EPA-453/R-92-011
United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park NC 27711
EPA-453/R-92-011
March 1993
Air
EPA Alternative Control
Technology Document
Control of VOC Emissions
From the Application of
Agricultural Pesticides
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Alternative Control
Technology Document
Control of VOC
Emissions from the
Application of
Agricultural Pesticides
X
Emission Standards Division
U. S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Radiation
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
March 1993
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DISCLAIMER
This report has been reviewed by the Emission Standards
Division of the Office of Air Quality Planning and Standards,
U. S. Environmental Protection Agency, and approved for
publication. Mention of trade names or commercial products is
not intended to constitute endorsement or recommendation of use.
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TABLE OF CONTENTS
Page
List of Figures viii
List of Tables ix
1.0 INTRODUCTION 1-1
2.0 SUMMARY 2-1
3.0 SOURCE CHARACTERIZATION AND PROCESS DESCRIPTION . . 3-1
3.1 PESTICIDES . 3-1
3.1.1 Herbicides ........ 3-1
3.1.2 Insecticides .............. 3-2
3.2 PESTICIDE FORMULATION ............. 3-2
3.2.1 Formulation Process 3-2
3.2.2 Types of Formulations 3-3
3.3 PESTICIDE APPLICATION 3-10
3.3.1 Liquid Pesticide Application 3-11
3.3.2 Dry Pesticide Application 3-14
3.3.3 Fumigation 3-15
3.3.4 Aerial Pesticide Application 3-17
3.3.5 Maintenance and Calibration ....".. 3-17
3.3.6 Minimizing Drift 3-17
3.3.7 Pesticide Application: Sources of VOC
Emissions 3-18
3.4 PESTICIDE USE AND TRENDS IN THE UNITED STATES . 3-27
3.4.1 Pesticide Use in the United States ... 3-28
3.4.2 Agricultural Pesticide Usage by Product 3-31
3.4.3 Trends in Agricultural Pesticide Use . . 3-36
3 .5 REFERENCES FOR SECTION 3.0 3-37
4.0 EMISSION ESTIMATION METHODOLOGIES 4-1
4.1 BACKGROUND 4-1
4.1.1 California Pesticide Usage 4-2
4.1.2 Resources for the Future 4-2
4.1.3 RFF Data Base Summary . 4-3
4.1.4 U.S. Department of Agriculture Data . . 4-5
111
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TABLE OF CONTENTS (continued)
Page
4.2 VOC EMISSION CALCULATION METHODS 4-6
4.2.1 Laboratory Test Method 4-6
4.2.2 The CARS Method for VOC Emission
Estimate Calculations .. 4-8
4.2.3 Use of Formulation Data . 4-11
4.3 ESTIMATION EQUATION 4-19
4.4 ESTIMATED VOC EMISSIONS 4-20
4.5 REFERENCES FOR SECTION 4.0 4-28
5.0 EMISSION REDUCTION TECHNIQUES 5-1
5.1 REFORMULATION OF LIQUID PESTICIDES . 5-2
5.1.1 Option Description 5-2
5.1.2 Benefits and Limitations 5-3
5.1.3 Emission Reduction Potential 5-4
5.2 REDUCED FUMIGANT USAGE 5-5
5.2.1 Option Description ...... 5-5
5.2.2 Benefits and Limitations 5-6
5.2.3 Emission Reduction Potential ...... 5-7
5.3 ALTERNATIVE APPLICATION METHODS . " 5-8
5.3.1 Option Description 5-8
5.3.2 Benefits and Limitations 5-9
5.3.3 Emission Reduction Potential ...... 5-9
5.4 MICROENCAPSULATION . 5-10
5.4.1 Option Description 5-10
5.4.2 Benefits and Limitations 5-11
5.4.3 Emission Reduction Potential 5-12
5.5 INTEGRATED PEST MANAGEMENT 5-12
5,5.1 Option Description 5-12
5.5.2 Benefits and Limitations 5-14
5.5.3 Emission Reduction Potential 5-14
IV
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TABLE OF CONTENTS (continued)
Page
5.6 REDUCED USAGE OF SELECTED PESTICIDE AI'S ... 5-14
5.6.1 Option Description 5-14
5.6.2 Benefits and Limitations 5-15
5.7 REDUCED USAGE OF CROP OILS 5-16
5.7.1 Option Description 5-16
5.7.2 Benefits and Limitations 5-17
5.7.3 Emission Reduction Potential 5-17
5.8 REFERENCES FOR SECTION 5.0 5-17
6.0 ENVIRONMENTAL ANALYSIS 6-1
6.1 AIR POLLUTION 6-1
6.1.1 Reformulation 6-1
6.1.2 Example of Reduced Fumigant Usage ... 6-3
6.1.3 Use of Alternative Application Methods . 6-3
6.1.4 Increased Use of Microencapsulated
Pesticides 6-3
6.1.5 Integrated Pest Management 6-4
6.1.6 Crop Oils 6-4
6.1.7 Active Ingredients 6-4
6.2 WATER POLLUTION ..... 6-4
6.2.1 Surface Water 6-5
6.2.2 Groundwater ...... 6-5
6.3 SOLID WASTE DISPOSAL 6-6
6.4 ENERGY ..... 6-7
6.5 BIOTA 6-7
6.6 REFERENCES FOR SECTION 6.0 6-8
7.0 CONTROL COST IMPACTS 7-1
7.1 REFORMULATION 7-1
7.1.1 Production Costs 7-2
7.1.2 Registration Costs ...... 7-2
7.2 APPLICATOR EQUIPMENT COSTS 7-7
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TABLE OF CONTENTS (continued)
Page
7.3 FUMIGANTS 7-9
7.3.1 Fumigants and Fumigant Alternatives . . 7-9
7.3.2 U.S. Department of Agriculture Study . . 7-9
7.4 ALTERNATIVE APPLICATION METHODS 7-11
7.5 MICROENCAPSULATION 7-11
7.6 INTEGRATED PEST MANAGEMENT (IPM) 7-12
7.7 REDUCED USAGE OF SELECTED PESTICIDES 7-12
7.8 REDUCED USAGE OF CROP OILS 7-13
7.9 REFERENCES FOR SECTION 7.0 . 7-13
8.0 REVIEW OF EXISTING REGULATIONS . 8-1
8.1 FEDERAL REGULATIONS 8-1
8.1.1 FIFRA and FDCA . 8-1
8.1.2 Other Federal Regulations . 8-8
8.2 STATE OF CALIFORNIA 8-11
8.2.1 Registration . 8-11
8.2.2 Labeling ......... 8-13
8.2.3 Inert Ingredients 8-13
8.2.4 Application 8-13
8.3 OTHER STATES 8-16
8.3.1 Registration 8-16
8.3.2 Labeling 8-19
8.3.3 Inert Ingredients 8-19
8.3.4 Application . 8-19
8.4 REFERENCES FOR SECTION 8.0 8-24
VI
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TABLE OF CONTENTS (continued)
Page
APPENDIX A. CALIFORNIA PESTICIDE DATA A-l
APPENDIX B. RESOURCES FOR THE FUTURE DATA BASE B-l
APPENDIX C. LABORATORY TEST PROCEDURES FOR VOC CONTENT IN
PESTICIDES C-l
APPENDIX D. OPP INERT INGREDIENTS POLICY STATEMENT ... D-l
VI1
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LIST OF FIGURES
Number Page
3-1 Total Agricultural Pesticide Use in the United
States 3-29
viii
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LIST OF TABLES
Number Page
2-1 Summary of VOC Emissions From Insecticides
and Herbicides 2-2
3-1 Comparison of Pesticide Formulations 3-5
3-2 Liquid Pesticide Application Equipment .... 3-13
3-3 Dust and Granule Application Equipment .... 3-16
3-4 Vapor Pressure Data for Selected Pesticide
Formulation Components ..... 3-20
3-5 Annual U.S. Agricultural Pesticide Use .... 3-30
3-6 Pesticide Use on Major Crops by Class 3-30
3-7 Annual Agricultural Use of Herbicides and
Insecticides 3-30
3-8 U.S. Annual User Expenditures on Pesticides . . 3-32
3-9 Annual Usage Estimates for the Leading
Pesticides by Volume in the United States ... 3-33
3-10 Application of Pesticides by Field Crops ... 3-34
4-1 Summary of Pesticide Volatilization Studies . . 4-13
4-2 Nationwide Solvent VOC Emission Estimates for
Insecticide Formulations 4-21
4-3 Ozone Nonattainment Area VOC Emission Estimates
for Insecticide Formulations . 4-22
4-4 Nationwide Solvent VOC Emission Estimates for
Herbicide Formulations 4-24
4-5 Ozone Nonattainment Area VOC Emission Estimate
Calculations for Herbicide Formulations .... 4-26
6-1 Summary of Estimated Emission Reductions ... 6-2
7-1 Summary of Estimated Costs for Registration . . 7-4
7-2 Summary of Cost Estimates for FIFRA Study
Areas 7-6
7-3 Summary of Estimated Costs for Amended or
"Me-Too" Registration 7-6
7-4 Summary of Applicator Equipment Costs 7-8
8-1 Summary of State Regulations 8-17
ix
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1.0 INTRODUCTION
In the 1990 Clean Air Act Amendments, Sections 107 and 110
provide that each State has the primary responsibility to ensure
that the air quality within the entire geographical area of the
State meets national-standards by submitting an implementation
plan. This plan specifies the manner in which the National
Ambient Air Quality Standards (NAAQS) will be achieved and
maintained within each air quality control region of the State.
If- any region does not meet the NAAQS for a given pollutant, the
area is designated as a nonattainment area. Each area designated
as nonattainment for ozone, pursuant to Section 107, will be
classified according to the degree of severity defined in Section
181 and a primary standard attainment date provided based on that
classification. These attainment dates range from 3 years after
enactment to 20 years after enactment.
In many States, some of the ozone nonattainment areas are
comprised primarily of agricultural counties where a potentially
significant contribution to the ozone may result from area
sources of volatile organic compounds (VOC's) emissions. A
potential source of VOC emissions in agricultural counties is the
release of organic compounds from the application of agricultural
pesticides. This report provides technical information that
State and local agencies can consider while developing strategies
for reducing VOC emissions. The focus of past work and study of
VOC emission reduction from agricultural pesticide application
has been on the solvent content in formulations of emulsifiable
concentrates. In addition to reducing the VOC content in
solvent-based liquid pesticides, reasonable control alternatives
include reducing the use of organic fumigants and improving the
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efficiency of application methods. In general, these control
alternatives can be applied to agricultural pesticides; however,
there may not be an alternative formulation for a given
emulsifiable concentrate or a pesticide substitute for a fumigant
in a certain situation.
An active ingredient in a synthesized pesticide is a VOC if
it is an organic compound and the AI has the potential to be
released into the atmosphere upon application. However, because
the vapor pressure of active ingredients usually is very low and
information on the fate of applied active ingredients usually is
not available, there may be much uncertainty in actual versus
potential emissions. In addition, it can be very difficult and
costly to identify or develop a substitute active ingredient.
This control option is perhaps the most undesirable. The
information in this document will allow planners to (1) identify
available alternative techniques for reducing VOC emissions from
the agricultural application of pesticides; (2) determine the
level of solvent VOC emissions and potential emission reductions;
and (3) evaluate the cost and environmental impacts associated
with implementing one or more of these techniques.
This document provides information on the total quantities
of pesticides used nationwide and in ozone nonattainment areas,
estimated VOC emissions and potential emission reductions, and
estimated costs and implications associated with alternative
techniques. Two methods are described for the determination of
the organic solvent VOC content of pesticide formulations. The
information presented in this document was obtained over 3 years
through literature searches, existing pesticide data bases, and
numerous discussions with EPA Office of Pesticide Programs
personnel, State and county agricultural extension personnel,
university agricultural personnel, pesticide manufacturers,
industry trade associations, farm equipment manufacturers, and
the California Air Pollution Control Officers Association
(CAPCOA) Pesticides Solvents Task Force. Section 2.0 presents a
summary of the findings of this study. Section 3.0 provides a
description of the agricultural pesticide industry and the
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processes emitting VOC's. Section 4.0 presents the estimated
total quantities of the major active ingredients used and solvent
VOC emissions from the agricultural application of pesticides on
a nationwide basis and in ozone nonattainment areas. Section 5.0
discusses an array of VOC emission reduction techniques, the
benefits and limitations of each technique, and the emission
reduction potential. Sections 6.0 and 7.0 present a summary of
the environmental impacts and the cost impacts, respectively,
that may result from implementing the alternative control
techniques. Section 8.0 discusses existing Federal and State
regulations that apply to the pesticide industry. Appendix A
presents a summary of the data base derived from the 1987
California Pesticide Use Report (PUR) and summary tabulations
from the data base. Appendix B provides a summary of the data
derived from the Resources for the Future data bases on
nationwide herbicide and insecticide usage. Appendix C presents
a summary of two analytical methods for determining the solvent
VOC content of pesticide formulations.
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2.0 SUMMARY
The purpose of this document is to provide technical
information that State and local agencies can use to develop
strategies for reducing volatile organic compound (VOC) emissions
from the application of pesticides for agricultural purposes.
Emphasis is placed on the solvent content of the pesticide
formulation. This section presents the findings of this study
including an estimation of solvent VOC emissions on a total
nationwide basis and nationwide in ozone nonattainment areas,
potential VOC reduction techniques based on the organic solvent
content of the formulation, and the estimated solvent VOC
emission reductions for each technique. Although emissions were
not estimated for active ingredients, control techniques are
discussed.
In most State and Federal laws, pesticides are termed
economic poisons and are classified either according to the type
of pest they are used to control or by their mode of action.
Although there are more than 25 pesticide classes, the most
widely used agricultural pesticides are herbicides and
insecticides. These two classes compose approximately 80 percent
of the total agricultural use of pesticides. The active
ingredient in these pesticides is packaged, or formulated, for
use in many different ways, depending upon the specific active
ingredient and the intended use of the product. Non-aqueous
liquid formulations have the greatest potential to emit VOC's
because of the volatile organic solvents used to prepare the
commercial product.
A summary of annual active ingredient (AI) usage and solvent
VOC emissions for insecticides and herbicides is presented in
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Table 2-1. The basis for these data and all AI usage and solvent
VOC emission estimates in this document is the database for
insecticides and herbicides developed by Resources for the Future
(RFF). Data are presented for total AI usage and emissions from
the solvent on a nationwide basis and for only nonattainment
areas. Estimations of VOC emissions from insecticides in ozone
nonattainment areas were made indirectly based on a proration of
herbicide data for VOC emissions nationwide and in nonattainment
areas. The total estimated combined VOC emissions due only to
nonaqueous solvents from agricultural herbicide and insecticide
applications are about 46,400 tons per year on a nationwide basis
and about 4,800 tons per year in nonattainment areas. The use of
total solvent quantities to estimate VOC emissions assumes
complete volatilization of organic solvents, e.g., xylene.
TABLE 2-1. SUMMARY OF ESTIMATED TOTAL AI USAGE
AND SOLVENT VOC EMISSIONS FROM INSECTICIDES AND HERBICIDES
Total nationwide -solvent
VOC emissions, tons/yr
Total nonattainment -solvent
VOC emissions, tons/yr
Total nationwide-AI usage
tons/yr
Total nonattainment-AI
usage tons/yr
Insecticides3
3,300
800
43,800
10,000
Herbicides3
43,100
4,000
212,000
26,000
Total3
46,400
4,800
255,800
36,000
3A11 usage data and emissions estimates are based on information
in the 1982-1984 and 1987-1989 Resources of the Future (RFF)
data bases.
In light of the uncertainties surrounding the fate of the
active ingredients, VOC emissions were not estimated for the
approximately 256,000 tons of active ingredients applied
annually. Active ingredients, except for fumigants, typically
have very low vapor pressures. Degradation, adsorption, and
absorption compete with volatilization for the fate of the
pesticide. Table 4-1 contains a summary of pesticide
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volatilization studies. Losses for 16 active ingredients from
application and post-application are presented. The California
Air Resources Board (GARB) has developed a method for estimating
emissions from pesticides. The CARS method, presented in
Appendix A, accounts for losses during application, losses from
soil or vegetation, and losses to competing mechanisms. Although
the CARB method is reasonable, more experimental data are needed
to better quantify the VOC emissions from active ingredients in
pesticides.
The results of the study indicate that several technically
viable methods may apply for reducing VOC emissions resulting
from the application of agricultural pesticides. These
techniques may be used singly or in combination to achieve the
desired level of VOC emission reduction. However, if multiple
techniques are suggested, the emission reduction potentially
achieved will not be the sum of the individual reduction
techniques. Since all the emission reductions were estimated
from the baseline condition, after one technique has been
implemented, subsequent implementation of additional techniques
will have a reduced effect from that discussed in this document.
Nonetheless, implementing more than one technique will result in
reductions greater than if only one technique were applied. The
techniques identified as technically viable for reducing VOC
emissions from the application of agricultural pesticides are:
1. Reformulating organic solvent containing pesticide
formulations (e.g., emulsifiable concentrates);
2. Reducing fumigant usage;
3. Using alternative application methods;
4. Applying microencapsulation techniques;
5. Using integrated pest management (IPM) ;
6. Using alternative active ingredients; and
7. Reducing the use of crop oils.
Reformulating existing organic solvent containing pesticides can
be an effective technique to eliminate or reduce VOC emissions
due to the inert constituents, primarily volatile organic
solvents. These solvent-based formulations are widely used
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because of low formulation cost and ease of application. A
reformulation requirement, implemented over a period of time,
would allow time for development and testing of.new formulations.
The reformulation technique is less costly and time consuming
than development of a new active ingredient, which can be a long
and costly process for the manufacturer. The annual volatile
organic solvent (VOC) contribution to liquid pesticide
formulations (e.g., emulsifiable concentrates) is about
93 million pounds (46,400 tons/yr). Of the 46,400 tons/yr,
approximately 15,000 tons/yr are found in emulsifiable
concentrates and the remainder is present in other organic
solvent based liquid formulations. Many manufacturers and
formulators of organic -solvent based liquid pesticide
formulations, in particular emulsifiable concentrates, are
attempting to reformulate these products.
Reducing the use of fumigants would lead to a significant
decrease in VOC emissions in those States that have a significant
usage of field-applied fumigants. In particular, States such as
California, Florida, and Texas may benefit from the reduced
usage. For many uses, alternative treatment methods or pesticide
formulations are available or could be developed. However, if
the alternative fumigant is less effective than the compound
being replaced, higher application rates may be necessary. This
could lead to an increase in VOC emissions. Because a reduction
in usage and not an outright ban would occur, the adverse impacts
would be considerably lessened on the growers who must use
fumigation. Fumigants represent a-large emission reduction
potential, and a maximum reduction could approximate 41.5 million
pounds per year (20,700 tons/yr). This value represents the
amount of ethylene dibromide (EDB) and dibromochloropropane
(DBCP) used annually as soil fumigants as reported in the RFF
data base (1982-1984). Registration for the agricultural use of
these two active ingredients has since been cancelled; however,
it is assumed that an equal quantity of substitute fumigants,
which are also VOC's, has replaced EDB and DBCP. Emission
reduction potential for fumigants is discussed in Section 5.2.
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Another potential reduction technique is the development and
use of alternative improved-efficiency application equipment.
One study in California with reduced-volume sprayers indicated a
reduction in pesticide application quantities in the 30 to
50 percent range. In addition to the decrease in application
quantities, using this equipment may significantly reduce worker
exposure and, depending upon the applicator, may reduce
drift-related problems.
Microencapsulation is a process whereby very small particles
or droplets of the active ingredient are encased by a coating to
form very small capsules. Most microcapsules can be envisioned
to be small spheres having diameters of a few micrometers to a
few millimeters. Using microencapsulation, to the extent it is
feasible, could result in a major reduction in VOC emissions from
organic solvents in pesticides currently formulated as liquids or
emulsifiable concentrates. This technique is not applicable to
all active ingredients, but current limitations on this method
often are more economic than technical for the manufacturer.
Integrated pest management (IPM) programs use numerous
methods to control pests, including pesticides. IPM results in a
more effective use of pesticides and, under certain
circumstances, may be a mechanism to potentially reduce the
overall usage of pesticides. An IPM program is a pest population
management system which integrates chemical, biological, and
cultural methods into a program to reduce or so manipulate pest
populations that these populations are maintained at tolerable
levels while providing protection against hazards to humans,
domestic animals, and the environment. The IPM program has been
used with varying degrees of success for more than 20 years and,
in selected instances, can be an effective program. In the
optimum situation, IPM can play a significant role in the
reduction of pesticide use, overall pesticide exposure to humans,
contamination of the environment, and potential impacts on
endangered and other species of wildlife.
Two other techniques that could be implemented are the
reduced usage of selected active ingredients in formulations and
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a reduced usage of crop oils. Both of these techniques require
that alternative formulations or the same formulation using
lower-VOC-content solvents can be developed or are already
available. Use of these techniques could be directed towards
selected crops or certain seasons of the year but neither of
these techniques are anticipated to be major methods to reduce
VOC emissions.
A plan to reduce the total usage of specific pesticide
active ingredients could be initiated to target those products
for which lower-VOC active ingredient substitutes are readily
available or could be developed. This technique may also be
employed if the use of the active ingredient at current levels is
considered optional or marginal. Careful analyses must be
performed to ensure that the alternative active ingredient
formulation would not increase VOC emissions due to a
significantly higher application rate necessary to achieve the
same efficacy as the active ingredient being replaced.
Crop oils are petroleum-based products used as herbicides,
carriers for synthetic herbicides, or insecticides. Typically,
crop oils are used as insecticides where the application is
designed to kill the insects by suffocation but allow the plant
to remain unharmed. The use of crop oils has been decreasing in
favor of synthetic substitutes that have lower VOC-emitting
potential because of lower application rates.
These seven VOC emission reduction techniques have many
potential impacts on current pesticide application methods.
Implementation of these techniques may result in corresponding
increased costs. Some of the techniques are based on an overall
reduction in pesticide usage whereas others necessitate a change
in the current formulation of the pesticide. Very few cost data
were available, but the most significant cost impacts are likely
to be Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA)
registration costs incurred by the manufacturers. With many of
the techniques, no change in applicator equipment will be
necessary for the consumer. For some techniques, the farmer may
need to purchase new or special equipment. The cost impact to
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the fanner depends upon the equipment owned by the farmer, size
of the farm, type of crops, and the chosen alternative
application method.
Please note that three independent data bases are discussed
in this report. The National Pesticide Use Inventory compiled by
RFF was used for emission and usage estimates in this report.
The RFF data base reflects usage of herbicides during 1987-1989
and insecticides during 1982-1984. The 1987 California Pesticide
Use Report compiled by the Department of Pesticide Regulation
(formerly compiled by the Department of Food and Agriculture) is
presented for the reader's information in Appendix A. Data from
the 1991 Field Crops Summary published by the U. S. Department of
Agriculture were used in Table 3-10, which gives 1991 usage
estimates for the top 30 pesticides used on eight crops.
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3.0 SOURCE CHARACTERIZATION AND PROCESS DESCRIPTION
This section provides a profile of agricultural pesticide
use. It discusses the major pesticide categories (Section 3.1),
presents information on formulations (Section 3.2) and
application processes (Section 3.3), and provides data on
pesticides use and trends (Section 3.4).
3.1 PESTICIDES
In most State and Federal laws, pesticides are called
economic poisons and are defined as "any substance used for
controlling, preventing, destroying, repelling, or mitigating any
pest." Pesticides are classified either according to the type of
pest they are used against (for example, fungicides kill fungi)
or by their mode of action (for example, growth regulators
stimulate or retard the growth of plants or insects). Although
there are more than 25 pesticide classes, the most widely used
pesticides, particularly in agriculture, are herbicides and
insecticides.
3.1.1 Herbicides
Herbicides are chemical weed killers that are used
extensively on farms and other areas. Herbicides are grouped
using a multiple-classification system based on selectivity, mode
of action (contact versus translocation), timing of application,
and areas covered. Herbicides are classed as selective when they
are used to kill weeds without harming the crop and as
nonselective when the purpose is to kill all vegetation. Contact
herbicides kill the plant parts to which the chemical is applied,
whereas translocated (systematic) herbicides are absorbed by
roots or above-ground parts of plants and then circulate within
the plant system to distant tissues.1
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Preplant herbicides are applied to an area a few days or
weeks before the crop is planted. Preemergent herbicides are
applied after planting but before the crop or weed emerges.
Postemergent herbicides are applied after the crop or weed
emerges from the soil. Banded herbicide applications treat a
continuous strip, as along or in a crop row. Broadcast herbicide
applications cover an entire area, including the crop. Spot
herbicide treatments are made to small areas of weeds. Directed
herbicide sprays are applied to selected weeds or to the soil to
avoid contact with the crop.
Herbicides are also grouped according to chemical
classification. Most herbicides used today are synthetic organic
compounds. Although inorganic compounds were, in fact, the first
chemicals used to control weeds, they are gradually being
replaced by organic compounds. The EPA restricted the use of
inorganic compounds because of their persistence in soil.
3.1.2 Insecticides
Until the introduction of synthetic organic insecticides in
1940, a variety of materials had been used as insecticides,
including extracts of pepper and tobacco, vinegar, turpentine,
fish oil, brine, sulfur, hydrogen cyanide gas, and petroleum
oils. Since the introduction of synthetic organic insecticides,
a variety of compound classes have been used, including
organochlorines, organophosphates, organosulfurs, carbamates,
formamidines, dinitrophenols, and synthetic pyrethroids.1 These
compound classes have various modes of action including physical
toxicants, axonic poisons, central nervous system synaptic
poisons, enzyme inhibition, metabolism inhibition, and narcotics.
3.2 PESTICIDE FORMULATION
This section presents a brief description of pesticide
formulations and overviews of the more common types of
formulations.
3.2.1 Formulation Process
Developing and manufacturing an active ingredient is only
the first step in developing an effective pesticide. A pesticide
is rarely used or applied in its pure state; instead, it is first
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processed into a more usable form that is applied directly or
diluted in the field and then applied. This process is known as
formulation. Pesticides are formulated in order to improve their
storage, handling, application, effectiveness, and safety
properties. The manufacturer of an active ingredient may
formulate the final product or sell the active ingredient to a
formulator. The formulator may then sell the pesticide under the
formulator's brand name or may custom-formulate a product for
another firm who sells the product using the firm's brand name.
Many different components may be included in a formulation,
depending on the type of formulation and its intended use. In
addition to containing a specific concentration of an active
ingredient, a formulation may include inert ingredients such as
emulsifiers, wetting agents, solvents, thickeners, and anticaking
compounds. The right c.ombination of all of these constituents is
necessary to ensure an effective final product.
A number of factors are involved in choosing the most
appropriate formulation type for an active ingredient. Among
these factors are the chemical and physical properties of the
active ingredient, including its state (liquid or solid),
solubility (oil, water, or neither), melting point, and
stability.1 Other factors considered in selecting a formulation
type are packaging requirements, storage and handling problems,
worker safety, and method of application. In many cases, one
formulation of an active ingredient may be best suited for one
purpose, while a different formulation is more appropriate for
another application. Several types of formulations might be
used, depending on the desired end use of the product, although
there are cases in which the chemical and physical properties of
the active ingredient preclude all but one formulation type.
3.2.2 Types of Formulations
Pesticides are generally classified according to their final
form or method of application. Sprays, dusts, aerosols,
granules, fumigants, and microencapsulations are common types of
formulations. Some of these categories are further divided
intomore specific subcategories. The advantages and
3-3
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disadvantages of each formulation type are summarized in
Table 3-1. The following subsections present an overview of the
most common formulation types.
3.2.2.1 Sprays
3.2.2.1.1 Emulsifiable concentrates. Emulsifiable
concentrates are concentrated solutions of active ingredients
dissolved in an organic solvent. Candidates for emulsifiable
concentrate formulations are water-insoluble, hydrolytically
stable active ingredients. An emulsifier, a surface active
substance that stabilizes the suspension of small solvent
droplets in water, is added to the concentrated solution so that
the concentrate will mix readily with water. The concentrated
solution is then diluted with water in the field before
application. After the concentrate is diluted with water, it
should remain suspended for several days. If it does not, a
precipitate may form in the spray tank, resulting in clogged
nozzles and uneven application. To avoid precipitation, the
emulsion should be agitated during application.
The solvent used in an emulsifiable concentrate is usually
an aromatic solvent such as xylene. The percentage of active
ingredient in the concentrate ranges from 10 to 50.1 A gallon of
concentrate normally contains 4 to 6 pounds of solvent.
Emulsifiable concentrates are common pesticide formulations
because many active ingredients are insoluble in water but are
soluble in organic solvents. Emulsifiable concentrates penetrate
porous material such as soil and plant surfaces better than
wettable powders, which improves their efficacy. Because they
are liquid, they are easy to pour and measure for mixing in the
field. They do have some drawbacks, however. Many of the
organic solvents can be harmful to sensitive plants. Because of
the toxicity of the solvent and the ability to penetrate porous
surfaces, emulsifiable concentrate spills can be hazardous to the
operator from potential inhalation and absorption through the
skin. The solvents are also a potentially large source of VOC
emissions. The movement by manufacturers away from EC's to dry
3-4
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TABLE 3-1. COMPARISON OF PESTICIDE FORMULATIONS
Formulation
Wettable powders
Dry flowables/
water dispersible
granules
Soluble powders
Emulsifiable
concentrates
Flowables
Solutions
Dusts
Granules
Microencapsulated
Organic solvent
based liquids
Mixing/loading
hazards
Dust inhalation
Fines inhalation
Dust inhalation
Spills and
splashes
Spills and
splashes
Spills and
splashes
Severe inhalation
hazards
Fines inhalation
Spills and
splashes
Spills and
splashes
Phytotoxicity
Safe
Safe
Usually safe
• Maybe
Maybe
Safe
Safe
Safe
Safe
Maybe
Effect on
application
equipment
Abrasive
Abrasive
Nonabrasive
May affect
rubber
pump parts
May affect
rubber
parts; also
abrasive
Nonabrasive
—
o— —
May affect
rubber
pump
parts
Agitation
required
Yes
Yes
No
Yes
Yes
No
Yes
No
Yes
Yes
Organic
solvent
used in
formulation
No
No
No
Yes
Sometimes
Sometimes
No
No
No
Yes
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flowables is also driven by the desire to eliminate the container
disposal problems for plastic and steel.
3.2.2.1.2 Wettable powders. Wettable powders are
concentrated dusts formulated with a finely ground dry carrier
(usually mineral clay) and a wetting agent. The wetting agent
enhances the ability of the powder to suspend and mix in water.
Wettable powders are relatively easy to formulate, are compatible
with other pesticides and fertilizers, and tend to be less
phytotoxic than other formulations because the carriers are inert
materials. However, they do have disadvantages. They require
agitation during application, the inert carrier is abrasive and
contributes to equipment wear, and dust inhalation by the
applicator is a potential problem during handling and mixing.
The fine dust particles normally contain a high concentration of
pesticide and can remain suspended in the atmosphere for hours.
To alleviate some of the handling and mixing problems associated
with wettable 'powders, some manufacturers are packaging wettable
powders in water-soluble bags that can be dropped unopened into
the filled spray tank.
3.2.2.1.3 Water-soluble powders. Water-soluble powders are
relatively simple formulations. The active ingredient is a
finely ground water-soluble solid that is mixed with other
formulation ingredients to form the water-soluble powder. For
application, the powder is added to the spray tank, where it
quickly dissolves. Because these formulations form true
solutions, they do not require constant agitation in the spray
tank and are not abrasive to the equipment. Because of their
dusty nature, however, these formulations are potential
inhalation hazards to applicators. As with wettable powders,
manufacturers are beginning to package soluble powders in water-
soluble packages. Although water-soluble powder formulations
have many advantages, they are not common because few pesticide
active ingredients are soluble in water.
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3.2.2.1.4 Flowables. A flowable is a pesticide formulation
consisting of a finely ground active ingredient mixed with a
liquid carrier and emulsifiers. This type of formulation is used
for solid active ingredients that cannot be dissolved in water or
other solvents. They have properties common to both emulsifiable
concentrates and wettable powders. They require continued
agitation to keep them in suspension, and they can cause abrasive
wear to equipment.
3.2.2.1.5 Dry flowables. Dry flowable formulations, also
known as water-dispersible granules, are small granules
containing an active ingredient and emulsifier. The granules are
mixed with water prior to application. Dry flowables require
little carrier, so they have a high percentage of active
ingredient per unit of weight. Another advantage is the
elimination of dust problems associated with wettable powders.
Because the granules are packaged in easy-to-pour containers,
they are easy to measure and mix. Like liquids, they are
measured out by volume rather than weight. However, they must be
agitated during application and they can be abrasive to
application equipment.
3.2.2.1.6 Ultralow-volume concentrates. Ultralow-volume
(ULV) concentrates are highly concentrated pesticide solutions,
usually containing between 80 and 100 percent active ingredient.1
If the active ingredient is a liquid, it is generally used
without dilution; if it is a solid, it is dissolved in a minimum
of solvent, usually vegetable oil. These formulations require
application equipment designed to apply a small quantity of
extremely fine spray over a large area. They are applied at
rates ranging from 0.5 pint to 2.0 gallons per acre, whereas
conventional formulations are normally applied at rates ranging
from 5 to 20 gallons per acre.1 They are most effective when
applied aerially, because aerial applications can distribute
small volumes over land areas more efficiently than can ground
applications. However, new ground application techniques such as
electrostatic air-atomization sprayers, are being developed to
apply ULV concentrates.2 When using ULV formulations, the
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application equipment must be carefully calibrated because of the
low volume and high concentration of the active ingredient. Due
to the potential toxic effects of such highly concentrated
formulations, ULV concentrates are available only for commercial
use.
3.2.2.1.7 Water-soluble concentrates or solutions. Liquid
pesticides that dissolve in water are called water-soluble
concentrates, or solutions. Solution formulations have the
advantage of requiring no further mixing or agitation once the
pesticide is dissolved. However, like water-soluble powders, the
number of water-soluble concentrates is limited by the avail-
ability of water-soluble active ingredients.
3.2.2.2 Dusts. Dust formulations consist of a finely
ground active ingredient combined with an inert carrier, usually
clay. They are easy to formulate and apply. Dusts are usually
formulated- to contain 1 to 10 percent active ingredient.1 Dusts
are particularly useful when the moisture from a liquid spray may
damage the crop or foliage. Despite the advantages of dusts,
they are used less frequently than spray applications and their
use is continuing to decline. The biggest disadvantage of dusts
is the drift hazard associated with their use and their increased
cost. In an aerial application of a dust formulation, as much as
90 percent of the pesticide may be lost due to drift.1 Even the
portion that reaches the crop may not deposit and stick on the
foliage unless the crop's surface is wet. Dusts can present
serious inhalation hazards to applicators if they do not use the
proper respiratory protection equipment.
3.2.2.3 Granules. Granules consist of an active ingredient
and carrier combined with a binding agent. The carrier, usually
clay, is formed into pellets, and the pellets are sprayed with a
solution of the active ingredient. The resulting product ranges
in size from 20 to 80 mesh, which makes granules much less
susceptible to drift than dusts.1 Granular formulations
generally contain from 2 to 25 percent active ingredient.1
Granules are applied to soils to control weeds, nematodes, and
soil insects. They are often soil-incorporated after
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application. Foliar applications of granular formulations are
not as common as soil applications because the granules bounce
off the leaves. However, they can be used on plants like corn
because the granules lodge in the leaf whorls. The active
ingredient in a granular formulation is usually released slowly
as the granule dissolves. This slow release is often an
advantage in terms of product efficacy, but it is potentially
hazardous to wildlife that eat the slow-dissolving granules.
3.2.2.4 Fumigants. Fumigants are volatile compounds used
to treat (l) pests in stored products; (2) soil pests such as
insects, nematodes, and micro-organisms; and (3) some weeds.
They are also used to control pests in ships, aircraft,
residences, warehouses, greenhouses, and commercial buildings.1
Fumigants may be solid, liquid, or gaseous. Solid and liquid
fumigants volatilize during or immediately after application.
Fumigants present a serious inhalation hazard to applicators and
others in or near the treated area. Applicators should use
respiratory protection equipment and wear protective clothing.
Soil fumigants are usually applied through an irrigation system
or injected into the soil. In many cases, the soil is covered
with plastic sheets for several days in order to retain the
volatile chemical and maintain an effective concentration.
Several factors influence the effectiveness of a soil fumigant,
including soil type, soil organic matter concentration, soil
temperature, and weather conditions during and after
application.^
3.2.2.5 Microencapsulated Pesticides. Microencapsulated
formulations consist of liquid or solid pesticide enclosed in
small plastic capsules. The microcapsules are then mixed with
water and sprayed on the target. During the spray application,
some drift may occur. After spraying, the active ingredient is
slowly released as the plastic coating degrades. The quantity of
VOC solvent contained in the microcapsule will be exposed to the
environment but at a much slower rate than for non-aqueous liquid
formulations (e.g., emulsifiable concentrates). Although
microencapsulated pesticides are not widely used, they have many
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advantages. Because the active ingredient is covered with a
coating, applicators do not have any contact with the active
ingredient and there is no odor. The slow-release mechanism
prolongs the effectiveness of the pesticide, which allows for
fewer and less precisely timed applications. The pesticide also
volatilizes more slowly, so post-application drift is minimal.
3.3 PESTICIDE APPLICATION
Pesticides may be applied as liquids, dry solids, or gases.
Liquid pesticides are applied as a spray of water or oil droplets
containing a solution or suspension of active ingredient.
Pesticides formulated as dusts or granules are normally applied
dry. Pesticides that exist in a gaseous state at ambient
temperature and pressure may be applied either as gases or
pressurized liquids or as solids that vaporize upon release.
This type of pesticide application is known as fumigation.
For all types of pesticide applications, the ultimate goal
is to develop an understanding of the factors that affect
application efficiency and how it can be improved.3 Application
efficiency is defined as follows:
Application _ Minimum pesticide volume required
efficiency, % ~ Actual pesticide volume applied
Few figures on the application efficiency of field spraying
operations are available, and those that are quoted vary widely
from <1 percent to 60 percent.3 If most farm spraying operations
are considered to have a spraying efficiency of only 5 to
10 percent, at best, the scope for improvement in efficiency from
better equipment and application practices can be significant.3
Improvements in spray efficiency are one means of reducing VOC
emissions from the application of pesticides.
Application efficiency can be improved in several ways. The
State agricultural extension service could make available
information on the basic principles of pesticide application and,
if needed, assist the farmer in applying these principals.
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Applying a liquid pesticide requires a knowledge of how spray
droplets are produced, how they are transported to the target,
and how they deposit and adhere to different types of targets.
Applying a granular pesticide requires a knowledge of soil
conditions that are most conducive to a high level of product
efficiency. Efficient fumigation requires that the applicator be
aware of the properties of the fumigant and its mode of action
and of soil conditions that have a major influence on fumigation
effectiveness. The applicator also needs to be familiar with all
of the equipment options available and what type of equipment can
most effectively deliver a particular product in a particular
situation. All measuring, mixing, and application equipment must
be well maintained and calibrated to ensure that the right amount
of product is delivered to the target. Application efficiency
can also be improved by minimizing drift, which reduces the
amount of pesticide reaching the target. In addition to reducing
application efficiency, drift can also endanger neighboring
crops, livestock, wildlife, and humans, as well as general
environmental contamination.
