
in a liquid. Flowables are mixed with water for application
Wettable Powder - Dry, finely ground formulations which look like dusts. The active
ingredient is combined with a finely ground dry carrier, usually mineral clay, along with
other ingredients that enhance the ability of the powder to suspend in water. Wettable
powders can be mixed with water for application as a spray and are one of the most
widely used pesticide formulations
Dry Flowable - Also know as water-dispersible granules, dry flowables are like wettable
powders except that the active ingredient is formulated on a granule instead of a powder.
Dry flowables require agitation, but are easier to pour and mix than wettable powders
because there is less dust
Soluble Powdrr - A dry formulation which, when mixed with water, dissolves readily
and forms a \ e solution. When thoroughly mixed, no agitation is necessary. Not
many formulations of this type are available because few active ingredients are soluble
in water
Ultra Low Volume Concentrate - A liquid formulation which may be applied with
specialized equipment as is or diluted with a small quantity of specified carrier. These
formulations are designed to be applied at rates of only ounces per acre
CH-92-139 5-6
-------
Low Concentrate Solution - Small amounts of active ingredient (one percent or less)
used without dilution for structural pests, space sprays in barns, mosquito control, etc
Aerosol - A system of particles dispersed in a gas. Liquid particles make up a fog and
solid particles form a smoke. In formulations, there are ready-to-use types such as
household sprays. The commercial type holds five to ten pounds of formulation and can
be refillable. In addition, aerosols formulations can be used for smoke or fog generators
which break the liquid formulation into a fine mist or fog using a rapidly whirling disc
or a heater surface
Invert Emulsion - A water soluble pesticide dispersed in an oil carrier. Forms large
droplets which do not drift easily
Dust - Low percentage of active ingredient on a very fine dry inert carrier like talc,
chalk or clay. Most are ready to use. Danger of drift
Bait - Active ingredient mixed with food or another attractive substance
Granule - Most often used for soil applications. The active ingredient is coated or
absorbed onto coarse particles like clay, ground walnut shells or ground corncobs
Pellets - Very similar to granules, although pellets are usually more uniform - or a
specific weight or shape
Micro Encapsulation - Particles of a pesticide, either liquid or dry, surrounded by a
plastic coating. Mixed with water and applied as a spray. Encapsulation makes timed
release possible
Water-Soluble Packets - Water-soluble packets are used to reduce the mixing and
handling hazards of some highly toxic pesticides. Pre-weighed amounts of wettable
powder or soluble powder formulations are packaged hi water-soluble plastic bags.
When the bags are dropped into a filled spray tank, they dissolve and release their
contents to mix with the water. There are no risks of inhaling or contracting the
undiluted pesticide during mixing as long as the packets are not opened. Once mixed
with water, pesticides packaged in water-soluble packets are no safer than other mixtures
Impregnates - Pesticides that are incorporated into household and commercial products.
Pet collars, livestock ear tags, adhesive tapes and plastic pest strips contain pesticides
that volatilize over a period of time and provide control of nearby pests
5.2.3 Equipment
The type of formulation determines, in part, the type of equipment used to apply the pesticides.
Various dusters, sprayers and blowers are used, with their corresponding tanks, nozzles, pumps
and hoses. Several types of equipment are described in the following pages (descriptions are
taken primarily from Reference 2).
CH-92-139 5-7
-------
5.2.3.1 Dusters'
Duster types include hand dusters, rotary-type hand dusters, knapsack dusters and power dusters.
In a hand duster, a plunger expels a blast of dust-laden air. The dust chamber may be at the end
of the plunger tube itself, or an enlargement at the end, or it may be located below the plunger
tube. A rotary-type hand duster is carried by a neck strap on the lower chest of the operator.
A hand crank revolves a fan to provide feed from the dust chamber to the delivery tube ahead
of the operator. Unlike the rotary-type hand duster, the knapsack duster is carried on the back.
It is operated by a bellows on top of a cylindrical dust container. The bellows are operated by
a hand lever at the side of the operator.
Power dusters can deliver dust in two ways: through a horizontal boom with a large number of
delivery pipes, often terminating in a fishtail nozzle; and through a single large orifice or circular
nozzle. A fan or a turbine blower delivers the dust-carrying air stream. The equipment can be
modified to meet the requirements of different field conditions. A nozzle air velocity of
approximately 5,000 feet per minute will allow good flotation with sufficient drive to carry dust
through the foliage of the plant and rebound, to some extent, from the ground.5
5.2.3.2 Sprayers*-5
The majority of field sprayers in use today are hydraulic sprayers in which the spray pressure is
built up by direct action of the pump on the spray mixture. They range from low-pressure
sprayers to high-pressure sprayers and can be mounted, pulled or self-propelled. The basic
sprayer components are the tank, pump, agitator, hoses, valves and fittings, and nozzles.
Compressed air sprayers, power sprayers, hand sprayers, knapsack sprayers and mist blowers are
examples of various sprayer types. Compressed air sprayers usually have a one- to three-gallon
capacity. They are equipped with an air pump to develop pressure and often have a shoulder
strap for carrying. They are generally not suitable for spraying at heights over six to ten feet.
CH-92-139 5-8
-------
In hand sprayers (often called Flit guns), the liquid pesticide is aspirated by a rapid flow of air
over the open end of a vertical tube. The other end of the tube is immersed in the liquid in a
container attached to a piston cylinder. The air flow is produced by the hand-operated piston,
with its outlet at a right angle to and in approximate contact with the open end of the aspirator
tube. A knapsack sprayer is a light-weight sprayer designed to be carried on the back of the
operator. Unlike the compressed air sprayer, the knapsack sprayer is fitted with a hydraulic
pump operated by a hand lever. This sprayer type is used for spraying small gardens and other
similar areas.
A power sprayer is a plunger-pump sprayer operated by a gasoline or an electric motor. The
equipment includes small, hand-drawn sprayers and larger trailer-type sprayers which use their
own engines or can draw power from the tractor. Power sprayers have been adapted for orchard
use with equipment arranged for spray coverage at considerable heights and for treating row and
field crops with nozzles spaced appropriately on a horizontal boom.
In a mist blower, hydraulic atomization of the liquid in the nozzle is added by an air blast past
the spray source. The air blast from the blower aims and carries the mist to the target. Mist
blowers can evenly apply much less liquid per acre than was possible with the older, heavy
plunger-pumps.
5.2.4 Area to be Treated/Type of Application and Treatment
Pesticides are used in and around homes and other structures; on gardens, lawns, field crops,
orchards, right-of-ways, roadsides, wetlands; and in water. The type of area (both in general,
e.g., field crops, and specifically, e.g., corn), the location, the pest to be controlled, and the size
of the area are important considerations in determining the application and treatment strategy.
Types of applications and treatments include band, basal, broadcast, directed, sequential, serial
and spot. These terms are defined as follows.2
CH-92-139
5-9
-------
Band application - application of herbicide in a narrow band on each side of a row crop
as a saving over treatment of the entire field area between rows. The remainder of the
area between rows may then be machine cultivated
Basal application - application of pesticide on plant stems or tree trunks just above the
soil line
Basal treatment - herbicidal treatment, with minimal foliage contact, to stems of woody
plants at and just above ground level so as to encircle just the stem
Broadcast application - application of a pesticide uniformly over the area to be treated
without regard to arrangement of crop (as in rows)
Directed application - precise application to a specific area, such as to a row or bed, or
to a plant organ, such as the lower leaves and stems
Sequential treatment - succeeding or consecutive actions or operations. Sequential
treatments in weed control as those of an herbicide as a pre-emergence overly following
preplant application of a different herbicide. The latter is applied before planting, the
sequential treatment after seeding and before emergence of crop plants
Serial application - the use of one pesticide immediately or shortly after the use of
another
Spot treatment - a treatment directed at specific plants or areas rather than a general
application
53 POLLUTANTS EMITTED
VOC, PM and air toxics can be emitted from pesticide application activities. Emissions can
occur initially when technical material is mixed with other materials to field strength by the
applicator. Emissions can also occur from the following activities.
• During application
• After application as the pesticide (including carriers and other additives) evaporates
• During farming operations such as field preparation and harvesting when organic
materials and soils are disturbed, allowing for additional pesticide evaporation and
movement of dust particles
• During mowing operations along treated roadsides and rights-of-way
CH-92-139 5-10
-------
5.4 ESTIMATE OF POLLUTANT LEVELS
Figures available from the U.S. International Trade Commission (TTC) indicate that U.S.
production of pesticides and related products in 1987 amounted to about 1.04 billion pounds.6
According to Reference 1, these figures are probably underestimates and do not differentiate
between the amounts actually used in the United States and those that are exported. Other
estimates suggest that between 0.9 and 1.1 billion pounds of active ingredients are used each year
in the United States.1 The U.S. EPA has also estimated pesticide usage in the United States
during recent years at 1.1 billion pounds of active ingredients.4
Reference 4 provides two per capita factors representing 1989 pesticide usage in terms of pounds
of active ingredient (a.i. stands for active ingredient):
Non-agricultural usage (active ingredient): 1.1 Ibs per capita
All usage (active ingredient): 4.28 Ibs per capita
Reference 3 provides the following assumptions about pesticides.
• The amount of solvent carrier is about 1.45 times the amount of active ingredient
• The total potential VOC emissions are 2.45 times the amount of active ingredient
Combining these assumptions with the per capita factors from Reference 4, potential VOC
emissions from all pesticide use can be calculated as follows:
(4.28 Ibs a.i./agHto)(2.45)(250,000,000)(l ton/2,000 Ibs) = 1,310,750 tons
The nonagricultural portion of potential VOC emissions would be
(1.1 Ibs a.i./azpito)(2.45)(250,000,000)(l ton/2,000 Ibs) = 336,875 tons
CH-92-139
5-11
-------
The agricultural portion of potential VOC emissions would be
(3.18 Ibs a.i./capito)(2.45)(250,000,000)(l ton/2,000 Jfcs) = 973,875 tons
Actual VOC emissions would be less since not all of the VOC will evaporate. Some of the
pesticide may be leached into the soil and water, may be broken down by various organisms into
other substances, or may remain in landfilled containers.
Other national, state and regional per capita factors and emissions estimates are available from
References 7 through 11. These estimates are briefly summarized in Tables 5-1 and 5-2.
No data were readily available to estimate PM emissions from pesticide application activity.
5.5 SOURCE ACTIVITY DATA AVAILABILITY
Many sources of data are available to estimate pesticide application activity. These sources are
identified under the appropriate user category (consumer, agricultural, commercial, municipal,
industrial).
5.5.1 Consumer
EPA's Office of Pesticides and Toxic Substances has recently made available results of its
national home and garden pesticide use survey.12 The following types of data were collected
from households surveyed about their pesticide use.
• Types of pesticides used
• What they were i: >ed for
• How often they were used
• How they were applied, including safety precautions
• How unused portions were stored and/or disposed of
CH-92-I39 5- 1
-------
TABLE 5-1. PER CAPITA FACTORS FOR PESTICIDE EMISSIONS
REFERENCE
NUMBER
7
7
7
7
7
7
8
8
8
8
8
8
8
8
8
8
8
REGION
CA
CA
NJ
NJ
NY
NY
New England
Mid Atlantic
E.N. Central
W.N. Central
S. Atlantic
E.S. Central
W.S. Central
Mountain
Pacific
U.S.
U.S.
