OCLC02608360
REVIEW OF PESTICIDE DISPOSAL RESEARCH
U.S. ENVIRONMENTAL PROTECTION AGENCY
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An environmental protection publication (SW-527) in the solid waste
management series. Mention of commercial products does not constitute
endorsement by the U.S. Government. Editing and technical content of
this report were the responsibilities of the Hazardous Waste Management
Division of the Office of Solid Waste Management Programs.
Single copies of this publication are available from Solid Waste
Information, U.S. Environmental Protection Agency, Cincinnati, Ohio 45268.
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REVIEW OF PESTICIDE DISPOSAL RESEARCH
This'report (SW-527) was prepared by
Douglas Munnecke, Harold R. Day, and Harry W. Trask,
U.S. ENVIRONMENTAL PROTECTION AGENCY
1976
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Summary
The disposal of unwanted pesticides and containers
has been the subject of limited research in recent years.
Although efforts have been devoted to finding the best ways
to safely dispose of pesticides, many questions remain
unanswered. This current report is an effort to identify
and describe what research has been undertaken, where it
is being conducted, and what organizations/institutions
were involved as of January 1975.
The impetus to conduct research into methods to
eliminate excess pesticides and containers derives from
problems created by excess (surplus, unwanted, canceled,
contaminated, etc.), pesticides currently held by both
public and private groups, as well as the containers
generated by the large volume of pesticides used annually
(estimated at over 800 million pounds in 1971).
This report describes the institutions involved and
provides an overview of four disposal avenues being researched:
biological and chemical degradation, incineration, and
landfill disposal. Abstracts of research in each disposal
area are provided.
The institutions which play an important role in
pesticide disposal research are mainly trade associations,
government agencies including the military, educational
institutions, and private companies. The funding for this
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research is mainly Federal,but with additional inputs by
private companies concerned with pesticides and their
safe disposal.
One research thrust in biological degradation of
pesticides includes studies of optimal conditions and
degradation products associated with elimination by natural
means in the field. Natural degradation in the field occur;
every time a pesticide is used, and the degradation
pattern is normally researched together with the
efficacy/environmental/other testing required during
the registration process. However, the effects of disposal
of large quantities over a short time at high concentrations
are uncertain. This method has the advantage of low
initial cost, and also the potential for long term higher
costs in those cases where the pesticide or its degradation
products enter the underground water system.
The other approach to biological degradation is by
treatment facilities designed specifically to degrade
pesticides under controlled conditions by microorganisms.
These facilities generally have been used for treatment of
manufacturing wastes. This technology has not been fully
developed and is complex.
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Oxidation, reduction, hydrolysis, catalysis, and
chlorinolysis are chemical processes which have been applied
to pesticide disposal. Disadvantages of chemical degradation
are incomplete destruction of the pesticide and subsequent
disposal of often unknown and potentially hazardous reaction
products. Other methods, which generally do not detoxify the
pesticide but rather remove the chemical, are conjugation,
fractionation, fixation, coagulation, precipitation, and ion
exchange or adsorption. Fractionation and chlorinoylsis
represent potentially viable methods for recovery of the
pesticide or its products for use. Unanswered questions
addressed are what pesticides are susceptible to hydrolysis,
how should the reaction products be disposed of, are there
simple chemical degradation procedures which can be used
by the layman, and are there permanent chemical fixation
methods. Chemical disposal methods have found only
limited application; most are used to treat pesticide
manufacturing wastes.
Incineration is restricted to organic pesticides.
To adequately combust a pesticide, the proper combination
of air, operating temperature, dwell time, and incinerator
design must be used. Additionally, scrubbers to remove
toxic gases, and ash disposal, must be considered. As a
general rule, if proper mixing occurs, 1000C for two seconds
is sufficient to destroy organic pesticides; however, it is
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unknown if this holds true for pesticide formulations.
Different equipment and designs have been employed and
incineration of pesticide/sewage sludge mixtures have been
tested with good results. Incineration remains the most
expensive disposal option, but large volumes can be disposed
of in a short time.
A major method of pesticide disposal is by landfilling.
This is widely practiced by manufacturers and others, but
little is known about the fate of pesticides in landfills.
The major environmental hazard associated with landfilling
is when chemicals or metabolities begin to move from the
disposal site, primarily downward and into the saturated
zone below. This involves a dynamic situation where the
pesticide in the leachate moves downward while chemical,
physical, and biological forces degrade the pesticide.
Pesticide mobility and half-life in soil are important
factors to consider when disposal site selection is made.
Concern about potential environmental damage has prompted
strict regulation by many States. Because no treatment is
required, this disposal method is the least expensive, but
also the one with the least assurance of pesticide destruction.
Most landfill research has been directed toward leaching
and soil migration studies and describing what happens to
pesticides in soil. Cases where the landfill failed to contain
the pesticide and the resultant effects are described.
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Table of Contents Page
I. Introduction 1
II. Structual Overview of Institutions
Active in Pesticide Disposal Research
a. Primary Agencies Providing
Financial Support 4
b. Research Coordination Groups 10
c. Research Institutions 11
III. Methods For Disposal of Pesticides: Biological
a. Introduction 18
b. Basic Research Findings 20
c. Present Technology Gaps 22
1. Soil Incorporation Techniques 22
2. Activated Sludge Techniques 23
d. Recommendations 24
e> Abstract of Biological Pesticide 25
Disposal Research
f. References 33
IV. Methods for Disposal of Pesticides: Chemical
a. Introduction 36
b. Basic Research Findings 38
c. Present Technology Gaps 40
d. Recommendations 41
e. Abstracts of Chemical Pesticide Disposal 42
Research
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Table of Contents (Cont.) Page
f. References 48
V. Methods for Disposal of Pesticides: Incineration
a. Introduction 50
b. Basic Research Findings 52
c. Present Technology Gaps 53
d. Recommendations 54
e. Abstracts of Pesticide 55
Incineration Research
f. References 61
VI. Methods for Disposal of Pesticides: Landfills
a. Introduction 63
b. Basic Research Findings 66
c. Present Technology Gaps 67
d. Recommendations 68
e. Abstracts of Research on Landfill 69
Disposal of Pesticides
f. References . 72
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REVIEW OF PESTICIDE DISPOSAL RESEARCH
INTRODUCTION
In the agricultural practices of the United States, pesticides
play an important role in helping to increase the productivity. Although
there have been efforts to replace organic chemicals with other methods
of pest control, some of which have been successful while others were
not, synthetic organic pesticides will continue to be used in tremendous
quantities(l,2). In 1971, approximately 800 million pounds of active
pesticidal chemicals were applied(3). With this widespread usage of
agricultural chemicals comes the subsequent problem of how to safely
dispose of unwanted pesticides and large numbers of pesticide containers.
It is estimated that in 1968, agricultural practices produced 240 million
empty pesticide containers(l). After use, these "empty containers" still
contain pesticide residue (approximately 0.02 to 0.37 percent}(4) and
must be disposed of properly in order to insure no environmental or
public health hazard is created(5).
Excess, surplus, or unwanted pesticides are derived from numerous
sources and create unique disposal problems. When registration of a
pesticide is canceled, as in the case of DDT, massive on-band quantities
of DDT at numerous facilities throughout the United States could no longer
be utilized, and therefore had to be either stored or disposed of properly.
Cancellations of other registrations could present a continuing problem of
disposal of large quantities of canceled pesticides. Other excess, surplus,
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unwanted pesticides derive from transportation and mislabeling
accidents, improper formulation, pesticides past their storage life,
and other surplus pesticides no longer wanted for their intended purpose.
Thus, there is a continuing need for proper methods of pesticide disposal
and correspondingly, safe and efficient collection systems, installations
and facilities capable of accepting these hazardous chemicals.
People in various governmental, industrial, university and private
institutions have long realized the need for proper methods for hazardous
*
pesticidal waste disposal. In fact, several conferences^!}, working groups
and disposal manuals(6) were initiated in order to help solve the numerous
public health and environmental problems associated with the use and disposal
of pesticides and their containers. In previous years, research efforts
and grants concerning disposal problems were organized and sponsored by
various governmental agencies which included the NIH, USDA, and DOI.
After the formation of the Environmental Protection Agency in 1970, this
Agency was given the lead responsibility for establishing proper procedures
for the disposal of pesticides and for funding and conducting research to
develop the technology necessary for implementing regulations governing
proper disposal methods. Specifically, this responsibility resides in the
Office of Pesticide Programs (OPP) which utilizes the Office of Solid Waste
Management Programs, Hazardous Waste Management Division (OSWMP/HWMD) as
its operating consultant.
* Federal Working group on Pest Management, Washington, and The
American Chemical Society, Washington.
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This report was initiated by HWMD in order to first define the
state-of-the-art for disposal of pesticides and containers by chemical,
incineration, biological, and landfill techniques and then to determine
what new technology was needed for 1) establishing prescriptive regulations
governing pesticide disposal, and 2) establishing a sound data base for
technical assistance. It is hoped that this report will summarize the
research efforts and directions taken by the many agencies and institutions
active in this field. For this reason, this review consists of two
sections. The first section identifies the primary agencies offering
financial support, the coordination groups, and the research institutions
concerned with the problem of disposal of concentrated pesticides.