3.3.1 Liquid Pesticide Application
3.3.1.1 Principles of Application. Producing and
delivering to the target optimum-sized spray droplets is probably
the most important aspect of liquid pesticide application. Most
conventional liquid sprayers produce a wide range of droplet
sizes, averaging from 40 to 500 microns (/xm) in diameter.3
Droplets at the lower end of this range, 40 to 100 jwm, generally
provide better target coverage, which is particularly important
when applying an insecticide or fungicide to foliage.3 However,
these droplets are also extremely susceptible to drift. Larger
droplets, 400 to 500 /*m, are much less susceptible to drift
because they are heavier and fall quickly, but they are less
effective for some types of pest control because they may bounce
or run off target surfaces and not provide adequate coverage for
pest control.3 The goal in liquid pesticide application is to
generate 'droplets that are small enough to provide adequate
target coverage but large enough to minimize spray drift. For
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most pesticide applications, the optimum range for droplets is
100 to 300 /zm.3
3.3.1.2 Application Equipment. A list and brief
description of liquid pesticide application equipment is included
in Table 3-2. Liquid pesticide application equipment ranges from
small aerosol cans to air blast sprayers with tank capacities of
up to 1,000 gallons capable of spraying up to 1,000 gallons per
acre. Of the application methods listed, controlled droplet
applicators, ultralow volume applicators, and electrostatic
sprayers have the greatest potential- for increasing application
efficiency.
In terms of application efficiency, wick applicators are
probably the best type of pesticide application available. Their
basic design consists of a cloth, rope, or wick saturated with
herbicide, which is wiped onto the leaves of target weeds.
Because these applicators apply the herbicide directly to the
weed, there is little if any pesticide wasted, and application
efficiency approaches 100 percent. Unfortunately, wick
applicators are limited to the application of systemic or contact
herbicides in situations where the weeds are taller than the
crop.
Controlled droplet applicators (CDA's) produce droplets
ranging in size from 100 to 400 jum.3 By limiting the size range,
these applications eliminate the production of small droplets
that are subject to drift and large droplets that may bounce or
roll off the target. Controlled droplet applicators may be used
in a variety of ways. Some are self-contained, hand-held units,
while others are connected to a backpack tank by a flexible hose.
One or more controlled droplet applicators can be mounted to a
boom and attached to a tractor. They may also be used in place
of nozzles in air blast sprayers. Controlled droplet applicators
are most often used to apply herbicides, but they can also be
used for some'insecticide and fungicide applications. They are
particularly useful in very-low-volume application because by
•applying uniform sized droplets they minimize the drift generally
associated with these types of applications.
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TABLE 3-2. "LIQUID PESTICIDE APPLICATION EQUIPMENT
Type
Powered backpack
sprayer
Controlled droplet
applicators
Low-pressure sprayers
High-pressure
hydraulic sprayer
Air blast sprayer
Ultralow-volume
applicators
Electrostatic sprayers
Uses
Aquatic, landscape,
right-of-way, forest,
and agricultural
applications.
Contact herbicides and
insecticides.
Common commercial
sprayer for multiple
pest control.
Landscape, right-of-
way, and agricultural.
Dense foliage and large
trees.
Applications to trees,
vines, and shrubs
Agricultural and
aquatic applications.
Agricultural
applications to trees,
vines, and row crops.
Suitable formulations
All. Some may
require agitation.
Usually water-soluble
formulations.
All. May include
agitator.
All. May include
agitator.
All. Usually equipped
with agitator.
Usually only pesticides
soluble in organic
solvents.
All. Some may
require agitation.
Comments
Requires frequent
maintenance.
Fragile.
Requires frequent
maintenance.
Requires frequent
maintenance. Pumps
and nozzles subject to
rapid wear.
Requires frequent
maintenance.
Requires extreme care
in calibration.
Usually equipped with
blower.
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Ultralow-volume sprayers apply from 0.5 pint to 2 gallons of
highly concentrated spray per acre.1 Low-volume nozzles or
controlled droplet applications are used to brea.k up the spray
into small droplets that are propelled to the target by air from
a fan or blower. Because ULV sprayers normally apply very small
droplets that are subject to rapid evaporation, the pesticide is
sometimes mixed with vegetable oil carriers, which reduce the
droplet evaporation rate. They are also usually limited to
application during low winds to minimize drift. It is extremely
important that ULV sprayers be calibrated accurately because of
the high concentration of pesticide being applied.
Electrostatic sprayers apply small, electrically charged
pesticide droplets. Droplets average about 50 /zm in diameter and
are given a negative electrostatic charge as they leave the
sprayer. In theory, plant material has a positive electrostatic
charge and the droplets are attracted to the surface thereby
increasing pesticide deposition and target coverage. Not all
experimental studies support this theory. A study by Law and
Cooper on orchard air carrier sprayers showed that while
significant deposition increases could be achieved by
electrically charging the more finely divided droplets, the
deposition was not increased to the level achieved by the larger
droplets produced by hydraulic nozzle in conventional orchard
sprayers.4 However, one of the study conclusions was that the
highly significant deposition controls achieved by charging
finely divided droplets shows that an electrostatic benefit can
be obtained in applications to orchard air carriers. These
results may initiate engineering design changes (e.g., increased
droplet charge level) leading to improvements in deposition that
could surpass levels currently achieved during treatment with
conventional large volume median diameter droplets.
3.3.2 Dry Pesticide Application
3.3.2.1 Principles of Dust Application. The application of
pesticides as dust formulations has declined considerably because
of operator safety and low application efficiency. Dusts are
extremely susceptible to drift. Particles that do reach the
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target often do not adhere to the target surface. Drift can be
minimized by limiting applications to days of favorable weather
conditions. Adhesion to the target can also be improved by
formulating the product with adhesives or stickers. However,
even under the most favorable conditions, dust application
efficiency is very low.
3.3.2.2 Principles of Granule Application. The application
efficiency for granular applications is most affected by soil
conditions. Because most granule formulations are designed to
release active ingredient through leaching by soil water, they
are most effective when applied to wet soil. Ideally, the soil
should be irrigated both before and after the granules are
applied and incorporated. Higher soil temperatures may also
increase the effectiveness by enhancing the release of the active
ingredient.
3.3.2.3 Dust and Granule Application Equipment. A list and
brief description of the equipment used to apply dusts and
granules is included in Table 3-3. Except for the bulb
applicators, which are normally only used for small indoor jobs,
all of the dust applicators present a considerable drift hazard.5
Because granules have a much lower drift potential than either
liquids or dusts, all of the granule applicators are fairly
efficient, although the mechanically driven granule applicator
requires extra attention to ensure it is accurately calibrated.
In general, differences among granule applicators are a
difference in scale, not in application efficiency.
3.3.3 Fumigation
Soil fumigants are applied in the following ways:
1. Injected into the soil as a liquid;
2. Applied in a granular form and incorporated by
cultivation; and
3. Released in a gaseous state above the soil surface but
beneath a sealed plastic cover. As with granule applications,
soil conditions are most influential in determining fumigation
effectiveness. The soil must be neither too wet nor too dry when
applying a fumigant. Wet soils trap the fumigant in soil water,t
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TABLE 3 - 3. DUST AND GRANULE APPLICATION EQUIPMENT
Type
Uses
Suitable formulations
Comments
Dust applicators
Bulb applicator
Compressed air
duster
Mechanical duster
Power duster
Applies dusts to small
cracks and crevices.
Applies dust in confined
spaces, e.g., wall voids.
Landscape and small
agricultural uses.
Vine crops. AJso used
in buildings.
Dusts
Dusts
Dusts
Dusts
Easy to use.
Inhalation hazard.
Drift hazard,
inhalation hazard.
Drift hazard.
Granule applicators
Hand-operated
applicator
Mechanically driven
applicator
Powered granule
applicator
Landscape, aquatic and
some agricultural areas.
Turf, landscape and
some agricultural areas.
Agricultural areas—
usually row crops.
Granules or pellets
Granules or pellets
Granules or pellets
Easy to use.
Requires accurate
calibration.
Requires frequent
maintenance.
3-16
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slowing down or preventing fumigant movement through the soil.
In soils that are too dry, the gas may diffuse so rapidly that it
is not retained long enough to be lethal to the target organism.
Fumigation effectiveness is also improved by higher soil
temperatures. Higher temperatures enhance vaporization and
diffusion of the fumigant in the soil, decreasing the
concentration and time required for a lethal dose. In addition,
some soil pests (e.g., nematodes) are more susceptible to
fumigants at higher soil temperatures.
3.3.4 Aerial Pesticide Application
Both liquid and dry pesticide formulations are applied
aerially. Liquids are usually applied from boom configurations
attached to the plane's wings. Aerial application efficiency can
be improved by proper nozzle placement, avoiding unfavorable
weather conditions, and using viscosity additives.^ Granules can
be applied aerially, but they must be heavy enough to reach the
target without being affected by wind drift. Aerial dust
applications are not recommended because dust particles are too
small to reach the target area.
3.3.5 Maintenance and Calibration
Effective pesticide application depends on properly
maintained and calibrated application equipment. A periodic
maintenance program can prevent accidents or spills caused by
ruptured hoses, faulty fittings, damaged tanks, or other
problems.5 Because operators often fail to understand how
quickly equipment becomes maladjusted and worn, most sprayers are
not calibrated often enough. The main reason for calibrating
pesticide application equipment is to determine how much
pesticide must be put into the spray tank to ensure that the
correct amount of chemical is applied. Failure to calibrate
equipment properly is a frequent cause of ineffective pesticide
applications and overuse of pesticides.
3.3.6 Minimizing Drift
Pesticide drift is movement of a pesticide away from the
treatment site. There are several factors that influence drift
and a number of ways to reduce it: lass volatile active
3-17
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ingredients can be used and thickeners can be added that reduce
pesticide evaporation potential by increasing liquid viscosity to
the spray tank. Thickeners do not act to reduce the total
emissions but rather to increase viscosity to minimize drift
problems.
Controlling spray droplet size may be the most important
factor in reducing drift. Small droplets, in particular those
less than 100 )m, are more vulnerable to both spray droplet drift
and vapor drift. Small droplets are more likely to drift away
from the target zone and to evaporate. Using larger nozzles and
lowering the output pressure of a sprayer reduces the production
of small droplets. Controlled droplet applicators generate
droplets ranging in size from 100 to 400 /zm, . eliminating the very
small droplets most susceptible to drift.5 Overall, drift
reduction procedures only work if the applicators actually reduce
the usage rate of the formulation to account for improved
efficiency.
3,3.7 Pesticide Application; Sources of VOC Emissions
Volatile organic compounds may be emitted via one or several
potential pathways. Emissions due to volatile active ingredients
and the organic solvents used in the formulations may be two
major sources of VOC's following field application of the
pesticide. Evaporation of volatile components in a pesticide
spray before it reaches the target or entrainment of the
pesticide as an aerosol may also contribute to VOC emissions.
During field application and subsequent to the application,
several factors influence the extent and rate of VOC emissions
such as target soil, type of vegetation, type of spray equipment,
physical and chemical properties of the active ingredient and
solvent, the type of surface to which the pesticide is applied,
and the extent of post-application incorporation.
Following field application, the fate of a pesticide, be it
xenobiotic or natural, is governed by several factors including
loss from soil surface, hydrolysis, biodegradation route and
rate, diffusion processes, sorption, mobility, binding, and
biological persistence. Superimposed on these factors,
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characteristics in three other areas also impact the fate of the
pesticide: (1) chemical structure of the pesticide, (2) soil
properties, and (3) climatic conditions. Chemical structure
includes reactivity, vapor pressure, photolytic stability,
adsorptive properties, and biological properties. Soil
properties include organic content, water content, soil texture,
pH, microbial availability, and water flow. Climatic conditions
include factors such as temperature, amount of sunlight,
rainfall, and evaporation rate. Fate is determined by the
complex interactions of all three of these areas. The key
processes by which the fate of the pesticide is defined are
generally recognized to be adsorption by the soil, volatilization
of the pesticide from the soil, and the rate of degradation by
biotic and abiotic processes. Several of the factors impacting
the fate of pesticides are briefly discussed in the following
subsections. .
3.3.7.1 Vapor Pressure. One of the major physical-
properties that governs the emission of a compound into the
environment is the vapor pressure. A pesticide formulation is
generally composed of a variety of constituents and each
constituent has a specific function in the product. Bach
constituent has a characteristic vapor pressure that will
dictate, in part, the emission of that constituent into the
environment and the range of the vapor pressures found in a
pesticide formulation can be very wide. Table 3-4 presents vapor
pressure data for selected active ingredients, fumigants, and
selected solvents commonly found in pesticide formulations. In
general, the nonfumigant active ingredients exhibit vapor
pressures that range from 10"4 to 10"7 mm Hg at ambient
temperatures. These vapor pressures are two to three orders of
magnitude less than either fumigants or the solvents. Because of
their mode of action, it is necessary for fumigants to have a
relatively high vapor pressure compared to other pesticide active
ingredients. If the potential for volatilization from a
pesticide formulation, particularly an EC, was based solely on
the vapor pressures of the active ingredients, an incorrect
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TABLE 3-4. VAPOR PRESSURE DATA FOR SELECTED
PESTICIDE FORMULATION COMPONENTS
Component
Phys. state
Vapor pressure
(mm Her) @20-25°C
ACTIVE INGREDIENTS
1. Insecticides; including miticides, larvicides,
nematicides, and acaricides
Chlorpyrifos
Terbufos
Fonophos
Carbofuran
Phorate
Methyl parathion
Aldicarb
Acephate
Dicrotophos
Dicofol
Ethoprop
Diazinon
Dimethoate
Permethrin
Proparqite
Trimethacarb
Azinphos -methyl
Ethyl parathion
Methomyl
Oxamyl
Profenofos
Thiodicarb
Disulfoton
Fenamiphos
Endosulfan
Methamidophos
solid
liouid
licruid
solid
licruid
solid
solid
solid
licruid
licruid
liquid
liquid
solid
solid
licruid
solid
solid
licruid
solid
solid
licruid
solid
liquid
solid
solid
solid
1.7 x 10'5
3.2 x 10~4
3.4 x 1CT4
6 x 10'7
6.4 x 10"4
1.5 x 10'5
3 x 10'5
1.7 x 10'6
1.6 x 10"4
4.0 x 10"7
3.8 x 10'4
6 x 10'5
2.5 x 10'5
1.3 x 10'8
3 x 10'3
5.1 x 10"5
2 x 10"7
5 x 10~6
5 x 10"5
2.3 x 10"4
9 x 10"7
1 x 10"7
1.5 x 10'4
9.8 x 10"7
1.7 x icr7
a 'x io~4
2 . Herbicides
Atrazine
Alachlor
solid
solid
2.9 x 10"7
1.4 x 10"5
3-20
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TABLE 3-4. (continued)
Component
Metolachlor
Cvanazine
Trifluralin
EPTC
Pendimethalin
Butylate
Propanil
2,4-D acid
Metribuzin
Molinate
Propachlor
Fluometuron
Clomazone
MCPA
Bromoxynil (octanoate)
Prometrvn
Ethalfluralin
Norflurazon
EPTC
Linuron
Simazine
Phys . state
licruid
solid
solid
licruid
solid
licruid
licruid
solid
solid
licruid
solid
solid
licruid
solid
solid
solid
solid
solid
licruid
solid
solid
Vapor pressure
(mm Ha) @20-25°C
3.1 x 10~5
1.6 x 10'9
1.1 x 10"4
3.4 x 10"2
9.4 x 10"6
1.3 x 10'2
4 x 10"5
8 x 10'6
<1 x 10"5
5.6 x 10"3
2.3 x 10'4
9.4 x 10'7
1.4 x 10"4
1.5 x 10"6
4.8 x 10'6
1.2 x 10'6
8.8 x 10"5
2 x 10~8
3.4 x 10"2
1.7 x 1CT5
2.2 x 10~8
3. Fumiqants, funqicides, and others
Chloropicrin
1 , 3 -Dichloropropene
Methyl bromide
Chlorothalonil
Tribufos
Ethephon
PCNB
Benomyl
Metam- sodium
Dimethipin
licruid
licruid
qas
solid
liquid
solid
solid
solid
solid
solid
18
29
1,824
5.7 x 10"7
1.6 x 10"6
<10"7
1.1 X 10"4
<1 x 10'10
20a
3.8 x 10~9
3-21
-------
TABLE 3-4. (continued)
Component
Thidiazuron
Phys. state
solid
Vapor
(mm Hq)
pressure
@20-25°C
2.3 x 10'11
SOLVENTS
Chlorobenzene (mono)
Ethylbenzene
Trimethylbenzene (1,2,4)
Water
m-Xylene
Xylene- mixtures
licruid
liquid
licruid
liquid
liquid
liquid
10
10
1 (est.
17.5
10
7
22°C
26°C
) 20°C
20°C
28°C
25°C
aValue for major residue:
Sources:
methyl isothiocyanate
1. Farm Chemical Handbook 1992. Meister Publications Company,
Wi11oughby, Ohio.
2. Handbook of Chemistry and Physics, 67th Edition (1986-1987).
CRC Press, Boca Raton, FL. 1987.
3. Wauchope, R.D., T.M. Buttler, A.G. Hornsby,
P.W.M. Augustijn-Beckers, and'J.P. Burt. The SCS/ARS/CES
Pesticide Properties Database for Environmental Decision-
Making. In: Reviews of Environmental Contamination and
Toxicology, G.w. Ware, Editor. Volume 23. Springer-Verlag,
New York. 1992.
3-22
-------
conclusion could be drawn that pesticides are basically
nonvolatile and that evaporation during and subsequent to field
application is limited. However, the most significant reductions
in emissions of volatile compounds results from reducing the
solvent content of the formulation and generally not from
reducing the quantity of active ingredient.
After application of the pesticide, several mechanisms can
affect the degree of emissions of the volatile components. The
vapor pressure of the components is a major factor in determining
those emissions. As evidenced in Table 3-4, the solvents have
significantly higher vapor pressures than the nonfumigant active
ingredients. For formulations having a high solvent content, the
solvent would volatilize and leave the active ingredient (and
other nonvolatile components) on the soil or plant surface. On
the soil or plant surface, the active ingredient may be taken up
by the plant, volatilize, be transported to the soil surface by
rain, or undergo degradative reactions on the surface.
3.3.7.2 Soil Moisture Content. For pesticides applied to
soils, the soil moisture content is one of the most important
factors affecting the rate of volatilization. Pesticides applied
to dry soils do not volatilize as rapidly as pesticides applied
to moist soils. As the soil is moistened, the rate of
volatilization increases.
A number of researchers have investigated the effect of soil
moisture on pesticide volatilization.7'^ Results from these
studies showed much smaller vapor losses for pesticides applied
to air dry soils than for pesticides applied to soils moistened
to field capacity. The same pattern of results were obtained
with soil types varying from sand to silty clay loam.
The inhibited volatilization of pesticides applied to dry
soil surfaces is believed to be due to increased adsorption of
the pesticide on dry soil. At and above a particular moisture
level there is a monomolecular water layer on the soil surface.
When the moisture content drops below this level, adsorption
sites are exposed. Pesticide molecules can then bond to these
exposed sites, thus reducing their fugacity (-escaping tendency)
3-23
-------
and vapor density. If the soil is remoistened, the water
molecules will displace the pesticide accumulated at the surface
adsorption sites and the pesticide will evaporate.
Soil moisture content is also an important factor in
determining the extent of volatilization of pesticides that have
penetrated beneath the soil surface or have been mixed into the
soil. Three factors affect the volatilization of pesticides that
are beneath the soil surface: desorption of the pesticide from
the soil, upward movement of the pesticide to the soil surface,
and vaporization into the atmosphere. The upward movement of the
pesticide to the soil surface is affected by the moisture content
of the soil. As water evaporates from the soil surface, it
creates a concentration gradient, which causes water in the soil
to move upward toward the surface to replace the evaporated
water. Pesticides in the solution will move to the surface with
the water. At the soil surface, the pesticide is available for
evaporation. This concurrent movement of pesticides to the
surface with the water has been called the "wick effect."9 In
dry soils, the water evaporation rate is low, so the movement of
pesticides to the surface is limited. For moist soils, the water
evaporation rate is higher and the pesticide moves more quickly
to the surface, where it may evaporate into the atmosphere.10
3.3.7.3 Pesticide Incorporation Into Soil. Some
pesticides, particularly preemergent herbicides, are incorporated
into the soil immediately after application; that is, they are
mechanically mixed into the soil by disking or tilling. The
pesticide may be incorporated by disking to shallow depths in
soils (2.5 cm), or it may be incorporated to greater depths
(7.5 cm) by tilling. For some pesticides, incorporation
increases the efficacy; for others, incorporation is required for
safety reasons. For incorporated pesticides the rate of
volatilization is controlled primarily by pesticide movement
through the soil to the surface.
Two factors are particularly important in limiting the
volatilization of incorporated pesticides. First, the soil
concentration of an incorporated pesticide may be as much as an
3-24
-------
order of magnitude less than the soil concentration of a surface-
applied pesticide because it is mixed into the soil at depths of
2 to 8 cm as opposed to the 3 to 5 mm depth to which formulation
spray drops generally penetrate. The lower concentration
decreases the pesticide equilibrium vapor pressure, thus reducing
the volatilization rate. Second, because the pesticide is
incorporated to a greater depth, it will have a greater distance
to travel before it reaches the surface and will encounter
greater upward movement resistance.9
3.3.7.4 Application to Foliage. When a pesticide is
applied to vegetated land, part of the total amount applied is
retained by the crop foliage, while some portion is deposited on
the underlying soil. The percentages which are deposited on soil
and on foliage are dependent upon several factors, including crop
_type, extent of foliage coverage, and application method. Field
studies evaluating the volatilization of pesticides applied to
vegetated surfaces have utilized this partitioning of the total
deposit to compare volatilization rates for pesticides from soil
and foliage. While volatilization has been shown to be a major
source of pesticide loss from foliage, photolytic degradation,
hydrolysis of the AI, and other degradation mechanisms may be
factors in pesticide loss.
Studies have demonstrated that the rate of volatilization
from vegetation is rapid for the first day, gradually decreases
for the next week, and then drops off significantly. Results
from field studies demonstrate that volatilization from plant
surfaces is much more rapid than volatilization from soil
surfaces for the first few days following the application.11
The gradual decrease in the rate of pesticide volatilization
that is observed during the first week is proportional to the
amount of remaining residue. When the pesticide is first
applied, the leaf surface is covered by a layer of pesticide
residue. When this layer quickly volatilizes, islands of
residues are formed. As these islands decrease in size, the
volatilization rate per unit of leaf area also decreases.
3-25
-------
Two theories have been proposed for the further decrease in
volatilization after the first week. The first theory suggests
that residues entrapped in leaf surface irregularities are the
last to volatilize. These residues have less exposed surface
area than the islands of residues, so that the rate of loss is no
longer proportional to the amount of residue remaining. The
other theory suggests that the last residues to evaporate are
those that have penetrated the leaf surface and become adsorbed
on intercellular material. This adsorption of the pesticide
reduces its equilibrium vapor pressure, thus reducing its
volatilization rate. Both mechanisms are probably partially
responsible for the observed reduction in evaporation rate.11
3.3.7.5 Pesticide Loss by Sorption. Adsorption and
absorption rates for pesticides vary depending on the chemical
nature of the pesticide, meteorological conditions, and the
application site. Most sorption processes are reversible. For
the majority of pesticides only a small percentage is
irreversibly adsorbed and unavailable for evaporation. Because
of the variables involved, it is impossible to determine a value
for sorption loss for every pesticide application. However, a
VOC emissions methodology developed by Eureka Laboratories for
the California Air Resources Board (CARS) recognized that some
portion of quantity pesticide applied per acre is unavailable for
evaporation due to sorption over a considerable or indefinite
time period. It was therefore assumed sorption losses to be
2 percent of the amount of the pesticide applied per month.12
3.3.7.6 Pesticide Loss by Degradation. Pesticides are
degraded in the environment by a number of mechanisms, including
chemical, photochemical, and biological degradation. Although
most pesticides are susceptible to one or more of these
degradation mechanisms, the quantity of hydrocarbon compounds
available for vaporization and atmospheric reaction is not
necessarily reduced. A pesticide may be split into two smaller
compounds by degradation mechanisms, but this does not change the
total mass available for evaporation.
3-26
-------
Although there is no established procedure or model for
predicting degradation losses for pesticides, it is apparent that
some portion of most pesticides is unavailable for evaporation
due to degradation processes. The GARB method to estimate
emissions from pesticide application assumed that 4 percent per
month is lost and unavailable for evaporation.12
There are, however, many possible fates and losses of
pesticides in the environment not considered in CARB's
calculations. Drift and evaporation occur during application.
Pesticides also volatilize from soil and vegetation surfaces.
Atmospheric precipitation runoff transports pesticides to aquatic
ecosystems. Pesticides adsorb to soils and may be transported by
erosion. Chemical, photochemical, and hydrolytic degradation of
the pesticide and its decomposition products occurs. Pesticides
are also degraded biologically or may bioaccumulate in various
organisms. Which of these several degradation mechanisms and
transport pathways occurs depends on the chemical and physical
properties of the pesticide and environmental conditions.
The rates of the various degradation processes vary widely
both within the type of process and between types of processes.
For example, the hydrolytic halftimes for some selected AI's are
as follows: chlordane (1.8 x 105 yr), lindane (182 d),
methoxychlor (365 d), heptachlor (4 to 5 d), captan (3 hr),
atrazine (2 to 3 hr), and chlorothalonil (38 d @ pH 9).13,14,15
Heptachlor and captan are no longer registered for use in the
U.S. Chlordane and lindane are "restricted use pesticides."
Soil degradation rates for selected AI's are: methomyl
(3 to 5 d), metolachlor (over 64 d), acephate (3 to 6 d), and
bentazon, Na salt (4 mo).15 Acifluorfen, Na salt has a reported
photodegradation halftime of 4.5 days.15
3.4 PESTICIDE USE AND TRENDS IN THE UNITED STATES
World usage of pesticides is valued at approximately
$23 billion annually. The United States is the leading user of
pesticides, accounting for an estimated 29 percent of the total
world volume of pesticide usage (in pounds of active ingredient)
in 1989. The United States produced approximately 1.3 billion
3-27
-------
pounds [Ib] of the active ingredients used in pesticides, valued
at $7.5 billion retail.16
In the United States, 120 firms manufacture the active
ingredients used in pesticides. The leading six companies
represent 65 percent of production.17 Active ingredients must be
prepared in suitable solutions and forms before they can be
applied to fields. This is accomplished by 3,000 formulators in
the nation, responsible for more than 21,000 registered
products.16 The agricultural market is the leading sector for
pesticide use in the United States and accounts for 75 percent of
the total usage. Industrial and government use follows with
18 percent of total pesticide use, while home and garden use
accounts for 7 percent.16
3.4.1 Pesticide Use in the United States
Figure 3-1 shows the total agricultural share of pesticide
use (in million pounds of active ingredient), based on EPA
estimates, in the United States from 1964 to 1989.ia The figure
shows a fairly rapid growth in pesticide use from the early to
late 1970's, followed by a period of slower growth through 1982.
In 1983 pesticide use declined sharply due to low crop prices,
acreage diversion, and land retirement programs.1^ Since 1984
pesticide use has remained fairly stable. Table 3-5 presents
annual agricultural pesticide use from 1986 to 1989.16
As can be seen in Tables 3-6 and 3-7, the overall increase
in pesticide use can be attributed primarily to the increased use
of herbicides. While insecticide use on the major crops
decreased from 1964 to 1982, herbicide use increased by a factor
of 6.5. The increase in total herbicide use is primarily due to
a rise in the use of herbicides in corn, soybean, and cotton
production. In the early 1950'3, 10 percent of corn acreage was
treated with herbicides. Today, herbicide treatment of corn has
stabilized at 90 to 96 percent of the acres planted. Similar
increases in the percentage of soybean and cotton areas receiving
herbicide applications have occurred.19
Insecticide use has also grown since the 1950's, but not as
dramatically as herbicide use. Because of the discovery of DDT
3-28
-------
900
800 -
700 -
600: -
500 -
400 -
300
r I I
1964
88
72
78
82
36
Figure 3-1. Total agricultural pesticide use in the United
States in millions of pounds of active ingredients.
3-29
-------
TABLE 3-5. ANNUAL U. S. AGRICULTURAL PESTICIDE USE16
Year
1986
1987
1988
1989
Million Ib active ingredienta
820
815
845
806
alncludes herbicides, insecticides, and fungicides only.
TABLE 3-6. PESTICIDE USE ON MAJOR CROPS BY CLASSa"b'9'16
(Million pounds active ingredients)
Year
1964
1966
1971
1976
1982
1989
Herbicides
70.5
101.2
213.1
373.9
455.6
520
Insecticides
116.7
108.3
127.9
130.3
71.2
151
Fungicides
5.8
6.0
6.4
8.1
6.6
65
Other0
31.7
35.7
29.8
35.3
24.3
70
Total
224.7
251.1
377.2
547.6
557.7
806
aActive ingredients, excluding sulfur and petroleum products.
"Major crops are cotton, corn, soybeans, sorghum, rice, tobacco, peanuts, wheat, other small grains,
alfalfa, other hay, and pasture.
°Includes rodenticides, fumigants, and molluscicides; does not include wood preservatives, disinfectants,
and sulfur.
TABLE 3-7. ANNUAL AGRICULTURAL USE OF HERBICIDES
AND INSECTICIDES
(Million pounds active ingredients)
Class of pesticide
Herbicides
Insecticides
TOTAL
198720
505a
179b
684
19889
510
185
695
198916
520a
151b
671
aIncludes plant growth regulators.
"includes miticides and contact nematicides.
3-30
-------
in 1940 and the widespread use of it and other organochlorines,
insecticide treatment was already well established in the 19'50's
on high-value crops (cotton, tobacco, potatoes, vegetables,
fruits, and nuts). By the 1960's usage was fairly stable, and it
has remained so through the 1970's and 1980's. As with
herbicides, the greatest impact on insecticide usage has been the
increase in insecticide applications to corn, from 10 percent of
the planted corn acres in the 1950's to 35 to 40 percent in the
mid-1970's. This increase has been offset somewhat, however, by
the introduction of new compound classes of insecticides that
have replaced the organochlorines. These classes of compounds,
the organophosphates, carbamates, and pyrethroids, are effective
at lower application rates than the organochlorines.
Table 3-8 shows total annual user expenditures on pesticides
in the United States from 1979 to 1989. The agricultural sector
represents approximately 75 percent of the conventional pesticide
usage in the United States. The effects of a poor agricultural
economy and an administrative freeze on farm programs are
reflected in the total user expenditure figures for 1986. Both
of these factors caused a decrease in pesticide demand, resulting
in increased price competition between manufacturers. During
this time pesticide manufacturers withdrew less profitable
products from the market and cut prices on many name-brand
products. 1 Since 1988, annual user expenditures have risen,
primarily because of the rapidly increasing costs associated with
developing new products today and increasing dealer costs,
particularly the increasing cost of liability insurance.2^
3.4.2 Agricultural Pesticide Usacre by Product and Crop
Table 3-9 lists the top 15 pesticides by volume used in the
United States in 1989. As can be seen from the table, the top
seven products are herbicides. The most popular herbicides in
terms of volume used are the amides and triazines, while
organophosphates dominate the insecticide market.
Table 3-10 lists the top 10 herbicides, insecticides, and
other AI's (including fungicides) used on farms during 1991 for
corn, cotton, peanuts, potatoes, rice, sorghum, soybeans, and
3-31
-------
TABLE 3-8.
U.S. ANNUAL USER EXPENDITURES
ON PESTICIDES3
Year
1979
1980
1981
1982
1983
1984
1985
1986
1987
1988
1989
Total expenditures,
millions of dollars
5,050
5,800
6,470
6,470
6,050
6,783
6,560
6,490
6,850
7,380
7,615
aYears 1979-1989 reference 16
3-32
-------
TABLE 3 - 9. ANNUAL USAGE ESTIMATES FOR THE LEADING
AGRICULTURAL PESTICIDES BY VOLUME IN THE UNITED STATES
(Approximate Values, 1989)a/16
Pesticide
Atrazine
Alachior
2, 4-D
Metolachlor
Trifluralin
EPTC
Cyanazine
Butylate
Carbaryl
Maneb/mancozeb
Glyphosate
ChJorpyrifos
Methyl parathion
Usage in million
pounds active
ingredient
70-90
60-75
40-65
40-55
30-40
20-30
20-30
15-25
10-15
8-12
8-13
8-16
8-12
Uses
Herbicide
Herbicide
Herbicide
Herbicide
Herbicide
Herbicide
Herbicide
Herbicide
Insecticide
Fungicide
Herbicide
Insecticide
Insecticide
Compound class
Triazine
Amide
Phenoxy
Amide
Aniline
Carbamate
Triazine
Carbamate
Carbamate
Dithiocarbamate
Phosphono amino acid
Organophosphate
Organophosphate
3The estimates represent all usage of the active ingredient including noncrop usage.
estimate does not include the pounds of ethyl parathion usage.
3-33
-------
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3-35
-------
wheat.23 The crops shown in this table are among the major crops
identified in Table 3-6, which reported total quantities of
herbicides, insecticides, fungicides, and other pesticides.
Comparison of the AI's and respective usage in Table 3-9 with
those in Table 3-10 shows that the same high usage herbicides
appear in both tables but for insecticides and lower volume usage
herbicides, the two tables show significant differences. A
contributing factor may be that the data in Table 3-9 represents
all 1989 usage, including noncrop usage, whereas the data in
Table 3-10 represent 1991 usage on specific crops.
3.4.3 Trends in Agricultural Pesticide Use
It is difficult to predict the direction pesticide use will
take in the near future because so many conflicting factors are
involved. The increased use of conservation tillage practices
mandated under the Food Security Act of 1985 and other Government
farm policies are expected to produce an increase in pesticide
use. The Integrated Pest Management Program, increased pressure
from a more environmentally aware public, the Conservation
Reserve Program, and the development of new pesticides that are
effective at significantly lower application rates are expected
to exert a negative influence on the volume of pesticides used.
These positive and negative influences will probably offset each
other, and pesticide use should remain fairly stable, as it did
from 1987 to 1989 (Table 3-5).
There also are indications that pesticide manufacturers are
changing formulations in response to safety and environmental
concerns. Some entulsifiable concentrates are decreasing in
availability as the manufacturer increases production of dry or
water-based formulations. Emulsifiable concentrates currently on
the market may be older products that are decreasing in market
share for their designated uses due to the introduction of new
products.24
3-36
-------
3.5 REFERENCES FOR SECTION 3.0
l. Ware, G. The Pesticide Book. Fresno, California, Thomson
Publications. 1989. p. 336.
2. Giles, K., and E. Ben Salem. Comprehensive Research on
Strawberries Annual Report. Agricultural Engineering
Department, U. C. Davis. February 1, 1990--January 31,
1991. 9 p.
3. Behncken, G. Pesticide Application Manual. Brisbane,
Queensland, Australia Department of Primary Industries.
1983.
4. Law, S. E., S. C. Cooper. Depositional Characteristics of
Charged and Uncharged Droplets Applied by An Orchard Air
Carrier Sprayer. Transactions of the ASEA. 31(4):984-989.
1988.
5. Marer, P. The Safe and Effective Use of Pesticides.
Oakland, University of California. 1988. p. 286.
6. Hutson, D. H., and T. R. Roberts (ed.) Progress in
Pesticide Biochemistry and Toxicology, Volume 7:
Environmental Fate of Pesticides. John Wiley & Sons.
1990. pp. 103-107.
7. Parochetti, J. Y., G. F. Warren. Vapor Losses of PCI and
CIPC. Weeds. 14:281-284. 1966.
8. Glotfelty, D., A. Taylor, B. Turner, and W. Zoller.
Volatilization of Surface-Applied Pesticides from Fallow
Soil. J. Agric. Food Chem. 32: p. 638-643. 1984.
9. Taylor, A.W., D. E. Glotfelty. In : Herbicides. Grover,
R. (ed.). Boca Raton, CRC Press. 1988. p. 94, 107.
10. Spencer, W. F., M. M. Cliath. Pesticide Volatilization as
Related to Water Loss from Soil. J*. Environ. Qual.
2(2):284-288. 1973.
11. Taylor, A. W., D. E. Glotfelty, B. C. Turner, R. E. Silver,
H. P. Freeman, and A. Weiss. Volatilization of Dieldrin
and Heptachlor Residues from Field Vegetation. J. Agric.
Food Chem. 21, (3): pp. 542-548. 1977.
12. Methods for Assessing Area Source Emissions in California.
California Air Resources Board, Technical Support Division,
Emission Inventory Branch, Sacramento, California.
September 1991.
3-37
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13. Kollig, H. P., J. J. Ellington, E. J. Weber, and N. L.
Wolfe. Pathway Analysis of Chemical Hydrolysis for 14 RCRA
Chemicals. Environmental Research Brief, EPA/600/M-89\009.
U. S. EPA, Environmental Research Laboratory. Athens, GA.
August 1990.
14. Mabey, W. and T. Mill. Critical Review of Hydrolysis of
Organic Compounds in Water Under Environmental Conditions.
J. Phys. Chem. Ref. Data, 7(2):407. 1978.
15. Farm Chemicals Handbook - 1992. Meister Publishing
Company, Willoughby, OH. 1992.
16. Aspelin, A.L., A.H. Grube, V. Kibler. Pesticide Industry
Sales and Usage: 1989 Market Estimates. U. S.
Environmental Protection Agency. Office of Pesticide
Programs. Washington, DC. July 1991. 21 p.
17. Chemical Industries Newsletter. SRI International. May-
June 1991. p. 8.
18. Osteen, C., and P. Szmedra. Agriculture Pesticide Use,
Trends and Policy Issues. U. S. Department of Agriculture.
Agriculture Economic Report No. 622. September 1989.
pp. 8-11.
19. Economic Research Service. Situation and Outlook Report.
U.S. Department of Agriculture. AR-13. February 1989.
20. Dumas, R., A. L. Aspelin. Pesticide Industry Sales and
Usage: 1987 Market Estimates. U. S. Environmental
Protection Agency. Office of Pesticide Programs.
Washington, DC. November 1988. 16 p.
21. Synthetic Organic Chemicals, U.S. Production and Sales.
U.S. International Trade Commission (data for Reported
Sales and Reported Sales Value). 1972-1986.
22. U.S. Exports, FT 410, U.S. Department of Commerce, Bureau
of the Census (data for total value of exports).
1972-1986.
23. Agricultural Chemical Usage: 1991 Field Crop Summary.
National Agricultural Statistics Service and Economic
Research Service, U.S. Department of Agriculture,
Washington, DC. March 1992.
24. Telecon. Marron, J., MRI, to Cline, D., Monsanto.
Agricultural Company. October 23, 1991. Pesticide
formulation and market information.
3-38
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4.0 EMISSION ESTIMATION METHODOLOGIES
Because various techniques may be used to reduce emissions
from agricultural pesticide formulations, a way must be found to
estimate the quantity of volatile organic compounds (VOC's)
emitted under existing conditions. Emissions of VOC's from
pesticide applications are the result of volatilization of the
active ingredient (AI), organic solvents, emulsifiers, and other
organic compounds that may be used in the formulation. For most
States, data are not available for total emissions from pesticide
application in ozone nonattainment areas and within the State in
general. This section provides information on available sources
of data for agricultural pesticide usage during the 1980's
(1987-1989 for herbicides and 1982-1984 for insecticides),
methods that can be used to estimate VOC emissions, and estimated
nationwide total VOC emissions and VOC emissions in ozone
nonattainment areas.
4.1 BACKGROUND
Estimating VOC emissions from agricultural pesticide
application requires data on total quantities applied by type of
formulation. Information is available from the U. S.
Environmental Protection Agency (EPA) Office of Pesticide
Programs (OPP) for the total annual quantity of pesticide used in
the United States, usage of selected pesticide classes on major
crops, and annual estimates of use for the 15 leading AI's.