EMISSION FACTOR
(Ibs VOC/capita)
0.67
0.15
0.56
0.12
0.64
0.14
0.041/0.428/0.815
0.041/0.428/0.815
0.038/0.404/0.769
0.038/0.404/0.769
0.059/0.622/1.186
0.059/0.622/1.186
0.059/0.622/1.186
0.040/0.418/0.797
0.040/0.418/0.797
0.180/0.184/0.188
0.000/0.156/0.313
USE/PRODUCT
Consumer/commercial insecticides
Consumer/commercial herbicides and fungicides
Consumer/commercial insecticides
Consumer/commercial herbicides and fungicides
Consumer/commercial insecticides
Consumer/commercial herbicides and fungicides
Consumer/commercial insecticides
Consumer/commercial insecticides
Consumer/commercial insecticides
Consumer/commercial insecticides
Consumer/commercial insecticides
Consumer/commercial insecticides
Consumer/commercial insecticides
Consumer/commercial insecticides
Consumer/commercial insecticides
Consumer/commercial moth control
Consumer/commercial herbicides and fungicides
COMMENTS
average
average
average
average
average
average
low/mid/high
low/mid/high
low/mid/high
low/mid/high
low/mid/high
low/mid/high
low/mid/high
low/mid/high
low/mid/high
low/mid/high
low/mid/high
t_n
-------
TABLE 5-2. PESTICIDE EMISSIONS ESTIMATES
REFERENCE
NUMBER
7
7
7
7
7
7
9
9
9
9
9
9
10
10
10
10
10
10
11
REGION
CA
CA
NJ
NJ
NY
NY
NYCMA
NYCMA
NYCMA
NY
NY
NY
CA
CA
CA
CA
CA
CA
CA
EMISSIONS
(tons VOC/year)
3,000.41 - 13,613.93
3,605.25
845.57 - 3.836.65
1,016.02
1,254.72 - 5,693.1
1,507.65
5/32
33/15
413/619
12/70
69/30
717/1,064
27,008.98
1,818.87
1,369.78
63,507.54
2,997.19
96,702.36
182,019,000
USE/PRODUCT
Consumer/commercial insecticides
Consumer/commercial herbicides and fungicides
Consumer/commercial insecticides
Consumer/commercial herbicides and fungicides
Consumer/commercial insecticides
Consumer/commercial herbicides and fungicides
Pet insecticides
Insect repellents
Other insecticides
Pet insecticides
Insect repellents
Other insecticides
Agricultural 47092 pesticide
Domestic 47100 pesticide
Unspecified 47118 pesticide
Agricultural 47126 pesticide
Domestic 47134 pesticide
All pesticides
Formula 10 pesticides
COMMENTS
low - high
high
low - high
high
low - high
high
household/commercial
household/commercial
household/commercial
household/commercial
household/commercial
household/commercial
total organics (TOG)
TOG
TOG
TOG
TOG
TOG - total of 5 above
TOG - Ibs/yr
-------
• How product containers were disposed of
• How child resistant packaging was used
• How effective the pesticides were judged to be
• Which pests were major problems (either treated or untreated)
The summary data are reported primarily in thousands and percents of households with specific
pesticide-related statistics. Rates of application and amounts of pesticides applied are not
reported in the summary.
Reference 1 provides various statistics in consumer pesticide use, such as the following.
Between 8 and 17 percent of pesticides used in the United States are used privately to
control household and home garden pests
About 90 percent of all U.S. households use pesticides
Reference 4 estimates that the following volumes of pesticide active ingredients are used in the
home and garden sector.
• 25 million Ibs herbicides (includes plant growth regulators)
• 30 million Ibs insecticides (includes miticides and contact nematicides)
• 11 million Ibs fungicides (does not include wood preservatives)
• 3 million Ibs other (includes rodenticides, fumigants and molluscicides)
• 69 million Ibs total (34,500 tons)
Other consumer pesticide usage data are available from References 7, 8, 9, 10, 11 and 13. Some
of these data are national, state or regional in their coverage and may report commercial and
consumer use together.
CH-92-139 5-15
-------
5.5.2 Agricultural
The Census of Agriculture contains information on the number of acres of various crops
harvested and the number of farms and number of acres on which agricultural chemicals are
used.14 These data are reported on the national, state and county level under the following
headings.
• Sprays, dusts, granules, fumigants, etc., to control: insects on hay and other crops;
nematodes in crops; diseases in crops and orchards; weeds, grass or brush in crops and
pasture
• Chemicals used for defoliation or for growth control of crops or thinning of fruit
State and county agricultural statistics are available from state Departments of Agriculture and
state and national Agricultural Statistics Services. These publications contain state and county
statistics on crops harvested and crop-specific information on percent of acres treated with
various herbicides and insecticides. Reference IS is an example of these state publications.
References 16 and 17 provide crop-specific agricultural chemical usage for field crops in 1991
and vegetables in 1990, respectively. In Reference 16, data include the crop, the name of the
agricultural chemicals applied, the area or acres applied (percent), the number of applications,
the rate per application and rate per crop per year (pounds per acre) and the total applied
(pounds) by major producing state. Similar data items for vegetables are reported in
Reference 17.
Many states regularly produce agricultural chemicals manuals. The 7997 North Carolina
Agricultural Chemicals Manual includes sections covering safety, application, specimen
identification, insect control, disease control, fruit disease, chemical weed control, plant growth
regulators, fertilizer use, and animal control.5 Crop-specific da'a by pest may include pesticide
name and available formulations, amount of formulation per acre, active ingredient per acre,
minimum interval between application and harvest, and precautions and remarks.
CH-92-139 5-16
-------
The Farm Chemicals Handbook and Thompson's Agricultural Chemicals provide compound-
specific information.2'18 For example, the pesticide index in Reference 2 includes definitions of
various pesticide activity-related terms, as well as detailed information on pesticides by brand
name and/or common name. Information that may be provided for a pesticide by brand name
includes: identification - common name, other name, code number, discontinued names;
chemistry - composition, family, properties, structure; action/use - action, use, formulations,
combinations; registration notes; environmental guidelines - signal word, toxicity class, toxicity,
protective clothing, handling and storage cautions; and emergency guidelines - flashpoint,
combustion products; fire extinguishing media, antidote, first aid, emergency telephone number,
basic producer.
Usage statistics for agricultural purposes are compiled in the National Pesticide Usage Database,
developed by Leonard Gianessi of Resources for the Future.19'20 This database is disaggregated
into county use for 25 widely used agricultural pesticides, but statistical significance may be
limited to the state level.
References 10, 11, 21 and 22 also provide some agricultural pesticide usage information.
References 10, 11 and 21 reflect activity hi California and include emissions estimation
methodologies.
5.5.3 Commercial/Municipal/Industrial
Reference 1 estimates that 8 to 24 percent of the pesticides used hi the United States are used
for industrial, commercial and government purposes. The National Home and Garden Pesticide
Use Survey - Final Report provides the following statistics:12
"About 15 percent of the 66.8 million households that have a private
lawn (about 10 million households) had pesticides applied in the past
year by someone other than a member of the household, usually by a
commercial lawn care company. Also, about 20 percent of all
households (about 16 million) had their homes commercially treated
for indoor pests, such as cockroaches, ants or fleas."
CH-92-139 5-17
-------
Most trade associations contacted either do not collect information on pesticide usage (amounts
in afferent user categories) or may only collect data on certain products, not on the scale needed
to make emissions estimates.23-24 State officials contacted indicate that while there are
recordkeeping requirements for pesticide applicators, the requirements may differ depending on
the pesticide use (agricultural, structural, etc.) and may or may not include the name of pesticide
or the amount or concentration.25126 The experts contacted suggested other potential sources of
information, including the Chemical Specialty Manufacturers Association, the Chemical
Manufacturers Association and other manufacturers and distributors.24'26 Individual municipalities
may keep records of amounts and types of pesticides applied by the municipality.
5.6 LEVEL OF DETAIL REQUIRED BY USERS
5.6.1 Consumer
The following information is needed to estimate use by consumers.
• Total amount of consumer pesticides used per county, state or region. This information
can then be used to estimate average consumer indoor pesticide use (per capita or per
household) by county, state or region; average consumer outdoor pesticide use (per
capita or per household) by county, state or region
• Percent of pesticide used that is volatile and is likely to evaporate
• PM emission rate per unit (gallon or pound) of pesticide used, developed into a per
capita or per household emission factor
5.6.2 Agricultural
The following information is needed to estimate use by agriculture.
• Amount of pesticide used per acre, by crop
Acres harvested, by crop, and percent of harvested crop that is treated with pesticides
Percent of total pesticides used applied aerially and percent of total pesticides used
applied from the ground
CH-92-139 5-lg
-------
• Percent of pesticide used that is volatile and is likely to evaporate, by application type
(ground or aerial)
• PM emission rate per unit (gallon or pound) of pesticide used, developed into a per acre
emission factor
5.6.3 Commercial/Municipal/Industrial
The following information is needed to estimate commercial/municipal/industrial use.
• Commercial, municipal and industrial pesticide use by county and medium (terrestrial
or aquatic)
• Percent applied aerially and percent applied from the ground by county and medium for
each user type
• Percent of pesticide used that is volatile and is likely to evaporate, by application type
(ground or aerial), by county and by medium for each user type
• PM emission rate per unit (gallon or pound) of pesticide used
5.7 EMISSION FACTORS AVAILABLE/REQUIRED
Table 5-1 provides the per capita VOC emission factors available from References 7 and 8.
These emission factors only address consumer/commercial use of insecticides, herbicides and
fungicides and are state- (California, New Jersey and New York) and region-specific. Reference
3 provides a general VOC emission factor for agricultural pesticide use.
VOC and PM emission factors need to be developed for all user categories. These emission
factors may include, but are not limited to, the following:
• Consumer - national, regional or state per capita or per household emission factors
• Agricultural - national, regional or state crop-specific emission factors for ground and
aerial application
• Commercial - national, regional or state per household emission factors
• General - herbicide/insecticide per acre emission factors
CH-92-139 5-19
-------
5.8 REGIONAL, SEASONAL AND OTHER TEMPORAL CHARACTERISTICS
Most household pesticides are used during spring and summer months when pest infestations are
greatest. Warmer weather may also increase volatilization of termiticides. Since insect
populations are generally larger hi more moderate climates, pesticide usage and corresponding
emissions should be greater in the southern states.1 However, high density population areas such
as center-city areas may show a higher per capita usage rate than other parts of the same city.
In general, greater consumption, and therefore, greater emissions, occur during the growing
season for all pesticide user categories. Rural areas may have greater emissions due to intensive
agricultural pesticide use.
5.9 POTENTIAL METHODOLOGIES
The following paragraphs present conceptual methodologies for estimating emissions from each
user category.
5.9.1 Consumer
To estimate consumer emissions from pesticide use, total pesticide use must be broken down into
the various user categories. Total consumer pesticide use should be allocated to specific regions
hi order to develop regional per capita or per household VOC and PM emission factors. County
population and housing data are available from the Census of Housing and the Census of
Population.21**
5.9.2 Agricultural
Data from Reference 16 can be used to determine the pounds of various agricultural chemicals
used per acre by crop by state. Although data from all states are not available from this
reference, it may be possible to infer regional patterns from the existing data. Additional
application rate information may be taken from publications like Reference 5. Data on acres
CH-92-139 5-20
-------
harvested by crop are available from the Census of Agriculture.14 Reference 16 also provides
data on percent of total area planted that is treated with herbicides, insecticides, fungicides and
other chemicals and number of applications per year, by crop and state. These data can be used
to adjust total county acreage to county acreage treated. This can be represented by the following
equation.
Number of acres ^ Percent of acres Lbs applied per Number of _ Total Ibs
(county, crop) treated (crop) acre (crop) applications ~ applied
Next, the VOC portion of the pesticide and the amount of VOC likely to evaporate must be
estimated. VOC emissions would be estimated by the following equation.