Literally, hundreds of institutions are actively involved with pesticide
research; however, only those concerned with disposal problems of
concentrated pesticides will be discussed in this review. The second
section is divided into four subsections which discuss methods for
disposal of pesticides: 1) biological, 2) chemical, 3) incineration,
and 4) landfill. Each subsection will list the respective active
agencies, their research findings, a brief state-of-the-art review,
and several recommendations for areas of future research.
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STRUCTURAL OVERVIEW OF INSTITUTIONS ACTIVE
IN PESTICIDE DISPOSAL RESEARCH
Primary Agencies Providing Financial Support
The first Federal agency to actively fund pesticide disposal
research was the U. S. Department of Agriculture through its Agricultural
Research Service (ARS) and Cooperative State Research Service (CSRS)
programs (Table 1). The Northeast Regional Laboratory, Beltsville,
Maryland, is USDA's leading in-house research center on pesticide disposal.
Outside research is often sponsored by joint efforts of the CSRS and land
grant universities. Currently the planning and management of this pesticide
disposal research is conducted by the National Program Staff for Plant
Science and Entomology. Although primary responsibility for pesticide
disposal research now resides with the Environmental Protection Agency,
USDA is still actively involved with this research.
Subsequent to the cancellation of the registration of DDT and the
halt in the use of Herbicide Orange defoliant in Viet Nam, the Department
of Defense (DOD) began funding research to identify methods for disposal
of their stockpiles of these pesticides (Table 2). Since the DOD uses
a multitude of pesticides, they began sponsoring research on the disposal
of many chlorinated and organophosphate insecticides. Most of this
research on biological, chemical and incineration techniques was contracted
out to various industrial and State agencies. The U.S. Air Force Academy,
Department of Life and Behavioral Sciences,is involved with biological
disposal and ecological effects. The current problem of disposal of large
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Table 1
Pesticide Disposal Research
Groups In the United States Department of Agriculture. (USDA)
A. Agricultural Research Service.
1. National Program Staff for Plant Science and Entomology
(Dr. Hugo Grauman).
2. Regional Laboratories.
a. Northeast Regional Laboratory, Beltsville, Maryland.
Pesticide Degradation Labortatory,
Dr. Philip Kearney, Director.
b. Northcentral Regional Laboratory,
Peoria, Illinois.
c. Western Regional Laboratory,
Berkeley, California.
d. Southern Regional Laboratory,
New Orleans, Louisiana.
B. U. S. Forest Service.
C. Economic Research Service.
D. Cooperative State Service.
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Table 2
Pesticide Disposal Research Groups in Department of Defense
A. Assistant Secretary, Health and Environment.
B. Department of Army.
1. Material Command.
a. Edgewood Arsenal, Aberdeen, Maryland.
b. Dugway Army Depot, Dugway, Utah.
c. Rocky Mountain Arsenal, Colorado.
d. Contract awarded to Stanford Research Institute.
2. Health Command.
a. Ft. Detrick, Maryland.
b. Edgewood Arsenal, Aberdeen, Maryland.
C. Department of the Air Force.
1. Systems Command.
Herbicide Orange.
a. Chemical Methods - Contract awarded to
Diamond Shamrock.
b. Incineration Methods - Contract awarded
to Marquardt Co.
c. Biological Methods - Contract awarded
to University of Utah.
2. U. S. Air Force Academy.
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quantities of Herbicide Orange is the responsibility of the U.S. Air
Force Systems Command.
The Department of The Army (DOA) also sponsors research on the
disposal of canceled DDT and other pesticides. This research is funded
through the Army Material Command, (AMC), which is primarily concerned
with disposal of stockpiled pesticides, and the Health Command, which
is concerned with developing safe procedures and techniques for the
disposal of pesticide wastes and excess pesticides derived from
everyday use. Much of this research is conducted in-house at Edgewood
Arsenal, Aberdeen, Maryland, and Ft. Detrick, Maryland. The contract
research work on biological, chemical and incineration methods for
pesticide disposal is coordinated through the Medical Research and
Development Command, Forrestal Building, Washington, D. C.
The two primary program offices within EPA which are concerned
with pesticide disposal are the Office of Pesticide Programs (OPP)
and the Office of Solid Waste Management Programs (OSWMP). Two other
offices within EPA are also involved with pesticide disposal research;
these are the Office of Planning and Management (0PM) and the Office
of Research and Development (ORD). Within ORD, the two National
Environmental Research Centers (NERC)* at Cincinnati and Corvallis
are responsible for conducting in-house research and for monitoring
EPA research contracts and grants (Table 3).
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* NERC Cincinnati is currently known as Municipal Environmental
Research Laboratory (MERL), and NERC Con/all is which includes the
Pacific Northwest Environmental Research Laboratory (PNERL) and
the National Ecological Research Laboratory (NERL).
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Table 3
Pesticide Disposal Research Groups in the
Environmental Protection Agency. (EPA)
A. Office of Planning and Management (0PM).
B. Office of Pesticide Programs (OPP).
C. Office of Solid Waste Management Programs (OSWMP)
Hazardous Waste Management Division.
1. Pesticide Haste Management Program
2. Technology Assessment Program.
D. Office of Research and Development (ORD).
National Environmental Research Centers (NERC).
1. NERC, Cincinnati, Ohio.
Solid and Hazardous Waste
Research Division (SHWRD),
Cincinnati, Ohio.
2. NERC, Corvallis, Oregon.
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Research Coordination Groups
Several governmental and industrial groups are active in coordinating
pesticide disposal research and in suggesting direction for a national
research program. The President's Council on Environmental Quality has
established a Federal Working Group on Pest Management (FWGPM) which is
housed within EPA. This working group is subdivided into seven panels,
two of which pertain directly to pesticide disposal. The Safety Panel
is concerned with public health and environmental problems associated
with the disposal of pesticides and pesticide containers. The Research
Panel has responsibility of reviewing and advising on pesticide related
research and has established an Ad Hoc Committee on Pesticide Disposal.
In additon to FWGPM, EPA has two offices directly concerned with
coordination of pesticide disposal research. The Office of Research
and Development has a Division of Program Integration which is subdivided
to handle research integration within EPA and with other governmental
agencies. ORD has also established a Science Advisory Board which
sponsors a Hazardous Materials Advisory Committee which helps overview
EPA's direction in this field. Helping to coordinate intergovernmental
pesticide disposal research is the Office of lederal Activities (OFA).
This office has established Interagency Agreements between EPA and other
government agencies active in the field of pesticide disposal. These
Interagency Agreements name contact officers who are directly involved
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with pesticide research in their respective agencies. Currently there
are Interagency Agreements between EPA/USDA and EPA and the Department
of Interior (DOI) (Table 4).
Industry has also been active in coordination of research efforts
and findings. The National Agricultural Chemical Association, (Washington,
D. C.) and the Western Agricultural Chemical Association, (Sacramento,
California) have written pesticide disposal manuals, helped sponsor
conferences and projects, and worked with Federal and State agencies
on pesticide disposal matters.
Research Institutions
There are many universities and industrial and governmental agencies
which have conducted pesticide disposal research to establish safe biological,
chemical, incineration, and landfill disposal methods. The institutions
involved have been divided into three sections i.e., government, universities,
and industry. These listings mention the major and most active research
institutions,but should not be considered complete (Table 5,6,7).
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Table 4
Coordinating Groups for Pesticide Disposal Research
A. President's Council on Environmental Quality.
Federal Working Group on Pesticide Management (FWGPM).
1. Safety Panel.
2. Research Panel.
B. Office of Federal Activities, EPA.
Interagency Agreements EPA/USDA, EPA/DQI.
C. National Agricultural Chemicals Association,
Washington, D. C.
D. Western Agricultural Chemical Association,
Sacramento, California.
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Table 5
Pesticide Disposal Research Institutions: Government
1. Defense Research Establishment, Ralston,
Alberta, Canada.
2. Dugway Army Depot, Dugway, Utah.
3. Edgewood Army Depot, Aberdeen, Maryland.
a. Biomedical Laboratory.
b. Health Services.
4. Fort Detrick, Maryland. U.S. Army Medical
and Bioengineering Research and Development
Laboratory.
5. National Environmental Research Center.
a. Cincinnati, Ohio.
b. Corvallis, Oregon.
6. U. S. Air Force Academy, Colorado Springs, Colorado.
7. USDA Pesticide Degradation Laboratory, Beltsville,
Maryland.
8. Wenatchee Research Laboratory, EPA, Wenatchee,
Washington.
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Table 6
Pesticide Disposal Research Institutions: Industrial
Midwest Research Institute, Kansas City, Missouri
Stanford Research Institute, Applied Microbiology,
Menlo Park, California.
Atomics International, Canoga Park, California.
Chem-Trol, Model City, New York.
Chemagro, Kansas City, Kansas.
Diamond Shamrock Co., Painesville, Ohio
Dow Chemical Co., Midland, Michigan.
Eli-Lilly and Co., Lafayette, Indiana.
Foster D. Snell, Florham Park, New Jersey.
General Electric Co., Pittsfield, Massachusetts.