However, very limited information is available for pesticide
usage by major class by State, use of individual AI's (except for
the top 15), use by type of formulation, or other detailed usage
data. Only two sources of data were found that would provide
sufficient detail to allow the estimation of VOC emissions.
4-1
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These two sources were the Resources for the Future (RFF) data
bases on herbicide usage (by county) and insecticide usage in
each State and the Pesticide Use Report (PUR) compiled by county
in California by the California Department of Pesticide
Regulation (DPR).
4.1.1 California Pesticide Usage
The DPR compiles data on an annual basis for the use of
pesticides in each county of the State. This data compilation is
the PUR. Until recently, the data were compiled only for a fixed
list of restricted-use pesticide AI's composed of
38 insecticides, 18 herbicides, 6 nematicides, 2 adjuvants
(substances added to aid the action of the AI), and
16 miscellaneous AI's and for pesticides applied by licensed
commercial applicators. Data are currently collected for all
pesticides used for agricultural purposes within the State;
however, these data have recently been completed by DPR. In each
county, farmers and commercial applicators provide selected
information for each pesticide to the county, which in turn
transmits the data to the DPR.
Currently, the California Department of Pesticide Regulation
is developing a mapping system to track applications of pesticide
products. Two data bases, the Product Label and Inert Ingredient
data bases, will be able to retrieve the identities and weight
percentages of active and inert ingredients in any California-
registered pesticide product.
Appendix A provides a more detailed description of the PUR
and selected tabular summaries of pesticide usage in California
during 1987, the most recent year for which data was available.
The PUR for 1990, which includes data for all pesticides and not
just restricted-use AI's, became available in June 1992.
4.1.2 Resources for the Future
The herbicide AI use information for nationwide emission
estimates was obtained from the National Pesticide Use Inventory
compiled by RFF. The insecticide information also came from
RFF. There are no other data bases available to provide
nationwide pesticide use information at a comparable level of
4-2
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detail. Resources for the Future gathers information on
pesticide use and compiles the information in a comprehensive
data base format. Funding for the RFF studies comes from EPA,
the U.S. Department of Agriculture (USDA), the National Oceanic
and Atmospheric Administration (NOAA), and several pesticide
manufacturers. Generally, the RFF data bases were created based
on pesticide usage estimates calculated using two coefficients:
the percent of acres that are treated and the average annual
application rate per treated acre.1 These coefficients are
typically provided in terms of Statewide average use for a
particular AI and crop combination. The only data available from
RFF are 1987-1989 for herbicides and 1982-1984 for insecticides.
The number of treated acres is estimated by multiplying the
percent of acres treated by estimates of the number of planted
crop acres reported in the 1982 Census of Agriculture for
insecticides or in the 1987 Census of Agriculture for herbicides.
The number of treated acres is multiplied by the application rate
per acre to estimate the total poundage of AI that is used on the
crop in a county.
Information on herbicides is available on the county level,
allowing analysis of herbicide use in ozone nonattainment areas.
Insecticide and fungicide data is currently available only on the
State level. No information on other types of pesticides has
been collected for the data base. However, herbicides,
insecticides, and fungicides account for 93 percent of the U.S.
pesticide market, and herbicides represent the largest volume of
pesticide used annually. Therefore, the data base contains the
majority of agricultural pesticide use information.
4.1.3 RFF Data Base Summary
According to the data base, 511 million pounds
(255,600 tons) of AI's were applied nationwide to cropland.
Because of the time period for which data are available, several
of the AI's included in these data bases are no longer registered
and in use. Herbicides accounted for over 84 percent of
pesticide use (424 million pounds [211,800 tons] of AI's).
Insecticide use amounted to 87.5 million pounds (43,800 tons) of
4-3
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AI's. The States with the largest contributions overall to total
pesticide use were Iowa, Illinois, Minnesota, Texas, and
California. For these States the majority of pesticide use
(85 percent or greater) is due to use of herbicides. Data base
information on the top four States indicates that the largest
volume of herbicide AI used in each of the States is those AI's
including atrazine, metolachlor, and alachlor used primarily to
control weeds in corn. The top three States contributed one
percent or less to the nationwide insecticide use. California
insecticide use (15 million pounds [7,500 tons] of AI's),
however, accounted for greater than half of the State's pesticide
use. In the 1982-1984 RFF data base for insectidides, this was
largely a result of the use of dibromochloropropane (DBCP), which
accounted for 65 percent of California's insecticide use.
According to California DPR, the use of DBCP in California was
suspended in 1977. Dibromochloropropane was a soil fumigant used
to treat a variety of crops including citrus, berries, grapes,
cotton, vegetables, and ornamentals. The registrations for all
DBCP products were cancelled in 1985 as a result of an Office of
Pesticide Programs (OPP) special review. The special review
determined that the benefits of DBCP did not outweigh its risks
which were identified as oncogenicity, ntutagenicity, reproductive
effects and impacts on ground water. Telone®, dazomet and metam
are fumigants that may have been used as substitutes for DBCP.
The next-highest insecticide-using State is Georgia, with a total
of 11.9 million pounds for the 14 AI's reported in the data base.
In this case, DBCP and ethylene dibromide (EDB), a fumigant that
had all agricultural uses cancelled in 1990, accounted for
17.9 percent and 27.1 percent of the total insecticide use,
respectively. Fumigant substitutes for EDB include Telone®,
methyl bromide, chloropicrin, and metam. Thus, approximately
45 percent of the insecticide use in Georgia has been eliminated
or likely replaced with other insecticides.
The highest herbicide use in ozone nonattainment areas was
found in California (12.2 million pounds [6,100 tons] of AI's),
which has 35 counties with whole or partial nonattainment status.
4-4
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The AI's with the highest use in California were dimethyl
tetrachloroterephthalate (DCPA) (1.1 million pounds [550 tons]),
molinate (0.97 million pounds 485 tons]), and glyphosate
(0.96 million pounds [480 tons]). The State with the next-
highest herbicide use in ozone nonattainment areas is Michigan
(11.2 million pounds [5,600 tons] of AI's,) which has 37 counties
with whole or partial ozone nonattainment status. The AI's with
the highest use in Michigan were atrazine (2.4 million pounds
[1,200 tons]), metolachlor (1.9 million pounds [950 tons]),
alachlor .(1.4 million pounds [700 tons]), and S-ethyl
dipropylthiocarbamate (EPTC) (1.1 million pounds [550 tons]).
Together California and Michigan account for 41 percent of the
herbicide use in ozone nonattainment areas nationwide. It should
be noted that Pennsylvania has the highest number of counties
with ozone nonattainment status (41) and accounted for
approximately 8 percent of the herbicide use in ozone
nonattainment areas nationwide. Connecticut, Rhode Island,
Massachusetts, and New Jersey were listed entirely as ozone
nonattainment areas such that 100 percent of these States'
pesticide use was in ozone nonattainment areas.
4.1.4 U.S. Department of Agriculture Data
The U. S. Department of Agriculture (USDA) publishes an
annual summary of the usage of agricultural chemicals in ten
selected field crops in the United States. Usage data for 1991
were presented in Section 3, Table 3-10 for the top
10 herbicides, insecticides, and other active ingredients for
each of the field crops. The 1991 Field Crops Summary reported a
total of 308 million pounds of herbicides, 33 million pounds of
insecticides, and 37 million pounds of other active ingredients,
including soil fumigants, fungicides, and others. These data
present a more accurate summary of the current AI usage on
specific crops than the RFF data base. However, these data
cannot be used to estimate nationwide usage or emissions because
they represent usage only on selected crops and are not
representative of total agricultural usage. In addition, no data
are available for usage in ozone nonattainment areas; this
4-5
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information is available in the RFF data. Therefore, the RFF
data will be used throughout this document to estimate total AI
usage and VOC emissions due to solvent loss.
4.2 VOC EMISSION CALCULATION METHODS
In general, the information necessary to calculate VOC
emissions from pesticide application includes an estimate of
pesticide use (pounds or tons of organic AI's); the formulations
of the AI's used, including the percent content of AI, organic
solvents, and other VOC inert constituents; and the percent of
the AI used in each type of formulation, i.e., liquid, granular,
etc. Additional required information includes the application
transfer efficiency, sorption and degradation losses, and other
fate estimates that are appropriate. Possible methods that can
be used to measure the organic solvent content of formulations or
to estimate VOC emissions are discussed in the following
subsections.
4.2.1 Laboratory Test Method
A test method development program was funded by the EPA
Office of Air Quality Planning and Standards (OAQPS) to develop
two test procedures for pesticide formulations. These test
procedures were developed to determine the organic solvent
content of emulsifiable concentrates (EC's) and liquid, non-EC
formulations of pesticides. The two test procedures are based on
thermal methods so the "organic solvent" content measured will
contain the actual solvent plus other formulation components that
will volatilze at 54 °C. The two methods selected were the
Volatile Organic Pesticide (VOP) Method, which-is a purge and
trap procedure, and ASTM E1131-86, thermal gravimetric analysis
(TGA). Each of the test methods is briefly described in this
section; additional information and the test procedures are
presented in Appendix C.
4.2.1.1 VOP Method Summary. The VOP Method is a test
method that allows direct measurement of the volatile organics in
a pesticide formulation. The procedure involves the dry nitrogen
purge of volatile organics in the pesticide formulation from a
weighed sample at a preselected temperature (54°C) and adsorption
4-6
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of these organics onto activated charcoal in preweighed tubes.
Any water, methanol, or other weakly adsorbed compound (e.g.,
ethanol, acetone, acrolein) will pass through the charcoal and be
adsorbed in preweighed tubes filled with adsorber material (e.g.,
Drierite). The sample is heated for a selected period of time
and, at the conclusion of the heating period, the final
adsorption weights for the sample residue, the charcoal tubes,
and the water tubes are determined. The weight percent organic
solvent and water in the pesticide formulation is determined from
the weight differential. The organic solvent content calculated
will contain solvent plus other constituents of the formulation
that volatilize at less than or equal to 54°C.
Use of this method has the advantage of requiring a
relatively inexpensive apparatus to perform the test. Because
the organic solvent can be desorbed from the activated charcoal,
analyses can be performed to determine if any active ingredient
is being evolved or identify the compounds evolved as organic
solvent.
The VOP Method requires a relatively large (1 gram) sample
compared to the TGA method and, although it is probably not a
major concern, the sample size presents more of a potential
safety and waste disposal concern than the smaller TGA samples.
Another disadvantage would be the potential diminished accuracy
of the method for low organic solvent content pesticide
formulations and for organic compounds with poor adsorption
properties on carbon.
4.2.1.2 TGA Summary. Thermal gravimeteric analysis (TGA)
is a technique in which the mass of the pesticide formulation is
continuously measured as a function of time or temperature.
During this measurement, the formulation is subjected to a
controlled temperature program and a constant flow of dry
nitrogen gas. Mass loss over specified temperature ranges can
provide a compositional analysis of the pesticide formulation
(e.g., organic solvent content, other VOC's). In this method, a
small quantity of the formulation (10 to 30 milligrams [mg]) is
placed in a sample holder in the apparatus and the heating
4-7
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program initiated. The change in mass is continuously recorded
over the selected temperature range. Mass loss can be recorded
as a function of increasing temperature or as a function of time
at a preselected temperature. Establishment of a mass loss
plateau can indicate the completed evolution of organic solvents
in the formulation at the selected temperature.
There are several advantages to the use of TGA, including:
I. The method can be a highly accurate procedure;
2. Instrumentation can be readily purchased or commercial
laboratories are available to perform TGA analyses;
3. The method is relatively simple to perform; and
4. This procedure uses small quantities of sample, thus
minimizing safety and waste disposal concerns.
There are two major disadvantages to this method. If
equipment purchase is considered, the TGA apparatus is relatively
expensive (e.g., $40,000 to $50,000) so use of commercial
laboratories may be necessary. The second major disadvantage is
the inability to determine if an active ingredient is being
evolved. Because the evolved compounds are not collected, no
analysis can be performed to determine if the active ingredient
is being volatilized. The water content of the formulation is
usually determined by using Karl Fischer reagent or gas
chromatography.
4.2.2 The CARS Method for VOC Emission Estimate Calculations
The DPR's PUR contains use and formulation data for
nonrestricted-use and restricted-use pesticides (those pesticides
that must be applied by a certified applicator) in California
(see Appendix A). Results from a California Air Resources Board
(CARS) survey on statewide use of pesticide oils (e.g., carrot
oil, weed oil) were used to determine the usage of nonsynthetic
pesticides, which are not reported in the PUR. Mr. Bill Lovelace
of CARB provided the 1987 statewide pesticide VOC emission
estimate at a meeting of the CAPCOA Pesticide Solvent Task Force
in Sacramento in March 1990. The estimated emissions for
synthetic pesticides were about 32,100 tons/yr (88 tons/d) and
nonsynthetic pesticides were about 18,600 tons/yr (51 tons/d).
4-8
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Estimation methods for emissions due to pesticide application
have been published by GARB.3
4.2.2.1 Emissions Due to Active Ingredients. In
calculating emissions, GARB assumed that there were no VOC
emissions from inorganic pesticides or from organic pesticides
with low vapor pressures (<10~7 millimeters of mercury [mm Hg]).
Additional factors related to the type of application were also
considered in calculating emissions, including:
1. Nonacreage application;
2. Applications to vegetated surfaces; and
3. Incorporation of a pesticide after application.
Prior to 1990, the GARB usage data did not necessarily include
nonrestricted-use pesticides. Only commercial applicators were
required to report nonrestricted-use pesticide applications. A
grower may or may not have reported use of a nonrestricted-use
pesticides. A correction factor was developed from information
obtained from county agricultural staff to correct for under
reporting. Based on pesticide use permit information supplied by
DPR, it was determined that a correction factor should be applied
to all reported restricted-use pesticide applications to
compensate for underreporting. Subsequent to 1990, the
California Pesticide Use Report will include data for all types
of pesticides, restricted and nonrestricted.
The VOC emissions were estimated beginning with emissions
during application due to immediate evaporation. Losses to the
remaining applied pesticide were estimated including loss due to
adsorption and absorption, and due to degradation. For most
pesticides, only a small percentage is irreversibly adsorbed and
unavailable for evaporation. Most pesticides are susceptible to
one or more degradation mechanisms, however, the quantity of
hydrocarbons available for vaporization is not necessarily
reduced. A pesticide may be degraded into two smaller compounds,
but this does not change the total mass available for
evaporation. Each of these losses were assumed to be small but
were considered in estimating VOC emissions.
4-9
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An evaporation rate is needed to calculate the VOC emissions
per month from the amount of pesticide applied. The method used
by GARB to estimate the evaporation rate was based on a model
developed by Hartley and modified by Spencer.4'5 The method is
based on the principle that the rate of loss of a pure substance
into the atmosphere from an inert surface is governed by two of
the substance's properties: the saturation vapor concentration
and the rate of diffusion through the still air layers bounding
the treated surface. Emission rates of pesticides applied to
soil surfaces, incorporated into the soil, and applied to
vegetation differ and VOC emissions were calculated separately
for each type of application (see Appendix A for details).
4.2.2,2 Emissions Due to Inert Ingredients. Many pesticide
formulations, particularly emulsifiable concentrates, contain
volatile organic solvents classified as inert ingredients.
Emissions of these compounds have not been estimated because of
the difficulties imposed by claims of confidentiality of the
pesticide formulations. Emissions calculated have traditionally
been based on the amount of AI applied. Because the pesticide
usage in California is reported as the total amount of
formulation applied, the amount of AI applied was derived for
this document from the percent content of AI reported by the
registrant of a formulation. Midwest Research Institute (MRI)
reviewed formulation data at the OPP in Washington, D.C., and
developed the inert content information. The amount of inert
applied was estimated by taking the appropriate percentage of the
total formulation applied. Using the 1987 PUR in California, the
estimated emission of inert (solvent) ingredients was
approximately 3,100 tons/yr (see Appendix A, Tables A-4 and A-5).
Unfortunately, calculating emissions from the inert portion
of the formulation is not as simple as taking the remaining
percentage of the total applied and using the same method as that
used for the AI because many different compounds and materials
are used as inerts in a formulation. Many of these compounds are
inorganic and are not a source of emissions. In order to
determine emissions from the inert portion of a pesticide, the
4-10
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identity and percentage of the VOC's in the formulation must be
known. If the identities of inerts are known, then their vapor
pressures can be used to calculate the maximum evaporation rate
as described in Appendix A. If the percentage of the inert is
known, then the total amount applied can be calculated from the
total usage reported in the PUR. This is the approach used in
the GARB emission inventory.
States may find data developed by the GARB VOC emissions
estimates useful in their estimates of VOC emissions. Average
data, such as percent of AI in each formulation, from the
California PUR may be used as estimates in calculations to
approximate another State's VOC emissions.
4.2.2.3 Nonsynthetic Data. The CARS also estimated VOC
emissions for nonsynthetic pesticides or pesticide oils (i.e.,
weed oils, carrol oil). Insecticidal oils are important because
one treatment with an oil can often replace more than one spray
application of a pesticide. The usage estimate, 18,600 tons of
pesticide oils, was obtained from a statewide inventory conducted
by CARB in 1980 of oils used as pesticides in 1979. Emissions
from nonsynthetic pesticides were calculated by the CARB method
described in Section 4.2.2.
4.2.3 Use of Formulation Data
The method used in this document (Section 4.3) to calculate
nationwide total VOC emissions and emissions from ozone
nonattainment areas using the RFF data bases makes several
assumptions not made in the CARB method. No correction factors
were applied to account for underreporting of pesticide use. The
VOC emissions are presented for total pesticides: AI's and
inerts.
4.2.3.1 Active Ingredients. The estimation of VOC
emissions from a pesticide formulation ready for field
application is very difficult because of the lack of experimental
data on losses resulting from field application. As an example,
volatilization losses of pesticide formulation components during
the actual application process represents an area where few
experimental data exist and studies in this area are only in the
4-11
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formative stages for cooperative studies between the U. S.
Department of Agriculture (USDA) and industry.6 Studies have
been conducted on the losses due to drift during aerial
application. The determination of actual losses due to
volatilization during application is complicated by the fact that
the evaporation is continuous from the time the formulation
leaves the spray boom and the overall process is best regarded as
a continuous, rapid, and dynamic system.7"9
In an attempt to obtain some insight into the magnitude of
pesticide losses during and subsequent to field application, the
available literature was reviewed. A summary of these pesticide
volatilization studies is presented in Table 4-1. This summary
includes data for 16 different AI's applied primarily by some
type of vehicle drawn sprayer (surface sprayer), although some
data are included for aerial application. Because this summary
focussed on volatilization, numerous studies on drift resulting
from aerial application have not been included. Soil types
ranged from sandy loam to clay with moisture levels ranging from
dry to wet. Because of the number of AI's and formulations, the
results showed the expected very wide range of volatilization.
The data shown in Table 4-1 were divided into three time groups:
(1) losses upon application and for up to 24 hours after
application; (2) losses during application and subsequent
cumulative time intervals between 1 day and 7 days; and
(3) losses during application and for subsequent cumulative times
of 21 days to 30 days. For surface sprayers, the results show
that the simple arithmetic average volatilization losses during
application and for periods up to 24 hours after application were
41 percent. The average losses during application and for times
greater than 1 day but not over 7 days after application were
55 percent. Losses during application and for times greater than
21 days but not over 30 days after application averaged
65 percent. There is a very large variance in the percent losses
within each of these three groupings. The vapor pressures of the
AI's ranged from approximately 10"2 to 10"7 but the majority were
in the range of 10"4 to 10"6. However, the results indicate that
4-12
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the highest percentage loss occurs during application and within
the first 24 hours after application. After this initial period,
the loss due to volatilization appears to slow markedly with
time. After a 30 day period, the losses resulting from
application and the subsequent 30 days showed an average of
65 percent compared to a 41 percent loss during application and
the next 24 hours. For time periods in excess of 30 days, many
other factors, including sorption, microbial degradation,
hydroysis, photolysis, and others, can lead to the loss of
pesticide formulations which do not necessarily result in VOC
emissions. Although the data show a wide variation, no other
results are readily available to estimate VOC emissions from
pesticide formulations. The remaining portion of the pesticide
formulation will undergo sorption, surface water runoff, and
natural degradative processes.
4.2.3.2 Solvents. Information was collected through an
informal survey of manufacturers of the major types of
formulations for the most used AI's by pounds used reported in
the data bases. Formulations with organic solvents were assumed
to consist of only AI and solvent and no other inert ingredients
such that 100 percent of the formulation by weight is accounted
for by AI and solvent. The percent of AI in organic solvent -
containing formulations and the percent organic solvent content
of those formulations were used to calculate VOC emissions due to
organic solvents in pesticides.
The factors used to calculate VOC emissions from the
pesticide use data obtained from RFF and from an informal survey
of pesticide manufacturers are nationwide pounds of AI used, the
fraction of AI production in a nonaqueous solvent-based
formulation, and the fraction of the formulation that is
nonaqueous solvent.1'10"25 Calculations are discussed in more
detail in Section 4.3. Results are discussed in Section 4.4.
Formulation information obtained from manufacturers
describes current pesticide formulations and, therefore, is not
necessarily representative of formulations used in the mid-1980's
that are reported in the data bases. The registrations of
4-17
-------
several AI's, (i.e., EDB, DBCP, etc.), have been cancelled since
the data base was compiled, and no formulation information was
obtained for these pesticides. However, since fumigants are
highly volatile, 100 percent of the pounds used was added to the
VOC emissions estimate. Cancelled nonfumigant pesticides were
not considered in the emissions calculations because no
information on their formulations was readily available from
manufacturers and no assumptions were made concerning their
volatilities. No formulation data was obtained for 51 percent of
the insecticide usage data. Ninety three percent of the
herbicide usage data was used in the emissions calculations and
formulation data were available on 87 percent of that herbicide
usage.
States that currently have no pesticide use data may obtain
pesticide use data for that State from RFF. This information may
be used to calculate VOC emissions estimates from data presented
in Section 4.4 on percent of AI in organic solvent-based
formulations and the percent of organic solvent content of the
formulation.
States that have compiled pesticide use information by AI
may estimate VOC emissions by using data presented in
Section 4.4. However, information presented here may not cover
all pesticides used by States and all use patterns. The
selection and use of formulation types is specific to certain
crops and geographic regions. Therefore, more specific
information than that presented in Section 4.4 may be necessary
to provide a more accurate estimate of VOC emissions.
Users of this method and data should be aware of the
assumptions made as discussed above. The assumptions were made
to simplify calculations due to the wide range of chemical and
physical properties of the organic solvents and AI's, the lack of
available data to characterize these properties, and the complete
AI formulations. More specific information such as
meteorological conditions and precise formulation information
will allow more representative VOC emissions estimates to be
calculated (e.g., by the CARS method). State or local agencies
4-18
-------
should conduct a survey of pesticide use in their area to
estimate their VOC emissions from pesticide application. An area
survey would focus on only those pesticides and formulations used
locally and would provide more accurate emissions estimates than
using the data presented in this document.
With the availability of pesticide use inventory
information, a more accurate VOC estimation can be made.
Formulator data or pesticide analysis can be applied to the use
data to more accurately represent VOC emissions due to pesticide
application within the State.
4.3 ESTIMATION EQUATION
The calculation of VOC emissions is based on the percentages
of AI and organic solvent content of the pesticide formulations .
The fraction of the AI formulated in an organic solvent -based
formulation was applied to the nationwide total pounds of AI used
to calculate the pounds of AI formulated in the organic solvent -
based formulation. Using this figure and the percent of organic
solvent in the formulation, the number of pounds of organic
solvent associated with each AI was calculated using the
following equation:
where :
X = AI pounds in organic solvent formulation;
Y = weight fraction of organic solvent in the formulation of
the specific AI; and
Z = pounds of volatile organics formulated with the AI,
volatile emissions per AI.
The maximum VOC emissions were estimated by adding the total
pounds of an AI to Z
Maximum VOC emissions = Z + S, (Eq. 2)
where:
S = specific AI pounds used nationwide.
4-19
-------
Total herbicide and insecticide solvent or maximum VOC emissions
were estimated by totalling each for AI's used either nationwide
or in ozone nonattainment areas. The combined total solvent and
maximum VOC emissions are the sums of herbicide and insecticide
totals.
4.4 ESTIMATED VOC EMISSIONS
The VOC emissions estimates due to solvent usage were
calculated by pesticide type--herbicide and insecticide--
nationwide and for ozone nonattainment areas in the United States
using data from the RFF data bases (see Section 4.1.2).
Nationwide the combined (herbicide plus insecticide) estimated
maximum AI usage and solvent VOC emissions from agricultural use
are 511 million pounds (255,600 tons) and 93 million pounds
(46,400 tons), respectively. Solvent VOC emissions are defined
as those emissions due only to the nonaqueous (organic) solvent
in the formulation. Aqueous-based formulations may also contain
organic constituents that could result in VOC emissions; however,
for these calculations only nonaqueous-based formulations were
considered. In ozone nonattainment areas, the approximated
combined maximum AI usage is 72 million pounds (36,000 tons).
The approximated combined solvent VOC emissions are 9.6 million
pounds (4,800 tons).
Insecticide-related VOC emissions for the period 1982-1984
were calculated on a nationwide basis (Table 4-2) and
approximated for ozone nonattainment areas (Table 4-3) from the
ratio of herbicide use in state ozone nonattainment areas to
herbicide use statewide. This approximation was necessary
because insecticide use data was not available at the county
level from RFF. The use patterns of herbicides and insecticides
may be quite different within States so the results obtained by
this method should be considered only rough approximations. The
estimated VOC emissions in Tables 4-2 and 4-3 are only for the
years 1982-1984 because this represents the time period of the
RFF data base (see Section 4.1.2) . Because of this, some of the
AI's shown in these tables are no longer registered or in use.
Table 3-10 presents a summary of the top ten herbicides,
4-20
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insecticides, and other AI's used for selected field crops in
1991.
The estimated maximum insecticide use (AI only) nationwide
are 87.5 million pounds (43,800 tons), or 17 percent of the
nationwide combined (herbicide plus insecticide) estimated AI
usage. Insecticide-related solvent VOC emissions nationwide are
estimated to be 6.6 million pounds (3,300 tons), or 7 percent of
the nationwide combined VOC solvent emissions. As noted above,
an approximation of individual insecticide AI use was made for
ozone nonattainment areas. Table B-l in Appendix B presents the
statewide and State ozone nonattainment area data for insecticide
use calculated from the corresponding ratios of herbicide use.
The individual insecticide AI usages in Table 4-3 were calculated
from the overall ratio (0.2284) of insecticide use nationwide and
in ozone nonattainment areas that results from Table B-l.
Approximate ozone nonattainment maximum AI usage was 20 million
pounds (10,000 tons), or 4 percent of the nationwide combined
maximum AI usage. Solvent VOC emissions from insecticide
application in ozone nonattainment areas were approximated at
1.5 million pounds (750 tons), or 2 percent of the nationwide
combined solvent VOC emissions.
Herbicide usage and herbicide-related VOC solvent emissions
were calculated for nationwide use and for herbicide use in ozone
nonattainment areas. These results are presented in Tables 4-4
and 4-5. The estimated usage and VOC solvent emissions in
Tables 4-4 and 4-5 are only for the years 1987-1989 because this
represents the time period of the RFF data base (see
Section 4.1.2). The estimated maximum herbicide usage nationwide
are 424 million pounds (212,000 tons), or 83 percent of the
nationwide combined estimated herbicide and insecticide usage.
The estimated solvent VOC emissions from herbicide use nationwide
are 86 million pounds (43,100 tons), or 93 percent of the
nationwide combined solvent emissions. The estimated maximum AI
usage from herbicides in ozone nonattainment areas is 52 million
pounds (26,000 tons), or 12 percent of the combined estimated
maximum herbicide AI usage nationwide. The estimated solvent VOC
4-23
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emissions from herbicide use in ozone nonattainment areas are
8.1 million pounds (4,000 tons), or 9 percent of the combined
estimated nationwide solvent VOC emissions.
4.5 REFERENCES FOR SECTION 4.0
1. Gianessi, L., et al. Pesticide Use in Coastal Counties.
Coastal Zone '89 Proceedings of the Sixth Symposium on
Coastal and Ocean Management. July 11 to 14, 1989. pp. 412
to 422.
2. Aspelin, A.L., A.H. Grube, and V. Kibler. Pesticide Industry
Sales and Usage: 1989 Market Estimates. Economic Analysis
Branch, Biological and Economic Analysis Division, Office of
Pesticide Programs. U.S. Environmental Protection Agency.
July 1991. 21 pp.
3. Methods for Assessing Area Source Emissions in California.
California Air Resources Board, Technical Support Division,
Emission Inventory Branch, Sacramento, California.
September 1991.
4. Hartley, G. S. Evaporation of Pesticides. Adv. Chem.
Series. £6:145. 1969.
5. Spencer, W. F., W. J. Farmer, and M. M. Cliath. Pesticide
Volatilization. Residue Review. 4_9_:l. 1973.
6. Telecon. Lapp, T., MRI, with Rice, Dr. Cliff, U. S.
Department of Agriculture, Beltsville, MD. February 25,
1993. Discussion of the availability of data on
volatilization of pesticides during field application.
7. Taylor, A. W., D. E. Glotfelty, B. C. Turner, R. E. Silver,
H. P. Freeman, and A. Weiss. J. Agric. Food Chem. 25
(3):542-548. 1977.
8. Glotfelty, D., A. Taylor, B. Turner, and W. Zoller.
Volatilization of Surface-Applied Pesticides From Fallow
Soil. J. Agric. Food Chem. 11:638-643. 1984.
9. Taylor, A. Post-Application, Volatilization of Pesticides
Under Field Conditions. JAPCA. 21(9):922-927.
September 1978.
10. Telecon. Marron, J., MRI, with Shue, J., Rhone-Poulenc.
October 23, 1991. Pesticide formulation and market
information.
11. Telecon. Marron, J., MRI, with Haefele, L., Drexel Chemical
Company. October 18, 1991. Pesticide formulation and
market information.
4-28
-------
12. Telecon. Marron, J., MRI, with Cline, D., and
S. Flemming, Monsanto Agricultural Company. October 23,
1991. Pesticide formulation and market information.
13. Telecon. Marron, J., MRI, with Pedersen, K., Cheminova Inc.
October 18, 1991. Pesticide formulation and market
information.
14. Telecon. Marron, J., MRI, with Sutton, D., Rohm and Haas
Company. October 23, 1991. Pesticide formulation and
market information.
15. Telecon. Marron, J., MRI, with Person, J., Crystal Chemical
Inter America. October 21, 1991. Pesticide formulation and
market information.
16. Telecon. Marron, J., MRI, with Hartsler, B., Department of
Agronomy, Iowa State University. October 21, 1991.
Pesticide formulation and market information.
17. Telecon. Marron, J., MRI, with Nelson, T., BASF
Corporation, Agricultural Chemicals. October 21, 1991.
Pesticide formulation and market information.
18. Telecon. Marron, J., MRI, with Burton, R., and Eilrich, G.,
. ISK Biotech Corp. October 21, 1991. Pesticide formulation
and market information.
19. Telecon. Marron, J., MRI, with Bozeman, L., Sandoz Crop
Protection Corp. October 23, 1991. Pesticide formulation
and market information.
20. Telecon. Marron, J., MRI, with Lafiles, J., Griffin Corp.
Agricultural Chemicals Group. October 25, 1991. Pesticide
formulation and market information.
21. Telecon. Marron, J., MRI, with Hendershot and
C. Bluwett, DowElanco. October 25, 1991. Pesticide
formulation and market information.
22. Telecon. Marron, J., MRI, with Customer Service and
Reed, J., ICI Americas, Inc. Agricultural Products.
October 25, 1991. Pesticide formulation and market
information.
23. Telecon. Marron, J., MRI, with Poppe, C., American Cyanamid
Company. October 23, 1991. Pesticide formulation and
market information.
24. Telecon. Marron, J., MRI, with Siegal, M., Ciba Geigy
Agricultural Division. October 28, 1991. Pesticide
formulation -and market information.
4-29
-------
25. Telecon. Marron, J., MRI, with Rookaird, L., DuPont
Agricultural Products. October 21, 1991. Pesticide
formulation and market information.
4-30
-------
-------
5.0 EMISSION REDUCTION TECHNIQUES
This section presents information on technically viable
methods that may be applied to reduce volatile organic compound
(VOC) emissions resulting from the application of agricultural
pesticides. The information will allow agency personnel and
others to identify the advantages, disadvantages, and probable
emission reductions associated with implementing these
techniques. A total of seven techniques are discussed, and each
is presented in the following format: description of the option,
benefits and limitations of the technique, and potential emission
reduction levels. The techniques may be used singly or in
combination to achieve a desired level of VOC emission reduction.
The implementation of the emissions reduction techniques
discussed in this section could occur under two different
scenarios. One scenario would have the regulatory strategies to
implement any of these emission reduction techniques occurring at
the State level rather than on a nationwide basis. The number of
ozone nonattainment areas, the level of nonattainment, and
agricultural practices vary considerably from one State to
another. Because of tjiis, the type of emission reduction
techniques and the number of techniques to be implemented may be
different for each State. Implementation at the State level
allows each State to tailor an emission reduction strategy to
fulfill the needs of the State. Under Section 24A of the Federal
Insecticide, Fungicide and Rodenticide Act (FIFRA), each State
may regulate the sale or use of any Federally registered
pesticide or device in the State, but only if and to the extent
that the State regulation does not permit any sale or use already
prohibited by FIFRA.
. 5-1
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The second scenario would have implementation occur at the
nationwide level. In New York State, the Department of
Environmental Conservation encountered problems in attempting to
reduce or ban the use of selected consumer products. Under a
State implementation scenario, similar problems may occur with
some of the control options presented in this section. A second
potential problem with State implementation is the creation of a
complex market for the pesticide producers which could lead to
greater impacts on farmers in some States than in others.
Because of the complex market and costs due to product
development, production, and registration, some producers may
choose to drop use labels for minor crops. Implementation of
emission reduction techniques at a nationwide level by EPA,
possibly by incorporating ozone air quality concerns into the
inert policy, could serve to minimize inconsistencies that may
arise at the State level.
Section 5.1 presents techniques for reducing VOC emissions
by reformulating liquid pesticides containing organic solvents.
Sections 5.2 and 5.3 present a reduction in fumigant usage and
alternative application methods, respectively. Sections 5.4 and
5.5 discuss the use of microencapsulation techniques and
integrated pest management (IPM) practices. Section 5.6
evaluates the use of alternative active ingredients (AI's), and
Section 5.7 presents a discussion of the applications of
materials known as "weed oils."
5.1 REFORMULATION OF LIQUID PESTICIDES
w
5.1.1 Option Description
This technique requires synthetic pesticide manufacturers to
reformulate existing emulsifiable concentrates (EC's) and other
liquid pesticide formulations containing organic solvents to
eliminate or reduce VOC emissions of the inert constituents,
primarily the volatile organic solvents. Organic solvent-based
liquids and EC's are widely used because they are low cost to the
formulator and easy for the farmer to apply in the field. For
example, many AI's are soluble only in petroleum solvents.
Liquid formulations also penetrate porous material well and may
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provide a more uniform coating on leaves, which improves
efficacy. Because the EC's are liquids, they are easy to pour
and measure for mixing in the field.
Several strategies could be employed to encourage the
reformulation of the existing liquid pesticides. One strategy
would be to ban all organic solvent-based liquid pesticides by
prohibiting distributors from selling and farmers from using
noncomplying pesticides in nonattainment areas. In this case,
the manufacturers/formulators would have to label products to
prohibit usage in the nonattainment areas. Any change in the
labeling requirements is under the authority of the EPA Office of
Pesticide Programs (OPP); States do not have authority to require
label modifications or changes. As stated earlier, a State has
the authority under Section 24A of FIFRA to regulate the sale or
use of any Federally registered pesticide or device in the State.
This, in effect, could be used to ban use of those formulations
whose labels allow use in nonattainment areas.
If all of the organic solvent-based formulations could be
phased out over a period of time instead of having an immediate
ban in nonattainment areas, this would provide time for
developing and testing new pesticide formulations and result in
the gradual substitution of organic solvent-based liquids, which
would minimize the impact on the growers, regulators, and the
pesticide industry.
5.1.2 Benefits and Limitations
The pesticide industry is already under considerable
pressure to reformulate organic solvent-based pesticides. The
OPP inert strategy is currently driving industry to reformulate
pesticides containing the inert ingredients on List 1 (inerts cf
toxicological concern) or remove the product from the market (see
Appendix D for lists 1 and 2). Only a very few of the List I
inerts are still used; essentially all of them have been
replaced. In addition, Department of Transportation restrictions
regarding the transport of highly flammable chemicals, which
include some pesticide inerts, have encouraged manufacturers to
reformulate to less flammable inerts. The problem with an
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immediate or complete removal of all EC's and other organic
solvent-based liquids is that it could have adverse impacts on
those crops, livestock, and forests that rely primarily on these
liquid pesticides. Considering that there may not be an
effective or appropriate substitute for the removed formulation,
the impact on the commodity production and the market could be
severe. Therefore, the grower may not have another option or an
effective way of resolving the problems caused by an immediate
removal.
This emission reduction strategy avoids addressing AI's.
Reformulating a pesticide is less costly and time consuming than
developing an entirely new AI, which can be a long and costly
process. All reformulations must be approved by OPP. Massive
reformulations under an air regulation could add years to the
process. Changes in the labeling process require an up-front
interagency coordination and may also slow down the overall
registration process. For individual States, Section 24 of FIFRA
may be used to control or restrict the use of a pesticide
formulation within that State.
5.1.3 Emission Reduction Potential
The solvent contribution of those pesticides formulated as
organic solvent-based liquid pesticides in Tables 4-2 and 4-4 is
about 46,400 tons per year.
Current OPP policy is to phase out the solvents on List 1 of
the inert ingredients in the pesticide products (see Appendix D).
The List 1 compounds are those of toxicological concern and
include many of the more common organic solvents that could be
used in liquid pesticides, such as the chlorinated hydrocarbons,
hexane, dioxane, and others. Inerts on List 1 currently being
used as solvents could be eliminated or restricted based on the
outcome of the hearings conducted under FIFRA Section 6(6)(2).
Current estimates are that those inert compounds presently on
List 1 will be replaced or suspended in about 2 years. However,
common solvents for liquid pesticide formulations, such as
xylene, toluene, and 1,I,1-trichloroethane, are on List 2
(Potentially Toxic Inerts) and could be used in alternate solvent
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systems. List 2 inerts are being reviewed and reevaluated by.OPP
and a number of the compounds currently on List 2 could be
promoted to List 1. A few of the current List 2 inerts may be
downgraded to List 4 (Inerts of Minimal Concern). Those inerts
upgraded from List 2 to List 1 could be replaced or suspended
sometime in the future. Therefore, the current OPP policy to
eliminate List 1 inerts from registered products will result in
little, if any, reduction in the organic solvent contribution to
liquid pesticides because alternative solvents are available from
List 2.
5.2 REDUCED FUMIGANT USAGE
5.2.1 Option Description
One option would restrict the volume of sales and the type
of application of all or selected fumigants on a State basis
under Section 24 of FIFRA. Most fumigants are used in some form
of controlled environment so the use and emissions of these
chemicals may be monitored. For selected commodities, fumigation
chambers are used and the emissions from the chambers can be .
controlled. Monitoring the use of these chemicals in many
agricultural fields should be fairly easy because the application
procedure, which uses large plastic sheets to cover the affected
area for days or weeks, is so visible. A major use of fumigants
is to control the spread of fungi and to reduce destruction of
the crop (e.g., grains, corn) by insects and rodents during crop
storage.