Total Ibs applied x weight percent VOC in pesticide x percent VOC evaporates = Ibs VOC emissions
Additional considerations in these equations are the percentage of pesticides applied aerially and
the percentage of pesticides applied from the ground. Harold Collins of the National Agricultural
Aviation Association stated that 30 percent of all agricultural pesticides are applied aerially. In
addition, the exact same formulations and levels of active ingredients are used aerially as are used
during ground applications. The quantity of diluent may vary with the application method, but
quantities do not exceed the manufacturer's recommendations. (Reference 18 contains
manufacturer's recommendations.) It is reasonable to expect that a greater proportion of
pesticides evaporates when applied aerially.29
To determine PM emissions, agencies may need to know more specific information on the types
and formulations of the pesticides applied in the area and the application or treatment activities.
If these data are unknown, many assumptions will need to be made regarding PM emissions per
acre treated or pounds applied.
CH-92-139 5-21
-------
5.9.3 Commercial/Municipal/Industrial
Very few data have been located on commercial pesticide usage. Reference 1 estimates that 8
to 24 percent of the pesticides used in the United States are used for industrial, commercial and
government purposes. An inventorying agency should be careful not to double-count residential
use of commercially applied pesticides. If this lawn and home use (pesticides being applied by
someone other than a member of the household) is being accounted for under the consumer use
category, it should not be included here.
Total commercial pesticide usage would be divided by number of households having lawn
treatment and number of households having home treatment to estimate pounds of pesticides
applied per lawn-treated household and pounds per home-treated household, respectively. The
Census of Housing can be used to identify the number of households with lawns and total number
of households. These figures are then multiplied by 0.15 and 0.20, respectively, to determine the
number of treated households in each category.
As with the other user categories, the percent of VOC in the pesticide and the percent that
evaporates needs to be determined to estimate the VOC emission factor. General assumptions
will need to be made concerning types, formulations and treatment activities as input to the
emission factor determination. These assumptions will also be needed to determine the PM
emission factor. The VOC and PM emission factors can then be applied to the number of treated
households in each category to estimate VOC and PM emissions.
Municipal pesticide use can be determined by contacting the local and state government agencies
to determine the pesticide amount, type and treatment in the area being inventoried. In addition,
these agencies may also have information on industrial pesticide application. VOC percent and
percent evaporation needs to be determined to estimate the VOC emission factor.
If the detailed information on municipal and industrial pesticide use is not available, the agency
may consider "scaling up" the inventory to account for this pesticide use. This scaling up activity
CH-92-139 5-22
-------
assumes that the pesticides used in these applications are used in the same relative amount and
have the same characteristics as those used in other user applications.
CH-92-139 5-23
-------
5.10 REFERENCES
1. Baker, Scott R., and Chris F. Wilkinson, Eds. Advances in Modern Environmental
Toxicology, Volume XVII - The Effects of Pesticides on Human Health, Princeton
Scientific Publishing Co., Inc., Princeton, NJ, 1990.
2. Farm Chemicals Handbook '91, Meister Publishing Company, Willoughby, OH, 1991.
3. Kersteter, Sharon L. Procedures for the Preparation of Emission Inventories for Carbon
Monoxide and Precursors of Ozone, Volume I: General Guidance for Stationary
Sources, EPA-450/4-91-016 (NTIS PB92-112168), U.S. Environmental Protection
Agency, Research Triangle Park, NC, May 1991.
4. Aspelin, A.L., A.H. Grube, and V. Kibler. Pesticide Industry Sales and Usage: 1989
Market Estimates, H-7503W, U.S. Environmental Protection Agency, Washington, DC,
July 1991.
5. North Carolina State University. 1991 North Carolina Agricultural Chemicals Manual,
College of Agriculture and Life Sciences, Raleigh, NC, January 1991.
6. Synthetic Organic Chemicals: United States Production and Sales, 1987, USITC
Publication 2118, U.S. International Trade Commission, Washington, DC, 1988.
7. Jones, A., et al. Photochemically Reactive Organic Compound Emissions from
Consumer and Commercial Products, EPA-902/4-86-001 (NTIS PB88-216940), U.S.
Environmental Protection Agency, New York, NY, November 1986.
8. U.S. Environmental Protection Agency. Compilation and Speciation of National
Emission Factors for Consumer/Commercial Solvent Use, EPA-450/2-89-008 (NTIS
PB89-207203), Research Triangle Park, NC, April 1989.
9. New York State Department of Environmental Conservation. Analysis of Regulatory
Alternatives for Controlling Volatile Organic Compound (VOC) Emissions from
Consumer and Commercial Products in the New York City Metropolitan Area, 3655/84,
Albany, NY, 1990.
10. Methods for Assessing Area Source Emissions in California, California Air Resources
Board, Sacramento, CA, 1982.
11. Leung, Steve, et al. Air Pollution Emissions Associated with Non-Synt^ ic
Hydrocarbon Applications for Pesticide Purposes in California: Use Pattern: . A
Alternatives, Draft Final Report, Vols. I, H and m, ARB A7-173-30, California Air
Resources Board, Sacramento, CA, 1980.
CH-92-139 5-24
-------
12. Whitmore, R.W., I.E. Kelly, and P.L. Reading. National Home and Garden Pesticide
Use Survey, Final Report, Executive Summary, EPA-540/09-92-190 (NTIS PB92-
174739), Prepared by Research Triangle Institute for the U.S. Environmental Protection
Agency, Washington, DC, March 1992.
13. Consumer Pesticides and Fertilizers. C.H. Kline and Company, Fairfield, NJ, 1981.
14. 1987 Census of Agriculture. U.S. Department of Commerce, Bureau of the Census,
Washington, DC, 1989.
15. 1991 Missouri Farm Facts. Missouri Department of Agriculture, Jefferson City, MO,
July 1991.
16. Agricultural Chemical Usage 1991 - Field Crops Summary, Ag Ch 1 (92), U.S.
Department of Agriculture, National Agricultural Statistics Services, Washington, DC,
March 1992.
17. Agricultural Chemical Usage 1990 - Vegetables Summary, Ag Ch 1 (91), U.S.
Department of Agriculture, National Agricultural Statistics Services, Washington, DC,
June 1991.
18. Thomson, W.T. Agricultural Chemicals, Books I, n, in and IV, Thomson Publications,
Fresno, CA, 1989.
19. Gianessi, Leonard P. The National Pesticide Usage Data Base, in "Agrichemicals and
Groundwater Protection: Resources and Strategies for State and Local Management,"
Conference Proceedings, October 24-25, 1988, Freshwater Foundation.
20. Gianessi, Leonard P., and Cynthia A. Puffer. Use of Selected Pesticides in Agricultural
Crop Production National Summary, Resources for the Future, Washington, DC, 1988.
21. Leung, Steve, et al Air Pollution Emissions Associated with Pesticide Applications in
Fresno County, ARB A7-047-30, California Air Resources Board, Sacramento, CA,
1978.
22. Osteen, Craig D., and Philip I. Szmedra. Agricultural Pesticide Use Trends and Policy
Issues, Agricultural Economic Report Number 622, U.S. Department of Agriculture,
Washington, DC, 1989.
23. Telecon. Kersteter, Sharon L., Science Applications International Corporation, with Phil
Gray, Association of American Pesticide Control Officials. Pesticide usage information.
May 1992.
24. Telecon. Kersteter, Sharon L., Science Applications International Corporation, with
Richard Kramer, National Pest Control Association. Pesticide usage information. May
1992.
CH-92-139
5-25
-------
25. Telecon. Kersteter, Sharon L., Science Applications International Corporation, with
Bettie Smith, North Carolina Department of Agriculture. Aerial application of
pesticides. June 1992.
26. Telecon. Kersteter, Sharon L., Science Applications International Corporation, with Carl
Falco, North Carolina Department of Agriculture. Commercial and industrial application
of pesticides. June 1992.
27. 7990 Census of Housing, U.S. Department of Commerce, Bureau of the Census,
Washington, DC, 1992.
28. 7990 Census of Population, U.S. Department of Commerce, Bureau of the Census,
Washington, DC, 1992.
29. Telecon. Henning, Miranda, Alliance Technologies Corporation, with Harold Collins,
National Agricultural Aviation Association. Pesticide application. July 1990.
CH-92-139 5-26
-------
SECTION 6.0
AGRICULTURAL OPERATIONS
6.1 BACKGROUND
Agricultural (farming) operations include plowing, disking, fertilizing, applying pesticides,
preparing seed beds, planting, cultivating and harvesting.1 All these operations can be generically
classified as soil preparation, soil maintenance and crop harvesting operations.2 For the purposes
of this discussion, agricultural operations have been divided into two major categories: tilling
and harvesting. Tillage operations include plowing, disking, fertilizing, pesticide application, seed
bed preparation, planting and cultivating activities, i.e., soil/site preparation and soil maintenance.
(Cultivation is defined as shallow tillage operations performed to create soil conditions conducive
to improved aeration, infiltration and water conservation, or to control weeds.2
Tilling and harvesting activities can result in emissions of PM, as well as VOC and air toxics
from the disturbed soil and organic matter (weeds, crop residue). Dust emissions from tilling are
greatest during periods of dry soil and during final seedbed preparation, and depend on surface
soil texture, surface soil moisture content and other conditions of a particular field being tilled.3
In addition, PM emissions are also generated by wind erosion of bare or partially vegetated soil.2
This discussion addresses only the dust and associated emissions from agricultural operations.
Fuel combustion emissions from the agricultural equipment are addressed in the off-highway or
non-road mobile sources portion of national and SIP inventories.
6.2 PROCESS BREAKDOWN
Tilling and harvesting activities can be broken down by crop (e.g., sugar cane, cotton, wheat,
etc.), soil type (e.g., clay, silt, loam, etc.) and site characteristics, and activity type (e.g., manual
harvesting versus machine harvesting).
CH-92-139
6-1
-------
6.2.1 Tilling
6.2.1.1 Crop
Tilling to prepare the seedbed is needed when planting small and/or high cost seed, such as
lettuce, tomatoes, sugar beets, alfalfa and clovers. It is not as important for vigorous large-seeded
plants such as corn, small grains, soybeans, dry beans and sorghum.1
Plowing under crop residues helps to control certain insects in certain crops. Examples include
the following:1
• Wheat - The Hessian fly can be controlled by plowing under infested wheat stubble and
volunteer wheat. The wheat jointworm is held in check by destroying all volunteer
grain
• Corn - Plowing under corn stalks reduces the next year's crop of European corn borers
• Cotton - The cotton boll weevil and pink boll worm can be controlled by early
destruction and plowing under of cotton stalks
Also, timely cultivation can reduce grasshopper infestations by drying out their eggs.
Periodic tillage can also help maintain the open furrows needed to channel the water for surface-
flow irrigation; helps break up soil crusts; and covers over the roots of crops such as sugar beets
and potato tubers.
6.2.1.2 Soil Type/Site Characteristics
Tilling can improve plant growth by improving aeration, water movement and root penetration
in f*ie soil profile. The physical condition of soil as related to its ease of tillage, fitness as a
sef id and impedance to seedling emergence and root penetration is known as tilth. Coarse-
textured soils usually exhibit good physical condition, but have a small capacity for supplying
enough water and plant nutrients. Fine-textured soils normally have a satisfactory nutrient and
water reserve, but often inhibit soil aeration because the fine particles pack closely together, thus
CH-92-139 6-2
-------
slowing air exchange. Plowing and cultivating coarse-textured soils do not seem to make them
a better medium for plant growth; tilling most fine-textured soils improves the air-water relations
immediately following the tillage operations, which result in better plant growth.1
Tillage operations should be conducted sparingly since tillage can lead to soil surface smoothing
and clod pulverization. Soil moisture at the time of tillage affects cloddiness. Different soils
have differing moisture contents at which soil pulverization is most severe. More clods are
produced if the soil is either extremely dry or moist than if it contains an intermediate moisture
content.4
6.2.1.3 Equipment Type
Tillage methods are widely different, ranging from the conventional (e.g., moldboard plowing,
disking, harrowing or dragging) to those of special sizing and bed shaping, deep chiseling, strip
tillage and zero tillage.1 Equipment used for tilling can vary depending on the tillage operation
to be performed. In addition, the type of tillage implement used influences the soil cloddiness
and surface roughness.4 Major types of planters available for small grains include hoes, single
and double disks, deep furrow drills and seeding attachments on one-ways and cultivators.