Hansa Co., Rotterdam, Netherlands.
Marquardt Co., Van Huys, California
Monsanto Co., Anniston, Alabama.
Rollins Environmental Service, Bridgeport, New Jersey.
Southern Dyestuff Co., Charlotte, North Carolina.
TRW Systems, Redondo Beach, California.
Union Carbide, Institute, West Virginia.
Velsicol Chemical Co., Memphis, Tennessee.
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Table 7
Pesticide Disposal Research Institutions: Universities
Cornell University, Dept. of Microbiology, Ithaca,
New York.
Mississippi State University, Agricultural Experiment
Station, State College, Mississippi.
Oregon State University, Dept. of Entomology,
Corvallis, Oregon.
U. S. Air Force Academy, Dept. of Life and Behavioral
Science, Colorado Springs, Colorado.
University of California, Dept. of Environmental
Toxicology, Davis, California.
University of California, Dept. of Soils and Plant
Nutrition, Riverside, California.
University of Connecticut, USDA Cooperative Extension
Service, Storrs, Connecticut.
University of Texas, Dept. of Civil Engineering,
Austin, Texas.
Utah State University, Water Resource Laboratory,
Logan, Utah.
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References
1. Proceedings; National Conference on Pesticide Containers, New Orleans,
Nov. 28-30, 1972. Washington, Federal Working Group on Pest Management,
Dec. 1972. 418 p.
2. Fox, A.S., and H.W. Delvo. Pesticide containers associated with crop
production. _In_ Proceedings; National Conference on Pesticide Containers,
New Orleans, Nov. 28-30, 1972. Washington, Federal Working Group on
Pest Management, Dec. 1972. p. 49-60.
3. Hillis, J.C. State regulations regarding pesticide containers - California
and the West, ^Proceedings; National Conference on Pesticide Container:
New Orleans, Nov. 28-30, 1972. Washington, Federal Working Group on
Pest Management, Dec. 1972. p. 203-205.
4. Hsieh, D.P.H., et al. Decontamination of noncombustible agricultural
pesticide containers by removal of emulsifiable parathion. Environmental
Science & Technology, 6(9):826-829, Sept. 1972.
5. Roper, W.E. Pesticide containers and disposal systems. Ir± Proceedings;
National Conference on Pesticide Containers, New Orleans, Nov. 28-30,
1972. Washington, Federal Working Group on Pest Management, Dec. 1972.
p. 185-190.
6. Disposing of pesticide containers. Washington, National Agricultural
Chemicals Association, 1975. 15 p.
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8. Roper, W.E. 1972. Pesticide containers and disposal systems.
In: Proceedings of the National Conference on Pesticide
Containers, New Orleans, La. pp. 185-190. Federal Working
Group on Pest Management, Washington, D.C.
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METHODS FOR DISPOSAL OF PESTICIDES: BIOLOGICAL
INTRODUCTION
Research in the area of biological disposal of pesticides can be
subdivided into two fields. The first involves research at university
and government laboratories where studies are conducted as to which
pesticides can be biologically degraded, their degradation products,
and the optimum conditions for this metabolism. These studies are
generally small-scale laboratory experiments with occasional scale-up
to field trials. The second research area is concerned with developing
biological treatment facilities for disposal of pesticides and their
manufacturing wastes. Most of this research is conducted by industrial
institutions, and therefore, the results are harder to obtain since
little or no reporting occurs in scientific journals. A listing of
the major agencies active in these two fields of biological research
on pesticide disposal methods is shown in Table 8.
Currently, the use of biological methods for waste pesticide
disposal is generally restricted to systems for treating wastes from
pesticide manufacturing processes, although there is potential for the
use of biological systems for disposal of pesticide wastes generated
by other means. There are several potential advantages biological
disposal systems have over chemical or incineration techniques. First,
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Table 8
Agencies Active in Biological Pesticide Disposal Research
1. U.S. Air Force Academy, Colorado Springs, CO
2. USDA Pesticide Degradation Laboratory, Beltsville, MD
3. Wenatchee Research Station, EPA Affiliate Laboratory,
Wenatchee, WA
4. National Environmental Research Center
a. Cincinnati, OH
b. Corvallis, OR
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biological systems can metabolize a wide variety of pesticide chemicals
under mild environmental conditions; in general, the resulting detoxification
is more complete than with chemical or physical procedures. Secondly,
biological treatment facilities are more easily established and therefore
could be more prevalent than pesticide incinerators of chemical treatment
plants. Currently, there are only a few facilities which could be adapted
for disposal of large amounts of pesticides, although many could accept
small amounts.
Basic Research Findings
Research on biological methods for disposal of pesticides can be
classified into the following three fields: soil incorporation, activated
sludge, and batch or continuous culture studies. Abstracts of basic
research efforts, both government and industrial, and a brief description
of where the research was done, who sponsored this research and its basic
findings are summarized at the end of this section.
Soil incorporation studies show vast differences between pesticides
in regard to their fate in soil. The incorporation of high concentrations
of some pesticides into the soil (40,000 ppm) triggered a rate of
degradation that was faster than at crop application levels of application
(17). However, for another pesticide, high dosages prolonged the persistence
of the chemical(16). Some pesticides at high concentration effectively
sterilized the soil environment(13,16), while others induced microbial
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metabolism. The pesticide formulation is a crucial factor in determining
the impact of the pesticide on the soil environment, and consequently,
its persistence(13). Soil moisture and temperature are other important
factors in governing the rate of pesticide degradation in soil. In some
environments, water was found to be rate limiting, while in others temperature
was the limiting factor(8,17). The volatility of pesticides is decreased
by soil incorporation (as compared to topical application), and the
predominant microbial organisms to thrive in soil with concentrated amounts
of pesticide are fungal organisms(13).
The second biological field for disposal of pesticides involves
activated sludge systems. While basicially capable of disposing of waste
pesticides, there are several problems associated with their use. An
activated sludge system can be operated either with input of only hazardous
wastes or can be adapted (as in a municipal sewage treatment system) to
accept specific quantities of such wastes. However, both systems are
susceptible to chemical shock or overload(2,12), and, therefore, chemical
concentrations in the influent must be carefully monitored. In some cases,
holding ponds up stream are required. Such systems are susceptible to
temperature fluctuations, with decreasing temperatures generally causing
decreased efficiency and necessitating longer retention times(6). Activated
sludge systems reduce influent pesticide concentrations by 80 to 100 percent;
however, due to the low water solubility of most organic pesticides, the
capacity of an activated sludge treatment system is relatively low(6,ll,12).
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The last field of biological research on methods of pesticide
disposal involves small-scale laboratory batch or continuous culture
experiments. These studies have been helpful in establishing the
necessary operating parameters for large-scale biological treatment
systems. It was found that each pesticide has its own optimum pH and
temperature for its microbial degradation(2,4,5,14). The most important
limiting factor in the rate of pesticide metabolism (once an appropriate
culture is obtained) is the pesticide's water solubility(4,5). Mixed
cultures of microorganisms are more efficient and complete in their
pesticide metabolism than pure microbial cultures(4,5).
Present Technology Gaps
Although much research has been conducted on biological disposal
of pesticides, much still remains to be learned before pesticide disposal
regulations can be promulgated or before certain methods can be recommended
as safe disposal procedures. More research is needed before the following
questions can be answered properly.
Soil Incorporation Techniques
1. How much of a given pesticide volatilizes during and
after soil burial or soil incorporation techniques? Is
there an exposure danger to workers in the area if soil
disposal is conducted on a large scale?
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2. What is the optimum pesticide concentration for the best
degradation rate and/or best land use? Which pesticide
formulations are toxic to soil microorganisms and at what
concentrations?
3. How far will concentrated pesticides move in the soil
after disposal by burial? What is the expected half-life
of a pesticide under these conditions? By knowing its rate
of soil movement and expected half-life, is it possible to
predict how far a pesticide will move? Will toxic, more
polar metabolites move through a soil column?
4. Can rinsate from pesticide containers be disposed of by
land disposal techniques? If so, at what concentrations?
What effect will the salts or detergents in the rinsate
have on the soil microorganisms? On subsequent crops?
What "waiting time" is necessary?
Activated Sludge Techniques
1. What pesticides and pesticide related wastes can be
detoxified using an activated sludge system? If a
system is adapted to metabolizing a specific pesticide,
what other chemicals can it also handle?
2. Is it both economically and biologically feasible to
develop lagoons for specific pesticides at a pesticide
disposal site?
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3. What are the economics of operating an adapted activated
sludge system capable of handling hazardous, pesticide
wastes? How can the capacity of these systems be increased?
How environmentally safe are these systems?
Recommendations
All of the above questions need proper answers, however, several
areas seem more urgent than others. Research should be undertaken in
the following areas to obtain data sufficient to allow a decision as to
whether or not a particular disposal system is both environmentally safe
and economically practical:
1. Research should be conducted to determine the feasibility
of using soil incorporation or burial as a biological method
of pesticide disposal. Parameters such as optimum pesticide
concentration, rate of pesticide degradation, effect of moisture
and temperature, movement of the pesticide through soil, and
metabolites produced should be examined for representative
pesticides.