A second option would be a complete ban on fumigant usage
and substitution of liquid or granular products to control
nematodes and fungi. Other methods, such as crop rotation and
biological means, are also options. Since the restriction on
1,3-dichloropropene, county agents state that many or all of
these options have been attempted by farmers in California with
varying degrees of success. The overall consensus of the agents
from four selected counties was that while substitutes were
available, there were efficacy or application problems with each
one and acceptable alternatives to some fumigants are not always
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available. The fumigants being used as a replacement- for
1,3-dichloropropene are discussed in Section 5.2.2.
5.2.2 Benefits and Limitations
Because of the limited number of products affected, a
restriction on the total quantity sold and the specific
application for the fumigants may be easier to implement than a
total ban. Since the use of fumigants is not totally banned, but
restricted, there may not be any adverse impacts on the growers
who have to use fumigation.
Currently, no substitutes are available in the market and
the impacts of the options must carefully be studied for each of
the fumigants. The use of one of the key fumigants,
1,3-dichloropropene (Telone®), is suspended in California pending
the outcome of testing to respond to air toxics concerns. In
addition, OPP's Special Review and Reregistration Division also
has this fumigant under special review, but the results are
unknown at this time. In California, alternative fumigants being
used during the suspension of l,3-dichloropropene include
Metarn-sodium, methyl bromide, and Nemacur®. Although each of
these pesticides can be substituted for 1,3-dichloropropene in
selected applications, each of these has its own problems or •
limitations.1 In addition, the issue of substitution concerning
each of these alternatives is very crop-specific.
Metam-sodium is formulated as a concentrated solution and is
stable so long as the solution remains concentrated. During
application, the concentrated solution is applied to the field
and the field watered. The AI is unstable in dilute solution,
and watering the field after application dilutes the concentrated
solution, resulting in hydrolytic decomposition of Metam-sodium.
The decomposition product(s) volatilizes and acts as the actual
fumigant. The major problems with this AI lie with handling the
concentrated solution and the resulting decomposition if the
solution is accidentally diluted.
Methyl bromide is a gas and must be handled in pressurized
containers. This AI is toxic to humans, and the potential
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problems lie with handling pressurized tanks during shipment and
application.
Nemacur® is formulated either as an EC or a granular and, in
Section 5.1, the emission reduction option is the reduction or
elimination of EC formulations. Currently, the AI is applied by
broadcast, in-the-row, in bands, and by drench methods.
5.2.3 Emission Reduction Potential
Fumigants could represent a large emission reduction
potential from a single class of synthetic pesticides depending
upon the application of the fumigant. Based on the data in
Table 4-2 for dibromochloropropane (DBCP) and ethylene dibromide
(EDB), the total quantity used is approximately 21,000 tons/yr.
Although the use of DBCP was discontinued in 1987 and EDB is not
registered for agricultural use in the United States, it has been
assumed that an equal quantity of substitute fumigant has
replaced DBCP and EDB.
In California, 1,3-dichloropropene accounted for a large.
volume fumigant usage until its use-was suspended in April 1990.
The three fumigants being used as replacements for the suspended
fumigant provide varying potential for emission reductions.
Metam-sodium is commonly applied to a field as a concentrated
solution and then diluted with water which results in hydrolysis
to form a volatile product. For this application, little or no
potential for emission reduction exists. This fumigant can be
used as a solid for selected applications (e.g., as a
nematicide). Although the potential for emission reduction is
significant, the quantity used for this application is small.
Methyl bromide is a gas so no potential for emission reduction
exists for this fumigant. Nemacur® is formulated as a granular
product and a potential for emission reduction is present.
The estimated maximum reduction potential is difficult to
predict because of specific application requirements. If solid
formulations can be used for field applications, the overall
potential for emission reduction could be significant because of
the much lower vapor pressure of solid formulations and also
because of incorporation into the soil. For crop storage in
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elevators or bins, a gas or volatile liquid product is the most
effective treatment method to obtain good mixing between the crop
and the fumigant. Use of these products would present very
little potential for emission reduction.
5.3 ALTERNATIVE APPLICATION METHODS
5.3.1 Option Description
This option would require the application equipment
manufacturer to develop and demonstrate improved-efficiency
application equipment. Current research from a limited study in
California on strawberry plants has resulted in promising
information on equipment to improve application efficiency. The
study, conducted at the University of California-Davis,
determined pest control efficacy achieved by reduced-volume
sprays of charged and uncharged droplets delivered to the plants
in air-carried jets. In early season trials, the reduced-volume
applications and the conventional high-volume applications
appeared to control mites equally well. Deposition studies
showed the reduced-volume equipment deposited slightly higher
amounts of pesticide on the leaf, with more persistent
deposition. Deposition studies conducted in July/August showed
the reduced-volume, charged sprayer achieved about 32 percent
greater deposition and 36 percent greater half-life than a
conventional application at the same AI amount per acre. Using
the reduced-volume sprayer, applying the AI at 50 percent of the
rate of a conventional sprayer gave almost the same deposition
quantity and half-life.
Soil incorporation during application can be an effective
method to reduce pesticide volatilization. Data in Table 4-1
showed this method significantly reduced the percentage of
pesticide lost compared to application by surface spraying.
An operator training program could be required in
conjunction with the sale of the improved-efficiency application
system and could be included as part of a Statewide licensing
program.
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5.3.2 Benefits and Limitations
Although the results of the reduced-volume sprayer study are
only for one type of crop using one alternative system, the
results indicate improvements in overall pesticide application
efficiency are possible. If equal improvements can be shown for
other systems, improved application efficiencies may result in
reduced pesticide application quantities of up to 30 to
50 percent.^
Improving application efficiency may significantly reduce
worker exposure and drift-related problems. The industry is
already under considerable pressure to reduce these types of
exposure, and an air regulation will be consistent with programs
that are currently underway, such as drift-reduction training.
Purchasing new application equipment or parts could place a
significant economic burden on individual farmers or commercial
applicators. The cost impact of the new equipment would depend
upon the type of equipment or the required parts. By phasing in
the regulation, the financial burden may be reduced significantly
and result in a considerably more receptive atmosphere for the
new regulation by the farmers and commercial applicators.
Revising application methods may result in formulation
changes, which may have emissions or other environmental impacts.
Important variables such as applicator training and
experience, weather conditions, equipment maintenance and
calibration practices, and formulation of the pesticide all
affect efficiency, and therefore need to be carefully considered.
5.3.3 Emission Reduction Potential
No information was found to identify those active
ingredients that could be applied with reduced-volume application
equipment. Therefore, there are no data to suggest that this
method would not be applicable to all liquid pesticide
formulations. If the results of the study at the University of
California-Davis are indicative of the reduction in application
rates that could be achieved, it is possible that new equipment
could result in an application rate one-half of the current rate
for a conventional spray applicator.
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5.4 MICROENCAPSULATION
5.4.1 Option Description4'5
This strategy would require pesticide manufacturers to
develop microcapsule formulations for all AI's currently
formulated as an EC or an organic solvent-based liquid or
demonstrate that this type of formulation is not technically
feasible for a specific AI.
Microencapsulation is a process whereby very small particles
or droplets are encased by a coating, usually polymeric, to
. produce" very small capsules. In simple terms, a microcapsule is
a small sphere with a uniform wall surrounding it. The material
inside the microcapsule is referred to as the core, internal
phase, or fill and the wall is called the shell, coating, or
membrane. For pesticides, the principal component of the core is
the specific AI; a small amount of solvent is also present in the
core. Most microcapsules are envisioned to be small spheres
having diameters in the range of a few micrometers to a few
millimeters. However, many microcapsules have shapes
considerably different from spheres because the core may be a
crystal, a jagged sorbent particle, a suspension of solids, an
emulsion, or a suspension of smaller microcapsules. The final
microcapsule may even have multiple walls.
In forming microcapsules for a pesticide AI, the basic
process is the formation of a plastic shell around a droplet
containing the AI. This process is carried out in an emulsion.
Many techniques are available to produce microcapsules but the
most common process for pesticide AI's is the chemical method of
interfacial polymerization. In this method, under the proper
conditions, two reactants in a polycondensation meet at an
interface and react rapidly to form thin flexible walls. For
pesticide AI's, two monomers are selected that will react to form
the microcapsule. One of the monomers is water-soluble and the
other is insoluble in water. The selection of the specific
monomers depends upon the solubility of the AI, the ultimate use
of the formulation, and the particular properties required of the
microcapsules. The pesticide AI is dissolved in one of the
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monomers, and this solution is combined with a solution of the
second monomer to form an emulsion. The microcapsules are formed
from this emulsion by interfacial polycondensation.
There are primarily three processes for forming
microcapsules, two patented processes based on the chemical
method of the interfacial polycondensation and the third on
coacervation. The process patented by Monsanto produces the
highest concentration of AI (4 pounds [Ib] of AI per gallon [gal]
of solution). In the patented Pennwalt process, the maximum
concentration of AI is approximately 2 Ib/gal. Formation of
microcapsules by coacervation, the third process, results in the
formation of very dilute concentrations of AI.
5.4.2 Benefits and Limitations
Microencapsulating a pesticide AI can be a very effective
method to reduce the quantity of solvent compared to EC's or
organic solvent-based liquids and to control the rate of release
of the AI and volatile constituents of the formulation into the
environment. The primary benefit of this method is the reduction
in the quantity of solvent.^ The reduced rate of release of the
components from the microcapsule does not necessarily correspond
to an additional reduction in VOC emissions. The slower release
rate only extends the quantity emitted over a longer period of
time unless it can be assumed that during that time hydrolysis
and microbial degradation will destroy a portion of the VOC's.
If this destruction occurs, a limited reduction in VOC emissions
could be anticipated. Monsanto originally developed the
microencapsulation process for alachlor because of groundwater
contamination problems associated with using EC formulations of
the AI.
Microcapsules can be produced at a size equivalent to a
grain of very fine sand or smaller. These microcapsules can be
suspended in water and applied to the target crops using ordinary
liquid spray equipment. Purchase of special spray equipment is
not required.
Microencapsulation is not a universal answer to reduced
organic solvent usage and the emission of VOC's from pesticide
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formulations. For some AI's, it is very difficult to form a
stable emulsion, which is necessary to produce the microcapsules.
A potential major production problem associated with
microencapsulation is the absence of any method to recover the AI
from a bad formulation. In many other processes, if a problem
occurs during formulation and the final product does not meet
specifications, adjustments can be made to the formulation to
bring the product within specifications and the AI is not lost.
In microencapsulation, if a problem occurs during production of
the microcapsules, there is no way to recover the AI and the
entire batch is lost. Thus, microencapsulation can be an
expensive production method unless it is used only with AI's that
will allow the formation of very stable emulsion systems.
The formation of microcapsules with high AI concentrations
(i.e., 4 Ib Al/gal) makes the product more economical to
manufacture. However, the patents for producing microcapsules at
this concentration are held by Monsanto and are not generally
available. These patents expire in July 1998. As the
concentration of the AI decreases, the product becomes less
economical to manufacture.
Subsequent to field application, microcapsules can present a
potential hazard to honey bees and other pollinators.
5.4.3 Emission Reduction Potential
The solvent contribution of all EC's and organic
solvent-based liquid formulations in Tables 4-2 and 4-4 is about
46,400 tons/yr. It cannot be anticipated that all of these
formulations could be converted to microencapsulation, and the
actual number of AI's that could be reformulated and used as
microcapsules is not known.
5.5 INTEGRATED PEST MANAGEMENT
5.5.1 Option Description
Integrated pest management (IPM) is an ecologically based
pest management program that combines biological and
nonbiological control techniques to suppress weeds, insects, and
diseases. This option has been defined as a pest population
management system that utilizes all suitable techniques in a
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compatible manner to reduce pest populations and maintain them at
levels below those causing economic injury. The IPM approach has
been used in varying degrees for 20 years and, in some instances,
may reduce the effects of pesticides on groundwater, soil, and
wildlife.^ This pest management program encompasses a variety of
farming practices including:
1. The use of naturally-occurring agents, such as predator
insects and biological agents;
2. Increased crop rotation and tillage in areas where
erosion is not an overriding factor;
3. Removal of crop refuse, close timing of planting dates,
and selection of optimal planting sites;
4. Careful management of water and fertilizer use; and
5. As appropriate, reduced and controlled pesticide use.
The IPM system encourages the coordinated use of a variety of
practices that are generally familiar to farmers.
Current IPM programs address the potential adverse health
and environmental effects that can result from instances of
excessive pesticide use. They also consider the decreased
effectiveness of some of the chemical pesticides because some
pests and plants have developed an increased resistance to these
substances. Integrated pest management customizes the use of a
variety of pest suppression techniques to selected individual
circumstances; IPM applies pesticides sparingly and only when
dictated by economic conditions. In the correct situation, IPM
has played and can continue to play a significant role in
reducing pesticide exposure to humans, contamination of the
environment, and potential threats to endangered species. This
can be accomplished while providing economic advantages to the
farmer. However, it should be recognized that IPM is not
currently successful in all situations. Each potential use of
the IPM concept should be evaluated on an individual basis.
The key word in all IPM programs is integration. Farmers
should consider all of the pest control methods available to them
to provide for the most effective use of pesticides. For
example, in some instances introduction of biological enemies of
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pests may prove to be a desirable alternative to the use of
certain pesticides. Because IPM systems can be customized to
address specific problems, they can accommodate a wide range of
agricultural and environmental needs.
5.5.2 Benefits and Limitations
The benefits from the IPM system vary with the circumstances
under which the system is used. Virtually all farmers,
regardless of the size of their enterprises, can benefit to some
degree from using this system. The principal benefits can be a
reduction in expenditures for pesticides, reduced economic risk
associated with rotating crop production versus single-crop
production, and maintenance of crop yield at essentially the same
levels.
Limitations of using the IPM system could include some
combination of reduced pest eradication efficiency, undesirable
environmental side-effects (e.g., increased soil erosion),
increased operating costs, difficulties in enforcement by State
agencies, and resistance to changes to long-established farming
policies within a realistic time frame. In addition, some IPM
opponents state that changes to current farming practices would
reduce the quality of the product, reduce crop yield, and result
in higher food prices.
5.5.3 Emission Reduction Potential
The overall reduction in VOC emissions attributable to the
accelerated incorporation of the IPM systems is difficult to
estimate. A study in 1977 stated that IPM may show a reduction
in pesticide usage as high as 33 percent to 67 percent.7 The
reduction in VOC emissions is a result of reduced use of EC's and
organic solvent-based liquid formulations. It is not known
whether the 33 to 67 percent reduction in usage would also apply
to these two formulations or whether reductions this high can be
achieved for other crops in different locations. .-
5.6 REDUCED USAGE OF SELECTED PESTICIDE AI'S
5.6.1 Option Description
A use-reduction plan for specific pesticide AI's could also
be instituted to reduce VOC emissions. The targeted pesticides
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may be AI's for which lower-VOC AI substitutes are readily
available (or which could be developed) or for which the use of
the AI at current levels is considered optional or marginal.
This type of regulation is more compatible with the current OPP
policy of evaluation on an AI basis.
5.6.2 Benefits and Limitations
The regulation could be integrated with current State
regulations and programs, such as a required license to apply
pesticides, or by a pesticide usage report, such as the one
required by the State of California. It could also be
implemented using Section 24 of FIFRA.
The data base used to select targeted AI's and emission-
reduction targets must be current because significant changes in
use patterns from year to year could reduce or negate the
potential emissions reduction. It would obviously be futile to
reduce or consider an AI that is no longer used at high levels
because use patterns have changed.
The targeted list must be constantly updated and reviewed to
ensure that the regulation is obtaining the desired emission
reduction. The potential benefit may be easily undermined by
increases in emissions from nonregulated pesticides. Some of the
alternative formulations may have equal or greater VOC impact
than the current EC formulations if an increase in volume usage
occurs. Because the AI's are volatile, VOC emissions from the
alternative pesticides may increase despite the lack of inert
solvent. This increase would occur if the efficacy of the AI is
decreased as a result of the formulation, requiring a greater
application rate. The less volatile solvents are also generally
poorer solvents. Therefore, a less concentrated formulation may
result and a higher application rate may be required to apply the
same quantity of AI.
One of the major limitations to this option is the potential
necessity for developing a new AI if an existing alternative AI
is not available. The development of a new AI can take years
with no assurance that the new AI can be competitive in terms of
efficacy, formulation type, or cost. After the manufacturer has
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decided to register the new AI, the FIFRA registration process
can take 3 or more years and the cost of a complete registration
can range from $50 million to $70 million (see Section 7.1).
5.7 REDUCED USAGE OF CROP OILS
5.7.1 Option Description
Crop oils and weed oils are defined as petroleum-based
products used as herbicides, carriers for synthetic herbicides,
or insecticides. Crop oils, used for controlling insects and
mites, are highly refined products that have to be registered
with EPA. Oils used for the indiscriminate destruction of
vegetation do not have to be registered. The most common usage
of crop oils is as insecticides; usage as herbicides and carriers
for herbicides is very limited. A major manufacturer of a
synthetic herbicide indicated that some weed oils, such as
Stoddard solvent for weed control, were used for many years but
the use of these products has decreased to a low level and they
are not considered as competition for the synthetic herbicides.8
For usage as a carrier for herbicides, the formulated product
often contained I to 1.5 percent AI, 1.2 to 1.5 percent crop oil,
and the remainder as organic solvent.
Typically, crop oils are used as insecticides. The oils are
paraffinic and highly refined with unsulfonated residues in
excess of 92 percent. The higher the percentage of unsulfonated
residues, the less toxic or harmful the oil is to the plants to
which it is being applied. Application of the crop oil is
designed to kill the insects but allow the plant to remain
unharmed. Action of the crop oils as insecticides is through
suffocation of the insects. For dormant application, the oil is
usually applied at a concentration of 3 to 4 percent oil in
water. For summer application, a concentration of about
2 percent oil in water is used. The cost of insecticidal oils
varies considerably but is usually determined by the labeling of
the products, location of the purchase, and other market factors.
Crop oils for summer application typically are more expensive
than dormant oils.
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5.7.2 Benefits and Limitations
Synthetic substitutes have a lower VOC-emitting potential
because they tend to be applied at lower rates.
The use of crop oils in California is decreasing, and some
of the major suppliers are leaving the market because of the cost
of meeting registration requirements.
The manufacturers of crop oils are not major pesticide
manufacturers, so they may be slightly affected by the reduction
because these products are a small portion of their overall
business.
Some crop oils can be used in organic farming and are an
integral part of IPM programs. Restricting the use of these
products could discourage farmers from using these programs,
which are perceived to have other significant environmental and
safety benefits. In addition, insecticide oils would likely have
to be replaced by one or more applications of other insecticides.
5.7.3- Emission Reduction Potential
The total quantity of crop oils used on a nationwide basis
is unknown. Because these products are not registered AT's, they
were not included in the Resources for the Future (RFF) data
base. Data obtained from the California Air Resources Board
(CARB) showed an estimated 1987 usage of 18,600 tons/yr.9 Draft
preliminary data from California has an estimated 1990 usage for
crop oils at 13,615 tons.10
5.8 REFERENCES FOR SECTION 5.0
1. Unconfirmed telecon. Lapp, T., MRI, with Jones, T.,
California EPA, Department of Pesticide Regulation.
December 20, 1991, Information on substitute for
2,3-dichloropropene.
2. Giles, K., et al. Comprehensive Research on Strawberries,
Annual Report. Agricultural Engineering Department,
University of California - Davis, Davis, California.
January 1991.
3. Law, S. S. and S. C. Cooper. Depositional Characteristics
of Charged and Uncharged Droplets Applied by an Orchard Air
Carrier Sprayer. Transactions of the ASAE, 31 (4) : 984-989
(1988). ~
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4. Sparks, R. E. Microencapsulation in Kirk-Othmer's Concise
Encyclopedia of Chemical Technology, 1985. pp. 762-763.
5. Telecon. Lapp, T., MRI, with Beestman, G., DuPont
Agricultural Products. December 19, 1991. Discussion on
microencapsulation process and applications to pesticides.
6. Frisbie, R. E., and J. M. Luna. Integrated Pest Management
Systems: Protecting Profits and the Environment In Farm
Management, Part V, Environmental Quality, 1989 Yearbook of
Agriculture. Texas Agricultural Extension Service, U. S.
Department of Agriculture. The Texas A & M University
System, College Station, TX.
7. Hall, D. C. The Profitability of Integrated Pest Management:
Case Studies for Cotton and Citrus in the San Joaquin
Valley. Entomol. Soc. Amer. Bull., 11:267 (1977).
8. Telecon. Marron, J., MRI with Wright, N., Sun Refining and
Marketing Co. March 21, 1991. Information on nonselective
weed control chemicals and oils.
9. Lovelace, B. Data presented at the CAPCOA Pesticides
Solvent Task Force meeting, Sacramento, California.
March-1990.
10. Pepple, M. California Department of Pesticide Regulation.
May 27, 1992.
5-18
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6.0 ENVIRONMENTAL ANALYSIS
This section discusses the environmental impacts associated
with implementing the various emission reduction alternatives
discussed in Section 5.0. The primary emphasis is on a
quantitative assessment of the impacts on air quality by volatile
organic compound (VOC) emissions as described in Section 4.0 and
after implementation of the control alternatives. The impacts of
these control alternatives on water quality, solid waste, energy,
and biota are also briefly discussed in this section.
6.1 AIR POLLUTION
The estimated percentage solvent VOC emission reductions for
each reduction technique nationwide and in ozone nonattainment
areas are presented in Table 6-1.
Although each of the reduction techniques is presented
separately, some could be implemented together to further reduce
emissions from this source. For example, emulsifiable
concentrates (EC's) can be reformulated to contain less organic
solvent at the same time that fumigant usage is reduced.
Implementing any of these reduction techniques would reduce
VOC emissions from pesticide application. However, the reduction
potentials as calculated are not additive-in all cases because
they may apply to the same VOC emissions. For example, addition
of the emission reductions due to reformulation of 100 percent of
an EC to a granule and reformulation of 50 percent of the same EC
to a microencapsulated formulation overestimates the solvent VOC
emission reduction.
6.1.1 Reformulation
Tables 4-2 and 4-4 list the nationwide solvent VOC emissions
from EC's and organic solvent formulations. Tables 4-3 and 4-5
6-1
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list the solvent VOC emissions in ozone nonattainment areas. The
reductions achieved by this reduction technique were assumed to
affect solvent content only and reflect no decrease in potential
AI VOC emissions. The maximum solvent VOC emission reductions
due to implementing this technique are 46,400 tons nationwide and
4,800 tons in ozone nonattainment areas.
6.1.2 Example of Reduced Fumigant Usage
The VOC emission reduction potential due to reducing
fumigant usage is assumed to be 100 percent of the contribution
due to dibromochloropropane (DBCP) and ethylene dibromide (EDB).
The nationwide and ozone nonattainment area contributions due to
these two fumigants in 1982-1984 are listed in Tables 4-2 and
4-3, respectively. The reduction indicated in Table 6-1 has
already taken effect due to the cancellation of agricultural use
registrations for EDB and DBCP. Usage data on other currently
used fumigants such as Telone®, metam, methyl bromide, and
chloropicrin were not available to calculate emission reductions.
The estimated maximum VOC emission reductions due to removing EDB
and DBCP are 20,700 tons nationwide and 4,750 tons in ozone
nonattainment areas.
6.1.3 Use of Alternative Application Methods
The reduction potential from using alternative application
methods was calculated for all solvents listed in Tables 4-2
through 4-5. A reduction factor of less than or equal to
30 percent (see the discussion in Section 5.3.2) can be used to
estimate the maximum solvent VOC emissions. The maximum solvent
VOC emission reductions due to implementing increased efficiency
application methods are estimated to be less than or equal to
14,000 tons nationwide and less than or equal to 1,400 tons in
ozone nonattainment areas.
6.1.4 Increased Use of Microencapsulated Pesticides
The reduction potential from increased use of
microencapsulated pesticides was calculated in the same manner as
reformulation, by estimating the effects of reformulating EC's
and organic solvent-containing AI formulations. The solvent VOC
emissions due to these AI's was subtracted from the maximum VOC
6-3
-------
emissions estimate. However, since 100 percent reformulation of
EC's and organic solvent-containing formulations into
microcapsules is not likely due to various formulation
constraints, a factor of less than 100 percent should be applied
to the solvent VOC contribution of this target to calculate the
VOC reduction. The reductions achieved by this alternative were
assumed to reflect no decrease any in potential AI VOC emissions.
Table 6-1 presents the reduction potential for this technique.
The maximum solvent VOC emission reduction due to implementing
this technique are less than or equal to 46,400 tons nationwide
and less than or equal to 4,800 tons in ozone nonattainment
areas.
6.1.5 Integrated Pest Management
The solvent VOC reduction potential of integrated pest
management (IPM) was calculated from the solvent VOC contribution
due to all pesticide applications from Tables 4-2 through 4-5.
The percent reduction for this technique is a factor of less than
or equal to 33 percent as discussed in Section 5.5.3. The
maximum solvent VOC emission reduction due to implementing IPM
are estimated to be less than or equal to 15,300 tons nationwide
and less than or equal to 1,600 tons in ozone nonattainment
areas.
6.1.6 Crop Oils
No VOC reductions could be calculated for the use of crop
oils due to insufficient information on reduction techniques.
6.1.7 Active Ingredients
The emission reduction estimates ascribed to two control
techniques, application efficiency and IPM, can also be applied
to VOC emissions due to active ingredients. For each of these
two control techniques, the potential for the reduction in
emission decreases as the overall potential for emissions is
reduced.
6.2 WATER POLLUTION
Implementing any of these control technologies would result
in no adverse water pollution impacts because no hazardous
6-4
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wastewater is produced by applicators correctly using these
alternatives.
6.2.1 Surface Water
The impact on surface water bodies from pesticide runoff may
be affected by a change in pesticide formulation. Subsequent to
the field application of those AI's dissolved in organic solvents
(i.e., EC's), these formulations could be susceptable to rapid
runoff during rain because the EC is not strongly sorbed to soil
particles. During the rain, an emulsion could be formed with the
rainwater to facilitate the runoff. As the organic solvent in
the EC volatilizes, the AI remains on the soil surface where it
can be more readily sorbed to the soil particles. Reformulation
of the EC's could result in products that would be less
susceptable to runoff than the liquid EC and could lead to
greater availability of the AI to be sorbed to the soil. In
general, water-insoluble AI's are more likely to be found in
sediments than in the water column of surface waters.
Improved application efficiencies or the use of IPM may, in
many instances, result in the overall reduced usage of AI's and a
net reduction in total surface water concentrations.
6.2.2 Groundwater
The impact on groundwater of water-insoluble AI's also
varies with the formulation of the pesticide. An EC may be
dissolved in the groundwater and be transported with the
groundwater flow.
Reformulation of the EC's to remove the organic solvents
that form an emulsion in water decreases the aqueous solubility
of the AI. The AI may be sorbed to soil particles or move
through the unsaturated zone above the groundwater. Rain may
wash the AI as a particle or as a droplet down into the
groundwater where it will be suspended if not soluble and be
transported with the groundwater flow. However, as described in
detail in Section 3.3.7.2, soil moisture content also affects
evaporation of the AI. An increase in soil moisture increases
the evaporation rate of the AI.
6-5
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Many of the other potential VOC control strategies may lead
to an overall reduction in the quantity of AI used or better
application efficiency resulting in greater AI utility by the
plant. The impact of these strategies is a further overall
reduction in the availability of the AI's to the soil and
therefore reduced potential for groundwater contamination.
The impacts of pesticides on groundwater are not guantitated
here. However, it has already been assumed that evaporation of
pesticides to the atmosphere is the most likely fate of applied
pesticides, even though there- are possible groundwater
contamination pathways. Contaminated groundwater in aquifers
used for drinking water supplies can seriously impact human
health. The Environmental Protection Agency (EPA) completed in
1990 a 5-year National Survey of Pesticides in Drinking Water
Wells (NFS). A summary of the final results of this survey was
published in the fall of 1990 and the complete Phase I report was
published in 1991. Between 1988 and 1990, EPA sampled
approximately 1,300 community water system (CWS) wells and rural
and domestic wells for the presence of 101 pesticides,
25 pesticide degradates, and nitrate.2 Pesticides and pesticide
degradates were detected much less frequently than nitrate. The
two pesticides most frequently detected were DCPA acid
metabolites and atrazine. Ten other pesticides were detected
above Survey reporting limits: DBCP, dinoseb, hexachlorobenzene,
prometon, simazine, alachlor, bentazon, EDB, ethylene thiourea,
and lindane. Of those pesticides with Lifetime Health Advisory
Limits (HAL's), EPA estimates that at most 750 CWS wells and
60,900 rural domestic wells nationally have at least one
pesticide above its respective HAL.2
6.3 SOLID WASTE DISPOSAL
The increased quantity of solid waste generated by
implementing these technologies is unknown but believed to be
insignificant. No apparent new application related waste streams
would be generated from any of the alternatives.
6-6
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6.4 ENERGY .
Implementing these control technologies would change energy
consumption related to a change in the manufacturing process of a
different pesticide formulation. The potential energy
consumption increase or decrease is unknown and would be highly
specific to the manufacturer. The difference in energy
requirements for applying various pesticide formulations is
believed to be insignificant.
6.5 BIOTA
In general, the formulation of a pesticide influences its
exposure, and therefore toxicity, to nontarget species. The
effects of formulation on toxicity are most apparent in aquatic
ecosystems. For fish, insecticide emulsions and oil solutions
are the most toxic types of formulations.3'4 Emulsifiable oil
preparations of benzene hexachloride were 25 times more- toxic to
golden shiners than wettable powder formulations containing the
same level of gamma isomer. Solvents may also contribute to the
toxic effects and absorption of pesticides by aquatic species.4'5
Granular formulations, wettable powders, and dusts, which usually
release the AI's into the aquatic ecosystem at slow rate, have
relatively low toxicities to fish.6 Pesticides that accumulate
in surface water sediments, if persistent, can impact benthic
organisms which are an important part of aquatic ecosystem food
chains. The entire ecosystem will be affected by changes in the
benthic community. Granular .formulations are under study by the
Office of Pesticide Programs for adverse effects on birds. Birds
have been found to consume granular pesticides after application
to the crop, which may result in increased avian mortality.
Studies of subsurface application of granular formulations have
shown promise for a partial reduction in bird exposure.
Comprehensive studies on ecosystem effects due to pesticide
formulations were not found in the literature or through contacts
with agricultural research centers.7'^
6-7
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6.6 REFERENCES FOR SECTION 6.0
1. Giles, K., and E. Ben Salem. Comprehensive Research on
Strawberries Annual Report. Agricultural Engineering
Department, U.C. Davis. February 1, 1990--January 31, 1991.
9 p.
2. National Pesticide Survey Summary Results of EPA's National
Survey of Pesticides in Drinking Water Wells. U. S.
Environmental Protection Agency. Office of Water, Office of
Pesticides and Toxic Substances. Fall 1990. 16 p.
3. Cope, O.B. Agricultural Chemicals and Freshwater Ecological
Systems. Research in Pesticides. New York, Academic.
1965. pp.' 115-128.
4. Meyer, P.P. The Effect of Formulation Differences on the
Toxicity of Benzene Hexachloride to Golden Shiners. Proc.
17th Ann. Conf. SE Assoc. of Game and Fish Comm. 1966.
pp. 186-190..
5. Hiltibran, R.C. Effects of Some Herbicides on Fertilized
Fish Eggs and Fry. Trans. Am. Fish. Soc. 96: 414-416.
1967.
6. Pickering, Q.H., C. Henderson, and A.E. Lemke. The Toxicity
of Organic Phosphorus Insecticides to Different Species of
Warm Water Fishes. Trans. Am. Fish. Soc. 91: 175-184.
1962.
7. Cope, O.B. Contamination of the Fresh-Water Ecosystem by
Pesticides. J. Appl. Ecol. i (Suppl.): 33-44. 1966.
8. Telecon. Marron, J., MRI, with Hall, F.R., Laboratory for
Pest Control Application Technology, Ohio Agricultural
Research and Development Center. March 11, 1991.
Environmental impacts of pesticide application methods.
9. Telecon. Marron, J., MRI, with McWhorter, C., Southern Weed
Science Laboratory, USDA. March 18, 1991. Environmental
impacts of pesticide application methods.
6-8
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7.0 CONTROL COST IMPACTS
This section discusses the range of control cost impacts
associated with implementing the control alternatives discussed
in Section 5.0. The majority of information is related to costs
of reformulating active ingredients (AI's), Federal and State
registration costs, and costs of banning fumigants. The cost
impacts of alternative application methods and integrated pest
management (IPM) are also briefly discussed in this section.
7.1 REFORMULATION
In general, there are several areas to consider when
identifying the individual costs associated with changing the
formulation of an AI. Manufacturing and packaging processes may
need to be changed, depending on the nature of the new
formulation. Registration of the new product is required under
the Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA).
Manufacturers are required to conduct various studies in order to
collect data on the pesticide product in support of its
registration. The number of studies required and, therefore, the
overall cost is related to a number of factors, which are
discussed below. Registration fees on the Federal and State-
levels are also required. Consumers of the new pesticide product
may be required to purchase new application equipment to
accommodate the new formulation. Consumers will also be affected
by increased prices from increases in manufacturing costs, if
any. Information is presented below on cost impacts due to
reformulating an AI.
7-1
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7.1.1 Production Costs
A range or average cost estimate for manufacturing
reformulation costs is not available due to the highly variable
nature of AI's and a number of manufacturing circumstances.1'2
The manufacturing process required to reformulate an AI to a
formulation other than an emulsifiable concentrate (EC) likely
will be more difficult and expensive because EC's are relatively
easy to make.2 Costs to retool the manufacturing process are
variable and unknown.1'2 Major retooling is necessary if the
production facility made only EC's and must change completely to
accommodate a new process. However, it is reasonable to expect
that some large facilities house more than one process and would
not require completely new equipment. Thus, a wide range in
costs is likely.
Some AI's are currently only formulated as EC's and would be
very difficult to reformulate due to chemrcal or physical
properties.1 However, it is impossible to generalize which
pesticide compounds can only be formulated as EC's. The
individual properties of compounds (e.g., AI's) vary greatly even
within a class of compounds or pesticides (e.g., chlorinated
hydrocarbons, organophosphorus, and carbamate compounds, which
are classes of AI's).1 Another consideration is costs added to
the manufacturing process due to the new formulation process.
For example, formulation processes that result in dust formation
(e.g., wettable powders, granules, dusts, baits) require measures
to suppress and control the dust during manufacturing and
packaging.2
7.1.2 Registration Costs
All pesticide products must be registered for sale or
distribution under FIFRA. It must be emphasized that a pesticide
formulation cannot be arbitrarily changed without the occurrence
of significant other impacts. Reformulation of an AI may be
considered minor or major depending on the nature of the changes
made. The determination of what constitutes a major or minor
change is made on a case-by-case basis by EPA.3 For example, a
minor change may consist of a change in the solvent or percent of
<
7-2
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solvent. If the change is minor, an amendment to the
registration of the original product may be all that is
required.^
A new registration is required for a product that has had a
major change in its formulation. For example, changing the
formulation from an EC to a dust is likely to be considered a
major change.^ The costs to complete a new registration for a
pesticide product vary considerably. Total costs obtained from
industry sources are presented in Table 7-1.
In addition, State laws and regulations also may apply to
the registration of pesticide products. State end-use product
registration fees vary from State to State. Not all States
require registration fees, but if a new product were to be
registered in all States that do require fees, the total cost in
the first year of registration would be $1,425.7 The State of
Iowa increases the fees of a pesticide product after the first
year according the sales of the product. Therefore, the total
for State fees could go as high as $3,000 a year in the following
years depending on the volume of sales of the pesticide in Iowa.
Most of the variability in the cost of registering a
pesticide product comes from the studies required to provide data
to EPA in support of the registration. According to FIFRA, the
registrant provides the study results to demonstrate that the
pesticide will not cause unreasonable adverse effects on human
health or the environment when it is used according to approved
label directions. Studies that are generally required are listed
in 40 CFR 158, Data Requirements for Registration.
The specific studies that are required or conditionally
required are determined by the general use pattern of the product
being registered (i.e., food crop use, nonfood crop use, forestry
use, domestic use, indoor use, minor crop use, etc.). The
studies are designed to provide information on the pesticide
product in the following areas: environmental fate, acute and
chronic toxicology, reentry protection, spray drift, effect on
wildlife and aquatic organisms, nontarget plant protection data,
nontarget insect data, and product performance. These studies
7-3
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TABLE 7-1. SUMMARY OF ESTIMATED COSTS FOR REGISTRATION.4"8
Category
FIFRA registration data
collection
FIFRA registration fees
State registration fees
Item
Theoretical product reregistration with one crop use,
one target insect, one method of application, one use
Estimated to take 3 years to complete
Actual industry figures—high end of range:
one Al (insecticide) with many uses and
avian and mesocosm studies required
- 1987 data call in
- 1988 registration standard
Actual industry figures—low end of range:
one Al nonfood use product with only one
use
- to fill data gaps
' to replace old studies
• probable maximum at completion of
registration
New product estimated cost range for complete
registration
Reregistration fee
Payable in two installments, may be shared by all
manufacturers of the Al
New chemical registration review
New biochemical and microbial registration review
New use pattern registration review
Experimental use permit review
Old chemical registration review
Estimated costs, $
110,000
17,100,000
789,000
1,475,000
1,200,000
5,029,000
50,000,000
to 75,000,000 -
150,000
184,500
64,000
33,800
4,500
4,500
1,425
7-4
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are conducted on the end-use product, technical-grade AI, radio-
labeled pure AI, typical end-use product, or manufacturing-use
product as specified in Part 158. Estimated costs for all
potential studies in these areas are listed in Table 7-2. One
estimate of costs consists of those costs provided by the Office
of Pesticide Programs (OPP) to the Office of Management and
Budget (OMB) in 1991. The other estimates were made in 1991 by a
representative of the California Department of Food and
Agriculture's Pesticide Registration Branch. All of the studies
possible in each of the study areas are not required in every
case. Therefore, the costs in Table 7-2 are conservatively high.
In cases where the Part 158 studies are not adequate to assess
the potential risk of a product, EPA may request additional
studies.
Changes to a pesticide formulation that would not alter the
potential risks of the pesticide product and, therefore, would
not require scientific review by EPA may be considered minor
changes by EPA. In the case of a minor change, the registrant
may be able to cite existing data to fulfill the data
requirements on various properties of the AI and include the
results of six acute toxicity studies (listed in Table 7-3)
conducted on the end-use product formulation that are required
for this type of amended registration.3 If a new use pattern is
requested, efficacy data is required. An amendment to the
registration also may be possible for minor changes to the use
pattern.
Another type of registration that does not require extensive
data collection is called a "me-too" registration. The "me-too"
end-use product must be essentially the same as a currently
registered product.3 The ingredients, use patterns, and
instructions for application must be the same. The registrant
for a "me-too" product must obtain permission from the other
registrant to use the registration data developed for the similar
product and include a copy of the other products' label. The
estimated costs of the acute toxicological studies required are
7-5
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TABLE 7-2. SUMMARY OF COST ESTIMATES FOR FIFRA STUDY AREAS
Study area
Product chemistry
Hazard evaluation: wildlife and aquatic organisms
Hazard evaluation: humans and domestic animals
Plant protection
Reentry protection
Environmental fate
Spray drift
Residue chemistry
-general
-per crop
Estimated cost9, $
148,400
690,000
2,864,000
358,500
185,300
1,616,500
28,000
509,000
468,500
Estimated cost10, $
300,000 to 500,000
2,700,000 to 3,000,000
50,000 to 75,000
TABLE 7-3. SUMMARY OF ESTIMATED COSTS FOR AMENDED OR
"ME-TOO" REGISTRATION9
Category
Amended registration data collection
Registration fees
Item
Acute oral tox.-rat
Acute dermal tox.- rabbit/rat
Acute inhalation tox. -rat
Primary eye irritation-rabbit
Primary dermal irritation
Dermal sensitization
Amended registration fee
State registration fee
Total
Cost, $
3,900
6,700
11,100
1,800
1,700
5,600
700
1,425
32,925
7-6
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presented in Table 7-3, along with the fees for an amended
Federal registration.