Implements used to provide a rough, clodding soil surface may include listers, duckfoot
cultivators and narrow-tooth chisel cultivators.2
6.2.2 Harvesting
Emissions from harvesting activities are dependent primarily on the crop and the equipment used.
Emissions from cotton harvesting are related to machine speed, basket and trailer capacity, lint
cotton yield, free silica content and transport speed. Emissions from grain harvesting are related
to combine speed, combine swath width, field transport speed, truck loading time, truck capacity
and truck travel time.5
CH-92-139
6-3
-------
6.2.2.1 Crop
Crops vary in the manner in which they are harvested. In some harvesting operations, only a
portion of the plant is harvested, such as in harvesting of cotton. In other harvesting operations,
such as mowing and baling hay, almost the entire plant is harvested. In addition, some crops are
"dustier" than others.
6.2.2.2 Equipment
The crop to be harvested determines the type of harvesting equipment to be used. For example,
types of harvesters used for cotton include pickers and strippers. However, these harvesters are
not appropriate for harvesting grain crops.
6.2.3 Wind Erosion
Emissions from wind erosion depend on several factors, including soil credibility, surface
roughness, vegetative cover and other site-specific factors.
6.3 POLLUTANTS EMITTED
All tilling and harvesting operations can result in PM, VOC and air toxics emissions. The type
of tilling operation affects the rate of emissions. In addition, the crop being harvested and the
crop residue that is tilled under after harvest can also add organic particles to the dust emissions.
PM emissions also result from wind erosion of the tilled soil.
6.4 ESTIMATE OF POLLUTANT LEVELS
The following national PM-10 emissions have been calculated using emission factors presented
in Gap Filling PMW Emission Factors for Selected Open Area Dust Sources.5
CH-92-139 6-4
-------
The emission factor for all wheat harvesting activities (harvest machine, truck loading and field
transport) is 1.68 pounds per square mile. The emission factor for all sorghum harvesting
activities (harvest machine, truck loading and field transport) is 7.83 pounds per square mile.
The emission factor for harvesting cotton, assuming the weighted values for a stripper, is 26
pounds per square mile. Using a default value for silt content, the PM-10 emission factor for
tilling is 5.7 pounds per acre. These emission factors have been applied to national statistics on
acres of crops harvested from the 1987 Census of Agriculture.6
Harvesting wheat:
53,224,174 acres x 1.68 lbs/mi2 x 0.0015625 mi2/acre = 139,713 Ibs or 69.9 tons
Harvesting sorghum:
9,760,574 acres x 7.83 lbs/mi2 x 0.0015625 mi2/acre = 119,415 Ibs or 59.7 tons
Harvesting cotton:
9,826,081 acres x 26 lbs/mi2 x 0.0015625 miVacre = 399,185 Ibs or 199.6 tons
Tilling (assuming one operation per harvested acre):
282,223,880 acres x 5.7 Ibs/acre = 1,608,600,000 Ibs or 804,338 tons
Tilling (assuming that the average farm size in the United States is 462 acres and one
operation per acre):
462 acres/farm x 5.7 Ibs/acre = 2,633 Ibs/farm or 1.3 tons/farm
The National Acid Precipitation Assessment Program (NAPAP) developed estimates of wind
erosion from natural and agricultural lands. National TSP emissions from this category for 1985
were estimated at 4,711,540 tons. PM-10 emissions were estimated to be 1,130,769 tons.7
No estimates of VOC or air toxics emissions from tilling and harvesting operations are available.
CH-92-139 6-5
-------
6.5 SOURCE ACTIVITY DATA AVAILABILITY
County-level data on acres harvested by crop and populations of equipment on farms are
available in the Census of Agriculture. Reference 8 contains data on number of tillings per year
by crop. Number of fertilizer and pesticide applications per year by crop by state are available
from Reference 9.
6.6 LEVEL OF DETAIL REQUIRED BY USERS
6.6.1 Tilling
The following data items are needed by users to estimate tilling emissions.
• Number of harvested acres, by crop
• Number of pesticide and fertilizer applications, by crop
• Local tilling practices and activity, by crop
• Generic emission factors for tilling activity or specific emission factors for each type of
tilling activity
6.6.2 Harvesting
The following data items are needed by users to estimate harvesting emissions.
• Number of harvested acres, by crop
• Harvesting equipment used, by crop (especially cotton)
• Emission factors by crop and equipment
CH-92-139 6-6
-------
6.6.3 Wind Erosion
The following data items are needed by users to estimate emissions from wind erosion.
• Number of tilled acres, by crop
• Soil-site characteristics including soil type, soil credibility, etc.
• Local climate information
6.7 EMISSION FACTORS AVAILABLE/REQUIRED
Emission factors are available from References 2, 3 and 5. Specifically, Reference 2 provides
emission factor equations for tilling and wind erosion. Area-specific data are needed for these
equations. The emission factor equation in Reference 2 is based on AP-42 (Reference 3).
Reference 5 provides emission factors for agricultural tilling, harvesting of cotton by various
types of harvesters, and harvesting of wheat and sorghum.
6.8 REGIONAL, SEASONAL AND OTHER TEMPORAL CHARACTERISTICS
Most emissions from agricultural operations occur in rural areas. Seasonally, tilling emissions
will occur primarily in the spring, especially around final seedbed preparation time. Harvesting
emissions occur primarily at the end of the growing season, in the fall. Wind erosion emissions
occur primarily when soils are dry and not protected by a vegetative cover, primarily during the
winter and spring.
6.9 POTENTIAL METHODOLOGIES
The following methodology approaches are derived from References 2,3 and 5. Most of the data
items needed for these methodologies are readily available.
CH-92-139
6-7
-------
6.9.1 Tilling
The PM emission factor for agricultural tilling can be described by the following equation.2-3-5
E = k(4.80)(s)°'6 Ibs/acre
where: k = particle size multiplier (dimensionless)
s = silt content (percent) of surface soil
The particle size multiplier, k, is 0.21 for PM-10. Thus the emission factor equation (with an
AP-42 rating of B) for PM-10 is
E10 = (0.21)(4.80)(s)°-6 Ibs/acre
1.1 (s)°-6 Ibs/acre
Silt content can be determined from soil survey maps. Soil Conservation Service personnel and
local Agriculture Extension Service personnel may also have these data. If silt content is
unknown, a default value of 18 percent can be used.2-5 Using the default silt content, the PM-10
emission factor equation (with a C rating) is
EIO = (0.21)(4.80)(18)06 Ibs/acre
= 5.7 Ibs/acre
The number of acres tilled depends on the amount of acres planted and harvested and the number
of times per season that the land is tilled. Reference 8 provides the following information on
number of tillings per year by crop:
Crop Tillings per year
Barley 3
Corn 3
Cotton 4 - East, 3 - West
CH-92-139 6-8
-------
Oats 3
Sorghum 2 - East, 3 - West
Soybeans 3
Wheat 3 - East, 2 - West
Number of acres harvested by crop is available from the Census of Agriculture and/or state
Departments of Agriculture.
The emissions estimation equation for PM-10 emissions from tilling (assuming 18 percent silt)
is
Emissions (Ibs/year) = (acres of crop harvested/year)(tillings per crop)(5.7 Ibs/acre)
6.9.2 Harvesting
PM emission factors for harvesting cotton, wheat and sorghum are available in Reference 5.
For cotton, the emission factors are given for different harvester types and for several harvesting
activities, including harvesting itself, trailer loading and transport. Specific equipment types are
not indicated for the wheat and sorghum emission rates and factors. Emission factors are given
for the harvest machine (generic), truck loading and field transport. Number of acres harvested
by crop is available from the Census of Agriculture and/or state Departments of Agriculture.
The generic emissions estimation equation for harvesting activity is
Emissions (Ibs/year) = (acres of crop harvested/year)(emission factor, Ibs/mi2)(0.0015625 miVacre)
CH-92-139
6-9
-------
6.9.3 Wind Erosion2
Wind erosion has the following emission factor equation:
E = kalKCLV
where: E = PM-10 wind erosion losses of tilled fields, tons/acre/yr
k = 0.5, the estimated fraction of TSP which is PM-10
a = portion of total wind erosion losses that would be measured
as suspended particulate, estimated to be 0.025
I = soil credibility, tons/acre/yr
K = surface roughness factor, dimensionless
C = climatic factor, dimensionless
L' = unsheltered field width factor, dimensionless
V = vegetative cover factor, dimensionless
"I" may be thought of as the basic credibility of a flat, very large, bare field in a climate highly
conducive to wind erosion. K, C, L' and V are reduction factors for a ridged surface, a climate
less conducive to wind erosion, smaller-sized fields and vegetative cover, respectively. This same
equation can be used to estimate emissions from a single field, a county or an entire state. As
more generalized input data are used for the larger land areas, the accuracy of the resulting
estimates decreases.
Reference 2 provides tables and figures to aid in quantifying the variables hi the above equation.
Additional sources of information include the following: the Soil Conservation Service for soil
maps for determining "I" and National Weather Service data for determining "C." "I" and "C"
values can be determined for individual jurisdiction, with the remaining three variables being
quantified as functions of crop type. Number of acres harvested by crop is available from the
Census of Agriculture and/or state Departments of Agriculture.
CH-92-I39 6-10
-------
The general emissions estimation equation for agricultural wind erosion emissions is
Emissions by crop (tons/yr) = (acres of crop harvested/year)(emission factor, tons/acre)
The calculated emissions from each crop are then summed to obtain agricultural wind erosion
emissions by county, state or other jurisdiction.
CH-92-139
6-11
-------
6.10 REFERENCES
1. Donahue, R.L., R.W. MiUer, and J.C. Shickluna. Soils: An Introduction to Soils and
Plant Growth, Fourth Edition, Prentice-Hall, Inc., Englewood Cliffs, NJ, 1977.
2. Cowherd, C, G.E. Muleski, and J.S. Kinsey. Control of Open Fugitive Dust Sources,
EPA-450/3-88-008 (NTIS PB89-103691), U.S. Environmental Protection Agency,
Research Triangle Park, NC, September 1988.
3. U.S. Environmental Protection Agency. Compilation of Air Pollutant Emission Factors,
AP-42, Volume I, Fourth Edition and Supplements, Research Triangle Park, NC,
September 1985 through October 1991.
4. Chepil, N.S., N.P. Woodruff, F.H. Siddoway, and L. Lyles. "Anchoring Vegetative
Mulches," Agriculture Engineering, Vol. 41, pp. 754-755, 1960.
5. Grelinger, M.A. et al. Gap Filling PMW Emission Factors for Selected Open Area Dust
Sources, EPA-450/4-88-003 (NTIS PB88-196225), Research Triangle Park, NC,
February 1988.
6. U.S. Department of Commerce. 7987 Census of Agriculture, Bureau of the Census,
Washington, DC, 1989.
7. Saeger, M., et al The 1985 NAPAP Emissions Inventory (Version 2): Development of
the Annual Data and Modelers' Tapes, EPA-6W7-89-012a (NTIS PB91-119669), U.S.
Environmental Protection Agency, Research Triangle Park, NC, November 1989.
8. Cowherd, C.C., Jr., C.M. Guenther and D.D. Wallace. Emissions Inventory of
Agricultural Tilling, Unpaved Roads and Airstrips, and Construction Sites, EPA-450/3-
74-085 (NTIS PB238-919), U.S. Environmental Protection Agency, Research Triangle
Park, NC, November 1974.