2. Since the low capacity of activated sludge systems to metabolize
pesticides is primarily due to low water solubility of these
pesticides, methods should be developed to increase the
availability of the substrate to the microorganisms. Enzymatic
pretreatment to increase polarity, increased aeration and
agitation, and use of emulsifiers are several promising
techniques which should be examined.
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3. A literature search followed by selective laboratory research
should be performed to determine which pesticides are
biologically degradable and which ones are simply too
recalcitrant for microbial detoxification.
Abstracts of Biological Pesticide Disposal Research
Cornell University, Ithaca, New York, Departement of Chemical
Engineering. Dr. Finn. 1974. 2,4-D, 2,4-Dichlorophenol.
Batch and continuous process. Laboratory scale.
Abstract:
Growth of a bacterial Pseudomonad specie s on 2,4-D and 2,4-
DCP was studied in batch and continuous cultures. The growth rate
was inhibited by 2,4-DCP at concentrations above 25 mg/1, whereas no
inhibition occurred with 2,4-D at concentrations up to 2,000 mg/l(14).
Eli-Lilly and Co., Tippecanoe Laboratory, Lafayette, Indiana.
Dr. Howe. In-house research. 1969. Trifluralin, cyanide wastes,
and phenols. Continuous fermentation and sewage treatment system.
Industrial scale.
Abstract:
A patented system of mixed microorganisms was developed to treat
Trifluralin manufacturing wastes. An activated sludge system could
remove phenols (up to 2,850 ppm) and Trifluralin (up to 1,500 ppm)
completely, while reducing other influent pollutants.
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Cyanide waste at concentrations up to 2,500 ppm could be
biologically degraded by a patented process. Other hazardous chemicals
were also successfully degraded biologically(4).
Mississippi State University, Department of Microbiology.
USDA-ARS. Grant 12-14-100-9182(34). 1972. 2,4,5-T, Picloram,
2,4-D, Malathion, Trifluralin, Paraquat, DDT, Dieldrin, Carbaryl,
DBCP, Bromacil, Dicamba, Vernolate, PMA, DSMA, Dalapon, Diruon,
DNBP, Atrazine, Zineb. Soil incorportation, Labortatory scale.
Abstract:
The above pesticides were incorporated into soils at a rate equivalent
to 10,000 Ib/acre active ingredient. The degradation of these pesticides
was then monitored by COo evolution. Some soil pesticide samples had
increased C0_ evolution (8 of 20), while the others had decreased CXL
evolution. The pesticides formulation was also important in inducing
or inhibiting C02 evolution. Since no chemical analyses were conducted,
it is impossible to correlate CO- evolution with chemical degradation.
Bacterial soil counts generally decreased whereas streptomyces and fungi
soil counts generally increased during exposure to concentrated
pesticides(13).
Oregon State University, Corvallis, Dept. of Entomology.
Dr. Goulding. EPA Demonstration Grant No. 5-G06-EC-00222.
1975. 2,4-D, DCP, and their manufacturing wastes. Soil
incorporation, field scale and container rinsing. (Preliminary
report.)
26
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Abstract:
There were basically two concerns in this demonstration grant.
One was to develop methods for container rinsing and disposal and the
other was to study biological soil degradation as a mechanism for
detoxification and disposal of these materials.
Preliminary results of application of 2,4-D (in a manufacturing
waste) to soil at concentrations from 100 to 500 Ib/acre active ingredient
showed complete disappearance by 540 days. Dichlorophenol, when applied
at equivalent rates was slightly more persistent. Results of container
rinse studies were meager; however, a three-step rinse procedure could
remove 95 percent of the residual 2,4-D from the container(3).
Stanford Research Institute, Menlo Park, California.
Dept. Applied Microbiology. Mr. Bohonos. U.S. Army
Medical Research and Development Command. 1974. DDT,
2,4-D, 2,4,5-T, Lindane, Dieldrin, Chlordane, Aldrin.
Chemostat, batch cultures. Laboratory scale.
Abstract:
Draft final report results indicate that 2,4-D could be successfully
biologically degraded by mixed microbial cultures, however, 2,4,5-T was
more resistant to biological attack.
Results on speeding up the metabolism of DDT showed some progress,
however, the project was terminated before results were conclusive. Work
on lindane, dieldrin, chlordane and aldrin consumed only 10 percent of
the contract time(7).
27
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U.S. Air Force Academy, Colorado Springs, Colorado,
Dept. of Life and Behavioral Science. Captain Young.
U.S. Air Force - Herbicide Orange Disposal. 1974.
2,4-D, 2,4,5-T and dioxin. Soil injection, aerial
spray application. Field scale.
Abstract:
Herbicide Orange (2,4-D, 2,4,5-T, and low levels of dioxin) was soil
injected at concentrations equivalent to 10,"000, 20,000 and 40,000 ppm.
After 1.2 years, approximately 83 to 88 percent of the Herbicide Orange
in all three groups was metabolized. 2,4,5-T was metabolized faster than
2,4-D, and a half-life for dioxin was calculated to be 88 days(18).
In a second study on the ecological consequences of massive applications
of Herbicide Orange over eight years, it was reported that Herbicide
Orange did not accumulate in the soil(17).
USDA, ARS. Pesticide Degradation Laboratory, Beltsville, Md.
Dr. P. Kearney. In-house. 1974. Various classes of chlorinated,
organophosphate, and carbamate insecticides. Soil incorporation.
Laboratory and field plots.
Abstract:
The Pesticide Degradation Laboratory has been active in studying the
persistence of pesticides in the soil. Some of their test plots have
contained relatively high concentrations (up to 500 ppm) and they have
monitored these plots over a period of years. Specifics may be obtained
from Dr. P. Kearney or Dr. Kaufman(8).
28
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University of California, Davis, Dept. of Environmental
Toxicology, Dr. D. Hsieh. U.S. National Institute of
Health. 1974. Parathion, paraoxon, methyl parathion.
Chemostat and soil incorporation. Laboratory scale.
Abstract:
Chemostat metabolism in a small (600 ml) fermenter was able to
metabolize 50 mg parathion/hr with only three percent of the influent
parathion remaining in the effluent. This metabolism was complete,
producing cell mass, C02 and H20 without p-nitrophenol as an end product
as in chemical hydrolysis procedures(5).
When the adapted mixed culture was placed in the soil with up to
5,000 ppm parathion, the rate of parathion metabolism was 20 times faster
than in uninoculated soils, thus showing the potential for decontaminating
parathion-containing soils biologically.
University of California, Riverside, Dept. of Soils
and Plant Nutrition, Dr. D. Focht. 1974. Chlorinated
hydrocarbons. Batch culture. Laboratory scale.
Abstract:
UC-Riverside Soils Department is conducting research in biological
methods for the disposal of chlorinated pesticides, and is particularly
active in research efforts on microbial metabolism of recalcitrant
(resistant) pesticides.
Work has been done on low concentration metabolism of DDT and related
chemicals, in an attempt to develop multi-phase systems for the complete
metabolism of these compounds. These studies have shown that cometabolism
29
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of pesticides is promising, and that combinations of enzyme systems plus
whole cells can dispose of "recalcitrant" pesticides(7).
University of Texas, Austin, Dept. Civil Engineering,
Dr. Armstrong. EPA, Edison Water Quality Lab., Edison,
N.J. Grant No. R802207. 1974. DDT, aldrin, toxaphene,
cyclic pesticides. Batch cultures. Laboratory scale.
Abstract:
This research grant is concerned with developing biological counter-
measures for the mitigation of hazardous material spills. The basic idea
was to develop microbial cultures which can degrade specific wastes and
which can be applied to contaminated soil and/or water and then degrade
the toxic chemical. After laboratory research, promising systems will
then be tried on a pilot scale(l,9).
Utah State University, Logan. Utah Water Research
Laboratory. U.S. Air Force - Systems Command. 1974.
2,4-D, 2,4,5-T. Adapted activated sludge, batch culture.
Laboratory scale.
Abstract:
An adapted mixed culture, "Phenobac" was able to metabolize chloropheno
compounds. The culture was more active than random soil or water samples
in degrading phenoxy compounds, and was tolerant to high concentrations
of the herbicide.
30
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After 16 days of incubation, 65 percent to 75 percent of the initial
concentration of Herbicide Orange was degraded. Concentrations studies
ranged from 230 mg/1 to 3,450 mg/1. The fate of TCDD in Herbicide Orange
during this metabolism was not determined(15).
Wenatchee Research Station, EPA Affiliate Laboratory.
Wenatchee, Washington. Dr. H. Wolfe. In-house. 1973.
Parathion. Soil incorporation. Field scale.
Abstract:
Parathion, a supposedly fairly non-persistent organophosphate, was
found to be very persistent when introduced in soils at the high concent-
trations. Soils containing initial concentrations of 30,000 to 95,000 ppm
active ingredient still contained 13,000 ppm parathion after five years.
Parathion, however, moved less than nine inches during this time period.
Soil microorganisms were reduced 100 fold by parathion addition, and the
soil remained relatively sterile(10,16).
31
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In addition to research institutions studying the biological
aspects of pesticide disposal, many industrial concerns dispose
of pesticides and related wastes by biological methods. Several
companies are listed below.