The EPA determines which studies are required to register an
EC that has been reformulated to a lower solvent content
formulation, a microencapsulate reformulated from a solvent -
containing formulation, and to add new uses to potential
alternatives for fumigants. The extent of the required studies
depends on many factors including the characteristics of a given
AI and pesticide formulation, whether or not there are
formulations similar to the desired formulation currently on the
market, and current use patterns of the formulation. Because of
this complexity, no estimates of testing requirements for
specific formulations can reasonably be made.
7.2 APPLICATOR EQUIPMENT COSTS
Consumers apply the pesticide products with a variety of
equipment depending on the formulation of the product. An
applicator or farmer may own one or more types of application
equipment. The equipment used may depend in part on the types of
formulations the farmer believes are most effective on the crops
treated and the formulations in which desired products are
available. The cost of application equipment varies
considerably. Table 7-4 presents a summary of the equipment
costs gathered from various agricultural equipment companies.
Another cost that the consumer may incur due to reformulation of
an AI is the increased cost of the new product compared to the
original. This price increase is particularly likely for
reformulation of EC's due to the inexpensive production costs of
EC's compared to other formulations.2
The costs associated with reformulating a pesticide product
are highly variable. The chemical and physical properties of the
individual AI dictate the type of pesticide (i.e., whether the
product is an insecticide or herbicide) and the feasible
formulations. Therefore, the use patterns and the nature of the
formulation content depend to some extent on the AI. The
registration costs of the product vary by the use of the product,
which again is linked to the individual AI. Since it is not
7-7
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TABLE 7-4. SUMMARY OF APPLICATOR EQUIPMENT COSTSa
General applicator type
Liquid applicators
Dust applicators
Granule applicators
Backpack sprayer
Controlled droplet
applicators
Low-pressure sprayers
Ul t ra - 1 ow - vol ume
applicators
Electrostatic
sprayers
Compressed air duster
Mechanical duster
Power duster
Hand-operated
applicators
Mechanically driven
applicators
Cost to purchase
range , $
140 - 3,550
274 - 7,200
1,000 - 50,000
1,195 - 7,595
1,395 - 30,000
200 and up
200 and up
200 and up
35 - 320
10,000 - 120,000
aJohn Deere Co., Moline, IL; Curtis Dyna-Products Corp.,
Westfield, IN; B & G Equipment Co., Plumsteadville, PA; Spyker
Spreader Works, North Manchester, IN; FMC Corp., Agricultural
Machinery Div., Jonesboro, AR; Earthway Products, Inc., Bristol,
IN; Farm Fans, Inc., Indianapolis, IN; Top Air Manufacturing,
Inc., Parkersburg, IA; London Fog, Inc., Long Lake, MN; Orchard
Machinery Corp., Yuba City, CA; Gandy Co., Owatonna, MN; Reddick
Equipment Co., Williamston, NC; Dempster Industries, Beatrice,
NE; AgChem Equipment Co., Jackson, MN; and Ess, Inc., Athens,
GA.
7-8
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possible to generalize the properties of the AI's, it is
difficult to generalize the costs of reformulating an AI. The
cost impacts on manufacturers and consumers also cannot be
generalized due to the wide variety of manufacturing capabilities
and the unknown applicator equipment requirements.
7.3 FUMIGANTS
Fumigant use is an area not adequately addressed by the
Resources for the Future (RFF) data base. The two fumigants,
ethylene dibromide and dibromochloropropane, listed in the RFF
data base had their agricultural uses cancelled in 1990 and 1985,
respectively. This section discusses currently used fumigants,
their alternatives, and the economic impacts of several scenarios
in which fumigants are banned.
7.3.1 Fumigarits and Fumigant Alternatives
Soil fumigants currently registered for use in agricultural
soils are methyl bromide, 1,3-dichloropropene (1,3-D or Telone®),
chloropicrin, and metam. These AI's are available alone or in
mixtures. Fumigants are general purpose compounds that control
nematodes, soil fungi, soil insects, and weeds. Telone® has been
under special review by the Office of Pesticide Programs (OPP)
since 1986. This process reviews the risk benefit analysis of
Telone® use. A decision on changes to Telone®'s registration is
expected by the end of 1992. There are nonfumigant compounds
that have been used on soils such as several registered
organophosphates (e.g., ethoprop, fensulfothion, fenamiphos) and
carbamates (e.g., carbofuran, aldicarb, oxamyl). However, these
types of compounds are less effective than fumigants and are
difficult to apply to the required soil depths.
7.3.2 U.S. Department of Agriculture Study
An assessment of economic effects of banning soil fumigants
was completed by the U.S. Department of Agriculture (USDA) in
1988.1 This assessment is based on an earlier biological study
of the effects of banning fumigants. It estimates how all soil-
borne pests would act during a growing season to affect crop
yields. The economic assessment considers the short-term effects
on both crop producers and consumers if the use of all soil
7-9
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fumigants were lost because of EPA cancellation, suspension, or
manufacturer withdrawal. The USDA analysis did not require usage
estimates in pounds of fumigant but estimates of acres planted
and acres treated of the affected crops. Several scenarios were
evaluated:
1. Telone® alone and in combinations is lost. All other
fumigants are available plus alternatives;
2. Methyl bromide alone and in combinations is lost. All
other fumigants and alternatives are available;
3. Chloropicrin alone and in combinations is lost. All
other fumigants and alternatives are available;
4. Metam is lost. All other fumigants plus alternatives
are available;
5. All fumigants are lost, but nonfumigant alternatives are
available;
6. All fumigants and aldicarb, carbofuran, and oxamyl are
lost for nematode control. Organophosphates are available; and
7. Metam, chloropicrin, and organophosphates are available.
All other fumigants and aldicarb, carbofuran, and oxamyl are lost
for nematode control.
The USDA concluded that producers who formerly used
fumigants would be worse off by $100 to $200 million per year,
despite higher prices, if soil fumigants were banned for citrus
fruit, potatoes, tomatoes, tobacco, and a few other crops,
because crop output would decline sharply. Producers who did not
use fumigants would be better off by $480 to $800 million per
year because of higher product prices received. Consumers would
pay $3.0 to $5.1 billion more annually in the short run. Average
annual consumer prices would rise 53 percent for fresh tomatoes,
11 percent for potatoes, 8 percent for canned tomatoes, and
4 percent for cigarettes. Loss of fumigants would have no effect
on prices of cotton products, citrus fruit, or frozen juice.
Fumigant formulations are unique in that they do not
generally contain ingredients other than the active ingredient.
The VOC emissions from fumigant application are due to escape of
the fumigant from the soil. Therefore, the cost impacts
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described in the USDA study as a result of banning fumigants on
certain crops also apply as a conservative assessment of cost
impacts from controlling VOC's from fumigants by restricting
fumigant use.
7.4 ALTERNATIVE APPLICATION METHODS
In general, control costs for alternative application
methods including ultra-low-volume (ULV) application and other
methods that often increased application efficiency are unknown.
Equipment costs as presented in Table 7-4 for ULV applicators and
electrostatic sprayers are a factor in the overall control costs.
However, no data are available to identify and contrast current
use of this equipment nationwide to its potential use nationwide
as a VOC emissions control alternative.
Costs associated with the pesticide formulations required
for ULV and increased efficiency applications, if any, are
unknown. Common pesticide formulations are likely available that
may be used with high-efficiency equipment at a lower application
rate, thereby minimizing added costs due to specially formulated
pesticides. However, the comparison between costs of
formulations currently used by a grower and costs of any new,
more expensive pesticide formulations required by this control
alternative is unknown. Therefore, the range of control costs
for this alternative has not been estimated.
7.5 MICROENCAPSULATION
No specific information is available to describe the cost
impacts of reformulating solvent-containing pesticides to
microcapsules. However, in general microencapsulation is an
expensive or impossible production method for AI's that do not
form stable emulsion systems. Microcapsules with high AI
concentrations (e.g., 4 pounds per gallon [Ib/gal] are more
economical to produce than more dilute concentrations. The
patents for high concentration production methods are held by
Monsanto, therefore, these methods are not generally available to
other manufacturers.
Microencapsulated formulations are mixed with water and
applied in spray form. Specialized equipment is not required for
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application. No costs are incurred for purchase of equipment if
the grower or applicator owns spray equipment.
7.6 INTEGRATED PEST MANAGEMENT (IPM)
The overall economic impact of the IPM system will be highly
dependent upon the specific program used, the type of crops, and
the geographical location. Advocates of the IPM concept state
that "....evaluation of IPM programs in 15 States documented that
IPM users overwhelmingly showed a profit while reducing their use
of pesticides."11 This reference further states that the farmers
using IPM increased their net profits over non-IPM users by an
estimated $578 million/yr and that private pest-management
consulting firms may attain revenues exceeding $400 million/yr.
These figures appear to indicate two conclusions. One conclusion
is that in some States, using IPM can be cost effective compared
to the more conventional farming practices. However, this
depends upon a number of factors, including the type of crop, the
geographical location, existing environmental conditions, the
size of the farm, and the degree to which the user adheres to IPM
practices. The second conclusion is that converting to IPM is
neither simple nor inexpensive. Private pest-management
consultants may be necessary to evaluate the individual
situations, and the advice of the consultants is not free. Use
of State agricultural extension service personnel, for both
technical advice and consultant references, usually can be
obtained at no cost and their knowledge and advice may be
sufficient for many situations. Conversion to IPM practices does
not occur in 1 year, and a period of time is necessary for the
conversion. Overall, the IPM program can be profitable and
decrease the level of pesticide consumption. The specific cost
impacts depend upon individual circumstances and the farmer.
7.7 REDUCED USAGE OF SELECTED PESTICIDES
No information is available to estimate the cost impacts of
this VOC reduction technique.
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7.8 REDUCED USAGE OF CROP OILS
No information is available to estimate the cost impacts of
this VOC reduction technique.
7.9 REFERENCES FOR SECTION 7.0
1. Telecon. Marron, J., MRI with Schmid, P., Ciba-Geigy
Agriculture Division. June 19, 1991. Costs to reformulate
an EC.
2. Unconfirmed telecon. Lapp, T., MRI with Brown, P., DuPont
Agricultural Products. June 12, 1991. Costs to reformulate
an EC.
3. Telecon. Marron, J., MRI with Schroeder, P., Insecticide
Branch, Registration Division. EPA:OPP. August 30, 1991.
Registration requirements.
4. Telecon. Marron, J., MRI with Fullner, D., Ciba-Geigy
Agricultural Division. April 25, 1991. Costs to register
pesticides under FIFRA.
5. Telecon. Marron", J., MRI with Donovan, D., DuPont
Agricultural Products. April 16, 1991. Costs to register
pesticides under FIFRA.
6. Pesticide Manufacturer Opts to Drop Key Uses Based on Costly
New FIFRA Fees. Inside EPA Weekly Report. Vol. 12, No. 16.
April 19, 1991, pp. 1, 10.
7. Telecon. Marron, J., MRI with Bishop, M., National
Agricultural Chemicals Association. July 1, 1991. State
registration fees.
8. Federal Register. Vol. 53, No. 102. May 26, 1988.
9. Memorandum from Nelson, J., EPA/OPP, Regulatory Coordination
Staff, to Hunt, T., OMB. May 8, 1991. Terms of clearance
for Phases 4 and 5 of reregistration.
10. Telecon. Marron, J., MRI with Jones, T., Pesticide
Registration Branch, California Department of Food and
Agriculture. April 12, 1991. Pesticide registration costs.
11. Frisbie, R.E., and J.M. Luna. Integrated Pest Management
Systems: Protecting Profits and the Environment In Farm
Management, Part V, Environmental Quality; 1989 Yearbook of
Agriculture. Texas Agricultural Extension Service, U. S.
Department of Agriculture. Texas A & M University System,
College Station, TX.
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8.0 REVIEW OF EXISTING REGULATIONS
8.1 FEDERAL REGULATIONS
The distribution, sale, and use of pesticides in the United
States is regulated primarily by EPA under the Federal
Insecticide, Fungicide, and Rodenticide Act (FIFRA), enacted in
1947, and the Federal Food, Drug, and Cosmetic Act (FDCA) . The
FIFRA requires that all pesticides be registered with EPA, and it
authorizes EPA to establish conditions for their use. The FDCA
requires EPA to establish maximum acceptable levels of pesticide
residues in foods. Within EPA, the Office of Pesticide Programs
(OPP) administers the regulations governing pesticides.
Other branches of EPA and other Federal agencies have also
adopted regulations which, though they may not be specifically
targeted at pesticides, may have an impact on their use, either
directly or indirectly. Under FIFRA, every State has responded
by adopting its own regulations. The main restrictions that
FIFRA places on States is that their regulations cannot be any
less strict than those required by FIFRA, except under special
limited conditions. The power to regulate pesticides does not
extend beyond the State level. Attempts by local communities to
adopt their own regulations have been rejected in several State
courts.1
8.1.1 FIFRA and FDCA
The Federal regulations under FIFRA and FDCA are summarized
as they relate to particular areas including registration,
labeling, restrictions on inert ingredients, application, and
food residues.
8.1.1.1 Registration. Section 3 of FIFRA requires that any
pesticide sold or distributed in any State be registered with OPP
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prior to its sale or distribution. Section 2(u) defines a
pesticide as "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."
For all products not previously registered, including new
active ingredients, new formulations, and new uses of registered
active ingredients, FIFRA requires that the intended registrant
apply for registration. In accordance with Section 3(c), an
application for registration must include a complete copy of the
labeling of the pesticide, a statement of all claims to be made
for it, a copy of all test data supporting the claims, usage
directions, the complete formula, and a request for
classification for general use, restricted use, or both. The
product will be registered if it meets the requirements outlined
in Section 3(c)(5): its chemical composition appears to support
the claims made for it, the labeling and data submitted meet the
established requirements, it will perform its intended function
without unreasonable adverse environmental effects, and when used
as directed it generally will not cause unreasonable adverse
environmental effects.
When registering a pesticide, OPP will classify it for
general use, restricted use, or both as per guidelines stated in
Section 3(d) of FIFRA. If OPP determines that use of the
pesticide in accordance with all specified directions and normal
application practices will not cause unreasonable adverse effects
on the environment, then the pesticide, or the particular use for
it, is classified for general use. If EPA determines that normal
use of the pesticide in accordance with all specified directions
may cause unreasonable adverse effects on the environment or
injury to the applicator unless additional restrictions are
imposed, then the pesticide, or the particular use for it, is
classified for restricted use. If a pesticide is classified for
restricted use, it may be applied only by or under the direction
of a certified applicator. Some pesticides with several uses may
be classified for restricted use and general use.
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Because new pesticide registration is often a process that
takes years to complete, FIFRA was amended in 1988
[Section 5(k)(3)] to require OPP to try to expedite applications
for initial or amended registration of products that are similar
to pesticides already registered. Similar products include those
identical in composition to pesticides already registered and
those that differ only in ways that do not significantly increase
risks to the public health. The OPP must also expedite requests
for selected minor amendments (for example, some reformulations)
to existing product registrations. The 1988 amendments to FIFRA
require OPP to notify the applicant in writing within 90 days of
receiving the completed application whether the request is
granted or denied, and if it is denied, the reasons why.
In addition to the initial registration of a pesticide,
Section 4 of FIFRA requires that each registered pesticide
containing an active ingredient that was first registered before
November 1, 1984, be reregistered, unless the pesticide has no
outstanding data requirements and it meets the initial
requirements for registration under Section 3(c)(5). Due to slow
progress in reregistering pesticides, the 1988 amendments to
FIFRA establish tight deadlines and a fee schedule in order to
expedite the reregistration process. Pesticide registrants are
required to meet a sequence of deadlines for supplying the
complete test data bases OPP needs to make reregistration
decisions. Then OPP must meet specific deadlines in analyzing
the data and making decisions. To meet the expected increase in
costs associated with meeting the new deadlines, two different
types of fees are levied on the industry: a reregistration fee
for each active ingredient and an annual fee for registration
maintenance to be assessed against individual products. These
fee provisions will be in effect for 9 years, which is the time
period allowed for OPP to complete reregistration.
8.1.1.2 Labeling. The FIFRA requires the following
information on all labels: the name, brand, or trademark of the
product; the name and address of the producer, registrant, or
person for whom the product was produced; the net contents; the
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product registration number; the producing establishment number;
the ingredients statement; warning or precautionary statements;
directions for use; and the use classification. All information
on the label must be clearly legible to a person with normal
vision. A draft copy of the label must be submitted with the
application for registration for approval.
The ingredients statement must include the name and weight
percentage of each active ingredient, the total weight percentage
of all inert ingredients, and a statement of the percentage of
total and water-soluble arsenic. Required warning or
precautionary statements vary according to the toxicity category
of the active ingredient. Highly toxic materials, Category I,
must be marked "Danger." If the active ingredient is in
Category I because of its oral, inhalation, or dermal toxicity,
the label must be marked "Poison" in red with an adjacent skull
and crossbones symbol. Toxicity Category II products must be
marked "Warning," and Categories III and IV products must be
marked "Caution." All product labels must be marked with the
warning, "Keep Out of Reach of Children." Other warnings that
may be required include "Hazard to Humans and Domestic Animals,"
"Environmental Hazard," and "Physical or Chemical Hazard."
Directions for use must be stated in such a manner that they can
be easily read and understood by persons who are likely to use
them or supervise their use. A statement indicating that it is a
violation of Federal law to use the product in a manner
inconsistent with its labeling must be included with the
directions for use along with information about application
site(s), target pest(s), dosage rate for each site and pest,
method of application, frequency and timing of application,
reentry limitations, and storage and disposal directions for the
pesticide and its container. The use classification, general or
restricted, must also be on the label. If a product is
classified for both depending on its particular use, then it must
be marketed as two separate products with separate labels.
„ 8.1.1.3 Inert Ingredients. In 1987, OPP released a policy
statement on inert ingredients in pesticide products. This
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policy statement was revised in 1989.2 Under FIFRA, the majority
of the data requirements and regulatory activities have focused
on the active ingredient. Acute toxicity tests are required for
the pesticide formulation, which includes the active and inert
ingredients, but inerts had not been addressed in detail until
the 1987 release of the policy statement. The policy divides the
1,200 intentionally added inert ingredients into four toxicity
categories:
1. Inerts of toxicological concern (List 1);
2. Potentially toxic inerts/high priority for testing
(List 2) ;
3. Inerts of unknown toxicity (List 3); and
4. Inerts of minimal concern (List 4).
Appendix D presents the 1989 policy statement and the
compounds included on List 1. Approximately 40 inert ingredients
have been identified and placed on List 1 based on their
carcinogenicity, adverse reproductive effects, neurotoxicity or
other chronic effects, or developmental toxicity (birth defects).
For an inert to be placed on List l, these effects must have been
established by peer-reviewed data. The OPP is encouraging
registrants of products containing List 1 inerts to substitute
nontoxic inerts for those of toxicological concern. If the inert
is not substituted, the registrant must amend the registration by
changing the label to include a warning stating that the inert is
present in the formulation. Pesticides containing List I inerts
will be subject to data call-in, for which the registrant may be
required to present data equivalent to that required for an
active ingredient. For some inerts on List 1, OPP intends to
hold hearings to collect and present information on their risks
and benefits. Based on this information, OPP will determine
whether products containing the inert should be cancelled,
subjected to additional restrictions, or allowed to continue
• without change. Some of the List 1 inerts are added to
formulations to act against a pest, although not necessarily the
same pest targeted by the formulation. The OPP may reclassify
some of these inerts as active ingredients. In addition, no new
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product containing a List 1 inert ingredient will be registered
unless the product is very similar to another product that is
already registered.
Appendix D also presents the compounds included on List 2.
Another 60 inert ingredients have been identified as potentially
toxic and placed on List 2 based on their structural similarity
to known toxic chemicals or data suggesting a basis for concern
about their toxicity. Due to ongoing testing, List 2 is expected
to change periodically. If additional testing demonstrates that
the health and environmental effects of the ingredient are such
that it should be placed on List 1, then the ingredient will be
reclassified. The OPP has no immediate plans to issue new
requirements for existing registrations containing List 2 inert
ingredients. For new registrations, very similar products will
continue to be registered. Applications for registration of
other products containing these ingredients will be reviewed on a
case-by-case basis.
List 3 and 4 inert ingredients will not be subject to any
new restrictions. Inert ingredients on List 4, which includes
items such as cookie crumbs and corn cobs, are considered
innocuous. Inert ingredients are placed on List 3 if there is no
basis for including them on any of the other lists.
For new inert ingredients, inerts not currently identified
as being present in an approved formulation, or inerts that have
never been present in a previously registered product, a minimal
data set and scientific review will be required before the
product is registered. The minimal data set will normally be a
subset of the types of data required for active ingredients,
including residue chemistry, product chemistry, and
ecotoxicology.
8.1.1.4 Application. The EPA regulates the application of
pesticides primarily through labels and labeling. Section 12 of
FIFRA prohibits using a pesticide "in a manner inconsistent with
its labeling." The FIFRA requires proper application methods and
safety precautions to be included on the product label. Thus,
anyone applying a pesticide in direct conflict with the
-------
directions and recommendations on the label is in violation of
FIFRA regulations.
When a pesticide is registered, EPA classifies it for
general or restricted use. A pesticide classified for restricted
use may only be applied by or under the direct supervision of a
certified applicator, ensuring that these products are applied by
qualified personnel. The FIFRA establishes two categories of
certified applicators: private and commercial. A private
applicator uses or supervises the use of restricted-use
pesticides on property owned or rented by the applicator or the
applicator's employer. Anyone who applies restricted-use
pesticides and is not covered by the definition of a private
applicator is a commercial applicator.
In most cases the State has assumed responsibility for
applicator certification. In order to qualify for the right to
certify applicators, a State must submit a certification plan for
EPA approval. In cases where the State does not have an EPA-
approved plan, EPA retains the authority to administer an
applicator certification program.
The EPA has also set occupational safety and health
standards for farm workers who might be exposed during and after
pesticide application. Under these regulations, 40 CFR,
Section 170.3, pesticide applications are restricted to
conditions in which there is no risk of exposing workers or other
persons who are not involved in the application, whether the
exposure is caused by direct application or drift. The area to
be treated should be vacated by unprotected persons before
application. In addition, workers not wearing protective
clothing are not allowed to enter a treated field until sprays
have dried or dusts have settled. Minimal reentry times, usually
24 to 48 hours, are required for some active ingredients.
8.1.1.5 Residues. In order for a pesticide to be approved
for use on food or on feed for animals used in food production,
OPP must establish a tolerance, or an exemption from the need for
a tolerance, for each active and inert ingredient in the
pesticide. A tolerance is the maximum residue level of a
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pesticide that can be legally present in raw agricultural
commodities (RAC's), food, or feed transported in interstate
commerce. In establishing tolerances, OPP must consider the
contribution of the pesticide to the production of an adequate
and economical food supply, ways in which the consumer might be
affected by the pesticide, the usefulness of the pesticide, and
protection of the public health. Under FDCA, the Food and Drug
Administration (FDA) must monitor residues and enforce the
tolerances set by OPP. The U.S. Department of Agriculture (USDA)
monitors meat and poultry for pesticide residues and reports the
information to EPA.
An application for registration of a pesticide will not be
approved unless tolerances are established. The procedure for
establishing a tolerance is covered in Section 408 of the FDCA.
The applicant for registration must file a petition for
tolerance, which must include product chemistry data, directions
for use, toxicity data, residue data, and a statement of proposed
tolerance levels for the pesticide and all of its components that
are subject to regulation. The data are evaluated by the Hazard
Evaluation Division (HED) of OPP, and the tolerance is granted or
denied based on HED's evaluation.
8.1.2 Other Federal Regulations
Other regulations that have an impact on the formulation,
sale, or use of pesticides are summarized in this section.
8.1.2.1 Clean Air Act. Under the Clean Air Act (CAA),
States must submit State implementation plans (SIP's) for
implementing, maintaining, and enforcing National Ambient Air
Quality Standards (NAAQS) for criteria pollutants in each air
quality control region within the State. Emissions of volatile
organic compounds (VOC's) from the application and use of
pesticides may lead to an increase of ozone, a criteria pollutant
for which NAAQS have been issued. To achieve attainment in this
area, States may restrict the registration, sale, or use of
pesticides with high VOC content.
8.1.2.2 Clean Water Act. The Clean Water Act (CWA) has
historically been aimed at establishing regulations for
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discharges from point sources, such as wastewater discharges from
manufacturing facilities. However, Section 319 of the Act
addresses nonpoint sources. This section requires that States
develop and submit to EPA for approval State assessment reports
and State management programs for controlling nonpoint sources of
water pollution. This provides the potential for States to
impose best management practices or other controls to reduce
agricultural runoff from farming operations.1 Options that
States have include cancelling a pesticide's registration or
restricting areas in which it may be used. In Wisconsin, for
example, the use of aldicarb was limited to specific geographic
areas after results from groundwater monitoring indicated that
State-established standards had been violated. After Wisconsin
imposed limitations on its use, the manufacturer of aldicarb
withdrew the product from sale in the State.1
8.1.2.3 1985 Food Security Act.
8.1.2.3.1 Conservation reserve program. In 1985 the USDA
adopted the Conservation Reserve Program, which is designed to
prevent the cultivation of fragile, erodible land. Under the
program, farmers sign a contract with the USDA to retire their
erodible land from crop production for 10 years and plant it with
trees or other protective vegetation. In return, farmers will
receive payments of up to $50,000 per year depending on the
acreage they enroll and up to 50 percent of the costs of planting
trees or other vegetative cover that will prevent soil erosion.
To be eligible for the program, the land must have been used for
crop pr6duction for 2 of the 5 years between 1981 and 1985. The
land must be too steep or too shallow, or be eroding at greater
than twice the rate at which new soil is being formed.^
9.1.2.3.2 Other conservation requirements.. The Food
Security Act also requires that highly erodible land not placed
in the conservation reserve program be protected by conservation
practices by 1995 in order to reduce erosion to a specified
level. Fanners not complying with che practices will be
ineligible for farm benefits. Under provisions of the Act,
farmers must have an approved conservation plan by 1990 and a
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fully implemented plan by 1995. There are several options for
meeting the requirements, including changing rotation systems,
changing tillage systems, or installing permanent structures. In
most cases changing to a no- till or limited- till policy is the
cheapest of these alternatives. Farmers generally choose this
option to meet the requirements of the bill.4
8.1.2.4 Endangered Species Act . The Endangered Species Act
(ESA) requires Federal agencies to identify the risks that the
products they regulate pose to endangered species and consult
with the Department of the Interior for a risk analysis. If the
Interior Department finds that there is jeopardy to an endangered
species, it puts out a "jeopardy opinion," which is a legally
binding document. In 1988 ESA was amended to include a
requirement that EPA work with the Interior Department and the
Department of Agriculture to identify reasonable alternatives for
implementing a pesticide labeling program. The stated goal for
this program is to protect endangered species from pesticides
while allowing agricultural production to continue. The FIFRA
requires EPA to take steps to prevent harm to endangered and
threatened species from the use of pesticides. The EPA has
agreed to develop a program that will satisfy the requirements of
the ESA, but the programs it has proposed have been criticized
and rejected for their inadequacies. The most recent program was
proposed on July 3, 1989. The proposed program utilizes a
threshold application rate approach for protecting endangered
species without placing unrealistic burdens on pesticide users.
The EPA' s rationale for using this approach is based on the
principle that protecting species is best accomplished by
focusing on the listed species. Under the program, EPA
determines and includes on the label the threshold (lowest)
application rate that may affect listed species. Rates are
established for the most vulnerable species first. The ranking
of a vulnerable species is determined by its status and
vulnerability to pesticides.2 The EPA hopes to finalize the
program in the spring of 1992. ^
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8.1.2.5 CERCLA. The Comprehensive Environmental Response
Compensation and Liability Act (CERCLA) requires immediate
notification to EPA's National Response Center whenever a
hazardous substance is released into the environment at or in
excess of the reportable quantity (RQ). Approximately
700 hazardous substances have been identified and placed on
CERCLA's list, including some pesticide active ingredients, inert
ingredients, and formulations. Section 103 of CERCLA exempts the
application of pesticides registered under FIFRA from this
reporting requirement for normal pesticide applications. The EPA
has released a statement emphasizing that the exemption from
reporting is limited to normal applications that are generally in
accordance with label directions.1
8.2 STATE OF CALIFORNIA
California's regulations are the most extensive and tend to
be the model for other States. A summary of these regulations is
presented below beginning with the regulations which relate to
registration, labeling, inert ingredients, application, and food
residues.
8.2.1 Registration
Article 4, Chapter 2, Division 7 of the California .Food and
Agricultural Code requires that "every manufacturer of, importer
of, or dealer in any economic poison, except a person that sells
any raw material to a manufacturer of any economic poison or a
dealer or agent that sells any economic poison which has been
registered by the manufacturer or wholesaler shall obtain a
certificate of registration from the department before the
economic poison is offered for sale." An economic poison is "any
spray adjuvant or any substance or mixture of substances which is
intended to be used for defoliating plants, regulating plant
growth or for preventing, destroying, repelling or mitigating any
and all insects, fungi, bacteria, weeds, rodents, or predatory
animals, or any other form of plant or animal life which is, or
which the director may declare to be, a pest which may infect or
be detrimental to vegetation, man, animals, or households, or be
present in any environment whatsoever."
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California's registration criteria are generally more
stringent than EPA's. In addition to submitting to California
Department of Food Pesticide Regulation (DPR) all data required
by EPA, potential registrants must also include dermal absorption
data and more extensive health effects studies. In accordance
with Section 12825 of Article 4, the Department of Food and
Agriculture may refuse to register a pesticide after a hearing:
1. If the product has demonstrated serious adverse effects
within or outside the agricultural environment;
2. If the benefits of using the product are of less public-
value or greater detriment to the environment;
3. If there is a reasonable and practical alternative which
has fewer adverse environmental effects;
4. If the use of the product is detrimental to vegetation
other than weeds or to domestic animals or the public's health
and safety;
5. If the product is of little use in achieving its
proposed claims; and
6. If false or misleading statements have been made or
implied about the product.
Section 6158 of the California Administrative Code requires that
special consideration be given to several factors when a product
is being reviewed, including acute and chronic health effects,
toxicity to aquatic biota or wildlife, the availability of
feasible alternatives, efficacy, and the potential for
environmental damage, including interference with the attainment
of environmental standards. All approved registrations must be
renewed annually, and renewals are evaluated in accordance with
procedures established for the initial registration process.
This annual review provides a continuing update and evaluation of
each registered product. Although pesticides registered by EPA
may be denied registration in California using State guidelines,
the applicant for registration of the product must be told the
basis for the decision and the reasons why the decision is
contrary to, different from, or inconsistent with that of EPA.
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8.2.2 Labeling
California's label requirements are similar to those
required by FIFRA. Section 6243 of the California Administrative
Code states that labeling requirements shall meet but not exceed
current EPA requirements. Directions for use and dilution, if
any is required, must be printed on the label or enclosed in each
container or package. As of September 1, 1989, the South Coast
and Sacramento districts also require that the VOC content be
included on the label. The California Air Resources Board,
(CARB) is encouraging other districts to do the same, even though
this is in direct conflict with Section 24(b) of FIFRA which
restricts States from imposing or continuing in effect labeling
requirements in addition to or different from those required by
FIFRA.6 The DPR is currently negotiating with EPA to reach an
agreement which will allow districts to require this information
without being in conflict with FIFRA.7
8.2.3 Inert Ingredients
•
Section 6190 of the California Administrative Code requires
chronic toxicity data be reported for specific inert ingredients
which are designated by the Director of the Department of Food
and Agriculture. If animal feeding data are not available for.
these inerts, then the applicant must submit data from short-term
mutagenicity tests. If these data indicate the ingredient is
mutagenic, then animal feeding studies must be conducted on two
species.
8.2.4 Application
3.2.4.1 Applicator Certification. Article 2, Section 6400
of the California Administrative code recruires that restricted-
-------
conditions at the site of application and be available to direct
and control the action of the noncertified applicator during the
application process. The level of availability required shall be
a function o'f the actual or potential hazard of the situation.
Applicants for a qualified applicator's license are examined
on the laws and regulations governing pesticide use. Applicants
may elect to be examined for licensing in one or more of
11 categories including agricultural pest control, forest pest
control, right-of-way pest control, and landscape maintenance
pest control. All licenses must be renewed annually. Applicants
for a license must furnish any information that may be requested
by either the county commissioner or the Director of the
Department of Pesticide Regulation, including information on
equipment, facilities, and operational plans for using restricted
pesticides. Applicants are given an oral evaluation of their
knowledge of label directions and restrictions, pests to be
controlled, required protective clothing and equipment, poisoning
- •
symptoms, and awareness of surrounding environmentally sensitive
areas. The license may be revoked or suspended for failure to
adequately supervise the use of a restricted material, failure to
comply with an applicable provision of the Code, or making false
or fraudulent records or reports.
California has additional regulations, Article 1 of the
Code, which govern aerial pesticide applicators. A pilot
operating an aircraft engaged in pest control must have a valid
pest control aircraft pilot's certificate, an appropriate and
valid commercial pilot's certificate, and a 'current medical
certificate issued by the Federal Aviation Administration. A
pilot will be certified as either an apprentice or a journeyman.
To receive either certificate an applicant must pass an
examination demonstrating his ability to legally and safely
perform aerial pesticide applications and his knowledge of the
potential effects of the materials to be applied. Apprentice
applicators can apply pesticides only under the direct and
personal supervision of a journeyman applicator. Pest control
8-14
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aircraft pilots must register with the agricultural commissioner
in each county in which they work.
8.2.4.2 Conditions for Application. Section 12972 of the
Food and Agricultural Code requires that all pesticides be used
in a manner which prevents substantial drift to nontarget areas.
Under Section 6614 of the Administrative Code, an applicator must
evaluate the equipment to be used, meteorological conditions, the
property to be treated and surrounding properties to determine
the potential for harm or damage before applying a pesticide.
The applicator should continue evaluating conditions during the
application process. If the applicator determines upon
evaluating these criteria that there is potential for
contaminating persons not involved in the application, that there
is a possibility of damage to nontarget crops, animals or
property, or that there is a risk of contaminating nontarget
property which may prevent normal use of that property, then no
pesticide application shall be made, and if started, it should be
discontinued. In addition, Section 6460 provides specific
guidelines for the application of selected liquid herbicides,
including 2,4-D, dicamba, and propanil. These guidelines include
limits on wind speed, distance above the target from which the
pesticide can be applied, and nozzle types and sizes.
Sections 6616 and 6618 of California's Administrative Code
require that the owner or operator of a property be notified of
and agree to any application before it is made. The property
operator must then notify all persons who are known to be on the
property or who are likely to enter the property. The
notification must include information on the nature of the
pesticide and any precautions which should be taken in accordance
with the label or other applicable laws or regulations. In
addition, if the pesticide is to be applied on public property,
warning signs, written in English and Spanish, must be posted if
there is the potential for public exposure.
8.2.4.3 Field Worker Safety. California has also adopted
regulations aimed at ensuring field worker safety during and
immediately after pesticide application. These regulations are
8-15
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covered in Sections 6760 through 6778 of Title 3 of the
California Administrative Code. The regulations are similar to
those required by FIFRA. Employees are not allowed to enter a
treated field until the pesticide spray has dried or the dust has
settled. Specific pesticides have minimal reentry times
prohibiting an employee from entering a treated area until the
required time interval since application has elapsed. The
regulations also require employers to orally warn employees who
might be anticipated to enter an area being treated or an area
that has been treated. For highly toxic pesticides, warning signs
must be posted.
8.3 OTHER STATES
Regulations from other States are noted below either as
representative examples or as unique or particularly pertinent
examples relating to an area of discussion. Although this
summary attempts to address current legislation, the reader
should be aware that State laws and regulations are updated
frequently. For example, State fees for registrations of
pesticides increase on almost an annual basis. Fees in many
States for 1991-1992 are markedly higher than those for 1988-1989
shown in the summary of State regulations in Table 8-1.
8.3.1 Registration
Under FIFRA, States are allowed to have their own
registration programs, although Section 24 of FIFRA prohibits
those States from registering products that are not Federally
registered. As is the case with California, the State may have
stricter requirements than FIFRA, although most States base their
programs on FIFRA guidelines. A State may allow additional uses
for a Federally registered pesticide formulated for distribution
and use within that State in order to meet specific local needs,
if registration for that use has not been previously denied,
disapproved, or cancelled by SPA. The EPA does reserve the right
to suspend a State's registration program, if they decide that
the State is not exercising adequate controls in administering
its program. Details of three representative State registration
8-16
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TABLE 8-1. SUMMARY OF STATE REGULATIONS
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
Florida
Georgia
Hawaii
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missoun
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyoming
Registration fee pesticide, $
$50/product
N
$25/product per year
$25/product
$200/product/year
$70/product
$60/year (multi-year)
$25
$20 first 10 products
$5 additional
$10
3-year/$45 nonrestricted use or $90
restricted use
Proposed
$250/company, $100/product
$75
$250-3000 maximum
$130/product/year
$20/product
$100
$85
$35/product
$100/EPA registered product
$15/product
$ ISO/product
$50/product
$15/product
$90/label
$40/product
$25/product
$33/product
$200
$35/product
$40/product < 10, $20 > 10
$30/product
$25/product
$50/product
$50/product
$95/product
$25/product
$65/product
$25/product, $500 maximum
$75/product
$20/product
$100/product
$15/product
$40/year
$125
$ 110/product < 25, $105 26 < 100,
$80 10K150, $55 > 150
Proposed
$100/first product
$5/product
Groundwater
law (Y-N)
N
N
Y
N
Y
Y
Y
N
Y
N
Y
Y
Y
Y
Y
N
N
Y
N
N
Y
N
Y
Y
Y
Y
Y
N
Y
N
Y
Y
N
N
N
Y
Y
N
Y
N
Y
Y
N
N
Y
N
N
N
Y
N
Chemigation regs
(Y-N)
N
N
N
N
N
Y
N
N
Y
Y
Y
Y
N
N
N
Y
N
N
N
N
Y
N
Y
N
N
N
Y
N
N
N
N
Y
Y
Y
N
N
N
N
Y
Y
N
N
N
N
Y
Y
N
Y
N
Pesticide use
reporting regs
(Y-N)
N
N
Y
Y
Y
N
Y
Y
Y
N
Y
Y
N
N
Y
Y
Y
Y
Y
N
N
Y
Y
N
Y
N
Y
Y
Y
Y
Y
N
Y
N
N
N
N
Y
N
Y
Y
Y
N
Y
N
Y
N
N
Y
8-17
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programs, Virginia, Michigan, and Florida, are presented in the
following paragraphs.
Although probably no State has adopted a registration
program as stringent as California, each has some type of
program. Potential registrants in Virginia must apply to the
Department of Agriculture and Consumer Services for a certificate
of registration. Section 7 of the Virginia Pesticide Law states
that the registrant is responsible for the accuracy and
completeness of all data submitted with the application for
registration. Any subsequent claims made for a pesticide must
agree in substance with representations made for the product when
it was registered. If a registered product's label or
formulation is later changed, then details of the changes must be
submitted to the Department of Agriculture and Consumer Services.