9. U.S. Department of Agriculture, Agricultural Chemical Usage 1991: Field Crops
Summary, Ag Ch 1 (92), National Agricultural Statistics Service, Washington, DC,
March 1992.
CH-92-139 6-12
-------
SECTION 7.0
ISSUES AND RECOMMENDATIONS
7.1 INTRODUCTION
This section describes various issues and recommendations for each of the missing sources
categories discussed in this report. The discussion includes additional work which may improve
methodologies and develop new or more accurate input data and emission factors. Issues and
recommendations are included for Catastrophic/Accidental Releases (7.2), Vehicle Repair
Faculties (7.3), Recycling (7.4), Pesticide Application (7.5), and Agricultural Operations (7.6).
7.2 CATASTROPHIC/ACCIDENTAL RELEASES
A number of issues require further attention before practical methods for estimating activity
levels and emission factors associated with catastrophic/accidental releases can be generated.
Although the NRC and ERNS databases provide estimates of the number of reported
catastrophic/accidental incidents and the quantity and type of material spilled, other pertinent
information and data are lacking. For example, data on the type of cleanup, area of the spill, and
quantity of spilled material recovered are generally not available. Some additional effort should
be expended to investigate the availability of other sources or approaches for obtaining this
information. In addition, these databases do not generally include small spills, therefore,
statistical extrapolation methodologies are needed to more accurately estimate total emissions.
Finally, considering the complexity of calculating emissions from catastrophic or accidental
releases, experts on volatilization and combustion of spilled materials should be contacted for
their input on the practicality of developing simple but meaningful estimates of air pollutant
emissions from catastrophic/accidental incidents.
7.3 VEHICLE REPAIR FACILITIES
The three potential methodologies for vehicle repair facilities presented in Section 3 were based
on product sales volumes, vehicle registrations, and service operations performed, respectively.
CH-92-139 '"1
-------
Each of these methodologies requires basic information that includes the current formulation of
products used in service stations; the relative use of products by service stations, other vehicle
repair facilities, and consumers; and the distribution of product use or repair activities over time
and geographic regions. Recent interaction between EPA and automotive product industry
representatives (Chemical Specialties Manufacturers Association and Motor Equipment
Manufacturers Association) has indicated that industry is willing to assist in the development of
information that would facilitate any of the three potential approaches. In particular, cooperation
should be obtained on the determination of formulations, VOC releases, sales by geographic area,
type of product form, and end user. In addition, industry representatives should be able to
provide valuable perspective in determining appropriate methodologies for estimating emissions
from vehicle servicing.
Before further work on the three potential methodologies is conducted, an initial screening phase
is recommended to provide both structure and prioritization. This preliminary screening phase
should consist of an assessment of the three potential methodologies and existing data resources;
consultation with industry on appropriateness of specific methodologies, readily-available
information, and potential future contributions to these methodologies; and preparation of a
proposed set of methodology development efforts and a plan for carrying them out.
7.4 RECYCLING
Emissions from recycling activities in general are difficult to quantify due to the variability of
recycling programs. This variability can arise from the materials included in the recycling
program, the collection method, the sorting/segregation step, or processing. The existence or
extent of program activity in a particular area is at least partially dependent on available waste
disposal alternatives, participation rates, and state and local regulations. Therefore, emissions
estimation from recycling programs may be most accurate if performed on a city by city basis.
Due to the lack of quantitative emissions data available for many recycling processes, a series
of emissions tests should be conducted to develop emission factors. For example, PM-10
emission factors could be developed from a properly designed paniculate sampling procedure for
CH-92-139
7-2
-------
a variety of commercially available glass crushers. These factors could then be applied to glass
crushing activities at a given facility to quantify emissions. Emissions tests should also be
performed for other common recycling processes, such as shredding/grinding, air classification,
loading/unloading/conveying, delacquering/melting, compaction, and extruding.
7.5 PESTICIDE APPLICATION
Important data are still missing from the methodologies developed for pesticide applications and
were not located when researching Section 5. These data items include the VOC portion of the
pesticide that evaporates and the emission rates (VOC and PM-10) for various pesticides and
formulations by user categories (consumer, agricultural, commercial, and general). In addition,
national- or state-level statistics on commercial, municipal, and industrial pesticide usage were
not found and are necessary for methodology development.
A separate issue that could be dealt with involves developing emission factors that account for
geographic variability effects on VOC and PM-10. Various geographical effects including
temperature and soil water content, can affect emissions, however, a great amount of effort would
be needed to develop this data. Also, the effect on an overall emissions inventory for a particular
area would probably be minimal. The more important issue would probably be from an air toxics
standpoint.
7.6 AGRICULTURAL OPERATIONS
Several data items are still needed for the methodologies developed to estimate emissions from
agricultural operations. Most importantly, harvesting emission factors are needed for crops other
than cotton, wheat, and sorghum. Also, due to the lack of quantitative emissions data available
for many agricultural operations, a series of emissions tests should be conducted to develop
emission factors. For example, PM-10 emission factors could be developed from a properly
designed particulate sampling procedure for a variety of harvester types. These factors could then
be applied to harvested acres in a particular area to quantify emissions. Emissions tests should
also be performed for other common agricultural operations including plowing, fertilizing, seed
bed preparation, planting, and cultivating.
CH-92-139 7-3
-------
APPENDIX A
INDEX OF CODES
(Source: National Response Center, U.S. Coast Guard, Washington D.C.)
AAC ACETIC ACID
AAD ACETALDHYDE
AAM ACRAYLAMIDE
AAN n-AMYL ALCOHOL
AAS sec-AMYL ACETATE
AAT AMMONIUM ACETATE
ABC AMMONIUM BICARBONATE
ABF AMMONIUM BIFLUORTOE
ABM ACETYL BROMIDE
ABR ALLYL BROMIDE
ABS ALKYLBENZENESULFONIC ACIDS
ABZ AMMONIUM BENZOATE
ACA ACETIC ANHYDRIDE
ACB AMMONIUM CARBONATE
ACC ACETYL CHLORIDE
ACD ACRIDINE
ACE ACETYLENE
ACF ALLYL CHLORAFORMATE
ACH AMMONIUM CHROMATE
ACI AMMONIUM CITRATE
ACL ALUMINUM CHLORIDE
ACM AMMONIUM CARBAMATE
ACN ACRYLONITRILE
ACP ACETOPHENONE
ACR ACRYLIC ACID
ACT ACETONE
ACY ACETONE CYANOHYDRIN
ADA ADIPIC ACID
ADN ADIPONITRILE
AEE AMINOETHYLETHANOLAMINE
AEX 2-(2-AMINOETHOXY) ETHANOL