Company
Chemagro
Kansas City, Mo.
Dow Chemical Co.
Midland, Mich.
Eli-Lilly & Co.
Tippecanoe Lab.
Lafayette, Ind.
Monsanto Chemical
Co., Anniston, Ala.
Southern Dyestuff
Co., Charlotte,
N. Car.
Union Carbide
Institute,
W. Va.
Wastes
Demeton,
Guthion.
2.4-D and
others.
System
Aerated lagoon,
activated sludge(6),
Activated sludge,
ponding(6).
Trifluralin, Activated sludge(ll),
cyanide wastes.
Parathion, Activated Sludge(2).
Methy!parathion.
Nitrophenols. Activated sludge,
aeration ponds(6).
Sevin.
Aeration ponds,
sewage treatment
system(12).
32
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Reference - Biological
1. Armstrong, N.E., et al. Biological countermeasures for the migration
of hazardous material spills. lr\_ Control of Hazardous Material
Spills; Proceedings; 1974 National Conference on Control of Hazardous
Material Spills, San Francisco, Aug. 25-28, 1974. New York, American
Institute of Chemical Engineers, p. 238-248.
2. Coley, G., and C.N. Stutz. Treatment of parathion wastes and other
organics. Mater Pollution Control Federation Jounal, 38(8) .-1345-1349,
Aug. 1966.
3. Goulding, R.L. Waste pesticide management; final narrative report,
July 1, 1969-June 30, 1972. Corvallis, Oregon State University,
Environmental Health Science Center, Aug. 1973. 81 p., app.
(Unpublished report.)
4. Howe, R.H.L. Toxic wastes degradation and disposal. Process Biochemistry,
4:25-28,37 Apr. 1969.
5. Munnecke, D.M., and D.P.H. Hsieh. Microbial decontamination of
parathion and p-nitrophenol in aqueous media. Applied Microbiology,
28(2):212-217, Aug. 1974.
33
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6. Ottinger, R.S., et al. (TRW Systems Group.) Recommended methods
of reduction, neutralization, recovery or disposal of hazardous
waste. U.S. Environmental Protection Agency, Aug. 1973. 16 v.
(Distributed by National Technical Information Service, Springfield,
Va., as PB-224 579.)
7. Personal communication. D. Focht, University of California at
Riverside to D. Munnecke, Office of Solid Waste Management Programs,
Sept. 25, 1974.
8. Personal communication. Drs. Kearney, Kaufman, and Plimmer to
D. Munnecke, Office of Solid Waste Management Programs, Sept. 4, 1974.
9. Personal communication. Dr. Armstrong, University of Texas, to
D. Munnecke, Office of Solid Waste Management Programs, Sept. 26, 1974.
10. Personal communication. Dr. Wolfe to D. Munnecke, Office of Solid
Waste Management Programs, Sept. 11, 1974.
11. Personal communication. Dr. Howe to D. Munnecke, Office of Solid
Waste Management Programs, Oct. 1, 1974.
12. Personal communication. E. Hall to D. Munnecke, Office of Solid
Waste Management Programs, Sept. 16, 1974.
34
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13. Stojanovic, B.J., M.V. Kennedy, and F.L. Shuman, Jr. Edaphic aspects
of the disposal of unused pesticides, pesticide wastes, and pesticide
containers. Journal of Environmental Quality, l(l):54-62, Jan.-Mar. 1972.
14. Tyler, J.E. and R.K. Finn. Growth rates of a pseudomonad on 2,4-
dichlorophenoxyacetic acid and 2,4-dichlorophenol. Applied Microbiology,
28(2):181-184, Aug. 1974.
15. Wachinski, A.M., V.D. Adams, and J.H. Reynolds. Biological treatment
of phenoxy herbicides 2,4-D and 2,4,5-T in a closed system; research
report to U.S Air Force. Logan, Utah State University, Utah Water
Research Laboratory, Mar. 1974 25 p.
16. Wolfe, H.R., et al. Persistence of parathion in soil. Bulletin of
Environmental Contamination and Toxicology, 10(1):109, July 1973.
17. Young, A.L., et al. The ecological consequences of massive quantities
of 2,4-D and 2,4,5-T herbicides; summary of a five year field study.
Colorado Springs, U.S. Air Forces Academy, 1974. 6 p. (Unpublished
report.)
18. Young, A.L., E.L. Arnold, and A.M. Wachinski. Field studies on the
soil persistence and movement of 2,4-D, 2,4,5-T, and TCDD. Colorado
Springs, U.S. Air Force Academy, 1974. 13 p. (Unpublished report.)
35
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METHODS FOR DISPOSAL OF PESTICIDES: CHEMICAL
Introduction
Chemical methods for the disposal of pesticides, and pesticide
related wastes have found only limited use as viable methods for the
disposal of concentrated or large quantities of pesticides. Those
chemical methods are currently used in the pesticide manufacturing
industry to treat their waste effluents. Many procedures generally
involve pH adjustment, coagulation, and precipitation. They are
primarily separation procedures, and usually only slight detoxification
of the active pesticidal ingredient is accomplished. Therefore, a
secondary waste treatment system is required, which usually involves
either burial at a chemical landfill or biological treatment in a
lagoon or activated sludge system. Hydrolysis and oxidation, using
caustic soda and hypochlorite, have also been used.
The two areas of most active research in the field of chemical
disposal techniques are 1) developing ways to dispose of very large
quantities of surplus pesticides or related wastes, as in the case of
Herbicide Orange and DDT, or 2) developing simple techniques for the
disposal of small amounts of pesticides. The major agencies active
in these two fields are shown in Table 9.
36
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Table 9
Companies and Agencies involved in developing
chemical methods for pesticide disposal
1. B.F. Goodrich.
2. Chemfix, Div. of Environmental Sciences, Inc.
3. Diamond Shamrock Co.
4. Environmental Protection Agency, Region VIII.
5. Hoechst-Uhde, West Germany.
6. Midwest Research Institute.
7. Mississippi State University.
8. Repro Chemical Co.
9. TRW Systems.
10. U.S. Army Medical Environmental Engineering Research
Unit, Edgewood Arsenal.
11. U.S. Army Medical and Bioengineering Research and
Development Laboratory, Ft. Detrick.
12. University of Texas, Austin, Dept. of Civil Engineering.
13. Worcester Polytechnic Institute.
37
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Chemical methods are used for a variety of reasons with several
advantages accruing to these procedures. First, chemical methods are
farily reliable and generally predictable. Secondly, on a manufacturing
process line, the detoxification or chemical treatment reactions are easy
to monitor and to control. However, for most chemical detoxification
processes, the degradation is not complete and the degradation products
and the chemical reactants still must be considered hazardous materials.
In some systems though, as in Chemfix's immobilization process(3), or as
in Diamond Shamrock's chlorinolysis reaction (1,2), the hazardous chemical
potentiality is rendered inert or converted to a useful end product. The
basic chemical treatment processes include oxidation, reduction, hydrolysis,
conjugation, catalysis, fractional on, ion exchange, and coagulation. A
comparison of chemical methods to biological, incineration, and landfill
disposal methods is made in Appendices I and II.
' Basic Research Findings
Some of the basic research findings on chemical disposal techniques
show that such methods are used either to detoxify the hazardous material
or to remove the intact chemical from the waste stream so it can be handled
safely or recycled. Oxidation, reduction, hydrolysis, catalysis, or
chlorinolysis are examples of processes which are designed to convert the
toxic chemical to less toxic compounds. Some serious drawbacks to most
of these systems are 1) they are generally not complete in their destruction
of the pesticide and 2) the chemical procedure effects changes on only certa
38
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chemical functional groups, leaving other functional groups unchanged.
They are, therefore, restricted to detoxification of particular chemical
classes of pesticides. Some reactions require harsh chemical environments
which in themselves create new environmental hazards.
Most of the research on chemical methods for the detoxification of
pesticides was conducted using low pesticide concentrations, generally
at levels below the pesticides' solubility in water. Thus, the half-life
or degradation kinetics from these studies are difficult to extrapolate
to conditions of high concentrations experienced in disposal situations.
Therefore, a system which looks promising at low concentrations, may not
prove economically feasible at high concentrations.
Methods which generally do not detoxify the hazardous pesticide but
rather remove the chemical are conjugation, fractionation, chlorolysis,
chemical fixation, coagulation, precipitation, and ion exchange or adsorption.
Some of these methods, such as ion exchange or adsorption, are excellent
only for low concentration pesticide disposal situations. However, others,
like fractionation and chlorinolysis, represent potentially viable methods
for recovery of the pesticide with the potential for reuse. Abstracts of
some of the research work discussed here are presented at the end of this
section.
39
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Present Technology Gaps
Most of the research results obtained concerning chemical disposal
methods were developed in controlled, highly sophisticated laboratory
environments; little research has been reported for techniques examined
under practical conditions or on a large scale. Therefore, there is a
large gap which exists between basic and applied chemical detoxification
research. Some of the questions posed help to show areas where future
research is needed.
1. What pesticides are susceptible to hydrolysis? What are
the degradation products from acid or base hydrolysis?