Section 286.558 of Act No. 171 for the State of Michigan
requires that any pesticide distributed, sold, or offered for
sale in the State be registered in the State. Applicants for
registration must submit the following for each product: a copy
of the labeling, the full product name, a complete description of
tests and test results, and the pesticide's complete formula,
including active and inert ingredients. Registrations must be
renewed annually.
Chapter 487 of the Florida Pesticide Law requires that all
pesticides distributed, sold, offered for sale, delivered for
transportation, or transported in intrastate commerce be
registered with the Department of Agriculture and Consumer
Services. Registrations must be renewed annually. If review of
the data submitted with an application for registration indicates
that the pesticide may have significant potential for causing
adverse effects on the environment or the public health, the
department shall provide a summary of the data to the Pesticide
Review Council. The council may then advise the Commissioner of
Agriculture regarding the registration of the pesticide.
Rule 5E-2.005 of the Florida rules restricts- the registration of
pesticides containing ethyl or methyl parathion to uses not
involving lawns, turfs or ornamental plants.
8-18
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8.3.2 Labeling
Because Section 24(b) specifically limits additional State
labeling requirements, States generally conform to FIFRA when
establishing their own labeling requirements.
8.3.3 Inert Ingredients
Regulations and definitions for inert ingredients are
similar to those of FIFRA. Total percentages of inert
ingredients must be reported on the label. The complete formula,
including all individual inert ingredients, must be reported when
the product is registered, but this formula is held as
confidential information by the States, as it is by EPA. Some
States have left openings for regulating inerts as active
ingredients, however. For example, in Virginia, the Commissioner
of Agriculture may require any ingredient be designated as an
active ingredient if, in his opinion, it enhances the
effectiveness of the product to an extent that it should be
considered an active ingredient.
8.3.4 Application
3.3.4.1 Applicator Certification. Only two States,
Nebraska and Colorado, do not have EPA approved plans for
certifying applicators of Federally registered pesticides. In
Nebraska, EPA administers tests and issues certificates for
qualified applicants. Colorado's State program requires that all
commercial applicators, whether they apply restricted use
pesticides or not, be licensed. The EPA certifies applicators
who apply Federally restricted pesticides.8
Because of the requirement that all certification programs
be approved by EPA, State certification programs for applicators
using restricted pesticides are similar from State to State,
although in addition to pesticides restricted by EPA, each State
may classify other pesticides for restricted use. Most States
require applicators be examined and certified in particular areas
of pesticide use; such as field crops, forest products,
structural pest control, landscape maintenance, or even for
specific crops. Examinations may be written or oral, depending
on the State. In some States, applicants for commercial
8-19
-------
applicator certification must take written exams, and applicants
for private applicator certification have to take oral exams.
Florida has three classifications for applicator licenses--
commercial, private and public. Public applicators use or
supervise the use of restricted use pesticides while working for
a public utility or governmental entity. Both public and
commercial applicators are subject to the same standards.
Rule 5E-9.003 of the Rules for the Florida Department of
Agriculture and Consumer Services lists the categories in which
commercial and public applicators may be certified. These
include agricultural plant, agricultural animal, forest,
ornamental and turf, public health, industrial, institutional,
structural and health-related pest control, and aerial
application pest control. To be certified in one or more of
these areas, applicants for certification must demonstrate their
knowledge of pest control and the safe use of pesticides. Areas
in which they must be knowledgeable include label and labeling
comprehension, safety factors, environmental consequences, pest
features, equipment characteristics, application techniques, and
laws and regulations. They must also meet specific standards of
competency in the area(s) in which they wish to be certified. In
addition, applicants for an aerial applicator's license must
submit proof of financial responsibility to be certified. Such
proof may consist of depositing a surety bond with the department
or obtaining an insurance policy.
Rule 5E-9-010 requires that all certified applicator
licenses be renewed every four years. To be recertified an
applicator must demonstrate continued competency either by
retaking the basic certification examination or by accumulating
the required number of continuing education units which can be
obtained by attending department sponsored professional meetings
or seminars.
8.3.4.2 Conditions for Application. Many States have
established guidelines for pesticide applications and
requirements for notification. Examples of some of these
regulations are detailed in the following paragraphs.
8-20
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Regulation WAC-228-185 provides guidelines for pesticide
applications in the State of Washington. Under these guidelines
pesticides cannot be applied in weather conditions which may
promote physical drift or volatilization thereby potentially
causing damage to adjacent land, humans, desirable plants or
animals. Pesticides must be applied in a manner which minimizes
the hazard to commercially important pollinating insect species,
particularly if the application is made to or around blossoming
plants, and in a manner which does not pollute water supplies,
waterways, streams and lakes. The regulations also prevent the
application of certain pesticides by aircraft or airblast
sprayers in areas adjacent to occupied schools, hospitals,
nursing homes and other similar establishments under conditions
that may cause contamination of these establishments.
Section 17 of the Virginia Pesticide Law establishes
standards for pesticide application equipment. The equipment
must be in sound mechanical condition; it must be equipped to
dispense the proper amount of material; and all mixing tanks,
storage tanks, holding tanks, and components of the spray
distribution system must be leakproof. Pumps for spray
distribution systems must be capable of operating at a pressure
which ensures an uniform and adequate rate of discharge. All
application equipment must be equipped with cut-off valves and
discharge orifices so that the operator may pass over nontarget
areas without contaminating them. All hoses, pumps, and other
equipment used to fill pesticide application equipment must be
fitted with a valve or other device which prevents backflow, in
order to protect water supply systems, lakes and other water
sources.
North Carolina specifies conditions that must be met for
aerial applications in order to reduce drift (North Carolina
Administrative Code—Title 2, Section .1003). Requirements
include spacing fixed nozzles on the boom to ensure a uniform
spray pattern; releasing pesticides applied as liquids, in liquid
carriers, or as dusts within 15 feet above the canopy of the
target, except where obstructions may endanger pilot safety;
8-21
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releasing pesticides applied as dry granules or pellets within
40 feet of the canopy of the target; and restricting droplet size
for all restricted use pesticides and other selected liquid
formulations, including paraquat and phenoxy herbicides.
Section .1005 restricts areas where aerial applications can be
made. Aerial applications are not allowed within 300 feet of the
premises of schools, hospitals, nursing homes, churches or any
occupied building used for business or social activities; on the
right-of-way of a public road or within 25 feet of the road,
whichever is greater; within 100 feet of any residence; and on
any nontarget area where there is a good chance of causing
adverse effects. For ground applications, Section 1404 states
that no pesticide shall be applied under conditions that may
cause drift from pesticide particulate or vapors.
Florida restricts the application of synthetic organo-auxin
herbicides. Limitations on the distance which must separate the
closest edge of the area to be sprayed with these compounds from
nearby susceptible crops are established based on the wind speed
and direction at the time of application. Droplet size is also
limited. Aerial applications of these herbicides by fixed-wing
aircraft is prohibited in specified areas during specific time
periods.
Connecticut Public Act 88-247 requires all commercial
applicators and homeowners to post signs every time they apply a
pesticide or fertilizer. If neighbors file a request for
notification with the Department of Environmental Protection,
then they must be notified at least 24 hours in advance by
telephone, by mail, or in person by the homeowner or applicator
using the pesticide.
8.3.4.3 Field Worker Protection. Regulations for States
concerning field worker protection are similar to FIFRA.
Section .1803 of the North Carolina Administrative Code states
that the reentry time shall be the period of time required for
sprays to dry or dusts to settle with the following exceptions:
EPA Toxicity Category I pesticides shall have a reentry time of
at least 24 hours; selected pesticides, including ethyl and
8-22
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methyl parathion, shall have reentry times of at least 48 hours,
and in cases where the label sets more stringent requirements
these shall apply. If workers must enter a field before the
reentry time expires, they must be warned either orally or by
posted signs of the hazards involved and the safety precautions
that should be taken.
8.3.4.4 Chemigation. Chemigation is a pesticide
application method in which the pesticide is mixed with
irrigation water before the water is applied to the crop or soil.
Because of the potential for groundwater contamination from these
systems, some States have adopted regulations restricting the use
of Chemigation.
Regulation 16-228-232 for the State of Washington bans the
application of pesticides through an irrigation system unless the
registered label contains statements which specifically permit
it. In situations where Chemigation is allowed, the regulation
requires that any person involved in any mode of operation of a
Chemigation system be knowledgeable about the system and under
the direct supervision of a certified applicator. Specific
equipment requirements are also mandated including a backflow
prevention device or system in the water supply line upstream of
the point of pesticide introduction; an automatic, quick-closing
check valve in the irrigation line; and an interlocking control
to automatically shut off the injection pump when the water pump
stops or the water pressure decreases to a level which can affect
pesticide distribution.
Florida and North Carolina both require antisyphon devices
to prevent backflow into the water supply when irrigation systems
are used to apply pesticides. North. Carolina prohibits the
direct connection of a chezr.igation system to a public water
system, unless the water frcrr. the system is discharged ir.to a
rsssrvcir tank cetors introducing the cssticide. Zn Florida
applicators must use this sar".e method or they ray use a rscVucsd-
pressure-zcr.e RPZ,' backflcw preventer. Both Florida and North
Carolina recruire extensive rra.ir.tenar.ee orc^rams for all svsterr.
-------
valves and switches to ensure that they are always in good
operating condition.
In 1986, Nebraska enacted Legislative Bill 284 to tighten
restrictions on chemigation. The bill requires applicators using
a chemigation system to obtain a permit from their local natural
resources district. Chemigators must pass a safety course and be
certified by the State Department of Environmental Control.9
8.4 REFERENCES FOR SECTION 8.0
1. Conner, ed. Pesticide Regulation Handbook. New York,
Executive Enterprises Publication. 1987. 325 p.
2. Meister, R. Farm Chemicals Handbook 1991. Meister
Publications Company. Willoughby, Ohio. pp. D1-D46.
3. Environmental Reporter. January 24, 1986. p. 1,793.
4. Tillage Practices and Residue Levels. Agricultural
Resources. August 1989. p. 6.
5. Telecon. Rasor, S., MRI, to Turner, L., EPA/OPP.
February 22, 1990.
6. Letter from Calkin, D. L., Chief Air Program Branch,
Region IX, to Helms, G. Tc, Chief, Ozone and Carbon Monoxide
Program Branch, Office of Air Quality Planning and
Standards. February 20, 1988.
7. Telecon. Rasor, S., MRI, to Campbell, J., California Food
and Drug Administration. February 27, 1990.
8. Keller, J. J. and Associates. Pesticide Guide. Wisconsin.
1988. pp. L/R3, 12.
9. Morandi, L. Protecting Groundwater from Farm Chemicals:
State Legislative Options. Environmental Reporter.
pp. 1,941-1,943. December 18, 1987.
8-24
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APPENDIX A.
CALIFORNIA PESTICIDE DATA
-------
A. CALIFORNIA PESTICIDE DATA
A.I CALIFORNIA PESTICIDE USE REPORT
The State of California EPA, Department of Pesticide
Regulation (DPR) compiles information on the annual use of
pesticides in each county of the State. This information is
entered into a data base and used to develop various summary
reports, including the annual Pesticide Use Report (PUR). In
each county, farmers and commercial applicators are required to
provide selected information on the usage of each pesticide to
the county, who in turn transmits the data to the DPR.
Information is required for 14 different data fields and
requested for 9 additional fields. At the DPR, the information
is entered into computer files. Depending upon the selection of
fields that are accessed, a wide variety of data can be obtained.
When total pesticide usage is estimated, the use data in the PUR
for restricted-use pesticides should be multiplied by 1.13 and
for nonrestricted-use pesticides by 1.47 to adjust for unreported
use. As discussed below, the correction factors were developed
from information obtained from county agricultural staff and
pesticide use permits. Table A-l presents a summary of the
information entered into the pesticide use data base. Table A-2
provides a more complete description of the fields shown in
Table A-l.
For years prior to 1990, commercial applicators were
required to report information on all pesticides applied in the
county. A grower was required to report data only for a list of
80 restricted pesticide active ingredients and other compounds.
The list of restricted pesticides is presented in Table A-3. A
grower applying a nonrestricted pesticide may or may not report
A-l
-------
this information. To correct for underreporting, a correction
factor of 1.47 developed from information obtained from county
agricultural staff was applied to all reported nonrestricted
products in order to include the grower nonrestricted
applications in the inventory. For example, if the PUR indicates
that 11,323 pounds of malathion, a nonrestricted pesticide, were
applied in a particular month, then the corrected usage would be:
11,323 x 1.47 = 16,645 pounds.
Based on pesticide use permit information supplied by DPR,
it was determined that a correction factor of 1.13 should be
applied to all reported restricted use pesticide applications.
At the present time, data are. collected for all pesticides
used for agricultural purposes within the State; however, these
data are not currently available from DPR. The most recent year
for which data are available is 1987 so that data base contains
entries primarily for only the restricted pesticide active
ingredients.
The data compiled by DPR through the annual use survey was
used to provide a basis for the volatile organic chemical
emission estimates for agricultural chemicals in California. In
1983, California estimated emissions due to active ingredients to
be approximately 21,800 tons. Using the data compiled for 1987,
the California Air Resources Board (CARB) estimated VOC emissions
due to synthetic pesticides were 32,100 tons/yr.
Depending upon the specific selection of fields accessed, a
wide variety of information can be obtained. Midwest Research
Institute (MRI) acquired a copy of the 1987 DPR data base, which
contained more than 1,000,000 entries, and used the information
to develop a variety of data aggregations. The DPR data base
contained information on the quantities of active ingredients
applied during 1987 but did not contain any information on other
constituents of specific types of formulations. Because
emulsifiable concentrates (EC's) contain quantities of organic
solvents, the data presented in Tables A-4 and A-5 were developed
using the data base to identify the active ingredients. The data
base was searched to separate those active ingredients formulated
A-2
-------
only as EC's and those formulated as EC's as well as other types
of formulations. Using the active ingredient information, MRI
searched the EPA Office of Pesticide Programs (OPP) formulation
files to develop "average" or "typical" solvent content for each
active ingredient in an EC. The data in Tables A-4 and A-5 show
that the solvents used in these EC formulations contribute
approximately 3,100 tons/yr to the VOC emissions in California.
Additional examples of different types of information
displays that were derived by MRI from the data base are shown in
Tables. A-6 to A-12. For each active ingredient, Table A-6 shows
the quantity of the active ingredient used in all of the types of
formulations. This type of table is very useful in showing the
major and minor formulations for each active ingredient. Table
A-7 shows the quantity of each active ingredient used in each of
12 different pesticide types. In Table A-8, agricultural and
non-agricultural uses are shown for each active ingredient. Many
active ingredients are formulated as an EC and applied to crops
by aerial spraying. For each active ingredient, Table A-9
provides data for the quantity of active ingredient and the
quantity of solvent used to form the EC, the quantity of each EC
applied using ground spraying, aerial spraying, and other
application methods, and the average application rates (Ibs per
acre) for ground and aerial spraying. Table A-10 provides data
on total pesticide active ingredient usage in each of the 58
counties. Thirteen counties used one million pounds or more of
active ingredient and the five counties with the highest usage
accounted for 46% of the total use in the State. Table A-11
shows the total quantity of active ingredients used on each
commodity; the two commodities with the highest usage are
strawberries and cotton. The use of each active ingredient by
month can be tracked as shown in Table A-12. Application of the
pesticides is highest in September and lowest in January.
Similar information could be obtained by other States if an
information collection system for pesticide usage was available
within the State.
A-3
-------
A.2 CROP OILS (NONSYNTHETIC OILS)
An Air Resources Board (ARE) survey of pesticide oil
determined the 1981 statewide use of pesticide oils in four
categories: carrot oil, weed oil, foliar oil, and dormant oil.
Survey forms were sent to manufacturers and distributors of
pesticides and pesticide oils requesting information on the
description of the oil, registration number, quantity sold,
approximate percent sold directly to users, and use (e.g.,
agricultural, home and garden, institutional). No data are
available for any years since 1981. The PUR reported the county
use of pesticide oils in six categories: petroleum hydrocarbons,
mineral oil, petroleum oil unclassified, petroleum distillate,
petroleum distillate aromatic, and aromatic petroleum solvents.
However, the amount of pesticide oil listed in the PUR was
incomplete since not all users were required to report these
data.
Based on the results of the survey, the ARB estimated
emissions from the use of all pesticide oils in California to be
approximately 18,600 tons in 1987. The California DPR, has
estimated the use data for pesticide oils (i.e., crop oils or
nonsynthetic oils) in 1990 to be 13,615 tons. This shows a
decrease of almost 5,000 tons from the 1987 use level.
A. 3 CARS EMISSIONS ESTIMATE METHODS
The data generated for the 1983 PUR was used by the
California Air Resources Board (CARS) to calculate an emissions
inventory for pesticide applications from all sources in the
State. The most recent year for which PUR data are available was
1987. The methods used by CARS to estimate emissions due to
various mechanisms are presented in the following sections.1
As stated on page 4-1-A-2 of the CARS estimation methods,
emissions are not calculated for chemicals with unknown vapor
pressure or a vapor pressure of less than 10"7 mm Hg. In
addition, pesticides having only inorganic constituents are not
considered to be sources of VOC emissions.
A-4
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A.3.1 Emissions During Application. The following equation
was used to calculate volatile organic emissions during
application:
A2 = A1{1- [(4.625) (log P± + 7) (0.0024T2) (0.01)] }, (Eq. 1)
where:
A2 = pounds of pesticide AI deposited after emission loss
during application per acre;
AI = pounds of pesticide AI applied;
Pj_ = vapor pressure of pesticide i at 20°C in mm Hg;
T « average temperature in the month of application in
degrees centigrade; and
A1-A2 = emissions in pounds during application through
immediate evaporation.
This equation is based on data indicating that application losses
of a pesticide seem to have an approximately linear relationship
to the log of the vapor pressure and are approximately
proportional to the square of the temperature within the range of
5° to 30°C.1
A.3.2 Pesticide Loss by Sorption. Adsorption and
absorption rates for pesticides vary depending on the chemical
nature of the pesticide, meteorological conditions, and the
application site. Most sorption processes are reversible. For
most pesticides, only a small percentage is irreversibly adsorbed
and unavailable for evaporation. Because of the variables
involved, it is. impossible to determine a value for sorption loss
for every pesticide application.
The GARB assumed that 2 percent per month--that is,
2 percent of the amount of pesticide deposited--is lost through
sorption and is unavailable for evaporation. For highly volatile
pesticides (vapor pressure .>0.3 mm Hg), it was assumed that none
of the deposited pesticide will be lost by sorption.
A.3.3 Pesticide Loss by Degradation. Pesticides are
degraded in the environment by a number of mechanisms, including
chemical, photochemical, and biological degradation. Although
most pesticides are susceptible to one or more of these
degradation mechanisms, the quantity of hydrocarbon compounds
A-5
-------
available for vaporization and atmospheric reaction is not
necessarily reduced. A pesticide may be split into two smaller
compounds by degradation mechanisms, but this does not change the
total mass available for evaporation. The ultimate degradation
products of an organic compound under favorable environmental
conditions are carbon dioxide and water, but studies indicate
that most pesticides are not degraded to that point.
Although there is no established procedure or model for
predicting degradation losses for pesticides, it is apparent that
some portion of most pesticides is unavailable for evaporation
due to degradation processes. Degradation losses were assumed to
be 4 percent per month of the pesticide remaining after sorption
losses for nonsynthetic hydrocarbon pesticides and is therefore
unavailable for evaporation.
A. Nonacreage Applications.. Nonacreage applications are
pesticide applications that are referenced in units other than
acres, such as head of livestock, tons of produce, and number of
bins. For nonacreage pesticide applications, emissions during
application are calculated using Equation 1. Pesticide losses
due to sorption and degradation are also calculated. The amount
of pesticide remaining after subtracting these losses is assumed
to evaporate in the month of application.
A.3.4 Maximum Possible Evaporation Rate of Deposited
Pesticides. Although several methods have been proposed in the
literature for estimating volatilization losses of pesticides
from soil surfaces, many of these methods require input data that
are not readily available on a wide-scale basis. The method used
by GARB is based on a model developed by Hartley and modified by
Spencer.2'3 The method is based on the principle that the rate
of loss of a pure substance into the atmosphere from an inert
surface is governed by two of the substance's properties: the
saturation vapor concentration and the rate of diffusion through
the still air layers bounding the treated surface. The modified
equation for estimating the evaporation rate is:
A-6
-------
EA Pi (Mi
Ep = TTRH* 172' (Eq' 2)
1 ^ PW(MW)1/2
where:
Ep = the maximum evaporation rate of compound i in pounds per
acre (Ib/acre) during the month under consideration. Ep
is calculated for each month that pesticide is available
for evaporation;
EA = adjusted water evaporation rate in Ib/acre; EA = 0.73E,
0.40E, and 0.70E for application to vegetated land, soil
surfaces, and water surfaces, respectively;
E = inches of water evaporated in the month x 226,600 Ib/in.
of water on one acre;
RH = average relative humidity during the month;
Pj_ = vapor pressure of compound i at cited temperature;
Mj_ = molecular weight of compound i;
Pw = vapor pressure of water at temperature cited for Pj_; and
My = molecular weight of water.
In calculating emissions, applications of insecticide,
fungicide, defoliant, and insecticide-herbicide mixtures are
considered to be applications to a vegetated surface, while
herbicide and nematicide applications are considered to be
applications to a soil surface.
A.3.5 Monthly Emissions From Deposited Pesticides. Monthly
emissions from the volatilization of deposited pesticides for
acreage application are calculated using the evaporation rate,
Ep, calculated using Equation 2. The monthly emissions are
calculated as follows:
A
Jet = 2.303 log \ , (Eg. 3)
A4~AX
where:
k = the rate constant (day"1);
t - time in days;
A4 » pounds of deposit per acre available for evaporation in
a given month; and
A-7
-------
Ax = pounds of pesticide i evaporated per acre in any month
for a time t.
The rate constant, k, is, calculated for each month that pesticide
i is available for evaporation by substituting Ep/number of days
in the month for A^. when t = 1 day.
The amount of pesticide evaporated each month, AX, is then
calculated by using the calculated rate constant, k, and setting
t = the number of days in the month. Total monthly emissions can
then be calculated by multiplying AX by the number of acres in
the application and adding the emissions during application
calculated using Equation 1.
If A4-AX is less than 0.1 Ib/acre, then it is assumed there
is no pesticide remaining to evaporate in the next month. If
A4-AX is greater than 0.1 Ib/acre, then the pesticide carryover
and resulting emissions are calculated until the remaining amount
is less than 0.1 Ib/acre or 12 months of carryover have occurred,
whichever comes first.
A.3.6 Maximum Evaporation Rate and Rate Constants for
Application to Vegetated Surfaces. For a pesticide applied to
foliage, a portion is deposited on plant leaf surfaces and a
portion falls through and is deposited on the soil surface. For
example, Grove et al. reported that the crop canopy intercepted
52 percent of 2,4-D ester applied to a wheat field.4 Taylor et
al. reported on field experiments in which a mixture of dieldrin
and heptachlor were applied to an orchard grass field.5 Analysis
of" soil and grass residue immediately after application showed
grass residues of dieldrin were approximately four times greater
than soil residues, while grass residues of heptachlor were
approximately two times greater than soil residues.5 From these
results it is obvious that the percentages deposited on each
surface vary substantially, even when two pesticides are applied
simultaneously, as in the Taylor experiments.5 Because both
studies indicate that at least half of the amount applied is
deposited on the plant surfaces, GARB assumed in calculating
emissions that 50 percent is deposited on the plant surfaces and
50 percent on soil surfaces.
A-8
-------
Evaporation from the pesticide deposited on the foliage is
generally much faster initially than evaporation of' the portion
deposited on the soil. These losses are actually more rapid than
those predicted using Equations 2 and 3. Equation 3 was modified
to compensate for the greater-than-expected losses from vegetated
surfaces by multiplying the rate constant, k, in Equation 3 by
eight, so that predicted losses matched experimental losses more
closely. This adjustment to the rate equation is only applied to
the half of the pesticide deposited on the foliage and is only
used for calculating emissions during the month of application.5
A.3.7 Rate Constants for Soil-Incorporated Pesticide.
Volatilization is greatly inhibited for pesticides incorporated
into the soil after application. Several models have been
developed for predicting volatilization of soil-incorporated
pesticides, but these models require input data that are not
available on a wide scale. Because the differences in
volatilization are so large and incorporation is a common
practice, GARB addressed these cases, even though the method used
was not ideal. For the purposes of GARB, an approach is used
that is similar to the one used for pesticides applied to
foliage. Based on the data from Glotfelty and Taylor, comparing
volatilization losses of soil-incorporated pesticides to losses
for nonincorporated pesticides, the rate constant is divided by
500 when calculating monthly emissions from soil-incorporated
pesticides. '7 Although differences in volatilization losses
vary depending on the extent of incorporation, the pesticide
used, and soil conditions, the factor of 500 is an average
difference based on percent loss per day between pesticides that
are incorporated and nonincorporated.
REFERENCES FOR APPENDIX A
1. Methods for Assessing Area Source Emissions in California.
California Air Resources Board, Technical Support Division,
Emission Inventory Branch, Sacramento, California.
September 1991.
2. Hartley, G. S. Evaporation of Pesticides. Adv. Chem.
Series. flfi:145. 1969.
A-9
-------
Spencer, W. F., W. J. Farmer, and M. M. Cliath, Pesticide
Volatilization. Residue Review. .49.: l. 1973.
Grove, R. , J. R. Shewchuk, A. J. Cessna, A. E. Smith, and
J. H. Hunter. Fate of 2,4-D Iso-octyl Ester after
Application to a Wheat Field. J. Environ. Qual . 14(2):
203-210. 1985.
Taylor, A. W. , D. E. Glotfelty, B. C. Turner, R. E. Silver,
H. P. Freeman, and A. Weiss. J. Agric. Food Chem. 25.
(3):542-548. 1977.
Glotfelty, D., A. Taylor, B. Turner, and W. Zoller.
Volatilization of Surface-Applied Pesticides From Fallow
Soil. J. Agric. Food Chem. H: 638-643. 1984.
Taylor, A. Post Application Volatilization of Pesticides
Under Field Conditions. JAPCA. 21(9) : 922 -927.
September .1978 .
A-10
-------
TABLE A-l. DPR PESTICIDE USE DATA
Data Held W«M
I. Record 10
2. ProcMS date
•ontn
*•«•
J. Jatcft nutter
4. County nueaer
S. locators
Section
towisnip
toMSfllp direction
range
range direction
base and) Meridian
«. Date applied
•ontn
dOJf
year
7. CunauilUy code
1. Applied eetftod
9. Acres/unit treated
10. Type unit
11. fteglstratlon nwMer
firm nuMir
label nuMer
revision co
-------
TABLE A-l. (Continued)
04C4
OMcripttM
Us*
1*. ,Ut«
17.
eadt
18. OMriC4l cade
19. QMilCxil pcrcmc
20. OMrical 4lpM CM*
21. COMPtfUy «I0A4 CO*
22. ToC4l 0oun«s
u
cautery af
(•.9., Mrteulturil, total t*l.
of tM far* In «*ien »•
pnt1C1lM IS MTtttM
(•.4.. wittMU goMMr,
•Mlstf1«ol« eonc«fitr«u. ~
Mlt. «te.)
MM to 4twr«ln« us* eau^ary
1it/ora*C1on
to
e)4M
nyar«C4rtKiRs, CITMMCM. tie.)
en«rie4l cantMt af
tM pHCteld*
lOOTCIflCAtiOA
US*tf tfl «lt*f«lf»«
*CtU4l
t Of
jrtjduet
(•.«.. «Mlr«l«. 2-4-0)
••Mlty cod*
«u«t af «eti«<
In tM pntici*t
t)M
A-12
-------
TABLE A-2. TAPE FORMAT-1984 AND AFTER
Column # Field
Description of field
1 Record type
1 - individual pesticide use reports
2 - monthly pesticide use reports
3 - corrections
THE FOLLOWING IS FOR RECORD TYPE 1, INDIVIDUAL USE REPORTS
2-77 This information
receive from the
2
8
10
19
24
- 7
- 9
- 18
- 23
- 27
28
For internal use
County Number
Locators
Date Applied
Commodity code
Application
me thod
is keyed in from the pesticide use reports we
counties.
only
Refer to attachment A for list of counties
Section, Township, Township dir., Range, Range dir.,
Base & Meridian
Date pesticide was applied to above location
Commodity treated - refer to attachment B
G - Ground application
A - Aerial application.
0 - Other type of application
A numerical amount of acres or units treated
for this application. 8 digit field, with 2
places to the right of the decimal.
A - Acres
U - Units
T - Tons
P - Pounds
C - Cubic feet
K - Thousands of cubic feet
S - Square feet
38 - 58 Registration # EPA Registration number of the product applied
29 - 36 Acres/Units
Treated
37 Type Unit
59 - 67 Total Product
Applied
68 - 69 Unit of Measure
Amount of product applied
9 digit field, with 4 places to the right of the
decimal.
GA - gallons
QT - quarts
PT - pints
OZ - ounces
LB - pounds
GR - grams
ML - milliliters
LI - liters
KG - kilograms
70 For internal use only
A-13
-------
ATTACHMENT C TO TABLE A-2
TYPE CODES
A
B
D
E
F
G
H
J
L
M
N
O
P
R
Q
Adjuvant (spreader, sticker, wetting agent) or Water Modifiers
Algeacide
Disinfectant (or Bacteriostatic or Water Conditioners)
Fungicides (boats, aquariums, paint)
Herbicides (plant killer, weeds)
Insecticides (also for snails and Miticide)
Nematicide
Rodenticide (and fish and birds)
Fungicide & Insecticide
Fungicide & Herbicide
Herbicide & Insecticide
Fungicide, Herbicide & Insecticide
Growth Regulator ( and root tone and thinning)
Repellent
Defoliant (and Desiccant)
USE CODES
A
B
C
D
E
G
H
I
J
K
L
M
N
0
P
Q
R
Agricultural
Home Garden
Hospital
Household
Industrial (if lots of things listed including Hospitals--code
Industrial--list Hospital and other things as commodities)
Manufacturing (and formulating growth regulators)
Residential (done by licensed peopl-e)
Structural
Swimming Pools (spas and hot tubs also)
Non-Crop (non-selective weed killer)
Turf Areas
Domestic Animals (used on them)
Nursery
Spreader Sticker
Soil Fumigation
Agricultural Disinfectant
Agricultural Commissioner
FORMULATION CODES
1 » Bait
2 = Coating (and paints and salves)
3 » Dust
4 s Emulsifiable Concentrates
(or Emulsifiable Liquid)
5 = Fertilizer
6 = Gels, Pastes (and creams)
7 = Granular, Tablets (such as
briquets, solids)
8 » Impregnated Material (such as
ear tags collars)
9 Liquid (and spray pumps)
10 Oil
11 Pressurized Dust
12 Pressurized Fumigant
13 Self-Generating Smokes
14 Pressurized Sprays (and
foggers and aerosols)
15 = Wettable Powder (& dry
flowable)
16 = Soluble Powder
(codes 4, 9, 10 all are reported in liquid measurements)
A-15
-------
TABLE A-3. LIST OF RESTRICTED PESTICIDES
I. Insecticides
1. Aldlcarb (Temik)
2. Aldrin
3. Carbaryl (Sevln)
4. Carbofuran (Furadan)
5. Carbophenothlon (Trlthlon)
6. Chlorobenzllate.
7. Chlordlmeforra (Fundal)
8. Azodrln (Monocrotophos)
9. Bldrln (Olcrotophos)
10. Dial1fos (Torak)
11. Oieldrin
12. Demeton (Systox)
13. 4, 6 01n1tro-o-cresol (Dnoc)
14. EPN
15. Chlordane
16. 01-syston
17. Endosulfan (Thiodan)
18. Ethion
19. Guthion
20. Heptachlor
21. Lindane (Ganma-BHC)
22. Methomyl (Lannate)
23. Methyl Parathion
24. Mocap (Ethoprophos)
25. Monitor
26. Endrin
27. Naled
28. Nemacur (Fenamiphos)
29. Ompa (Schradan)
30. Parathion
31. Phorate (Thiraet)
32. Phosdrln
A-16
-------
TABLE A-3. (Continued)
33. Phosphamidon
34. Phostox.in
35. Supracide
36. Starllclde
37. Avltrol
38. Tepp (Sulfotepp)
II. -Herbicides
1. 2, 4-0
2. 2, 4-0 Affllne Salt
3. 2, 4-0 Butyl Ester
4. 4 (2-4-OB) Isoctyl Ester
5. 4 (2-4-OB) Butoxyethanol Ester
6. MCPA Dimethyl amine Salt
7. MCPA Isooctyl Ester
8. Propanll
9. Paraquat 01 chloride
10. Oef/Folex
11. ONBP (Olnoseb)
12. 2-4-OP
13. 2, 4-5T
14. 2, 4 01n1trophenol
15. Dlcamba
16. Plcloram
17. SI 1 vex (Fenoprop)
18. Nltrofen (Tok)
III. Nematocides
1. Chloropicrin
2. OBCP
3. Methyl Bromide
4. 1,3 Olchloropropene (Telone)
5. Ethylene 01bromide
6. Ethylene 01 chloride
A-17
-------
TABLE A-3. (Continued)
IV. Adjuvants
1. Diethyl amine Salt of Coconut
2. Triethanol a/nine
V. Others
1. Cadmium containing pesticides
2. Calcium Cyanide
3. Carbon Bisulfide
4. Carbon Tetrachloride
5. Compound 1080
6. Oasanlt
7. 000 (no longer manufactured)
8. DOT
9. Inorganic Arsenicals other than Sodium Arsenite
10. Mercury containing pesticides
11. Sodium Cyanide
12. Sodium Arsenite
13. Strycanine
14. Tel one (00)
15. Toxaphene
16. Zinc Phosphide
A-18
-------
TABLE A-4
ACTIVE INGREDIENTS USED ONLY IN EC
FORMULATIONS (1987)
Active ingredient
Quantity of active
ingredient (pounds)
Solvent (pounds)
Total Act. + Sol.
(pounds)
Tributylphosphorotrithioate
Profenofos
Methidathion
Merphos
Pebulate
Oxyfluorfen
Diclofop-methyl
Sulprofos
Bensulide
Diethatyl-ethyl
Chlorobenzilate
Metolachlor
Demeton
Bromoxynil, butyric acid ester
TOTAL
749,282
450,102
411,038
229,738
127,401
89,903
60,517
42,562
40,289
26,848
24,910
22,264
15,526
7,671
2,298,051
281,645
193,859
1,138,777
86,356
26,501
194,326
92,906
8,924
40,289
30,196
25,457
14,851
24,590
2,158,677
1,030,927
643,961
1,549,815
316,094
153,902
284,229
153,423
51,486
80,578
57,044
50,367
22,264
30,377
32,261
4,456,728
A-19
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-------
TABLE A-10. PESTICIDE USAGE BY COUNTY
County Total
Fresno 5,650,586
Kern 5,521,522
Monterey 3,943,322
Santa Barbara 3,086,341
San Joaquin 2,768,163
Merced 2,532,019
Imperial 2,264,743
Tulare 2,207,021
Ventura 1,840,200
Stanislaus 1,793,864
Kings 1,533,678
Sutter 1,230,876
Riverside 1,189,470
Santa Cruz 969,904
San Luis Obispo" 958,220
Butte 824,288
Colusa . 797,489
Madera 676,935
Yolo 671,154
San Diego 613,624
Glenn 611,179
Orange 510,813
Solano 370,334
Sacramento 326,653
Yuba 317,404
Sonoma 232,543
Shasta 227,364
Lassen 218,771
Napa 208,091
Siskiyou 156,091
Modoc 131,509
Del Norte 123,156
Tehama 121,453
Santa Clara 120,586
San Penito 109,292
San Bernardino 87,556
Los Angeles 86,588
San Mateo 77,411
Placer 70,339
Humboldt 57,048
Contra Costa 30,691
Alameda 25,221
El Dorado 24,365
LaJce 23,870
Plumas 17,338
Mendocino 13,335
Calaveras 9,745
Mono 9,471
Alpine 4,810
Nevada 4,548
Marin 4,293
Amador 3,301
Sierra 1,176
Invo 1,063
A-34
-------
TABLE A-10. (Continued)
County Total
Trinity 955
Tuolomna 658
San Francisco 448
Mariposa 200
Total 45,413,088
A-35
-------
TABLE A-11. 1987 PESTICIDE USAGE BY COMMODITY (LB ACTIVE)
Commodity
Total
Strawberries
Cotton
Almonds
Rice
Carrot
Tomato
Sugarbeet
Grapes
Open Land
Alfalfa
Broccoli
Lettuce (head)
Fallow Farm Land
Orange
Sweet Potato
Potato
Roses
Cauliflower
Peppers (bell)
Peach
Turf
Melons
Wheat
Beans
Walnut
Corn
Ornamentals
Brussels Sprouts
Flowers
Onions
Celery
Soil Fumigation
Lemon
Prune
Apple
Bulbs
Cabbage
Watermelons
Non-Agricultural Areas
Plum
Asparagus
Pistachio
Nectarines
Orchard Floors
Barley
Citrus
Lettuce (leaf)
Safflower
6,379,891
4,942,391
3,030,404
2,758,342
2,479,263
2,379,459
1,845,839
1,748,177
1,616,960
1,519,930
1,458,534
960,544
955,197
820,624
767,679
756,243
708,181
700,427
687,351
591,788
573,288
564,979
478,299
454,789
435,767
419,384
409,045
367,066
335,992
303,479
286,075
256,538
241,883
234,284
200,198
142,187
142,004
137,893
127,668
125,052
124,770
122,550
121,324
118,084
112,107
104,461
103,734
75,227
A-36
-------
TABLE A-11. (Continued)
Commodity Total
Oats 74,877
Parsley 74,571
Berries, other 64,647
Apricot 62,765
Pear 59,103
Artichoke 58,226
Cherries 57,834
Olives 57,730
Squash 54,020
Water Areas 53,575
Pasture/Rangeland 45,314
Spinach 43,762
Grapefruit 36,365
Garlic 35,317
Forest/Timberland 34,703
Conifers 32,473
Pumpkins 27,555
Cucumber 25,139
Avocado 23,806
Clover • 23,443
Figs 14,381
Beets 12,369
Deciduous Ornamental Trees 11,173
Rutabaga ' 11,052
Kiwi 10,749
Eggplant 10,174
Date 9,834
Miscellaneous . 9,233
Peas 8,117
Nuts, other 7,310
Sorghum 7,310
Parsnip 7,154
Poultry Buildings 6,148
Sunflower 6,128
Food Processing Plants 5,310
Vegetable Seed 5,076
Peppers (chili) 4,969
Kale 4,063
Chives 3,600
Grain 2,886
Tangerine/Tangelo 2,841
Sudangrass 2,749
Forage, hay & silage 2,689
Dried Fruit 2,586
Turnip 2,583
Swiss Chard 2,202
Pecan 2,136
Mustard 1,286
A-37
-------
TABLE A-11. (Continued)
Commodity Total
Pomegranate 1,203
Alfalfa Sprouts 1,193
Radish 1,131
Greenhouse Fumigation 1,046
Wild Rice 988
Anise 945
Chicken 776
Mushrooms 756
Industrial Areas 7.40
Evergreen Trees 704
Quince 608
Collard 522
Oriental Vegetables 485
Shrubs 423
Citrus/ other 339
Leeks 311
Hemp 286
Small fruits 240
Sweet Basil _ 220
Limes ~ 200
Rye 172
Nuts 150
Livestock Buildings 139
Weed Control 135
Vetch 124
Structural Control 103
Okra 99
Sub-tropical fruits, other 59
Kohlrabi 58
Cattle, Beef, & Dairy 57
Triticale 49
Endive 38
Soybean 24
Residential areas 21
Ryegrass 7
Recreational Areas-Parks 4
Rights of Way 4
Flax " 3
A-38
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APPENDIX B
RESOURCES FOR THE FUTURE DATA BASE
-------
-------
APPENDIX B. RESOURCES FOR THE FUTURE DATA BASE
B.I DATA BASE CONTENT
Two dBase data bases were obtained from Resources for the
Future (RFF) to estimate pesticide usage information summarized
in this document. The herbicide active ingredient (AI) use
information was obtained from the National Pesticide Use
Inventory compiled by RFF.1 The insecticide information also
came from RFF. Resources for the Future gathers information on
pesticide use and compiles the information in a comprehensive
data base format. Funding for the RFF studies comes from the
Environmental Protection Agency (EPA), the U.S. Department of
Agriculture (USDA), the National Oceanic and Atmospheric
Administration (NOAA) and several pesticide manufacturers. The
RFF data bases were created based on pesticide usage estimates
calculated using two coefficients: the percent of acres that are
treated and the average annual application rate per treated
acre.1 These coefficients are typically provided in terms of
Statewide average use for a particular AI and crop combination
for a year typical of the 1980's (1987-1989 for herbicides and
1982-1984 for insecticides). Multiplying these coefficients by
estimates of the number of planted crop acres reported in the
1982 Census of Agriculture for insecticides and the 1987 Census
of Agriculture for herbicides provides estimates of the number of
acres that are treated. The number of treated acres is
multiplied by the application rate per acre to estimate the total
poundage of AI used on the crop in a county.