AFB AMMONIUM FLUOBORATE
AFM AMMONIUM FORMATE
APR AMMONIUM FLUORIDE
AGC AMMONIUM GLUCONATE
AHP AMMONIUM HYPOPHOSPHTTE
AID AMMONIUM IODIDE
ALA ALLYL ALCOHOL
ALC ALLYL CHLORIDE
ALD ALDRIN
ALF ALUMINUM FLUORIDE
ALM ALUMINUM SULFATE
ALN ALUMINUM NITRATE
ALS AMMONIUM LAURYL SULFATE
ALT AMMONIUM LACTATE
AMA AMMONIA, anhydrous
AMB AMMONIUM MOLYBDATE
AMC AMMONIUM CHLORIDE
AMD AMMONIUM DICHROMATE
AMF AMMONIUM SULFTTE
AMH AMMONIUM HYDROXIDE
AMK n-AMYL METHYL KETONE
AML AMYL ACETATE
AMM n-AMYL MERCAPTAN
AMN AMMONIUM NITRATE
AMP AMMONIUM PERCHLORATE
AMR AMMONIUM STEARATE
AMS AMMONIUM SULFATE
AMT AMMONIUM THIOCYANATE
AMY n-AMYL CHLORIDE
ANB AMMONIUM BROMIDE
ANI iso-AMYL NTTRILE
ANL ANILINE
ANP AMMONIUM NITRATE-PHOSPHATE
MIXTURE
ANS AMMONIUM NTTRATE-SULFATE MIXTURE
ANT n-AMYL NITRATE
ANU AMMONIUM NITRATE-UREA SOLUTION
AOL AMMONIUM OLEATE
AOX AMMONIUM OXALATE
APB AMMONIUM PENTABORATE
APC ANTIMONY PENTACHLORIDE
APE AMMONIUM PERSULFATE
APF ANTIMONY PENTAFLUORIDE
APO ARSENIC PENTAOXIDE
APP AMMONIUM PHOSPHATE
APS ACETYL PEROXIDE SOLUTION
APT ANTIMONY POTASSIUM TARTRATE
ARD ARSENIC DISULFIDE
ARF ASPHALT BLENDING STOCKS: ROOFERS
FLUX
ARL ACROLEIN
ART ARSENIC TRISULFIDE
ASA ARSENIC ACID
ASC ANISOYL CHLORIDE
ASF AMMONIUM SULFIDE
ASL AMMONIUM SILICOFLUORIDE
ASM AMMONIUM SULFAMATE
ASP ASPHALT
ASR ASPHALT BLENDING STOCKS: STRAIGHT
RUN RESIDUE
AST ARSENIC TRICHLORIDE
ASU AMMONIUM BISULFITE
ATA ACETYLACETONE
ATB ANTIMONY TRTOROMIDE
ATC ALLYLTRICHLOROSILANE
ATF AMMONIUM TfflOSULFATE
ATH ANTHRACENE
CH-92-139
A-l
-------
ATM ANTIMONY TRICHLORIDE BRX
ATN ACETONTTRILE BTA
ATO ARSENIC TRIOXIDE BTB
ATR AMMONIUM TfflOSULFATE ETC
ATS n-AMYLTRICHLOROSILANE BTD
ATT ANTIMONY TRIFLUORTOE BTF
ATX ANTIMONY TRIOXIDE BTL
ATZ ATRAZINE BTM
AYA tert-AMYL ACETATE BTN
AZM AZINPHOSMETHYL BTO
BAG BORIC ACID BTP
BAD iso-BUTYRALDEHYDE BTR
BAI iso-BUTYL ACRYLATE BUA
BAL BENZYL ALCOHOL BUD
BAM n-BUTYLAMINE BUT
BAN n-BUTYL ALCOHOL BYA
BAS sec-BUTYL ALCOHOL BZA
BAT tert-BUTYL ALCOHOL BZC
BBR BENZYL BROMIDE BZD
BBZ BROMOBENZENE BZM
BCF BENZYL CHLOROFORMATE BZN
BCL BENZYL CHLORIDE BZO
BCN n-BUTYL ACETATE
BCP BOILER COMPOUND BZP
BCR BARIUM CHLORATE CAA
BCS BUTYLTRICHLOROSILANE CAC
BCY BARIUM CHLORATE CAF
BDE BISPHENOL A DIGLYCIDYL ETHER CAH
BDI BUTADIENE CAL
EDO 1,4-BUTANEDIOL CAM
EEC BERYLLIUM CHLORIDE CAO
BEF BERYLLIUM FLUORIDE CAP
BEM BERYLLIUM CAR
BEN BERYLLIUM NITRATE CAS
BEO BERYLLIUM OXIDE CAT
BBS BERYLLIUM SULFATE CBA
BHC BENZENE HEXACHLORIDE CBB
BHP tert-BUTYL HYDROPEROXIDE CBC
BMA BENZYLTRIMETHYLAMMONIUM CHLORIDE CBD
BMN n-BUTYL METHACRYLATE CBF
BNT BARIUM NITRATE CBN
BNZ BENZENE CBO
BOC BISMUTH OXYCHLORIDE CBR
BPA BISPHENOL A CBS
BPC BARIUM PERCHLORATE CBT
BPD BENZENE PHOSPHORUS DICHLORIDE CBY
BPF BROMINE PENTAFLUORIDE CCA
BPH BUTYL BENZYL PHTHALATE CCB
BPM BARIUM PERMANGANATE CCC
BPO BARIUM PEROXIDE CCH
BPT BENZENE PHOSPHORUS TfflODICHLORIDE CCL
BRA n-BUTYRIC ACID CCN
BRC BARIUM CARBONATE CCP
BRT BORON TRICHLORIDE CCR
BRU BRUCINE CCT
BROMINE
sec-BUTYL ACETATE
BORON TRIBROMIDE
n-BUTYL ACRYLATE
1,4-BUTYNEDIOL
BROMINE TRIFLUORIDE
sec-BUTYLAMINE
n-BUTYL MERCAPTAN
BUTYLENE
1,2-BUTYLENE OXIDE
p-tert-BUTYLPHENOL
n-BUTYRALDEHYDE
tert-BUTYLAMINE
1,4-BUTENEDIOL
BUTANE
tert-BUTYL ACETATE
BENZOIC ACID
BENZOYL CHLORIDE
BENZALDEHYDE
BENZYLAMINE
BENZONITRILE
BENZYLDIMETHYLOCTADECY-
LAMMONIUM CHLORIDE
BENZOPHENONE
COPPER ACETOARSENITE
CHLOROACETYL CHLORIDE
CALCIUM FLUORIDE
CALCIUM HYDROXIDE
CALCIUM PHOSPHATE
CALCIUM
CALCIUM OXIDE
p-CHLOROANILINE
CARENE
CALSIUM ARSENTTE
CADMIUM ACETATE
COBALT ACETATE
CARBON BISULFIDE
COBALT CHLORIDE
COPPER BROMIDE (OUS)
CARBOFURAN
4-CHLOROBUTYRONrTRILE
CARBOLIC OIL
CYANOGEN BROMIDE
COBALT SULFATE
CARBON TETRACHLORIDE
CARBARYL
CALCIUM ARSENATE
CALCIUM CARBIDE
CALCIUM CHLORATE
CYCLOHEXANONE
CYANOGEN CHLORIDE
CALCIUM CYANIDE
CALCIUM PEROXIDE
CALCIUM CHROMATE
CREOSOTE, COAL TAR
CH-92-I39
A-2
-------
CCY COPPER CYANIDE (OUS)
CDA CACODYLIC ACID
CDC CADMIUM CHLORIDE
CDN CHLORDANE
CDO CARBON DIOXIDE
CES CUPRffiTHYLENE DIAMINE SOLUTION
CFB CADMIUM FLUOROBORATE
CFM COBALT FORMATE (OUS)
CGE CRESYL GLYCIDYL ETHER
CHA CYCLOHEXYLAMINE
CHC CHARCOAL
CHD CHLOROHYDRINS
CHN CYCLOHEXANOL
CHP CYCLOHEXANONE PEROXIDE
CHS CHROMIC SULFATE
CHT CYCLOHEXENYLTRICHLORO-SILANE
CHX CYCLOHEXANE
CHY CALCIUM HYPOCHLORTTE
CDD COPPER IODIDE
CIT CITRIC ACID
CLC CALCIUM CHLORIDE
CLD COLLODION
CLS CAPROLACTAM
CLT COPPER LACTATE
CLX CHLORINE
CMA CHROMIC ANHYDRIDE
CMB CADMIUM BROMIDE
CMC CHROMYL CHLORIDE
CME CHLOROMETHYL METHYL ETHER
CMH CUMENE HYDROPEROXIDE
CMN CADMIUM NITRATE
CMO CARBON MONOXIDE
CMP p-CYMENE
CMS CADMIUM SULFATE
CNI COPPER NITRATE
CNN COPPER NAPHTHENATE
CNO o-CHLORONTrROBENZENE
CNT CALCIUM NITRATE
COB COBALT BROMIDE (OUS)
COF COBALT FLUORIDE
COL COPPER OXALATE
CON COBALT NITRATE
COP COPPER ACETATE
COU COUMAPHOS
COX CADMIUM OXIDE
CPA COPPER ARSENTTE
CPB COPPER BROMIDE
CPC COPPER CHLORIDE
CPF COPPER FLUOROBORATE
CPG COPPER GLYCINATE
CPH CAMPHENE
CPL CHLOROPICRIN
CPN p-CHLOROPHENOL
CPO CAMPHOR OIL
CPP CALCIUM PHOSPHIDE
CPR CYCLOPROPANE
CPS CAUSTIC POTASH SOLUTION
CPT CAPTAN
CRA CHLOROACETOPHENONE
CRB CHLOROBENZENE
CRC CHROMOUS CHLORIDE
CRE CALCIUM RESINATE
CRF CHLOROFORM
CRL m-CRESOL
CRN p-CHLOROTOLUENE
CRO o-CRESOL
CRP CHLOROPRENE
CRS CRESOLS
CRT CHROMIC ACETATE
CSA CHLOROSULFONIC ACID
CSF COPPER SULFATE
CSN COPPER SULFATE.AMMONIATED
CSO p-CRESOL
CSS CAUSTIC SODA SOLUTION
CST COPPER SUBACETATE
CSY CORN SYRUP
CTA CROTONALDEHYDE
CTC CATECHOL
CTD 4-CHLORO-o-TOLUIDINE
CTF CHLORINE TRIFLUORIDE
CTT COPPER TARTRATE
CUF COPPER FORMATE
CUM CUMENE
CYA CYANOACETIC ACID
CYG CYANOGEN
CYP CYCLOPENTANE
DAA DIACETONE ALCOHOL
DAC DIMETHYLACETAMIDE
DAE DffiTHYLETHANOLAMINE
DAI DODECYLBENZENESULFONIC ACID,
ISOPROPYLAMINE SALT
DAL DECALDEHYDE
DAM DIPHENYLAMINE
DAN n-DECYL ALCOHOL
DAP Di-n-AMYL PHTHALATE
DAS DODECYL BENZENE SULFONIC ACID,
SODIUM SALT
DBA Di-n-BUTYLAMINE
DBC DHSOBUTYLCARBINOL
DBE DI-n-BUTYL ETHER
DBK Di-n-BUTYL KETONE
DEL DHSOBUTYLENE
DBM m-DICHLOROBENZENE
DBO o-DICHLOROBENZENE
DBP p-DICHLOROBENZENE
DBR DECABORANE
DBS DODECYLBENZENESULFONIC ACID,
TRffiTHANOLAMINE SALT
DBT DBUTYLPHENOL
DBZ n-DECYLBENZENE
CH-92-139
A-3
-------
DCA 2,4-DICHLOROPHENOXYACETIC ACID DMP
DCB DICHLCROBUTENE DMS
DCE 1-DECENE DMT
DCF DICHLORODIFLUOROMETHANE DMZ
DCH 1,1-DICHLOROETHANE DNA
DCL DICHLONE DNB
DCM DICHLOROMETHANE DNC
DCP 2,4-DICHLOROPHENOL ONE
DCS DODECYLBENZENESULFONIC ACID, DNH
CALCIUM SALT DNL
DCV DICHLORVOS DNO
DDE DODECYLBENZENE DNP
DDC 1,DODECENE DMT
ODD ODD DNU
DON DODECANOL DNZ
DOS DODECYL SULFATE, SODIUM SALT DOA
DDT DDT DOD
DDW DIMETHYLHEXANE DIHYDRO PEROXIDE OOP
DBA DffiTHANOLAMINE DOX
DEB DffiTHYLBENZENE DPA
DEC DIETHYL CARBONATE DPB
DED DffiLDRIN DGM
DEE 2,2-DICHLOROETHYL ETHER
DEC DIETHYLENE GLYCOL DPC
DEL 1,2-DICHLOROETHYLENE DPD
DEM DIETHYLENE GLYCOL MONOBUTYL ETHER DPE
ACETATE DEN DffiTHYLAMINE DPF
DEP DI(2-ETHYLHEXYL)PHOSPHORIC ACID DPG
DBS 2,4-D ESTERS DPH
DET DIETHYI.ENETRIAMINE DPM
DEZ DIETHY: INC DPN
DFA DIFLUOROPHOSPHORIC ACID DPO
DFE 1,1-DIFLUOROETHANE DPP
OFF DISTILLATES: FLASHED FEED STOCKS DPT
DGD DIETHYLENE GLYCOL DIMETHYL ETHER DPU
DGE DIETHYLENE GLYCOL MONOETHYL ETHER DSA
DHN DECAHYDRONAPHTHALENE DSD
DHP DfflEPTYL PHTHALATE
DIA DHSOPROPLYAMINE DSF
Dffi DICHLOBENIL DSL
DIG DICAMBA DSM
DID DHSODECYL PHTHALATE DSR
Dffl OnSOPROPYLBENZENE HYDRO-PEROXIDE DSS
DIK DHSOBUTYL KETONE DST
DIM DIMETHYL ETHUR
DIP DIISOPROPANOLAMINE DTC
DIQ DIQUAT DTK
DIS DISULFTON DTM
DIU DIURON
E:P DALAPON DTN
D:.iA DIMETHYLAMINE DTS
DMD DIMETHYLDICHLOROSILANE DTT
DME DIETHYLENEGLYCOL MONOBUTYL DUR
DMF DIMETHYLFORMAMIDE DZN
DMH • ;-DIMETHYLHYDRAZINE
DIMETHYLPOLYSILOXANE
DIMETHYL SULFOXIDE
DIMETHYL TEREPHTHALATE
DIMETHYLZINC
DI-n-PROPYLAMINE