What toxicity and fate do these chemcials have in our
environment?
2. What effect does the "detoxified waste" have on the
environment in which it is placed? What burial
precautions are necessary?
3. What are the chemical detoxification kinetics for
pesticides at concentrations above their solubility?
4. Are there any currently available chemical disposal
systems which the layman can use safely and efficiently
for detoxification of small quantities of pesticides?
5. How permanent are "permanent" chemical fixation methods?
6. How sucessful are the chemical clean up procedures for
accidental spills? What are the toxicities of residues,
and burial precaution?
40
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Recommendations
There have been several review papers on chemical degradation of
pesticides (4,8,11) which have defined the possible chemical detoxification
processes. However, very few of these techniques have been examined from
a practical point of view. Therefore, the recommendations for research
which follow deal primarily with establishing practical methods for the
disposal of excess pesticides.
1. Determine whether or not there are practical, viable
methods for chemical detoxification of pesticides,
including rinsate, by the layman in the field.
2. Develop ways to combine chemical pretreatment with
biological treatment to effect complete degradation of
the pesticide molecule.
3. Conduct large-scale chemical degradation studies to
determine if such systems are industrially feasible in
regard to equipment demands, economics, and ecological
effects.
41
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Abstracts of Chemical Pesticide Disposal Research
B.F. Goodrich. In-House. 1974. No actual pesticide, but
rather, waste chlorinated hydrocarbons. Pilot scale project,
patented process.
Abstract:
B.F. Goodrich has developed a catalytic process for disposal of
waste chlorinated hydrocarbons. The process is called Catoxid and is
reported to operate with lower costs than conventional incineration
disposal systems with allowance for reclamation of chlorine. No
further information was provided in the ACS News concentrate.
Chemfix, Division of Environmental Sciences, Inc. Pittsburgh,
Pennsylvania. In-house research. 1974. Chemical fixation
process which immobilizes wastes. Industrial scale.
Abstract:
The Chemfix process involves the reaction of at least two chemical
components with the hazardous waste material to form chemically and
mechanically stable solids. The reaction occurs at normal, ambient
temperature and is not adversely affected by temperature variations.
The resulting chemical block is then stable when exposed to soil, water,
air, microorganisms, and sunlight. The particular ratio, qualities and
choice of reagent used for any given waste treatment application depends
on three factors: 1) the waste, 2) speed of reaction required, and 3) the
end use of the solidified material.
42
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Diamond Shamrock Co., Painesville, Ohio. U.S. Air Force,
Herbicide Orange disposal. 1974. Herbicide Orange. Pilot
scale chlorinolysis, 100 g/hr.
Abstract:
Under an Interagency Agreement between the U.S. Air Force and EPA,
Diamond Shamrock studied the chlorinolysis of Herbicide Orange. Their
system used higher temperatures and lower pressures than does the Hoechst-
Uhde process for chlorolysis. The carbon tetrachloride produced from this
reaction was reportedly without dioxin (less than 10 ppt) and was tested
for toxicological effects. (1,2).
Hoechst-Uhde, West Germany. In-house research. 1972.
HCB, Commerical system for chlorolysis, 25 tons/day.
Abstract:
This West German company has developed a process where chlorine
gas reacts with hexachlorobenzene to produce carbon tetrachloride. This
chlorolysis process operates at temperatures of 500 to 600 C, at high
pressures (3,000 psi), and required a nickel alloy liner. The system
has been operated for 18 months beginning in mid-1971(1,7).
Midwest Research Institute, Kansas City, Missouri. EPA.
Project No. 15090 HGR, Contract No. 68-01-0098. January 1975.
Literature review, 550 common pesticides.
43
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Abstract:
The chemical procedures for disposal of small quantities of excess
pesticides described in this book are mainly laboratory procedures. They
include oxidation, hydrolysis, dechlorination, hydrogenation, reduction,
and other basic chemical reactions. Generally, the chemical detoxification
procedures described were conducted in the laboratory with low concentrations
of pesticide and require adaptation for field disposal problems.
No original research was conducted to determine degree of decomposition,
degradation products, or toxicity of remaining chemicals(8).
Mississippi State University, Agricultural Experiment Station.
State College, Mississippi. USDA, ARS Grant No. 12-14-100-9182(34).
1972. Atrazine, Malathion, Nemagon, Carbaryl, Dieldrin, Trifluralin,
Bromacil, Picloram, Diuron, Dicamba, DNBP and 2,4-D. Laboratory
scale reactions with acids, bases, and hydrogen peroxide.
Abstract:
Pesticides, when treated with sodium biphenyl reagent, were decomposed
to the extent of 80 to 99 percent. However, when these compounds were
treated with a mixture of metallic sodium and liquid ammonia, 15 of the
19 compounds were completely degraded. When metallic lithium was substituted
for metallic sodium, the mixture was less effective but still completely
degraded eight of 19 compounds. The decompostion products resulting
from these reactions were not tested for toxicity(5).
44
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Strong nitric or sulfuric acid, or strong sodium or ammonium hydroxide
partially decomposed the eight pesticides examined. However, no hydrolysis
of any pesticide was complete in the time studied(5,6).
TRW Systems. Redondo Beach, California. EPA Contract No.
68-03-0089. 1974. Representative polychlorinated, phenoxy,
and organophosphate pesticides. Literature review of chemical
decontamination systems.
Abstract:
The literature review by TRW as it pertains to chemical disposal of
concentrated pesticides primarily discussed the work done by Kennedy, et
al.(5,6) and by Sweeny and Fischer(12). Although some methods could
destroy the parent pesticide, no single method could destroy all the various
pesticides discussed. The lack of toxicological studies on the degradation
products and the failure of chemical methods to completely and quickly
destroy the pesticides prohibited the recommendations that chemical methods
be used to dispose of pesticides(ll).
U.S. Army Medical Environmental Engineering Research Unit,
Edgewood Arsenal, Maryland. U.S. Army Medical Research and
Development Command. 1972. Chlorinated, organophosphate,
and carbamate pesticides. Literature review of chemical
degradation procedures.
Abstract:
Degradation of pesticides and structurally related compounds by
dechlorination, photochemical reactions, cleavage of ethers, oxidation,
biodegradation and hydrolysis are reviewed. Due to the great variation
in chemical structure, reactivity, and pesticide solubility, no single
45
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method of chemical degradation is presently available. Four approaches
to chemical degradation are proposed for the detoxification of the
entire spectrum of pesticides and herbicides. The methods proposed are
hydrolysis, dechlorination, photolysis and oxidation. Recommendations
are made for the study and development of the proposed degradation methods(4)
U.S. Army Medical and Bioengineering Research and Development
Laboratory, Ft. Detrick, Maryland. In-house. 1974. Baygon,
diazinon, and other organophosphate insecticides. Layman
techniques for disposal of excess spray solutions.
Abstract:
This research group is studying the rate and efficiency of chemical
hydrolysis of pesticides by strong acid, base, or hypochlorite. After
hydrolysis, the breakdown products are examined for toxicity, persistence,
and potential for causing environmental harm. The major purpose is to
develop practical methods for the disposal of spray solutions of commonly
used pesticides.
University of Texas, Austin, Dept. of Civil Engineering. EPA.
Project No. 12021 FYE. 1972. DDT, Carbaryl, Parathion, Methyl
parathion, 2,4-D, 2,4,5-T, MCPA. Literature review of manufacturing
processes and treatment techniques.
Abstract:
This report reviews the manufacturing processes and the wastes which
are generated form manufacturing DDT, Carbaryl, Parathion, Methyl parathion,
2,4-D, 2,4,5-T, MCPA, and diolefin-based pesticides. Treatment methods
46
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which were reviewed included oxidation, coagulation, absorption, photo-
chemical degradation, liquid-liquid extraction, biological degradation,
and foam fractionation.
Treatment and disposal practices presently employed by the pesticide
manufacturing industry include: pH adjustment, chemical, physical, and
biological treatment, incineration, and burial.
Worchester Polytechnic Institute. EPA, SHWRD. 1975.
Chlorinated pesticides. Laboratory scale catalyzed
reactions.
Abstract:
Under an EPA research grant (ROAP 21BKU Task 002), which began in
1974, Worcester Polytechnic Institute investigated catalytic techniques for
decomposition of pesticides. The first technique involved an amine-
catalyzed dechlorination reaction. Under an Interagency Agreement between
EPA and the U.S. Army, 'Edgewood Arsenal will help evaluate the toxicity
of the various degradation products formed by chemical detoxification.
47
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References - Chemicals
1. Emerging technology of chlorinolysis. Environmental Science & Technology,
8(10): 18-19, Jan. 1974.
2. Trip report on visit to Diamond Shamrock Corporation Research Center,
Painesville, Ohio, Jan. 11, 1973. Washington, U.S. Environmental
Protection Agency, Office of Solid Waste Management Programs, Hazardous
Waste Management Division.
3. Chemfix process; technical data information-chemistry. Data sheet no. 101
Pittsburgh, Chemfix, Division of Environmental Sciences, Inc., Nov. 1972.
2 p.