Information on herbicides is available on the county level
which allows analysis of herbicide use in ozone nonattainment
areas. Insecticide and fungicide data were available only on the
B-l
-------
State level. No information on other types of pesticides was
compiled for these data bases.
The file names and structures of each data base are
presented in Attachment 1. In general, a data base file is
comprised of records, and one record consists of one set of the
fields outlined in the data base structure. Data may be
organized by any field or any combination of fields. The two
data bases contain information on the major insecticide AI's and
herbicide AI's in terms of use in the United States. The two
pesticide classes, insecticides and herbicides, constituted over
80 percent of the total U.S. pesticide market in 1990.2
Therefore, it is assumed that these data bases cover the majority
of the pesticide market in terms of pesticide classes and the
number of AI's. Based on 80 percent of the market, it is assumed
that herbicides and insecticides will constitute the major
sources of volatile organic compound (VOC) emissions from the
application of agricultural pesticides. The use of the term
"total pesticides" refers to herbicides plus insecticides.
The first data base contains insecticide use data from 1982
to 1984 for 16 AI's. Information is organized by insecticide, by
crop, and by State. Other information provided in fields
include: acres of crop grown (or harvested) according to the
1982 Census of Agriculture, percent crop treated, pounds of AI
per acre treated per year, pounds of AI used per year, and number
of acres treated. This data base file contains 2,042 records of
information.
The second data base contains use information from 1987 on
94 herbicides organized by herbicide, five-digit Federal
Information Processing Standard (PIPS) code, and.crop code. A
five-digit FIPS code is a numerical code; the first two numerals
identify the State, and the last three numerals identify the
county. The crop code is simply a three-digit code that
corresponds to one of 84 crop types used in the data base. Other
types of information provided in fields include harvested crop
acreage by county, percent of acres treated with the herbicide,
average annual use of AI per treated acre or rate of application
B-2
-------
(calculated by RFF from pounds Al/acre/year), total acres treated
in a given county (calculated by RFF from total acres x percent
treated x 0.01), and total pounds of AI used on a crop in the
county (calculated by RFF from: acres treated x rate). The
herbicide data base contains 191,000 records of information.
For purposes of analysis, MRI appended the FIP's code field
to the herbicide data base to identify pesticide use in counties
designated as whole or partial ozone nonattainment areas. This
was done by matching FIPS codes with the 1990 Clean Air Act
Amendment information on county ozone nonattainment status.
Pesticide usage information comes from the field "pounds of
AI used" in each data base. Resources for the Future estimated
the pounds of AI used from two coefficients: the percent of
acres that are treated and the average annual application rate
per treated acre. State-level usage coefficients were obtained
from surveys published for individual States, Extension Service
personnel, and USDA usage surveys.1 County-level usage
coefficients were calculated from State average coefficients,
assuming a uniform application rate within a State.1 Then the
State- or county-level coefficients were multiplied by the
corresponding number of planted crop acres to estimate the total
State or county pounds of AI used on a crop.1 Pesticide usage is
calculated by totalling the field "pounds of AI" according to
other factor(s) such as county, State, crop, etc.
B.2 PESTICIDE USAGE AND SOLVENT EMISSIONS TABLES
Tables highlighting different aspects of the available
pesticide use information were constructed. Total pesticide
(herbicide plus insecticide) usage nationwide and in ozone
nonattainment areas nationwide is presented in Table B-l. The
data in this table were taken from both the herbicide and
insecticide data bases.
The insecticide data base was indexed by State and then by
insecticide. The pounds of AI used were totalled for each AI
across all crops for each State and then totalled across all AI's
for each State (Table B-l) to obtain nationwide insecticide
usage. Total usage of an AI nationwide was also calculated and
B-3
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B-5
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the usages from all of the AI's ranked in descending order
(Attachment 2). Since the insecticide data base did not contain
county-level information, ozone nonattainment information was
estimated from the herbicide ozone nonattainment data. For each
State, the percent of total herbicide use in ozone nonattainment
areas was calculated and this percentage applied to the total
insecticide use in order to approximate the insecticide use in
ozone nonattainment areas.
The herbicide data base was manipulated in a slightly
different manner. In order to extract information for herbicide
use in ozone nonattainment areas, both county- and state-level
data were used. The original data base was obtained from RFF on
nine diskettes organized primarily by herbicide and crop. For
our purposes, the diskettes were combined on a Bernoulli disk to
allow access to information by State and county organization.
Nationwide (Table B-l) and county-level (Attachment 3) herbicide
use data for ozone nonattainment areas were taken from this data
base. Use rankings for herbicides in the data base nationwide
and in ozone nonattainment areas are provided in Attachments 4
and 5, respectively.
The data base was then divided by State into smaller, more
easily handled pieces. The State data bases were indexed by
herbicide, and the field "pounds of AI used" was totalled across
crops and county for each AI and for ozone nonattainment areas
only on the State level (Table B-l).
Table B-2 presents the solvent emissions calculated for each
state nationwide and in ozone nonattainment areas. These
emissions are based only on the approximated solvent content of
the following herbicide and insecticide AI's: methyl parathion,
ethoprop, diazinon, oxamyl, alachlor, metolachlor,
2,4-D, butylate, pendimethalin, propanil, propachlor and
bromoxynil. The method used to calculate nonaqueous solvent
emissions is described in section 4.3. The contribution of
insecticides to solvent emissions in ozone nonattainment areas
was estimated based on the ratio of herbicide contributions in
ozone nonattainment areas and nationwide.
B-6
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B-8
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B.3 PESTICIDE USAGE ESTIMATES
Total pesticide usage estimates for each State as well as
nationwide are presented in Table B-l. Data are listed for total
pesticide, herbicide, and insecticide use in pounds of AI's used
and total pesticide, herbicide, and insecticide use in pounds of
AI's used only in ozone nonattainment areas. These data were
compiled for each State from both the herbicide and insecticide
data bases. The data bases include information only for the
contiguous States; therefore, no data are presented for Hawaii
and Alaska.
Nationwide, 554 million pounds of herbicide and insecticide
AI's were applied to cropland. Herbicides accounted for over
80 percent of the total use (458 million pounds of AI's).
Insecticide use amounted to 96 million pounds of AI's. The
States with the largest contributions overall to total pesticide
use were Iowa, Illinois, Minnesota, Texas, and California. The
percent contributions of these States to the nationwide total
pesticide use, nationwide total herbicide use, and nationwide
total insecticide use are presented in Table B-3.
Of these States, the majority of pesticide use (85 percent
or greater) is due to the use of herbicides. Data base
information on the top four States indicates that the largest
volume of herbicide AI used in each of the States is used
primarily for weed control in corn including atrazine,
metolachlor, and alachlor. The top three States contributed one
percent or less to the nationwide insecticide use. California
insecticide use (15 million pounds of AI's), however, accounted -
for greater than half of the State's pesticide use. This was
largely a result of the use of dibromochloropropane (DBCP), which
accounted for 65 percent of California's insecticide use.
Dibromochloropropane is a soil fumigant used to treat a variety
of crops including citrus, berries, grapes, cotton, vegetables,
and ornamentals. Its registration was cancelled in 1985. The
major soil fumigants listed in the 1987 California Pesticide Use
Report compiled by the California Department of Food and
Agriculture (CDFA) were 13.65 million pounds of
B-9
-------
TABLE B-3.
COMPARISON OF CONTRIBUTIONS TO TOTAL PESTICIDE USE BY
THE TOP PESTICIDE USING STATES
State
Iowa
Illinois
Minnesota
Texas
California
Total
Percent
of total
pesticide
use
8.9
8.4
5.9
5.7
5.3
34.2
Percent
of total
herbicide
use
10.6
9.9
6.9
5.9
3.0
36.3
Percent of
total
insecticide
use
0.7
1.0
0.9
4.8
15.7
23.1
Percent
contribution
of herbicides
to total State
pesticide use
.98.6
97.9
97.4
85.6
48.3
...
B-10
-------
1,3-dichloropropene (Telone®) and 6.0 million pounds of methyl
bromide. Registration of 1,3-dichloropropene was suspended in
California in 1990 and the suspension has not been lifted. This
fumigant is also undergoing special review by EPA Office of
Pesticide Programs (OPP). The RFF data base showed that
California reported use of 12 insecticides other than DBCP in the
data base. The next-highest insecticide-using State is Georgia,
with 11.9 million pounds of 14 AI's reported in the data base.
In this case chlorothalonil, a fungicide, accounted for
approximately one-third of the insecticide use. However, DBCP
and ethylene dibromide, a fumigant that had all of its
agricultural uses cancelled in 1990, accounted for 17.9 percent
and 27.1 percent of the total insecticide use, respectively.
Thus, approximately 45 percent of the insecticide use in Georgia
has been replaced with other insecticides.
Pesticide use in ozone nonattainment areas of the States is
also presented in Table B-l. Since the insecticide data base did
not contain county-level information, the amount of insecticide
used in ozone nonattainment areas was approximated. Fifteen
States were designated with no ozone nonattainment areas. These
include Iowa and Minnesota, two of the largest pesticide-using
States in the country.
The highest herbicide use in ozone nonattainment areas was
found in California (12.2 million pounds of AI's), which has
35 counties with whole or partial nonattainment status. The AI's
with the highest use in California were DCPA (1.1 million
pounds), molinate (0.97 million pounds), and glyphosate
(0.96 million pounds). The State with the next highest herbicide
use in nonattainment areas is Michigan (11.2 million pounds of
AI's), which has 37 counties with whole or partial nonattainment
status. The AI's with the highest use in Michigan were atrazine
(2.4 million pounds), metolachlor (1.9 million pounds), alachlor
(1.4 million pounds), and EPTC (l.l million pounds). Together
California and Michigan account for 50 percent of the herbicide
use in ozone nonattainment areas nationwide. Connecticut, Rhode
Island, Massachusetts, and New Jersey were listed as entirely
' B-ll
-------
ozone nonattainment areas such that 100 percent of these States'
pesticide use was in ozone nonattainment areas.
B.3.1 Attachments
The attachments provide a more detailed presentation of the
data obtained from the two RFF data bases. Information on the
individual AI's by State and county is available through the
Pesticide or Pest field and FIPS field, respectively. The
pesticide code and FIPS code keys are provided in Attachment 1.
B.3.2 Summary
Certain weaknesses of-the data base should be noted. The
data contained in the data base are outdated. Several widely
used AI's have had their registrations cancelled by EPA since the
data base was compiled. While the data base still contains
important historical data in these cases, the information is not
an accurate representation of current uses of these specific
AI's. A significant impact may occur at the county- or State-
levels, especially for States like California where once heavily
used AI's have been cancelled.
B.4 REFERENCES FOR APPENDIX B
1. Gianessi, L.P., C. Puffer. Herbicide Use in the United
States National Summary Report. Quality of the Environment
Division, Resources for the Future. December 1990, Revised
April 1991. 128 p.
2. Aspelin, A. L., A. H. Grube, and V. Kibler. Pesticide
Industry Sales and Usage: 1989 Market Estimate. Economic
Analysis Branch, Biological and Economic Analysis Division,
Office of Pesticide Programs. U. S. Environmental
Protection Agency. July 1991. 21 p.
B-12
-------
ATTACHMENT 1
Structure for herbicide data base.
Field
1
2
3
4
5
6
7
8
9
Field Name
FIPS
CRO
PEST
ACTES
PCT
RATE
ACTRT
LBSAI
OX
Type
character
character
character
numeric
numeric
numeric
numeric
numeric
numeric
Width
5
3
4
10
5
6
9
8
1
Decimal
1
3
Structure for insecticide data base.
Field
1
2
3
4
5
6
7
8
Field Name
AC87
CROP
PESTICIDE '
STATE
PCTFNL
LBSFNL
LBSAI
ACTRT
Type
numeric
character
character
character
numeric
numeric
numeric
numeric
Width
9
16
16
15
3
7
9
9
Decimal
2
KEY:
FIPS
STATE
CRO
CROP
PEST
PESTICIDE
ACRES, ACS7
PCTf PCTFNL
RATE, LBSFNL
standard 5-digit county code
State name
crop code
crop name
pesticde code
pesticide name
harvested crop acreage of the crop in the county (from 1987
Census of Agriculture)
percent of acres treated with specified active ingredient
Average annual use per treated acre with specified active
B-13
-------
ingredient. (lb> AI/Acre/year)
ACTRT total acre* treated in county with specified active
ingredient.
LBSAZ total pounds of active ingr«di«nt us«d on «p«cifi«d crop in
th« county (ACTRT x RATE)
OX county oxon« nonattainnwnt status
B-14
-------
PESTICIDE CODES
1002
1005
1011
1018
1051
1098
1099
1109
1116
1124
11 76
1183
1191
1282
1287
1289
1298
1299
1302
1305
1307
1308
1209
1261
L262
1366
1369
1374
1375
1296
1397
1414
1417
1419
1422
1477
1616
1629
17QO
1309
133?
1363
1365
1367
1372
13:3
1335
1333
ACT FLUOR FEN
OICLOFOP
METOLACHLOR
NORFLURAZON
PICLORAM
3ENSULIDE
GLYPHOSATE
TERBACIL
3ROMOXYNIL
MSMA
3 ARE AN •
C3LORPROPHAM
PROPACHLOR
PROPANIL
3ENTAZON
OALAPON
3ICAMBA
C3LORAMBEN
2.— 0
MCPA
2.4-Ofl
3IFENOX
TRIFLURALIN
3ENEFIN
OIPHENAMID
C7ANAZINE
DIFENZOQUAT
3INOSE3
710FLJJRALIN
-LUC3LURALIN
SO LIN ATE
PS3ULATS
:«:??
PARAQUAT
PSNDIMETHALIN
TRIALLATE
3ROMACIL
3UTVLAT2
AUC-ILOR
3ICHLOBENIL
ISOPP.OPALIN
1889
1900
1903
1910
1913
1948
1950
1963
1974
1975
1977
1979
1980
1981
1982
1984
1987
1988
1991
1993
I9°8
2053
2069
2070
2158
2220
2250
4000
4001
-002
-003
-004
-005
-007
i008
4009
4010
5000
5003
?000
OR?ZALIN
CDAA
PSONAMIDE
?009
?012
?014
?015
9016
MCP3
MAPROPAMIDE
THIOBENCARB
SETHOXYDIM
CHLORSULFURON
ENDOTHALL
DIOUAT
7E3UTHIURON
DIPROPETRYN
METRIBUZIN
TERBUTRYN
PROPAZINE
ATRAZINE
SIMAZINE
AMETRYN
5IDURON
PROMETRYN
TRICLOPYR
DIURON
LINUROH
rLUOMETURON
CHLOROXURON
C7CLOATE
HEXAZINONE
PROPHAM
PSENMEOIPHAM
PYRAZOM
OXYFLUORFEN
DSHA
TLOPYRALID
9096
THIAMETURON
IMAZIQUIM
TRIDIPHANE
C3LORIMURON
LACTOFSN
FOMESAFEN
CLUMAZONE
"SNOXAPSOP
2MACETHAPYR
"LJA::?"?
-7HALFLURALIN
£THO FUMES ATE
DESMEDIPHAiM
D I ETHYL -ETHYL
DIALLATE
ASULAM
MSTHAZOLS
B-15
-------
CROP CODE CONCORDANCE
CRO CROP
100
101
102
103
104
1CS
107
108
109
110
111
112
115
116
117
113
119
1-0
• •• i
_ ..a.
122
113
126
127
129
1 "5
136
1J9
140
143
145
147
1:0
1 = 2
1 = 3
150
2:6
243
244
245
4CO
4C1
502
520
30
13
; 5
40
"0
00
505
6 = 3
3RUSS2L SPROUTS
SWEET PEPPERS
ARTICHOKES
STRAWBERRIES
GREZN PEAS
P2CANS
SUGAR3ESTS
ALMONDS
3RCCCOLI
CAULIFLOWER
GRAPES
NECTARINES
WALNUTS
ASPARAGUS
GARLIC
COLLARDS
MELONS
PLUMS
SUNFLOWERS
APRICOTS
AVOCADOS
SPINACH
SQUASH
3EZTS
2-Livss
PISTACHIOS
rIGS
rlADISHSS
IGGPIANT
OKRA
3WEZT POTATOES
3ATSS
KIWI
PCMEGRANTiS
GR£IN CNICNS
SZZD CROPS
PARSL2Y
CORN
CATS
3ARLZY
WHEAT
SCP.GHUM
SOYBEANS
RICZ-
ALJALFA
654
670
690
700
701
702
703
704
705
706
707
709
710
711
712
713
714
715
715
^ * ^
/ - /
aoo
901
342
910
911
913
914
915
941
943
949
952
999
OTHER HA*
TOBACCO
PEANUTS
CITRUS
APPLES
PEACHES
PEARS
CHERRIES
WATERMELONS
TOMATOES
SWEET CORN
ONIONS
LZTTUC2
GREEN 3EANS
CUCUMBERS
CZLZR::
CARROTS
CANTALOUPES
CABBAGE
POTATOES
DRY BEANS
DR2 PEAS
PASTURE
MINT
HOPS
FILSERTS
CRANBERRIES
2LACK3ERRIES
HOT PEPPERS
FLAX
SCO
SUGARCANE
GUAR
B-16
-------
State
Alabama
Arizona
Alaska
Arkansas
California
Colorado
Connecticut
Delaware
Florida
Georgia
Hawaii
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine _
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyoming
Two Digit
FlPScode
01
04
02
05
06
08
09
10
12
13
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
44
45
46
47
48
49
50
51
53
54
55
56
B-17
-------
-------
ATTACHMENT
Record* PESTICIDE LBSAI
1 DBCP 29072029
2 EOB 12409524
3 CHLOROTHALONIL 8875999
4 CARBARYL 8620584
5 METHYL PARATHION 7650238
6 CARBOFURAN 7154396
7 OINOSEB 6846644
8 ALDICARB 5317156
9 ETHOPROP 2486933
10 METHOMYL 2345308
11 DISULFOTON 2021997
12 DIAZINON 1842044
13 LINDANE 561045
14 OXAMYL 410083
15 FENAMIPHOS 406622
16 2,4-5T 386698
B-18
-------
-------
ATTACHMENT 3
Attachment 3 contains data on individual herbicide use for
ozone nonattainment counties nationwide. Due to its length this
attachment has not been provided here but is available on request.
B-19
-------
-------
ATTACHMENT 4
TABLE 1. HERBICIDE USAGE RANKED NATIONWIDE
Activ* lngr«di«nt
Atrazine
Alachlor
Metolachlor
EPTC
2,4-D
Trifluralin
Cyanazine
Butylate
Pendimethalin
Glyphosate
Dicamba
Bentazon
Propanil
MSMA
Metribuzin
Molina te
MCPA
Propachlor
Propazine
Simazine
Ethalfluralin
Triallate
Chloramben
Picloram
Paraquat
Clomazone
Bromoxynil
Linuron
Fluometuron
DCPA
Diuron
Prometryn
Norflurazon
DSMA
Diclofop
Pounds Us«d
68232131
55025302
49544375
37119783
33074201
27005509
22847387
19070536
12475522
11535166
11254300
8190359
7487432
4968375
4792132
4396189
4332397
4313802
3972392
3903902
3506483
3505008
2989035
2933901
2825000
2713716
2620914
2599149
2391268
2008871
1966524
1793996
1740280
1655019
1449949
B-20
-------
Active Ingredient
Oryzalin
Acifluorfen
2,4-DB
Thiobencarb
Bromacil
Benefin
Cycloate
Terbutryn
Imaziquin
Asulam
Diphenamid
Vernolate
Sethoxydim
Fluazifop
Napropamide
Pebulate
Naptalam
Profluralin
Tebuthiuron
Oxyfluorfen
Bensulide
Diethyl-Ethyl
Oipropetryn
Oalapon
Oinoseb
Terbacil
Hexazinone
Imazethapyr
Ethofumesate
Prophaxn
Pyrazon
Methazole
Chlorimuron
Difenzoquat
Chlorpropham
Pronamide
Fomesafen
Tridiphane
Pounds Used
1413826
1404719
1352037
1351709
1146606
1146339
1120883
1106989
1072648
1057773
910984
848840
838065
726637
679147
649317
637468
618729
606009
583158
541686
492562
491456
445549
398862
376118
343166
332646
320393
309650
305777
297520
288897
281812
247956
247499
226347
222444
B-21
-------
Active ingredient
Endothall
Ametryn
Phenmedipham
Diquat
Desmedipham
Bifenox
Diallate
Lactofen
Isopropalin
Chlorsulfuron
Triclopyr
Chloroxuron
Dichlobenil
Thiameturon
Bar ban
MCPB
Metsulfuron
Clopyralid
Fenoxaprop
CDAA
Fluchloralin
MCPP
Siduron
Pounds Used
196078
183338
166142
160713
134524
125147
119250
101841
97659
76966
70964
58642
58066
54839
51535
42445
40881
26208
26154
22012
20095
17950
3559
B-22
-------
-------
ATTACHMENT 5
TABLE 1. HERBICIDE USAGE FOR OZONE NONATTAINMENT AREAS
Pest Code Pounds Used
1002 109726
1005 68506
1011 7398163
1018 201668
1051 40159
1098 153715
1099 2223640
1109 152457
1116 216040
1124 53384
1176 14474
1183 91665
1191 46431
1282 626907
1287 692275
1289 211435
1298 709061
1299 766220
1302 1952924
1305 441538
1307 100282
1308 212581
1309 10637
1361 1665625
1362 115303
1366 363813
1369 2688130
1374 33954
1375 56967
1396 47595
1397 17736
1414 2896725
1417 1289449
1419 296238
1432 103195
1477 12076
1616 992326
1629 1439202
1790 11688
1809 123681
1839 2333538
1863 5967411
1865 16839
1867 6603
1872 1289430
1873 842561
1885 11711
1388 83948
1889 5005
1900 450935
1903 432190 B-23
-------
TABLE 1. HERBICIDE USAGE FOR OZONE NONATTAINMENT AREAS CONT
Peat Code Pounds Used
1910 ' 75777
1913 1592
1948 94494
1950 40608
1963 1890
1974 7117
1975 723406
1977 18824
1979 119335
1980 9630754
1981 1221504
1982 64735
1984 3559
1987 335275
1988 9060
1991 542325
1993 750603
1998 18310
2053 47678
2069 227766
2070 119927
2158 66718
2220 53537
2250 246520
4000 462086
4001 16488
4002 1247
4003 707
4004 2716
4005 89290
4007 4901
4008 37366
4009 -3620
4010 12976
5000 244123
5003 1499
9000 23798
9007 63434
9009 134840
9012 112289
9014 41128
9015 255509
9048 893030
9096 851
B-24
-------
APPENDIX C
LABORATORY TEST PROCEDURES FOR
VOC CONTENT IN PESTICIDES
-------
-------
METHOD DEVELOPMENT SUMMARY:
DIRECT MEASUREMENT OF VOLATILE ORGANICS
IN LIQUID PESTICIDE FORMULATIONS
1. METHODS EVALUATED
Two methods for measuring the volatile organic (VO) content
of liquid pesticides were evaluated. The first method, widely
used in the industry, involves measurement of volatile content by
thermogravimetric analysis (TGA), measurement of water content by
Karl Fischer titration, and calculation of VO content as the
difference. The proposed method, Volatile Organics in Pesticides
(VOP) Method, is a purge and trap procedure at constant
temperature. The VOP Method allows direct gravimetric
measurement of nonvolatiles, VO, and water in a single analysis.
Both methods should be conducted in triplicate and the average
reported.
1.1 Thermoqravimetric Analysis
The determination of volatile material in pesticide
formulations is typically determined by thermogravimetric
analysis (TGA). The "American Standard Test Method (ASTM) for
Compositional Analysis by Thermogravimetry" is included for
reference. The procedures in section 11 of the referenced method
should be followed to determine the volatile material in samples
of the pesticide with the following additional specifications:
11.9: Purge samples with nitrogen at 54°C and with a
constant flow rate between 50 to 100 ml/min. (A temperature
of 54°C is used to test the chemical stability of
agricultural formulations during development. Little or no
decomposition of any type is considered to occur at that
temperature.)
11.10: Purge until a constant weight is achieved or for a
maximum of 4 hours, whichever comes first.
12.1.1: This basic equation should be applied to determine
the weight percent of volatiles in the sample. (The weight
e
C-l
-------
lost is divided by the original weight and multiplied by 100
to determine the percent volatile material.)
Water content of a pesticide may be determined by Karl
Fischer titration. Volatile organic (VO) content can then be
determined as the difference between volatile content and water
content.
The method is less precise for water-based formulations than
it is for solvent-based formulations, and the imprecision
increases as water content increases.
The California Department of Pesticide Regulation (DPR) is
currently developing a TGA method to determine the VOC content of
various pesticide formulations. The major differences between
the California method and this method are the temperature and
duration of the test. In the California method, the sample is
heated at a temperature of 115°C until a constant weight is
attained for a specified period of time,-usually about 15
minutes. The overall time required for the test is approximately
one hour. If the active ingredient is known to be unstable or
volatilize at the test temperature, a lower heating temperature
and longer heating time are to be used. The DPR has stated that
lower heating temperatures have been required for some of the
formulations tested to date. Further information concerning the
California test method can be obtained from Ms. Judy Pino,
Environmental Monitoring Section, California EPA/DPR; phone
number (916) 654-1141.
1.2 VOP Method
Recently, a method that allows the direct measurement of
volatile organic compound (VOC) content of water-based coatings
was adapted to pesticide analysis. The method is a purge and
trap procedure conducted at constant temperature, similar to EPA
Method 24. The procedure involves purging volatiles from a
weighed sample of material with dry nitrogen at an appropriate
temperature (54°C for pesticide formulations), adsorption of VO
in the volatile fraction onto activated charcoal in pre-weighed
tubes, determination of final weights for both the sample residue
C-2
-------
and the charcoal tubes, and computation of weight percent of VO
in the original sample.
Water, if present, can also be measured directly by adding
collection tubes containing an anhydrous material (e.g.,
Drierite) to the exit port of the last charcoal tube. Water,
which is not adsorbed by charcoal, is collected quantitatively in
the Drierite tubes. The weight gain of the Drierite tubes
represents the weight of water present in the original sample.
The weight percent of water in the liquid pesticide is then
calculated.
Nonvolatiles are measured directly by determining the weight
of the residue after heating. Weight percent nonvolatiles is
then calculated in the usual way.
Mass balance can be demonstrated by computing the sum of
weight percent VO, weight percent water, and weight percent
nonvolatiles. The sum is typically in the range of 96 to
99 percent. If the sum is less than 95 percent, the results
should by discarded. The material loss is generally attributed
to a leak that develops during the 4-hour heating period.
The method removes some of the inherent imprecision in the
TGA/Karl Fischer method and could be easily extended to include
speciation of VO. This could be accomplished by desorption
(liquid or thermal) of the charcoal (or other suitable sorbent)
and analysis by gas chromatography with mass selective detection
(GC-MS). Individual VO could be identified by library matching
of mass spectral data and quantified by the use of appropriate
standards.
Additional work is being conducted to develop precision and
bias data for this method. Information on the status of this
work can be obtained by contacting the EPA Work Assignment
Manager, Dr. Joseph E. Kroll, in Research Triangle Park, North
Carolina. Dr. Kroll can be reached at (919) 541-2952.
2.0 COMPARISON OF T6A AND VOP METHOD
In the current study, weight percent nonvolatiles measured
by thermogravimetric analysis (TGA) and by Volatile Organics in
Pesticides Method (VOP) were compared to see if there was any
03
-------
relative bias in the two methods. Twelve commercial pesticides,
sold as emulsifiable concentrates, were used in the study. Of
the twelve, ten were solvent-based and two were water-based. All
ten of the solvent-based and one of the water-based pesticides
were analyzed by TGA. All 12 pesticides were analyzed by VOP.
A summary to TGA data for the eleven pesticides analyzed is
presented in Table 1. All TGA data was collected at 54°C and the
sample size was approximately 25 mg. All TGA analyses except the
one with Lasso were allowed to run for 4 hours (240 min). All
volatiles had been removed from Lasso within the first 90 min.
Weight percent nonvolatiles ranged from 28.65 percent to
88.28 percent. The one water-based pesticide (Blazer) is
indistinguishable from the solvent-based pesticides.
Hourly measurement for the samples analyzed by VOP were
obtained by stopping the run, disassembling the apparatus,
allowing the sealed components to cool to room temperature,
weighing the appropriate components, reassembling the apparatus,
and continuing the run. Using this approach, ten pesticides were
allowed to run for a total heating time of 6 hours, one
(Basagran) for 4 hours, and one (Lasso) for 2 hours. A summary
of weight percent nonvolatiles measured by VOP, paired with
appropriate TGA data, is presented in Table 2.
A statistical analysis of the paired VOP and TGA data for
nonvolatiles at the end of 4 hours (2 hours for Lasso) confirmed
that the two methods give equivalent results for nonvolatiles at
the 95 percent confidence level. A summary of the statistical
comparison is presented in Table 3.
A summary of the VOP analysis of two water-based pesticides
is given in Table 4. According to the Material Safety Data Sheet:
(MSDS) for Blazer, the formulation contains 8.5 percent butyl
cellosolve, which has a boiling point of I7l°c. Because of its
high boiling point, only 3.78 percent of the butyl cellosolve was
collected on the charcoal tubes after 6 hours at 54 °C. The MSDS
for Basagran claims no VO is present and none (-0.21 percent) was
measured by VOP after 3 hours at 54°C.
C-4
-------
3. CONCLUSIONS
The two methods, TGA and VOP, give equivalent results for
nonvolatiles. VOP offers the added advantage of also directly
measuring VO and water in the same analysis. Neither of the two
methods differentiates between volatile organics from solvent,
from emulsifiers, or from active ingredients. VOP has the
potential for speciation, which would allow subtraction of
volatilized active ingredients, and/or other exempt compounds,
from the total VO. In addition, if a liquid pesticide contains
no water, EPA Method 24 may be used.
C-5
-------
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C-7
-------
TABLE 3. STATISTICAL COMPARISON OF MODIFIED METHOD 24 AND TGA
Pesticide
Nonvolatiles (Wt. %)'
Modified
Method 24
TGA
Paired-Data Statistical Analysis
Difference
X
(X, -X)
(X, -X)2
Acclaim 1EC
Baythroid 2
Blazerb
Buctril
Folex 6 EC
Garlon 4
Lasso
Poast
Poast Plus
Prowl 4E
Treflan E.C.
Weedone LV6
46.35%
76.56%
38.80%
42.11%
74.53%
71.27%
51.59%c
28.03%
87.13%
56.90%
64.34%
88.57%
49.25%
76.99%
39.83%
42.94%
75.24%
69.36%
52.92%d
28.64%
87.77%
58.98%
60.16%
88.28%
EXi
n
x
-2.90 -2.62 6.84
-0.43 -0.15 0.02
-1.03 -0.68 0.47
-0.83 -0.54 0.30
-0.71 -0.42 0.18
1.90 2.19 4.80
-1.33 -1.04 1.08
-0.61 -0.33 0.11
-0.64 -0.36 0.13
-2.08 -1.79
3.20
4.18 4.47 19.97
0.29 0.58
= -4.18
= 12
= -0.348 ** 3
0.34
£(XrX)2 = 37.46
ECX.-X)2
3 fl T TV /
(n-l)n
Student's t test:
df = n-1 = 11
confidence level = 95%
'.able • ±2'201
t^ = *. = -0.653
ST
. The two methods give equivalent results for nonvolatiles at the 95% confidence level.
'Volatiles were purged at 54"C for 240 min for all pesticides except Lasso.
bBlazer is water-based; all others in list are solvent-based.
CA11 volatiles had been removed from Lasso in 120 min.
dAverage of two 120-min TGA runs.
C-8
-------
TABLE 4.
ANALYSIS OF WATER-BASED PESTICIDES
BY MODIFIED METHOD 24a
Water-Based
Pesticide
Blazer
Basagran
Time
(min)
60
120
180
240
300
360
60
120
180
Weight %
Nonvol.
41.50%
39.82%
39.21%
38.80%
38.62%
38.46%
52.85%
51.57%
50.92%
Weight %
VOC
5.13%
3.83%
3.40%
3.37%
3.56%
3.78%
1.19%
-0.09%
-0.21%
Weight %
Water
50.37%
53.06%
54.05%
54.33%
53.55%
54.34%
40.73%
43.82%
45.32%
Mass
Balance
Total
97.00%
96.71%
96.66%
96.50%
95.72%
96.58%
94.78%
95.30%
96.03%
'All analyses were conducted at 54°C.
09
-------
Designation: E 1131 - 86
Standard Test Method for
Compositional Analysis by Thermogravimetry1
This standard is issued under the fixed designation E I I3l: the number immediately following the designation indicates the year of
original adoption or. in the case of revision, the year of last revision. A number in parentheses indirjin the year of last reapproval. A
superscript epnlon (<) indicates an editorial change since the last revision or reapproval.
1. Scop*
1.1 This test method is intended to provide a general
technique incorporating thermogravimetry to determine the
amount of highly volatile matter, medium volatile matter,
combustible material, and ash content of compounds. This
test method will be useful in performing a compositional
analysis in cases where agreed upon by interested parties.
1.2 This test method is applicable to solids and liquids.
1.3 The temperature range of test is typically room
temperature to 1000'C. Composition between 1 and 100
weight % of individual components may be determined.
1.4 This test method utilizes an inert and reactive gas
environment.
1.5 Computer or electronic-based instruments, techniques, or
data treatment equivalent to this method may also be used.
Users of this test method are expressly advisSTthat all such
instruments or techniques may not be equivalent It is the
responsibility of the user of this test method to determine the
necessary equivalency prior to use. In the case of dispute,
only the manual-procedures described in this test method are
to be considered valid.
1.6 This standard may involve hazardous materials, oper-
ations, and equipment. This standard does not purport to
address all of the safety problems associated with its use. It is
the responsibility of the user of this standard to establish
appropriate safety and health practices and determine the
applicability of regulatory limitations prior to use.
2. Referenced Documents
2.1 ASTM Standards:
D1603 Test Method for Carbon Black in Olefin Plastics2
D 3172 Practice for Proximate Analysis of Coal and Coke3
E 472 Practice for Reporting Thermoanalvtical Data4
E 473 Definitions of Terms Relating to Thermal Analysis4
E 691 Practice for Conducting an Interlaboratory Study to
Determine the Precision of a Test Method4
E914 Practice for Evaluating Temperature Scale for
Thermogravimetry4
3. Terminology
3.1 Definitions:
3.1.1 The definitions relating to thermal analysis ap-
pearing in Definitions E 473 shall be considered applicable
to this test method.
1 This test method is under the jurisdiction of ASTM Committee E-37 on
Thermal Measurements and is the direct responsibility of Subcommittee E37.01
on Test Methods and Recommended Practices.
Current edition approved Sept. 26, 1986. Published November 1986.
: Annual Boon of ASTM Standards. Vol 08.02.
3 Annual Book of ASTM Standards. Vol 05.03.
4 Annual Book of ASTM Standards. Vol 14 02.
3.1.2 thermogravimetry— technique in which the mass of
a substance is measured as a function of temperature or time.
while the substance is subjected to a controlled temperature
program.
3.2 Descriptions of Terms Specific to This Standard:
3.2.1 highly volatile matter— moisture, piasticizer. re-
sidual solvent or other low boiling (200*C or less) compo-
nents.
3.2.2 medium volatile matter—medium volatiliu mate-
rials such as oil and polymer degradation products. In
general, these materials degrade in the temperature range
200 to 750'C.
3.2.3 combustible material—oxidizable material not vola-
tile (in the unoxidized form) at 750*C. or some stipulated
temperature dependent on material. Carbon is an example of
such a material.
3.2.4 ash—nonvolatile residues in an oxidizing atmos-
phere which may include metal components, filler content or
inert reinforcing materials.
3.2.5 mass loss plateau—a region of a thermogravimetnc
curve with a relatively constant mass.
4. Summary of Method
4.1 This test method is an empirical technique using
thermogravimetry in which the mass of a substance, heated
at a controlled rate in an appropriate environment, is
recorded as a function of rime or temperature. Mass loss over
specific temperature ranges and in a specific atmosphere
provide a compositional analysis of that substance.
5. Significance and Us«
5.1 This test method is intended for use in quality control.
material screening, and related problem solving where 2
compositional analysis is desired or a comparison can be
made with a known material of the same type.
5.2 The parameters described should be considered as
guidelines. They may be altered to suit a particular analysis.
provided the changes art noted in the report.
5.3 The proportion of the determined components in a
given mixture or blend may indicate specific quality or end
use performance characteristics. Particular examples include
the following:
5.3.1 Increasing soot (carbon) content of used diese!
lubricating oils indicates decreasing effectiveness.
5.3.2 Specific carbon-to-polymer ratio ranges are required
in some eiastomeric and plastic parts in order to achieve
desired mechanical strength and stability.
5.3.3 Some filled eiastomeric and plastic products require
specific inert content (for example, ash, filler, reinforcing
agent etc.) to meet performance specifications.
5.3.4 The volatile matter, fixed carbon, and ash content 01
coal and coke are important parameters. The "ranking" ^
C-10
-------
E1131
r ABU i wompawaanw Mnaiyws irnvrwoorwory i «*i
Pararrwtars
Test Parameters by Material
Material
Coal
Lubricant
Sample
Mass4
-------
E1131
TABLE 3 Summary of Bias
Andy*. Analytto, "-"— •
* *
COM
cofnbustlbto nwmi
•an
vOUtftW
flwdOfOon
Cateun Oxalatt Monoftydratt
COfTlDUCttbto fTWMflW
art
CHtxm monoxhto
wmr
40.4
53.6
6.1 6
«
.4
11.6
18.1
30.8
39.5
2
3.4
3.9
312
184
29.7
1i2
a reactive compressed gas such as air or oxygen are required
for this method.
8.2 Purity of Purge Gases:
8.2.1 0.01 % maximum total impurity.
8.2.2 1.0 ug/g water impurity maximum.