m-DINITROBENZENE
DINTTROCRESOLS
2,5-DDSriTROPHENOL
2,6-DINITROPHENOL
2,6-DINITROTOLUENE
o-DINTTROBENZENE
2,4-DINITROPHENOL
2,4-DINITROANILINE
3,4-DINITROTOLUENE
p-DINTTROBENZENE
DIOCTYL ADIPATE
DODECENE
DIOCTYL PHTHALATE
1,4-DIOXANE
DIBUTYL PHTHALATE
1,1 -DICHLOROPROPANE
DIETHYLENE GLYCOL MONOMETHYL
ETHER
1,3-DICHLOROPROPANE
DIPHENYLDICHLOROSILANE
DIPHENYL ETHER
2,3-DICHLOROPROPENE
DIPROPYLENE GLYCOL
DIETHYL PHTHALATE
DIPHENYLMETHANE DHSOCYANATE
DIPENTENE
DIBENZOYL PEROXIDE
1,2-DICHLOROPROPANE
DICYCLOPENTADIENE
1,3-DICHLOROPROPENE
DODECYL BENZENE SULFONIC ACID
DODECYL SULFATE, DffiTHANOL-AMINE
SALT
DIMETHYL SULFATE
DIMETHYL SULFIDE
DODECYL SULFATE, MAGNESIUM SALT
DISTILLATES: STRAIGHT RUN
DIOCTYL SODIUM SULFOSUCCINATE
DODECYL SULFATE, TRIETHANOLAMINE
SALT
DODECYLTRICHLOROSILANE
DOWTHERM
4,4-DICHLORO-alpha-TRICHLOROMETHYl
BENZHYDROL
DEMETON
DEXTROSE SOLUTION
2,4-DINTTROTOLUENE
DURSBAN
DIAZINON
CH-92-139
A-4
-------
DZP DI-(p-CHLOROBENZOYL) EAA ETHYL
ACETOACETATE
EAC ETHYL ACRYLATE
BAD ETHYLALUMINUM DICHLORIDE
EAI 2-ETHYLHEXYL ACRYLATE
EAL ETHYL ALCOHOL
EAM ETHYLAMINE
EAS ETHYLALUMINUM SESQUI-CHLORIDE
EBA n-ETHYL-n-BUTYLAMINE
EBR ETHYL BUTYRATE
EBT ETHYL BUTANOL
ECA ETHYL CHLOROACETATE
ECF ETHYL CHLOROFORMATE
ECH ETHYL CHLOROHYDRIN
ECL ETHYL CHLORIDE
ECS ETHYLDICHLOROSILANE
EDA ETHYLENEDIAMINE
EDB ETHYLENE DffiROMIDE
EDC ETHYLENE DICHLORIDE
EDR ENDRIN
EOT ETHYLENEDIAMINE TETRACETIC ACID
EEE ETHYLENE GLYCOL DffiTHYL ETHER
EET ETHYL ETHER
EFM ETHYL FORMATE
EGA ETHYLENE GLYCOL MONO-ETHYL ETHER
ACETATE
EGD ETHYLENE GLYCOL DIMETHYL ETHER
EGE ETHYLENE GLYCOL MONO-ETHYL ETHER
EGL ETHYLENE GLYCOL
EGM ETHYLENE GLYCOL MONO-BUTYL ETHER
EGY ETHYLENE GLYCOL DIACETATE
EHA ETHYLHEXALDEHYDE
EHP ETHOXYDIHYDROPYRAN
EHT ETHYL HEXYL TALLATE
EHX 2-ETHYL HEXANOL
ELT ETHYL LACTATE
EMA ETHYLENE GLYCOL MONOBUTYL ETHER
ACETATE
EMC ETHYL MERCAPTAN
EME ETHYLENE GLYCOL MONO-METHYL ETHER
ENB ETHYLJDENE NORBORNENE
ENP ETHOXYLATED NONYLPHENOL
EOD ETHOXYLATED DODECANOL
EOP ETHOXYLATED PENTADECANOL
EOT ETHOXYLATED TETRADECANOL
BOX ETHYLENE OXIDE
EPA 2-ETHYL-3-PROPYLACROLEIN
EPC EPICHLOROHYDRIN
EPD ETHYL PHOSPHONOTfflOIC DICHLORIDE
EPP ETHYL PHOSPHORODICHLORIDATE
EPS ETHYLPHENYLDICHLOROSILANE
ESC ETHYL SILICATE
ESF ENDOSULFAN
ETA ETHYL ACETATE
ETB ETHYLBENZENE
ETC ETHYLENE CYANOHYDRIN
ETD ETHOXYLATED TRIDECANOL
ETC ETHOXY TRIGLYCOL
ETH ETHANE
ETI ETHYLENEIMINE
ETL ETHYLENE
ETM ETHYL METHACRYLATE
ETN ETHYL NITRITE
ETO ETfflON
ETS ETHYLTRICHLOROSILANE
EVO EPOXIDIZED VEGETABLE OILS
FAC FERRIC AMMONIUM CITRATE
FAL FURFURYL ALCOHOL
FAO FERRIC AMMONIUM OXALATE
FAS FERROUS AMMONIUM SULFATE
FCL FERRIC CHLORIDE
FCP FERRIC GLYCEROPHOSPHATE
FEC FERROUS CHLORIDE
FFA FURFURAL
FFB FERROUS FLUOROBORATE
FFX FERRIC FLUORIDE
FMA FORMIC ACID
FMS FORMALDEHYDE SOLUTION
FNT FERRIC NITRATE
FOX FERROUS OXALATE
FRS FERROUS SULFATE
FSA FLUOSULFONIC ACID
FSF FERRIC SULFATE
FSL FLUOSILJCIC ACID
FUM FUMARIC ACID
FXX FLUORINE
GAK GASOLINE BLENDING STOCKS:
ALKYLATES
GAT GASOLINES: AUTOMOTIVE (<4.23g lead/gal)
GAV GASOLINES: AVIATION (<4.86g lead/gal)
GCM GLYCIDYL METHACRYLATE
OCR GLYCERINE
GCS GASOLINES: CASINGHEAD
GLA GALLIC ACID
GOC GAS OIL: CRACKED
GOS GLYOXAL
GPL GASOLINES: POLYMER
GRF GASOLINE BLENDING STOCKS:
REFORMATES
GSR GASOLINES: STRAIGHT RUN
GTA GLUTARALDEHYDE SOLUTION
HAC HEXADECYLTRIMETHYL-AMMONIUM
CHLORIDE
HAI 2-HYDROXYETHYL ACRYLATE
HAL n-HEXALDEHYDE
HAS HYDROXYLAMINE SULFATE
HER HYDROGEN BROMIDE
HCC HEXACHLOROCYCLOPENTADffiNE
HCL HYDROCHLORIC ACID
HCN HYDROGEN CYANIDE
CH-92-139
A-5
-------
HDA HYDROXYLAMINE
HOC HYDROGEN CHLORIDE
HDQ HYDROQUINONE
HDS HYDROGEN SULFIDE
HDZ HYDRAZTNE
HFA HYDROFLUORIC ACID
HFX HYDROGEN FLUORIDE
HMD HEXAMETHYLENEDIAMINE
HMI HEXAMETHYLENIMINE
HMT HEXAMETHYLENETETRAMINE
HPA HYDROXYPROPYL ACRYLATE
HPM HYDROXYPROPYL METHA-CRYLATE
HPO HYDROGEN PEROXIDE
HPT HEPTANE
HSS HEXADECYL SULFATE, SODIUM SALT
HTC HEPTACHLOR
HTE 1-HEPTENE
HTN HEPTANOL
HXA n-HEXANE
HXE 1-HEXENE
HXG HEXYLENE GLYCOL
HXN n-HEXANOL
HXX HYDROGEN
IAA ISOAMYL ALCOHOL
IAC ISOPROPYL ACETATE
IAI ISODECYL ACRYLATE
IAL ISOBUTYL ALCOHOL
IAM ISOBUTYLAMINE
IAT ISOAMYLACETATE
IBA ISOBUTYL ACETATE
ffiL ISOBUTYLENE
IBN ISOBUTYRONITRILE
IBR ISOBUTYRIC ACID
ffiT ISOBUTANE
IDA ISODECALDEHYDE
fflA ISOHEXANE
IOA ISOOCTYL ALCOHOL
IOC ISOOCTALDEHYDE
IPA ISOPROPYL ALCOHOL
IPC ISOPROPYL PERCARBONATE
IPE ISOPROPYL ETHER
IPH ISOPHORONE
IPL ISOPHTHALIC ACID
IPM ISOPROPYL MERCAPTAN
IPP ISOPROPYLAMINE
IPR ISOPRENE
IPT ISOPENTANE
ISA ISODECYL ALCOHOL
IVA ISOVALERALDEHYDE
JPF JET FUELS: JP-4
JPO JET FJELS: JP-1
JPT JET ELS: JP-3
JPV JET >UELS: JP-5
KPE KEPONE
KRS KEROSENE
LAC LEAD ACETATE
LAH LITHIUM ALUMINUM HYDRIDE
NOX NITROGEN TETROXIDE
NPH 4-NITROPHENOL
NPP 2-NTTROPROPANE
NSS NAPHTHA: STODDARD SOLVENT
NSV NAPHTHA: SOLVENT
NTA 2-NrrROANILINE
NTB NITROBENZENE
NTC NTTROSYL CHLORIDE
NTE NTTROETHANE
NTI NAPHTHENIC ACIDS
NTL NITRALIN
NTM NAPHTHALENE
NTO NITROUS OXIDE
NTP 2-NTTROPHENOL
NTR m-NTrROTOLUENE
NTT p-NTTROTOLUENE
NTX NITRIC OXIDE
NVM NAPHTHA: VM & P
NXX NITROGEN
OAC OLEIC ACID, SODIUM SALT
OAN OCTANE
OAP OLEIC ACID, POTASSIUM SALT
OAS OILS, MISC.: ABSORPTION
OCA OILS, EDIBLE: CASTOR
OCC OILS, EDIBLE: COCONUT
OCF OILS: CLARIFIED
OCR OILS, MISC.: CROTON
OCS OILS, EDIBLE: COTTONSEED
OCT OILS, MISC.: COAL TAR
ODS OILS: DIESEL
GET OCTYL EPOXY TALLATE
OFR OILS, FUEL: 4
OFS OILS, EDIBLE: FISH
OFV OILS, FUEL: 5
OIL OILS: CRUDE
OLA OLEIC ACID
OLB OILS, MISC.: LUBRICATING
OLD OILS, EDIBLE: LARD
OLM OLEUM
OLS OILS, MISC.: LINSEED
OMN OILS, MISC.: MINERAL
QMS OILS, MISC.: MINERAL SEAL
OMT OILS, MISC.: MOTOR
ONF OILS, MISC.: NEATSFOOT
OOD OILS, FUEL: 1-D
OOL OLS, EDIBLE: OLIVE
OON OILS, FUEL: NO. 1
OPM OILS, EDIBLE: PALM
OPN OILS, EDIBLE: PEANUT
OPT OILS, MISC.: PENETRATING
ORD OILS, MISC.: ROAD
ORG OILS, MISC.: RANGE
ORN OILS, MISC.: ROSIN
CH-92-139
A-6
-------
ORS OILS, MISC.: RESIN
OSB OILS, EDIBLE: SOYA BEAN
OSD OILS, MISC.: SPINDLE
OSF OILS, EDIBLE: SAFFLOWER
OSP OILS, MISCELLANEOUS: SPERM
OSX OILS, FUEL: 6
OSY OILS, MISC.: SPRAY
OTA OCTANOL
OTB OILS, MISC.: TURBINE
OTC OILS, EDIBLE: TUCUM
OTD OILS, FUEL: 2-D
OTE 1-OCTENE
OTF OILS, MISC.: TRANSFORMER
OTL OILS, MISC.: TALL
OTN OILS, MISC.: TANNER'S
OTW OILS, FUEL: 2
OVG OILS, EDIBLE: VEGETABLE
OXA OXALIC ACID
OXY OXYGEN
PAA PERACETIC ACID
PAC PHOSPHORIC ACID
PAD PROPIONALDEHYDE
PAH PROPIONIC ANHYDRIDE
PAL n-PROPYL ALCOHOL
PAN PHTHALIC ANHYDRIDE
PAS POTASSIUM ARSENATE
PAT n-PROPYL ACETATE
PBO POTASSIUM BINOXALATE
PBP PROPYLENE BUTYLENE POLYMER
PBR PHOSPHORUS TROBROMIDE
PCS POLYCHLORINATED BIPHENYL
PCH POTASSIUM CHROMATE
PCL PERCHLORIC ACE)
PCM PERCHLOROMETHYL MERCAPTAN
PCP PENTACHLOROPHENOL
PCR POTASSIUM CHLORATE
PDC PENTADECANOL
PDH PARALDEHYDE
PDL PHENYLDICHLOROARSINE
PDT POTASSIUM DICHLORO-s-TRIAZINETRIONE
PET PENTAERYTHRrrOL
PFA PARAFORMALDEHYDE
PGA PYROGALLIC ACE)
PGC POLYPROPYLENE GLYCOL
PGM POLYPROPYLENE GLYCOL METHYL ETHER
PHD PHOSDRIN
PHG PHOSGENE
PHH PHENYLHYDRAZINE HYDROCHLORTOE
PHN PHENOL
PE PROPYLENEIMINE
PLB POLYBUTENE
PLP POLYPROPYLENE
PLT beta-PROPIOLACTONE
PME PROPYLENE GLYCOL METHYL ETHER
PMN n-PROPYL MERCAPTAN
PNA PROPIONIC ACE)
POA POTASSIUM ARSEMTE
POP POTASSIUM PEROXTOE
POX PROPYLENE OXEDE
PPA POLYPHOSPHORIC ACE)
PPB PHOSPHORUS BLACK
PPG PROPYLENE GLYCOL
PPI POLYMETHYLENE POLYPHENYL
ISOCYANATE
PPL PROPYLENE
PPO PHOSPHORUS OXYCHLORTOE
PPP PHOSPHORUS PENTASULFIDE
PPR PHOSPHORUS, RED
PPT PHOSPHORUS TRICHLORIDE
PPW PHOSPHORUS, WHITE
PPZ PIPERAZINE
PRA n-PROPYLAMINE
PRO PYRTOINE
PRO PROPARGITE
PRP PROPANE
PRR PYRETHRINS
PTA PENTANE
PTB PENTABORANE
PTC POTASSIUM CYAMDE
PTD POTASSIUM DICHROMATE
PTE 1-PENTENE
PTH POTASSIUM HYDROXTOE
PTI POTASSIUM IODIDE
PTL PETROLATUM
PTM POTASSIUM