4. Dennis, W.H., Jr. Methods of chemical degradation of pesticides and
herbicides-a review. Edgewood Arsenal, Md., Army Medical Environmental
Engineering Research Unit, Oct. 1972. 36 p. (Distributed by National
Technical Information Service, Springfield, Va., as AD-752 123.)
5. Kennedy, M.V., B.F. Stojanovic, and F.L. Shuman, Jr. Chemical and
thermal methods for disposal of pesticides. In F.A. Gunther ed.
Residue reviews; residues of pesticides and other foreign chemicals
in foods and feeds, v. 29. New York, Springer-Verlag, 1969.
p. 89-104.
6. Kennedy, M.V., B.J. Stojanovic, and F.L. Shuman, Jr. Chemical and
thermal aspects of pesticide disposal. Journal of Environmental Quality,
l(10):63-65, Jan.-Mar. 1972.
48
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7. Krekeler, H., and H. Weber.Chlorinolysis of aliphatic and aromatic
compounds to carbon tetrachloride. Ll Abstracts of papers; 164th
National Meeting, American Chemical Society, New York City, Aug. 27-
Sept. 1, 1972. Hyattsville, Md., Creative Printing, Inc. Abstr. INDE
no. 22.
8. Lawless, E.W., T.L. Ferguson, and A.F. Meiners (Midwest Research Institute)
Guidelines for the disposal of small quantities of unused pesticides.
Washington, U.S. Government Printing Office, 1975. 330 p. (Distributed
by National Technical Information Service, Springfield, Va., as PB-244
577.)
9. Disposing of pesticide containers. Washington, National Agricultural
Chemicals Association, 1975. 15 p.
10. Manual for minimizing cross contamination of pesticide chemical, rev.
Washington, National Agricultural Chemicals Association, Apr. 1975.
17 p.
11. Ottinger, R.S., et al. (TRW Systems Group). Recommended methods of
reduction, neutralization, recovery or disposal of hazardous waste.
v.5. National disposal site candidate waste stream constituent profile
reports—pesticides and cyanide compounds. U.S. Environmental
Protection Agency, Aug. 1973 144 p. (Distributed by National Technical
Information Service, Springfield, Va., as PB 224 584.)
12. Sweeny, K.H., and J.R. Fischer (Aerojet-General Corp.) Investigation
of means for controlled self-destruction of pesticides. Washington,
U.S. Environmental Protection Agency, June 1970. 131 p. (Distributed
by National Technical Information Service, Springfield, Va., as PB-198
224.)
49
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METHODS FOR DISPOSAL OF PESTICIDES: INCINERATION
Introduction
Incineration techniques for the disposal of pesticides and pesticide-
related wastes present viable methods for the safe disposal of large
quantities of pesticides. A Task Force on Excess Pesticides(9), after
evaluating various available disposal procedures, recommended incineration
techniques as the most desirable methods for disposal of large quantities
of pesticides. The pesticide industry is currently incinerating much of
its manufacturing wastes(2,5) and a hazardous waste disposal industry is
now developing and will have capabilities for incineration of pesticides.
There are several advantages to the use of incineration as a pesticide
disposal procedure. First, incinerators can combust a wide variety of
pesticides, pesticide formulations and conceivably, pesticide mixtures at
various concentrations (3,4). Secondly, incineration systems are quite
stable and dependable(lO). Third, adverse air emissions can be scrubbed
to meet environmental air requirements, and fourth, incinerators can
dispose of large amounts of pesticides(10). Other advantages include:
technology is well developed, volume reduction of waste requiring ultimate
disposal is achieved and incineration has the potential for energy recovery.
Research on incineration of pesticides has been conducted at various
university, governmental, and industrial laboratories (Table 10).
Basically, this research has evolved around either attempting to develop
methods for the disposal of specific wastes, DDT, Herbicide Orange, industria
manufacturing wastes (7,10), or trying to establish the parameters needed
to insure complete incineration of representative pesticides (3,4).
50
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Table 10
Agencies involved in developing incinerator
methods for the disposal of pesticides
1. Atomics International.
2. Canadian Defense Research Establishment.
3. Chem-Trol Pollution Services.
4. Dow Chemical Co.
5. Foster D. Snell, Inc.
6. General Electric Co.
7. Hansa Co.
8. Marquardt Co.
9. Midwest Research Institute.
10. Mississippi State University.
11. Monsanto Chemical Co.
12. Rollins Environmental Services.
13. TRW Systems.
14. Velsicol Chemical Co.
15. Versar.
51
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Basic Research Findings
The amount of literature available on the incineration of pesticides
is growing quickly, and it is not the intent of this paper to discuss all
of the major findings reported. An excellent review paper on incineration
of hazardous wastes has recently been completed(2) and is available through
the Office of Solid Waste Management Programs, Hazardous Waste Management
Division, U.S. EPA. This report reviews the various types of incinerators
available and discusses the research activities related to each type of
incinerator. The abstracts of some of the papers reviewed in this
presentation are given at the end of this section.
There are certain basic research findings which pertain to pesticide
incineration which should be discussed in this report. From various studies
it has been shown that pesticides require a combination of operating
conditions to achieve a high degree of combustion. In order to maximize
combustion efficiency, the pesticide must be thoroughly mixed with the
oxygen supply. Additionally, the pesticide must be exposed to a proper
combination of temperature and residence (dwell) time. A range of time/
temperature conditions exists which can produce good combustion efficiencies.
As a general rule of thumb, where good mixing occurs, most pesticides can
be destroyed by incineration at a temperature of 1000 C and a residence
time of 2 sec. At this time, it is difficult to estimate what the proper
parameters for a given incinerator will be for a given pesticide formulation
Generally, incinerator effluent gases must be scrubbed to remove hazardous
gaseous emissions such as carbon monoxide, hydrogen chloride, cyanide,
hydrogen sulfide, and phosgene(3,10). Non-chlorinated pesticides can
be combusted without damage to the incinerator; however, hydrogen chloride,
if produced in sufficient quantities, forms hydrochloric acid and can cause
corrosion problems(4,6).
52
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More information on the incineration of pesticides is presented in
the abstracts of the various institutions involved with incineration
research. Each abstract is referenced to the original report. A
comparison of incineration methods to the other pesticide disposal
methods discussed in this report is shown in Appendix I and II.
Present Technology Gaps
As is generally true in any scientific field, regardless of the
amount of previous research work, there are certain questions which
remain unanswered until further research can be conducted. Listed below
are several questions which spotlight missing technology in the field
of incineration of pesticides.
1. What pesticides and their formulations can safely be incinerated?
Which pesticides should not be incinerated? How can heavy metals
be removed from certain pesticides prior to incineration?
2. What effect does the formulation and pesticide concentration have on
the feed rate required to maintain a fixed efficiency level?
3. What are the necessary operating conditions with regard to dwell time,
temperature, and turbulence for the various commerical incinerators
currently available?
4. What gases are produced from organophosphates, chlorinated hydro-
carbons, and nitrogen-containing compounds during incineration?
5. What are the best methods for burning combustible containers?
53
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Recommendations
The report by the Task Force on Excess Chemicals(9) and several other
reports(8), have compiled lists of recommended research areas concerning
pesticide incineration disposal techniques. Most of these recommendations
are concerned with the technology gaps listed in the previous section. In
addition to the specific recommendations presented in the report by the
Task Force on Excess Pesticides, there are several general recommendations
which can be made in regard to needed research in this field.
1. Future government-funded research should be conducted in commerical,
readily available, and commonly used incinerators. Then, research
data may not have to be extrapolated to field conditions. (HWMD-
funded demonstrations are currently in planning stages).
2. Since 1000 C is the recommended temperature for the incineration of
pesticides (39FR15236, May 1, 1974), all test pesticides should be
first incinerated at this temperature to insure that the recommended
temperature is sufficient to destroy the pesticide and all intermediate
degradation products at the desired efficiency.
3. The air quality and pesticide disposal activities within EPA should
establish guidelines or standards for emissions from a pesticide
incinerator. It is not sufficient to require a certain percent
destruction, but instead it should be established what quantity of
pesticide and resulting toxic gases can be discharged into the
atmosphere.
54
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Abstracts Of Pesticide Incineration Research
Atomics International, Canoga Park, California. November 1973.
Chlordane, Weed-B-Gon, Malathion, Sevin. Molten salt bed.
Laboratory scale.
Abstract:
Atomics International has conducted laboratory bench scale experiments
to determine the feasibility of destroying four commerical pesticide
formulations by injecting them into a molten mixture of sodium carbonate
and sodium sulfate (90:10) at temperatures of 1500 to 1800 F (815-980 C).
Complete destruction (99.9 percent) of each of the four pesticides was
obtained under these conditions. There were reportedly fewer off-gases
from this system when compared to conventional incineration techniques;
however, one disadvantage is the need for the disposal or reclamation of
the salt beds(l).
Canadian Defense Research Establishment, Suffield, Ralston,
Alberta, Canada. Canadian Federal Government. October 1971.
DDT. Liquid injection. Large scale.