8.2.3 1.0 ug/g hydrocarbon impurity maximum.
8.2.4 The inert purge gas must not contain more than 10
u£/g oxygen.
^
9. Test Specimens
9.1 Specimens are ordinarily measured as received. If
some heat or mechanical treatment is applied to the spec-
imen prior to test, this treatment shall be noted in the report
9.2 Since the applicable samples may be mixtures or
blends, take care to ensure that the analyzed specimen is
representative of the sample from which it is taken. If the
sample is a liquid, mixing prior to taking the specimen is
sufficient to ensure this consideration. If the sample is a
solid, take several specimens from different areas of the
sample and either combine for a single determination, or
each run separately with the final analysis representing an
average of the determinations. Note the number of determi-
nations in the report
10. Calibration
10.1 Calibrate the apparatus according to prescribed pro-
cedures or appropriate operating manual at the heat and
purge gas flow rates to be used.
11. Procedure
11.1 Establish the inert (nitrogen) and reactive (air or
oxygen) gases at the desired flow rates. For most analyses,
this rate will be in the range of 10 to 100 mL/min. Higher
flow rates may be used for some analyses, particularly when
utilizing high heating rates.
11.2 Switch the purge gas to the inert (nitrogen) gas.
11.3 Zero the recorder and tare the balance. It is recom-
mended that this be done in a range at least one recorder
setting more sensitive than that to be used in the final ash
weighing.
11.4 Open the apparatus to expose the specimen holder.
11.5 Prepare the-specimen as outlined in 8.2 and carefully
place it in the* specimen holder. Typically, a sample mass of
10 to 30 mg shall be used (see Table 4).
NOTE 1—Specimens smaller thin 10 mg miy be used if larger
specimens cause instrument fouling or poor rqproducibility.
11.6 Position the specimen temperature sensor to the
same location used in calibration (See Section 10).
11.7 Enclose the specimen holder.
11.8 Record the initial mass. If the apparatus in use has
provisions for direct percentage measurements, adjust to
read 100%.
11.9 Initiate the heating program within the desired
temperature range. See Table 4 for suggested heating rates
and temperature ranges. Record the specimen mass change
continuously over the temperature interval.
11.9.1 The mass loss profile may be expressed in either
milligrams or mass percent of original specimen mass.
Expanded scale operation may be useful over selected
temperature ranges.
11.9.2 If only one or two components of the composi-
tional analysis are desired, specific, more limited tempera-
ture ranges may be used. Similarly, several heating rates may
be used during analysis in those regions of greater or lesser
interest Isothermal periods may be necessary for some
materials. See Table 4 for suggested parameters.
11.10 Once a mass loss plateau is established in the range
600 to 950"C, depending on the material, switch from inert
to reactive environment
11.10.1 If a distinct plateau is not observed in this range.
the atmosphere change is made based on the zero slope
indication of the recorded first derivative or upon some
agreed upon temperature. Suggested temperatures for this
region are given in Table 4.
11.10.2 The resolution of this region may be enhanced.
where carbon is present in large quantities or of special
interest, by maintaining the specimen at constant tempera-
ture for several minutes after switching environments.
11.11 The analysis is complete upon the establishment of
a mass loss plateau following the introduction of the reacuve
gas.
11.12 Switch to the inert purge gas.
TABLE 4 SuggMttd Compottttoml AraJyate PwwwMra
Sampia
Matahal Siza
mg
coal 20
tharrnopiaatlcs 20
lubncants 20
marmoaata 20
* Mav oiflar deeanttno uoon nstrur
Flow Rat*
50
SO
50
40 to 500
50
nant daann.
Purga
Mm
5
2
2
1
2
Ttynpflraturv
mutt
•ynbitnt
vnttwit
wnfitant
50
aVntttnt
X
110
325
200
150
200
Y
900
550
600
600
550
Z«
900
750
750
750
750
Haatlng
•C/mn
10U150
10
10
10 to 100
10
Gas
Swttcnover
•c
900
600
600
600
600
* Z is not nwMMrty ma final tamparatura.
C-12
-------
E1131
Sample: Rubber, lot 63
Date: 30 Sept. 83
MASS
(mg)
Highly volatile 6.6%l V
Medium
Volatile Matter 49 5*
Asrt11.S% A
1000
TEMPERATURE (*C)
Fia 1 SemptoThw
rime*
11.13 Calculate and report the sample composition.,.
12. Calculation
12.1 Highly volatile matter is represented by a mass loss
measured between the starting temperature and Tempera-
ture X (see Fig. 1). Temperature X should be taken in the
center of the first mass loss plateau or, if no resolvable
plateau exists, at an .agreed upon temperature value.- Sug-
gested values for Temperature X are given in Table 1.
12.1.1 Highly volatile matter content may be determined
by the following equation:
where:
V * highly volatile matter content, as received basis (%),
W m original specimen mass (mg), and
R m mass measured at Temperature JT(mg).
12.2 Medium volatile matter is represented by the mass
loss measured from Temperature X to Temperature Y (see
Fig. 1). Temperature Y should correspond to the mass loss
Rubov* lot 83* flppfOooRMUfy 30 % cvtoon (V
TO (Mod* XX)
AMim to 1000*C *t 10*C/mM
AmOMnt to aOQ*C-*Mregjn 99.99 %
SOO*C to 1000*C-AJr. Z*o <3rad>
Flow-50 mt/irtn
Ttne
^rf^MOV^I
wwnrwi
CofnpOMoon in W^^ftt
10mm
Quota*
Highly Vetatfe
Medium VoftOe
6.0*
49J*
32.4%
AMI
no. 2 Example Report
plateau used for switching atmospheres.
12.2.1 Medium volatile matter content can be determined
using the following equation: ~
R-S
W
x iOO%
where:
O » medium volatile matter content, as-received basis, %,
R » mass measured at Temperature X, (mg),
5 - mass measured at Temperature ?, (mg), and
W~ original specimen mass, (mg).
12.3 Combustible material content is represented by the
mass loss measured from Temperature Y to Temperature Z
(see Fig. 1). This region corresponds to the mass loss as a
result of the oxidation of carbon to carbon dioxide.
12.3.1 Combustible material content may be calculated
by the following equation:
C-
S-T
W
x 100%
where:
C « combustible material content, as-received basis, (%),
S =• mass measured at Temperature Y, (mg),
T * mass measured at Temperature Z, (mg) and
W * original specimen mass, (mg).
12.4 The residual weight remaining after the evolution of
carbon dioxide is taken as ash content This component is
measured at Temperature Z. This temperature is not neces-
sarily the final temperature. Suggested values for Tempera-
ture Z are given in Table 4.
12.4.1 The ash components of some materials may slowly
oxidize and subsequently gain or lose weight at high temper-
atures. In such materials, a value for Temperature Z must be
chosen prior to such transitions.
12.4.2 The ash content may be calculated using the
following equation:
C-13 :-
-------
E1131
where:
A * ash content, as received basis, (%),
T - mass measured at Temperature Z, (mg) and
W m original specimen mass.
NOTE 2—The use of the recorded first derivative may be useful in
locating the value ofX, Y, and Z by examining areas of the curve where
the derivative returns to, or approaches the baseline (see Fig, 1).
13. Report
13.1 The report shall include the following: .
13.1.1 Description of the material, including the name of
the manufacturer and information on lot number and
proposed chemical composition, when known,
13.1.2 Description of any sample pretreatment prior to
analysis,
13.1.3 Description of the thermogravimetric analysis ap-
paratus, including, where appropriate, the make and model
of commercial equipment used,
13.1.4 Temperature range over which the various compo-
nents are measured and the respective heatinjfrates,
13.1.5 Purge gas, flow rate, and composition,
13.1.6 Pre-analysis purge time,.
13.1.7 Number of determinations,
13.1.8 The weight percent highly volatile matter, medium
volatile matter, combustible material, and ash content, and
. 13.1.9 Original (or photocopy) of the thermal curve.
14. Precision and Bias
14.1 Precision—On the basis of an interiaboratory test- of
this test method, in which nine laboratories tested four
materials on two days close together, using the test parame-
ters in Table 1, the test results in Table 2 were obtained.
. NOTE 3—The precision values stated in Table 2 are based on four
specific materials studied in this interiaboratory test. These precision
values may vary with the type of material analyzed and the testing
parameters selected.
14.2 The interpretation of this data will produce indi-
vidual precision statements for each material and compo-
nent using the following as an example: two test results
obtained by different laboratories on replicate samples of
lubricating oil of about 2.5 % combustible material would
not be expected to differ by more than 0.5 %.
14.3 Bias—No reference materials were selected for the
interiaboratory testing of this test method, however data was
provided for coal using Method D3172 for proximate
analysis. In addition, the results from the calcium oxalate
compositional analysis can be compared to calculated theo-
retical values for each mass loss plateau. The bias indicated
for this method is summarized in Table 3.
9 Supporaof dm aviiUbfc from ASTM. Request RJfc 1009.
with any Htm mtntionttt in tftt ttanaart. Utan of that standtra an axpnttty »0va»d thm OaHrmnmon at ma raiairy tH any sueft
pmnr righa. tnathamHat nnnngtmtat at sucft ngna. an artnly tftrtr own rmponuoaty.
Tha standard it sub/act to motion at any lima oy tha n
If net rtvtsatJ: Mhtr rtapprovid or withdrawn.
itachnicaH
ttaa and mot be ravwwvd evtry fnra yaars and
tor rtntion or tnts staneard or for additional standards
and snoutd M addrttaad to ASTM Haaoquartari. Your oommam will raouva cartful eontatratan at a mattmg of tna rttponsioit
ttehmeU commaaa, wHeh you may attand. If you (til that your eommarm havt not rtoantd a fair ntamg you should makf your
vnw$ mown to tha ASTM Commutt on SttnotrOt, 1918 ftaca St.. PtOtoatphm. PA 19103.
C-14 .
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VOP METHOD PROCEDURE:
Direct Measurement of Volatile Organics
in Liquid Pesticide Formulations
1. SCOPE
The proposed method has been evaluated using commercially available pesticides sold
as emulsifiable concentrates. The eleven solvent-based pesticides used in the evaluation had
measured volatile organic (VO) content in the range 11-69% by weight and nonvolatiles in
the range 28-88%. Two water-based pesticides were also analyzed.
Methanol, if present in the pesticide, will not be measured with other VO's since
methanol is not adsorbed well by charcoal. Typically, a small amount of methanol will not
be purged from the second charcoal tube. Methanol that is purged from the charcoal is
trapped by the Drierite. Ethanol, if present, will be collected primarily on the first charcoal
tube with the second charcoal tube collecting approximately 30% of the total.
2. SUMMARY OF TEST METHOD
The proposed method involves purging volatiles from a weighed sample of liquid
pesticide with dry nitrogen at 54 °C, adsorption of VO in the volatile fraction onto activated
charcoal in pre-weighed tubes, determination of final weights for both the pesticide residue
and the charcoal tubes, and computation of weight percent of VO in the original pesticide.
Water content may also be measured directly by trapping water from the stripped volatile
stream emerging from the second charcoal tube on a dessicant (e.g., anhydrous CaSO4 or
Drierite). Mass balance can be demonstrated by determining the weights of nonvolatiles
(pesticide residue), VO, and water after heating, taking the sum of the three measurements,
and comparing the result to the weight of the original pesticide sample.
3. SIGNIFICANCE AND USE
This gravimetric test method allows direct measurement of the VO content of liquid
pesticides. It also allows the direct measurement of nonvolatiles and water in pesticides.
This method cannot differentiate between volatile active ingredient(s) and other VO present
in the pesticide. However, speciation could be accomplished by desorption of the charcoal,
analysis of the desorption solution by gas chromatography with mass spectrometric detection
(GC-MSD), identification of the compounds present by library matching of the mass spectra,
and quantification by means of appropriate standards.
4. APPARATUS
4.1 Volatilization Chamber, shown schematically in Figure 1, is custom-made from 80 mm
C-15
-------
flow
dispersion
tube
1/4 in OD
18.5cm long
#7 Ace-Threds
with
Teflon O-rings
Size 80
flange joint
with
Viton O-ring
aluminum
foil dish
horseshoe clamp
FIGURE 1. VOLATILIZATION CHAMBER
C-16
-------
OD (75 mm ID) glass tubing with a size 80 flange joint. The lower section is approximately
5 cm high and has a planar bottom. The upper section has two vertical #7 Ace-Thred
connectors: one in the center (N2 inlet) and one near the side (N2 outlet). Use a Viton CD-
ring to seal the two sections of the chamber and a flange joint clamp to hold them firmly
together. The N2 inlet tube is a 7V*-in long by #-in OD glass tube,-sealed at the lower end,
but with eight 1-mm holes around the tube Vi to Vi in above the sealed end. The holes
disperse the purge gas laterally and prevent spattering of the pesticide. The outlet tube is W-
in OD Teflon tubing. The inlet and outlet tubes of the chamber are attached with #7 Ace-
Thred connectors with Teflon O-rings. Adjust the height of the N2 inlet tube so that its lower
end is approximately Vi in from the bottom of the chamber.
4.2 Aluminum Foil Dish is 75 mm in diameter by 15 ram high with a planar bottom
surface. Precondition aluminum foil dishes in an oven for 30 min at 120°C and store them in
the oven (or in a dessicator) prior to use.
4.3 Charcoal Tube, shown schematically in Figure 2, is 18 cm long glass tube with 3.5 cm
lower portion W-in OD, 12.5 cm middle section 16-mm OD (14-mm ID), and a #7 Ace Thred
connector on upper end, packed with activated charcoal. Wash tubes. Place a plug of glass
wool in the tube near the lower, narrow end. Add 5 ± 1 g activated charcoal into the upper
end. Place a second plug of glass wool in the tube so that the charcoal is held firmly
between the two plugs. Prepare two charcoal tubes for each pesticide sample to be run.
Condition the unsealed charcoal tubes for 12 hours in an oven at 175°C. Remove the
charcoal tubes from the oven and seal the ends with coded #7 Ace Thred plugs and end caps
(for y*'in OD end). Allow the tubes to cool with plugs and end caps in place. Do not heat
the #7 Ace Thred plugs or the plastic end- caps.
4.4 Drierite Tube, shown schematically in Figure 2, is 20 cm long glass tube with 3.5 cm
lower portion M-in OD, 14.5 cm middle section 25-mm OD (23-mm ID), and a #7 Ace Thred
connector on upper end, packed with anhydrous indicating Drierite. If indicating Drierite
contains any pink granules, heat it in an oven at 175°C until it is uniformly blue (anhydrous).
Wash collection tubes and dry them in an oven. Place a plug of glass wool in the tube near
the lower, narrow end. Add 30 ± 3 g anhydrous indicating Drierite into the upper end. Place
a second plug of glass wool in the tube so that the Drierite is held firmly between the two
plugs. Prepare two Drierite tubes for each pesticide sample to be run. Seal the ends of the
Drierite tubes with coded #7 Ace Thred plugs and end caps (for tf-in OD end) as they are
removed from the oven. Allow tubes to cool with plugs and end caps in place. Drierite may
be reused if heated as described above. Do not heat the #7 Ace Thred plugs or the plastic
end caps.
4.5 Oven, gravity convection oven with ports added for inlet and outlet nitrogen lines.
4.6 Union Elbow, stainless steel Swagelok union elbow with teflon ferrules.
4.7 Union Tee, stainless steel Swagelok union tee with teflon ferrules.
4.8 Flange Joint Clamp, horseshoe style for flange joint size 80.
C-17
-------
Charcoal
Tube
18 cm long
16mmOD
charcoal
(5g)
Drierite
Tube
20 cm long
25 mm OD
Drierite
(30 g)
FIGURE! COLLECTION TUBES
5. REAGENTS
5.1 Activated Charcoal, 6-14 mesh (Fisher Scientific, 3315 Atlantic Avenue, Raleigh, NC
27604; catalog number 05-685A).
5.2 Indicating Drierite, 8 mesh anhydrous CaSO4 (W. A. Hammond Drierite Company,
Xenia, OH 45385). .
6. PROCEDURE
6.1 Initial Set-up. Procedures described in Sections 6.1.1 and 6.1.2 must be done before
any samples are analyzed. Nitrogen flow rates and oven temperature should then be checked
(and readjusted, if necessary) at the beginning of each analysis.
6.1.1 Set Nitrogen Flow Rates. Provide for two dry-nitrogen supply lines to the apparatus.
Both lines should be V4-OD tubing, preferably made of teflon for flexibility. One line will
supply N2 to the inlet of the volatilization chamber inside the oven, the other will supply N2
to the union tee in the outlet line just outside the oven. Nitrogen supplied through the
by-pass line is not heated and thus lowers the temperature of the first charcoal tube and
decreases the potential for breakthrough of VO. The additional N2 flow from the by-pass line
C-18
-------
also facilitates the removal of water from the second charcoal tube. With a bubble flowmeter,
adjust the N2 flow through the line to be attached to the chamber inlet to 1.0 ± 0.1 L/min. In
the same fashion, adjust N2 flow through the bypass line to be attached to the union tee to
2.0 ±0.1 L/min.
6.1.2 Set Oven Temperature. Assemble and seal an empty volatilization chamber in the
oven (as shown in Figure 3, but do not attach the union tee or collection tube assembly).
Attach a bubble flowmeter to the nitrogen outlet line from the chamber where it exits the
oven. Adjust N2 flow through the chamber to 1 L/min. Remove the bubble flowmeter. Run
a thermocouple down into the chamber through the teflon N2 outlet line. Position the
thermocouple so that it is very near but not touching the bottom of the volatilization chamber.
Adjust the temperature of the oven until the temperature inside the chamber remains at
54 ± 2°C for 1 hour. Record the temperature of the oven and the control setting required to
give a temperature of 54 ± 2°C inside the volatilization chamber. The oven should be set at
this temperature setting during subsequent pesticide analyses.
6.2 Analysis. Procedures described in Sections 6.2.1 through 6.2.11 must be done for each
analysis. At least three replicate analyses should be performed on each pesticide.
6.2.1 With a bubble flowmeter, check the nitrogen flow through the bypass line to confirm
that it is 2.0 ±0.1 L/min. In the same fashion, check the nitrogen flow through the chamber
to confirm that it is 1.0 ±0.1 L/min. If either flow rate is outside the given range readjust it
as described in Section 6.1.1. Record the measured flow rates.
6.2.2 Measure the temperature inside the oven to confirm that it is within ±5°C of the oven
temperature measured in Section 6.1.2. If the temperature is outside this range, readjust it as
described in Section 6.1.2. Record the measured temperature.
6.2.3 Mix the pesticide until it is homogeneous.
6.2.4 Label and weigh separately two charcoal tubes and two Drierite tubes to 0.1 mg.
Tubes should be sealed before they are weighed. Record the weights.
6.2.5 Refer to Figure 3. Attach the two charcoal tubes in series and the two Drierite tubes in
series. With N2 flows off, attach the first charcoal tube to the union tee in the outlet line just
outside the oven. Attach the first Drierite tube to the second charcoal tube.
6.2.6 Weigh an aluminum foil dish to 0.1 mg and record the weight. Add 1.0 ± 0.1 g of
pesticide to the dish, weigh it to 0.1 mg, and record the weight. The weighing of the
pesticide and the transfer of the dish to the volatilization chamber must be done quickly to
avoid loss of volatiles.
6.2.7 Quickly place the aluminum foil dish into the volatilization chamber, place the large CD-
ring between the top and bottom sections of the chamber, and place #7 Ace Thred plugs in
the N2 inlet and outlet ports. Use the flange joint clamp to obtain an air-tight seal between
the two sections of the chamber.
C-19
-------
vent
2 Umin N,
Umin N,
1
2nd Drierite tube
1 st Drierite tube
2nd charcoal tube
1st charcoal tube
oven
FIGURE 3. ASSEMBLED APPARATUS
C-20
-------
6.2.8 Place the volatilization chamber containing the aluminum fof dish in the oven.
Remove the stopper from the #7 Ace Thred in the center of the top section of the chamber
and install the nitrogen dispersion tube. Remove the remaining stopper and attach the N2
inlet and outlet lines as shown in Figure 2.
6.2.9 Leak Check. With the apparatus fully assembled, measure the leak rate by attaching a
water-filled manometer (or a 24-in loop of clear plastic tubing with water in the bottom Vb of
the loop) to the outlet of the second Drierite tube. Allow just enough N2 into the system to
displace the water in the manometer by 3 ± 1 in. With both N2 flows off, measure with a
stopwatch the time required for the difference in water level on the two sides of the
manometer to be reduced by 2 in or measure the change in difference in water level after
1 min, whichever comes first. Calculate the leak rate of the apparatus according to
Equation 1.
leak rate = *d c
8t
Eq. 1
d » ID of manometer tube (cm)
c = change in difference of water levels (cm)
t = time (min)
If the leak rate is 4 mL/min or less, continue with the next section of the procedure. If the
leak rate is greater than 4 mL/min but less than 20 mL/min, tighten all connectors and
measure the leak rate again. If the initial leak rate is 20 mL/min or greater, or if all leak
problems are not solved within 5 min after placing the chamber in the oven, discard the
pesticide sample and start over with a fresh one.
6.2.10 Turn on the nitrogen gas flows through both the bypass inlet and the volatilization
flask inlet, pleasure the flow to insure that the outlet flow equals the sum of the two inlet
flow rates measured in 6.2.1. Leave the apparatus in the oven at 54 ± 2°C with N2 flowing
for four hours.
6.2.11 Turn off the N2 flows and disassemble the apparatus. Replace the coded caps on the
ends of the collection tubes. Weigh the cooled charcoal tubes (separately), the Drierite tubes,
and the aluminum foil dish (containing the nonvolatile) to 0.1 mg. Record these weights.
7. CALCULATIONS
Weight of the original pesticide sample, the nonvolatiles remaining after heating, the weight
of VO collected on each charcoal tube, and the weight of water collected on each Drierite
tube are calculated by difference. The weight of VO collected on the second charcoal tube
typically should not be more than 10% of the weight of VO collected on the first charcoal
tube. If it is more than 10%, either there has been breakthrough of some poorly sorbed VO
(e.g., methanol) or water has not been completely purged from the second charcoal tube. In
either event the results are invalid.
7.1 Weight of Original Pesticide Sample. The weight of the aluminum foil dish plus the
C-21
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pesticide minus the weight of the empty aluminum foil dish (Section 6.2.6) gives the weight
of the pesticide sample taken for analysis.
7.2 Weight of Nonvolatile*. The weight of the aluminum foil dish with the pesticide
residue after heating (Section 6.2.11) minus the weight of the empty-aluminum foil dish
(Section 6.2.6) gives the weight of nonvolatile in the pesticide sample taken for analysis.
7 J Weight of Volatiles. The weight of the aluminum foil dish with the original pesticide
sample (Section 6.2.6) minus the weight of the aluminum foil dish with the pesticide residue
after heating (Section 6.2.11) gives the weight of volatiles in the pesticide sample taken for
analysis.
7.4 Weight of VO. Weight of a charcoal tube after the heating step (Section 6.2.11) minus
the weight of the same charcoal tube before the heating step (Section 6.2.4) gives the weight
of VO collected on that charcoal tube. Calculate the weight gain of each charcoal tube
separately to determine if breakthrough occurred as described above, then add the two weight
gains to get total weight of VO in the pesticide sample taken for analysis.
7.5 Weight of Water. Weight of a Drierite tube after the heating step (Section 6.2.11) minus
the weight of the same Drierite tube before the heating step (Section 6.2.4) gives the weight
of water collected on that Drierite tube. Calculate the weight gain of each Drierite tube
separately, then add the two weight gains to get total weight of water in the pesticide sample
taken for analysis.
7.6 Calculation of Weight Percent Nonvolatile (%Nonvol):
%Nonvol * (weight of pesticide residue after heating) ,.,m» Eq 2
, * (weight of original pesticide sample)
7.7 Calculation of Weight Percent Volatiles (%VoI):
(weight lost by pesticide sample during heating)
(weight of original pesticide sample)
7.8 Calculation of Weight Percent VO (%VO):
(total weight gained by the two charcoal tube's) (irin> E 4
(weight of original pesticide sample)
C-22
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7.9 Calculation of Weight Percent Water (%H2O):
%H O (total weight gained by the two Drierite tubes) ,inn, Eq 5
2 (weight of original pesticide sample)
7.10 Calculation of Mass Balance Total (%TOT):
%TOT = %Nonvol + %VO + %H2O Eq. 6
The sum of %Nonvol, %VO, and %H2O should be 100 ± 5%.
8. PRECISION AND BIAS
8.1 Relative standard deviation (RSD) of VO content, as a rule, should be less than 10% for
solvent-based pesticides.
8.2 Absolute bias has not been determined. In measurements of nonvolatile content of
eleven pesticides, this method gave results that were equivalent, at the 95% confidence level,
to those obtained by thermogravimetric analysis.
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•APPENDIX D
OPP INERT INGREDIENTS POLICY STATEMENT
D-l
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48314 Federal Register / Vol. 54. No. 224 / Wednesday. November 22. 1989 / Notices
IOPP-M140A; Fm. 3W7-9]
Policy StatMiwnt; Revision and
Modification of Uat*
AQCNCV: Environmental Protection
Agency (EPA).
ACTIO«C Notice. _
SUMMARY: EPA is revising and
modifying previously published lists of
inert ingredients in pestidda products
that are of lexicological concern and
require priority testing. EPA is also
addressing the period of time allowed to
• exhaust stocks of old formulations.
•Pncnvi DATE The modified lists are
effective on November 22. 1389.
AOOftlsftU: Three copies of written
comments bearing the document control
number [OPP-36140A] should be
submitted, by mail to: Public Docket
and Freedom of Information Section.
Field Operation Division (H7504C).
Office of Pesticide Programs.
Environmental Protection Agency, 401 M
St.. SW.. Washington. DC 20460.
In person, deliver comments to: Rm.
246. CM -2, 1921 Jefferson Davis Kwy.t
Arlington. VA.
Information submitted as a comment
in response to this Notice may be
claimed confidential by marking any
part or all of that information as
"Confidential Business Information"
(CBI). Information so marked will not be
disclosed except in accordance with
procedures set forth in 40 CFR part 2. A
copy of the comment that does not
contain CBI must be submitted for
inclusion in the public docket
Information not marked "confidential"
will be included in the public docket
without further notice. The public
docket is available for public inspection
in room 246 at the address given above
from 8 a.m. to 4 p.nu Monday through
Friday, except legal holidays.
ran PUfrrHUt INFORMATION CONTACT:
Lynn M Bradley. Registration Support
Branch, Registration Division (H7505C),
Environmental Protection Agency. 401M
St.. SW.. Washington, DC 20460. (202)-
703-557-7700.
SUmiMCNTAMY INFORMATION: EPA
announced its policy on toxic inert
ingredients in pesticide products in the
Federal Register of April 22.1987 (52 FR
13305). Through this policy. EPA
encourages the use of the least toxic
inert ingredients available and requires
the development of data necessary to
determine the conditions of safe use of
products that contain toxic inert
ingredients. In developing this policy,
EPA categorized inert ingredients into
the following four lists according to
(oxicity.
List l Inerts of toxicologies! concern
List 2 Potentially toxic inert*, with high
priority for testing
List 3 Inert* of unknown toxiaty
List 4 Inerts of """'>"• i concent
List 1 and List 2 were published as
part of the April 22.1987 policy
statement.
The criteria developed by EPA to
categorize List 1 inerts were reviewed
by the Federal Insecticide. Fungicide.
and Rodenticide Act's Scientific
Advisory Panel (FIFRA SAP). Chemicals
were placed on the list of inerts of
toxicologicai concern if they met any
one of the following criteria.
(1) Cardnogenicity:
—A rating as a human carcinogen of
probable human carcinogen (rating 1.
2A or 2B) by International Agency for
Research on Cancer.
—Characterized by the National
Toxicology Program as an animal
carcinogen in at least one species and
one sex.
D-2
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Federal Register / Vol. 54. No. 224 / Wednesday. November 22. 1989 / Notices 4331;
—Being regulated by some Federal
agency as a carcinogen.
(2) Neurotoxicity and other Chronic
Effects:
-Identified in the Occupational
Diseases, a Guide to their Recognition
(1977). as causing neurotoxicoiogicai
and other chronic effects in the
workplace environment
—Being regulated by some Federal
agency as a neurotoxin.
—Peer reviewed study, included in the
Toxicology Data Bank of the National
Library of Medicine, reporting
neurotoxic or other chronic effects.
(3) Adverse Reproductive Effects:
—Being regulated by some Federal
agency as causing adverse
reproductive effects.
—Peer reviewed study, included in the
Toxicology Data Bank of the National
Library of Medicine, reporting advene
reproductive effects.
(4) Ecological Effects:
—An LC50 of less than one part per
million.
Revision of Lists of Inert Ingredients
Since the publication of the policy,
EPA has received additional data on
some of the listed inerts. EPA scientists
have reviewed this information
according to criteria previously
developed and used in the creation of
the initial lists. As a result of this recent
examination of new data. EPA proposed
modifications to the lists. These
modifications were submitted to the
FIFRA SAP for review. The FIFRA SAP
concluded that the proposed changes
were justified,
EPA is announcing the following
revised List 1 and List 2.
LIST 1.— INERTS OF TOXICOLOGICAL
CONCERN
CAS No.
6243-3
1332-21-4
1332-21-9
7440-43-9
56-234
6748-3
108-48-7
103-23-3
78474
117474
68-12-2
123-91-1
106484
11040-9
111-19-9
10748-2
10948-4
14048-9
110-94-3
30241-2
78-59-1
7439-92-1
56844-2
591-784
.Ctwictfnanw
An*w
AaMMM flbar
i,24feMorepreoeir*
Otoara
C^^^^MM^MflaMtM
B|J9U mM VN IfWWl
Ethyl acryiM
Hydrwn*
L*«d compound*
Maiacrvtt gmn
UST 1.— IN6BTS OF TOXICOLOGICM.
CONCERN— Continued
CAS No, Qwmical n«m*
7447-3
7549-2
2515442-3
127-18-4
108-99-2
90-43-7
79-56-9
8003444
81484
10588414
26471424
79404
56494
79414
1330-784
78-304
Mwflnywnv CnlOnQv
Sodium dKtvomiM
Tnbufyl on ondt
^SSSSSSSi^SS
UST 2,— POTENTIALLY Toxic INERTS/
HIGH PRIORITY FOR TESTING
CAS NO.
6948-7
84-74-2
8448-2
131-114
117444
99-494
1319-774
99-48-7
108-44-9
108-39-4
10844-1
9940-1
112444
111404
111-774
111-78-2
5131484
124-184
10748-2
29387484
23198 48 1
141-79-7
108-10-1
98-29-7
10840-7
79424
10848-3
29399-43-1
99-14-7
12042-1
79404
88444
97-23-4
100-41-4
14840-4
74434
79-43-4
79-43-4
79-494
79474
79484
2916848-3
1330-20-7
10042-7
10848-7
79-244
79494
71494
102-714
111-42-2
Butyl osmyl phftatat*
Ofeutyt phtMM
dttfiyt plwisissitf
wNTMtffyl pntfUtaM
Dtoctyl pMftalaM
Crwott
o-Cfwol
m-CfMo) '
Cyoohaxanona
atfiar
MMiyt «ny< kMonm*
NUmimnam
To*uana
ToM mania
UJUUJiWU*14
p-CMord m KyUnpj
OfCMOfOpfMne)
I&OQfOp)A pfWnOJS PCVOMURI FiydVO*
Xytarw
aufywwajaoa
Ofetnanotafnrw
D-3.
UST 2.— POTENTIALLY Toxic INERTS/
HIGH PRIORITY POR TESTING— Continued
CAS No. 1 Cft»ffvca) nama
1
9748-1 i 9uty1 mathacryiata
80424 : Mttfyt matnacryttta Xytanawang*
1 aromatw joivants
9542-9 2.5-CiCfMoroan*na
95-76-t ' 3.4-OicftlOfoanilina
629-43-7 I 3.5-OtcmofoanMma
59440-7 | 2.4-Otctikxoamlioa
Aflll-27-$ ' 9 3 PfrJikyoafMlM^
60841-1 1 2.9-d«MoroanUina
76-13-1 I TncMorotnfluoreatftan*
7549-4 | Tncfltorotnfluoreatnan*
75-714 | Dicfttofodrtluoromwnana
79-14-2 Oictiiorotatraftuoroamana
The changes made and the reasons foi
the changes are explained below.
Additions to List 1
Di-(2-ethylhexyl)adipate and
dimethyl-formamide (DMF} were moved
to List 1 from Lists 3 and 2, respectively.
Baaed on a National Toxicology
Program bioassay. positive results for
oncogenicity were indicated for di-{2-
ethyi-hexyl)adipate: This chemical
caused increased Incidences of
hepatocellular carcinomas in female
mice, and thus meets one of the criteria
for categorization as a List 1 inert.
For dimethylformamide (DMF}.
hepatotoxicity has been reported at ver?
low doses in animal studies and is
commonly observed in case reports of
industrial exposure. Developmental
toxicity has also been reported to occur
in animal studies in the literature. In
addition, recent reports of clusters of
testicular cancer associated with human
exposure to DMF have added to the
weight of evidence which supports
upgrading this compound from List 2 to
Listl.
Additions to List 2
Based on data available at the time oi
the April 22. 1987. FR Notice.
monochlorobenzene was determined to
be an oncogen as well as an ecotoxm,
For these reasons, it was placed on List
1. The EPA Science Advisory Board has
reviewed the oncogenicity data on
monochlorobenzene and concluded that
it is a class D oncogen, i.e., not
classifiable. EPA scientists have
reevaluated the ecotoxicity data and
concluded that monochlorobenzene
does not meet List 1 ecotoxicity triggers
Because of these determinations.
monochlorobenzene is being moved
from List 1 to List 2 and is now
considered as a high priority for testing.
Methyl ethyl ketoxime has been
moved from List 3 to List 2 because of it
close structural relationship (o
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48316
Fedorai Register / Vol. 54. No. 224 / Wednesday. November 22. 1989 / Notices
acetoxime. which has been reported as
being carcinogenic in preliminary tests
and :s also positive in a mouse
/.mpiioma test. Methyl ethyl ketoxime
his been proposed for testing under
section 4 of the Toxic Substances
Control Act.
Additions to Lists 3 and 4
To accommodate revision of the lists.
EPA has decided to subdivide List 4 into
two parts. The previous List 4.
representing inerts generally regarded
as safe, has become List 4A. and a new
List 4B has been created. List 4fi is
composed of ir.erts for which EPA has
sufficient information to reasonably
conclude that the current use patterns in
pesticide products will not adversely
affect public health and the
environment. List 4B inerts in
formulations proposed for new us*
patterns which cause significant
increases in exposure will receive
further scrutiny.
Two inerts. gammabutyrolactone and
dioctyl sodium sulfosuccinate (DSS], are
•being removed from List 2 because EPA
now has a complete human health
effects data base indicating that they do
not meet the criteria for List 1 and that
their current use in pesticides should not
adversely affect human health.
The placement of
gammabutyrolactone on List 2 was
based on structural analogy to the
known oncogen, betabutyrolactone.
Further review indicates this analogy ii
inappropriate. In addition, a review of
toxicity data for gammabutyrolactone,
. including acute and subchronic data.
developmental toxicity, mutagenitity,
and oncogenicity indicates a low order
of toxicity. Thus EPA haa decided to
remove gammabutyrolactone from List 2
and add it to List 4B because current oat
patterns pose minimal risk for human
health. Because gammabutyrolactoae>
has not been adequately tested for
ecotoxicity. however, it ia being placed
on List 3 for these effects. EPA decided
to list the inert on two lists to reflect the
different degree of knowledge the
Agency has about the inert'i various
effects. EPA considered it appropriate to
place the inert on List 4B because it haa
sufficient information about human
health effects, and to also place it on
List 3 to reflect inadequate information
concerning the ecotoxicity of this inert
OSS was placed on List 2 because of
developmental and reproductive toxidty
concerns as well as ecotoxicity concern
for surfactants. Data have now been
reviewed for these effects, and indicate
a low order of toxicity. Thus. OSS ia
added to List 4B for nonadverse effects
on human health. Because of limited
ecotoxicity testing, however. DSS
remains on List 3 (unknown toxicity) for
-these effects.
Deletions From All Lists
Further investigation of ethylene
thiourea, carbon disculfide, and 1.1-
dimethylhydrazme (UOMH. the impurity
in Alar, which is in Special Review), has
revealed that these are only impurities,
not intentionally added inerts.
Furthermore, betabutyrolactone.
benzene, dichlorvos. 1.2-dimethyl-
hydrazine. pentachlorophenol and
sodium pentachiorophenate.
cresol. dinitrophenol. ethyl methyl
phenylgiyddate-formaldehyde and
paraformaldehyde. hexachlorophene,
mercury oieate. 2-r.itropropane. 1.2-
dichloropropane. and thiourea are not
now used as inerts in any pesticide
products. Therefore, these chemicals
have been removed from all lists of inert
ingredients and are not currently cleared
for use as inerts in any pesticide
product Thus, in the event a registrant
or applicant proposes to include one of
these chemicals as an inert ingredient in
a pesticide product EPA will consider
the chemical a new inert
Impurities in registered products are
contaminants from the manufacturing
process for the active ingredient rather
than intentionally added inert
ingredients. The presence and toxicity of
impurities is routinely evaluated during
the normal Agency review processes.
Impurities are identified in the product
chemistry review, and would probably
have been present as part of the teat
material, during testing considered for
support of the registration. Thus, it is not
appropriate to subject impurities to the
Inerts Strategy.
As discussed in the April 22.1987
Notice, registrants with products
containing List 1 inert ingredients must
amend their product registrations by
adding the following statement to the
label:
This product contains the toxic inert
ingredient (name of inert).
The wording should be placed in dose
proximity to the ingredients statement in
a type size comparable to other front
panel text Since dimethyiformamida
and di-(2-ethylhexyI) adipate have been
added to List 1. registrants of products
containing these inerts are required to
submit applications to amend their
product labels not later than May 22,
1990. Products containing one or more of
these inert ingredients released for
shipment after May 22.1991 must have
the amended label in place.
Registrants of products containing
(Smethyiformaznide have already
received a Oata Call-In. All registrants
have either voluntarily cancelled or
committed to reformulate the product.
Most reformulations have been
received: a few time extensions were
granted to allow fcr necessary testing of
the reformulated product.
A Oata Call-in for di-(2-ethylhexyl)
adipate will be issued, at the same time
as for diethylhexylpthalate. since the
uses are similar and we expect to find
them in the same types of products.
Data Call-Ins for other original List 1
inerts were mailed in March 1989.
Stocks of Old Formulations
Registrants are encouraged to
substitute or remove any List 1 or List 2
inert ingredient from their products by
submiting a new Confidential Statement
of Formula as a proposed amendment to
the registration. The April 22.1987
Policy statement did not address
provisions governing the sale of stock of
old formulations. If a registrant
reformulates its product to replace a List
1 or List 2 inert ingredient with a less
toxic inert EPA has determined that
some limit on continued sale of stocks of
the old formulation is appropriate.
Once a registrant submits the revised
formulation, registrants may
manufacture only the old formulation.
properly labeled as containing a toxic
inert as described above, until EPA
accepts the new formulation. Stocks of
the old formulation, bearing the required
labeling, may be released for shipment
by the registrant for a period not to
exceed twelve months from the data
EPA accepts the new formulation.
Products already in channels of trade
(retailers, distributors, dealers) are not
subject to this limitation.
Dated; October 10,1980.
OoiifiM 0. Cunpt,
Dinctor. Qffict of Pfsticidt Programs.
[FR Doc 8&-27213 Filed 11-21-88:8:43 am)
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