PTN PETROLEUM NAPHTHA
PTO PARATfflON
FTP POTASSIUM PERMANGANATE
PTS POTASSIUM OXALATE
PTT PROPYLENE TETRAMER
QNL QUINOLINE
RSC RESORCINOL
SAB SODIUM ALKYLBENENESULFONATES
SAC SULFURIC ACE), SPENT
SAL SALICYLALDEHYDE
SAM SODEJM AMIDE
SAR SODIUM ARSENTTE
SAS SODEJM ALKYL SULFATES
SAZ SODIUM AZE)E
SBF SODEJM BffLUOREDE
SBH SODEJM BOROHYDRDDE
SBS SODEJM BISULFITE
SET SORBITOL
SCO SODEJM CACODYLATE
SCH SODEJM CHROMATE
SCL SULFURYL CHLORIDE
SCM STRONTEJM CHROMATE
SCN SODEJM CYAMDE
SCR SODEJM DICHROMATE
SCY SODEJM TfflOCYANATE
CH-92-139
A-7
-------
SDA SODIUM ARSENATE TDB
SDB SODIUM BORATE TDC
SDC SODIUM CHLORATE TDI
SDF SODIUM FLUORIDE TON
SDH SODIUM HYDRIDE TEA
SON SODIUM NITRATE TEB
SDS SODIUM SULFIDE TEC
SDT SODIUM DICHLORO-s-TRIAZINETRIONE TED
SOU SODIUM TEG
SFA SULFURIC ACID TEL
SFC SODIUM FERROCYANIDE TEN
SFD SULFUR DIOXIDE TEP
SFL SULFOLANE TES
SFM SULFUR MONOCHLORIDE TET
SFR SODIUM SILICOFLUORIDE TFA
SHC SODIUM HYDROCHLORTTE TFC
SHD SODIUM HYDROXIDE TFE
SHR SODIUM HYDROSULFIDE SOLUTION TFR
SLA SALICYLIC ACID TGC
SLD SELENIUM DIOXIDE THF
SML SODIUM METHYLATE THN
SNT SODIUM NITRITE THR
SOX SODIUM OXALATE TIA
SPH SODIUM PHOSPHATE tribasic TLI
SPP SODIUM PHOSPHATE TLO
SRA STEARIC ACID TMA
SRS SUCROSE TMC
SSC SODIUM SILICATE TML
SSE SODIUM SEUNTTE TNA
SSF SODIUM SULFTTE TOL
STC SILICON TETRACHLORIDE TPA
STF STANNOUS FLUORIDE
STO SELENIUM TRIOXIDE TPE
STR STRYCHNINE
STY STYRENE TPG
SVA SILVER ACETATE TPH
SVC SILVER CARBONATE TPO
SVF SILVER FLUORIDE TPT
SVI SILVER IODATE TRC
SVN SILVER NITRATE TRN
SVO SILVER OXIDE TSU
SVS SILVER SULFATE TTD
SXX SULFUR TIE
TAL TRIETHYLALUMINUM TTG
TAP p-TOLUENESULFONIC ACID TTN
TAS 2,4,5-TRICHLOROPHENOXYACETIC ACID, TTP
SODIUM SALT TTT
TBT TETRABUTYL TTTANATE TXP
TCA 2,4,5-TRICHLOROPHENOXY ACETIC ACID UAN
TCE TRICHLOROETHANE UDB
TCP TRICHLOROFLUOROMETHANE UDC
TCL TRTCHLORETHYLENE UNO
TCP IT 'RESYL PHOSPHATE UPO
TCS TI, 'HLOROSILANE URA
TCT TRICHLORO-s-TRIAZINETRIONE URE
TETRADECYLBENZENE
t-TRIDECENE
TOLUENE 2,4-DHSOCYNATE
TRIDECANOL
TRffiTHANOLAMINE
TRIETHYLBENZENE
TETRACHLOROETHANE
TETRAETHYL DITHIOPYROPHOSPHATE
TRffiTHYLENE GLYCOL
TETRAETHYL LEAD
TRIETHYLAMINE
TETRAETHYL PYROPHOSPHATE
2,4,5-T ESTERS
TRIETHYLENETETRAMINE
TALLOW FATTY ALCOHOL
TRIFLUOROCHLOROETHYLENE
TETRAFLUOROETHYLENE
TRIFLURALIN
TRIPOPYLENE GLYCOL
TETRAHYDROFURAN
TETRAHYDRONAPHTHALENE
THIRAM
TRnSOBUTYLALUMINUM
o-TOLUIDINE
TALLOW
TRIMETHYLAMINE
TRIMETHYLCHLOROSILANE
TETRAMETHYL LEAD
TANNIC ACID
TOLUENE
2-(2,4,5-TRICHLOROPHENYOXY)
PROPANOIC ACID
2-(2,4,5-TRICHLOROPHENOXY) PROPANOI
ACID, ISOOCTYL ESTER
TfflOPHOSGENE
TRICHLOROPHENOL
TRIS(AZIRIDINYL)PHOSPHINE OXIDE
TURPENTINE
TRICHLORFON
THORIUM NTTRATE
THALLIUM SULFATE
1-TETRADECENE
TETRACHLOROETHYLENE
TETRAETHYLENE GLYCOL
TETRADECANOL
TETRAETHYLENEPENTAMINE
TITANIUM TETRACHLORIDE
TOXAPHENE
URANYL NITRATE
n-UNDECYLBENZENE
1-UNDECENE
UNDECANOL
UREA PEROXIDE
URANYL ACETATE
UREA
CH-92-139
A-8
-------
URP URANIUM PEROXIDE
URS URANYL SULFATE
VAL VALERALDEHYDE
VAM VINYL ACETATE
VCI VINYLIDENE CHLORIDE
VCM VINYL CHLORIDE
VEE VINYL ETHYL ETHER
VFI VINYL FLUORIDE
VME VINYL METHYL ETHER
VNT VINYLTOLUENE
VOT VANADIUM OXYTRICHLORIDE
VOX VANADIUM PENTOXIDE
VSF VANADYL SULFATE
VTS VINYLTRICHLOROSILANE
WCA WAXES: CARNAUBA
WPF WAXES: PARAFFIN
XLM m-XYLENE
XLO o-XYLENE
XLP p-XYLENE
XYL XYLENE
ZAC znsrc AMMONIUM CHLORIDE
ZAR ZINC ARSENATE
ZBC ZINC BICHROMATE
ZBO ZINC BORATE
ZBR ZINC BROMIDE
ZCA ZIRCONIUM ACETATE
ZCB ZINC CARBONATE
ZCL ZINC CHLORIDE
ZCN ZINC CYANIDE
ZCO ZIRCONIUM OXYCHLORIDE
ZCR ZINC CHROMATE
ZCS ZIRCONIUM SULFATE
ZCT ZIRCONIUM TETRACHLORIDE
ZDP ZINC DIALKYLDITHIOPHOSPHATE
ZEC ZECTRAN
ZFB ZINC FLUOROBORATE
ZFM ZINC FORMATE
ZFX ZINC FLUORIDE
ZHS ZINC HYDROSULFITE
ZIR ZIRCONIUM NITRATE
ZNA ZINC ACETATE
ZNT ZINC NITRATE
ZPC ZINC POTASSIUM CHROMATE
ZPF ZIRCONIUM POTASSIUM FLUORIDE
ZPP ZINC PHOSPHIDE
ZPS ZINC PHENOLSULFONATE
ZSF ZINC SULFATE
ZSL ZINC SnJCOFLUORIDE
CH-92-139 A-9
-------
APPENDIX B
HYPOTHETICAL EXAMPLE OF AN NRC ACCIDENT REPORT
Date: 01/01/92 Time: 1020 D.O. SJS
Report* 1
(A) Reporting Company: ABC Trucking CO. Type: PE
Spffler? T
Address: P.O Box 100
City: Anytowne State: NC Zip: 11111
(B) Suspected Discharger: Type:
Address:
City: State: Zip:
Spill Date: 12/31/91 Spill Time: 1420 Location:
City: Noname County: Hambone State: NC
Description: Intersection of hwy 1 and hwy 2
CHRIS Code Material Name Total Qty Units In Water Units
ACR Acrylic Acid 2,500.00 GAL 0.00 NONE
Source/Cause: Tanker truck struck by train.
Transportation Mode: Highway
Affected Medium: Land
Medium description: Soil and Pavement
Injuries: Fatalities: Evacuation: Damage? Amountf$:
Caller Notified:
Remedial Action / Additional Information
Unknown railroad company
National Responce Center Notifications
Time Agency
1048 EPA Region 4
CH-92-139 B-l
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/R-93-045
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE identification and Characterization of
Five Non-traditional Source Categories: Catastrophic/
Accidental Releases, Vehicle Repair Facilities, Recy-
cling. Pesticide Application, and Agricultural
5. REPORT DATE
March 1993
6. PERFORMING ORGANIZATION CODE
Operations
7. AUTHORIS) s> sieva, J. Pendola, J. McCutcheon, and
K.Jones (TRC); and S.Kersteter
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS TKC
10. PROGRAM ELEMENT NO.
tal Corp. , 100 Europa Dr. , Suite 150, Chapel Hill, NC
27514; and Science Applications International Corp. ,
206 University Tower, 3101 Petty Rd. , Durham, NC
27707
11. CONTRACT/GRANT NO.
68-D9-0173, Tasks 2/220 and
3/304
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Air and Energy Engineering Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final; 9/91- 9/92
14. SPONSORING AGENCY CODE
EPA/600/13
is. SUPPLEMENTARY NOTES AEERL project officer is E. Sue Kimbrough. MD-62. 919/541-
2612.
16. ABSTRACT The report gives results of work that is part of EPA's program to identify
and characterize emissions sc es not currently accounted for by either the exis-
ting Aerometric Information R*. xeval System (AIRS) or State Implementation Plan
(SIP) area source methodologies and to develop appropriate emissions estimation
methodologies and emission factors for a group of these source categories. Based on
the results of the identificati n and characterization portions of this research, five
source categories were selected for methodology and emission factor development:
catastrophic/accidental releases, vehicle repair facilities, recycling, pesticide ap-
plication, and agricultural operations. The report gives emissions estimation meth-
odologies and emission factor data for these source categories. The discussions of
each category include general background information, emissions generation activi-
ties, pollutants emitted, sources of activity and pollutant data, emissions estimation
methodologies, issues to be considered, and recommendations. The information used
in these discussions was derived from various sources including available literature,
industrial and trade association publications and contracts, experts on the category
and activity, and knowledgeable federal and state personnel.
7.
KEY
AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. cos AT i Field/Group
Pollution
Emission
Estimating
Identifying
Properties
Analyzing
Accidents
Vehicles
Repair Shops
Circulation
Pesticides
Agriculture
Pollution Control
Stationary Sources
Characterization
Accidental Releases
Recycling
Pesticide Application
13 B
14G
14B
13 L
15E
06F
02
3. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
205
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
B-2
-------
|