Abstract:
The "Thermal Destructor" was designed and built specifically for
incineration of hazardous materials (DDT). Using information developed
by Mississippi State University and the Canadian Combustion Research
Laboratory, DDT was incinerated at 380 1/hr at a temperature of 1650 F
(890 C). At least 107,000 gal of five percent DDT were incinerated at
efficiencies above 99.9998 percent. This report summarized the incineration
operation after two months of operation in 1970. During that time, no
problems had developed and the system seemed to be environmentally safe(10).
55
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Foster D. Snell, Inc. Florham Park, New Jersey. U.S.
EPA, CPE 69-140. 1971. DDT, Malathion, Dalapon,
Diazinon, Sevin, Aldrin, PCNB. Pyrolysis. Laboratory
scale.
Abstract:
Pesticides were alleged to be completely destroyed (99 percent) by
combustion at the temperatures (500 to 690 C) normally achieved by
burning wood, paper, cardboard, or plastics. Combustion products such
as carbon dioxide, carbon monoxide, hydrogen sulfide, hyrogen chloride,
and phosgene were produced. At low temperatures (200 C), the pesticides
volatilized or sublimed.
Binding agents, i.e., mineral oil, paraffin wax, etc., were important
in decreasing volatilization of the pesticide and oxidizing agents, i.e.,
potassium chlorate and potassium nitrate, were instrumental in lowering the
temperature required for complete pesticide combustion.
Marquardt Co., Van Nuys, California. Department of the Air Force,
Systems Command. F41608-74-C-1482. 1974. Herbicide Orange (2,4-D,
2,4,5-T), DDT. Sudden Expansion Burner (SUE).
Abstract:
A converted jet engine (SUE) was used to incinerate test quantities
of Herbicide Orange. The system could accept 150 1/hr and when operated
at temperatures from 1230 to 1470 C was capable of 99.98 percent to
99.999 percent destruction of Herbicide Orange.
56
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Dichlorophenol, 2,4-D, and 2,4,5-T were detected in the scrubber
system, as well as C aliphatic hydrocarbons, a substituted aromatic,
and a biphenyl compound. Nitrogen oxide emissions averaged 54 ppm.
Coke deposits occurred on interior surfaces and noise created by the
jet created a problem(7).
Midwest Research Institute, Kansas City, Missouri, EPA
Solid and Hazardous Waste Research Laboratory, Cincinnati,
Ohio. 1975. DDT, aldrin, picloram, malathion, Projected:
toxaphene, zineb, captan, atrazine, mi rex. Liquid injector.
Pilot scale.
Abstract:
This investigation evaluated the effect that pesticide feed rate,
incinerator chamber temperature, and excess air-to-fuel ratio had on the
overall efficiency of pesticide destruction. The following pesticides
were incinerated at the following efficiencies and temperatures: DDT
(99.997 percent) at 1000 C; aldrin (99.999 percent) at 850 C; picloram
(99.999 percent) at 1000 C; malathion (99.999 percent) at 950 C. The
pesticides feed rate and the air-fuel ratio were important factors in
obtaining high combustion efficiencies. The concentration of cyanide,
a breakdown product from picloram and other N-containing pesticide was
strongly affected by the combustion temperature(4).
57
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Mississippi State University, State College, Mississippi.
USDA-ARS, Contract No. 12-14-100-9182. 1967-1970. Atrazine,
Bromacil, Carbaryl, Dalapon, DDT, Dicamba, Dieldrin, Diuron,
DSMA, Malathion, Nemagon, Paraquat, Picloram, PMA, Trifluralin,
2,4-D, 2,4,5-T, Vernam, and Zineb. Liquid Injector. Pilot
scale.
Abstract:
Most of the commercial pesticide formulations tested were satisfactorily
(99 percent) combusted at 1000 C. However, combustion efficiencies for the
following pesticides were low: Atrazine (89 percent), Zineb (73 percent),
Bromacil (91 percent), Dalapon (91 percent), Diuron (96 percent), DSMA
(81 percent), and Sevin (90 percent). There was no mention of the fate of
the heavy metals in zineb and DSMA or the products of incomplete combustion
due to incomplete mixing with air or insufficient time of exposure to high
temperatures(3).
TRW Systems, Redondo Beach, California. U.S. Army, Material
Command. 1975. 2,4-D, 2,4,5-T, Chlordane, Dieldrin, Endrin,
Heptachlor, Lindane and DDT. Liquid injection. Pilot scale.
Abstract:
No final report is available at this time. However, preliminary data
indicate that proper nozzle design is critical and that good air/fuel
mixture is important to insure complete pesticide combustion. Under proper
operating conditions, 1000 C caused complete combustion of the chlorinated
pesticides tested. Combustion of certain concentrated pesticides
58
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(Chlordane, 78 percent) created high concentrations of HC1, which caused
corrosion in the incinerator. Therefore, this formulation had to be
diluted before incineration to prevent damage to the incinerator(6).
Versar, Inc., Springfield, Virginia. EPA, Office of Planning
and Evaluation (OPE) and OSWMP. 1975. DDT, 2,4,5-T. Sewage
sludge incinerator.
Abstract:
The two pesticides were blended into the sewage sludge (40 percent solids)
at a ratio of two to five percent and then incinerated. The completeness of
pesticide combustion was 99.9 percent.
59
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In addition to research institutions previously mentioned, several
industrial concerns dispose of pesticides and derived wastes by incineration.
The completeness of combustion and/or the difficulties involved with these
systems have not been evaluated in this report, and the reader should contact
the individual companies for further details.
Industry
1. Chem-Trol Pollution
Services, Inc., Model
City, New York.
2. Dow Chemical Co.,
Midland, Michigan.
3. General Electric Co.,
Pittsfield, Mass.
4. Hansa Co., Rotterdam,
Netherlands. (Incin-
erator ship)
5. Monsanto Chemical Co.,
St. Louis, Missouri.
6. Rollins Environmental,
Bridgeport, N.J.
7. Velsicol Chemical Co.,
Memphis, Tenn.
Waste
Product and industrial
waste disposal. '
In-house manufacturing
wastes.
Polychlorinated bi-
phenyls, DDT.
Chlorinated hydro-
carbons.
Polychlorinated bi-
phenyl wastes.
Incineration
Temperature (C)
1650
980
980-1132
1100-1600
1100
Contact waste disposal. 1200
Heptachlor and Endrin
?
manufacturing wastes.
60
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References - Incineration
1. The Atomics International molten salt process for special applications.
Canoga Park, Calif., Atomics International Division of Rockwell
International, Inc., Nov. 16, 1973. 54 p.
2. Scurlock, A.C., A.W. Lindsey, T. Fields, Jr., and D.R. Huber.
Incineration in hazardous waste management. Environmental
Protection Publication SW-141. (Washington), U.S. Environmental
Protection Agency, 1975. 104 p.
3. Kennedy, M.V., B.F. Stojanovic, and F.L. Shuman, Jr. Chemical and
thermal methods for disposal of pesticides. lr± F.A. Gunther, ed.
Residue reviews; residues of pesticides and other foreign chemicals
in foods and feeds, v. 29. New York, Springer-Verlag, 1969. p. 89-104.
4. Ferguson, T.L., F.J. Bergman, and R.T. Li. Determination of incinerator
operation conditions necessary for safe disposal of pesticides;
monthly reports, nos. 1-19, July 1973-Jan. 1975. Submitted to D.A.
Oberacker and R.A. Carnes, U.S. Environmental Protection Agency,
Solid and Hazardous Waste Research Laboratory, Cincinnati. Kansas City,
Mo., Midwest Research Laboratory.
5. Ottinger, R.S., et al. (TRW System Group). Recommended methods of
reduction, neutralization, recovery or disposal of hazardous waste.
v.5. National disposal site candidate waste stream constituent profile
reports—pesticides and cyanide compounds. U.S. Environmental Protection
Agency, Aug. 1973. 144 p. (Distributed by National Technical Information
Service, Springfield, Va., as PB 224 584.)
6. Personal communication. R.S. Ottinger and C.C. Shih, TRW Systems, to
D. Munnecke, Office of Solid Waste Management Programs, Sept. 30, 1974.
61
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7. Hutson, J.E. Report on the destruction of "orange" herbicide by
incineration; final report. Prepared for U.S. Air Force Environmental
Health Laboratory, Kelly Air Force Base, Texas. Van Nuys, Calif.,
The Marquardt Company, Apr. 1974. 58 p., app.
8. von Rummker, et al. Review of EPA's pesticide research and development
strategy. Washington, U.S. Environmental Protection Agency, Office of
the Principal Science Advisor, Mar. 22, 1974. 17 p. (Unpublished draft
report.)
9. Appendix IX; technical capabilities for dealing with excess pesticides.
In_ J.P. Lehman, chairman. Task force on excess chemicals; final report.
Washington, U.S Environmental Protection Agency, Office of Solid Waste
Management Programs, Aug. 24, 1973. 1 v. (various pagings.) (Unpublish
report.)
10. Montgomery, W.L., B.G. Cameron, and R.S. Weaver. The thermal destructor;
a facility for incineration of chlorinated hydrocarbons. Suffield
Report No. 270. Ralston, Atla., Defense Research Establishment Suffield
Oct. 1971. 14 p.
62
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METHODS FOR DISPOSAL OF PESTICIDES: LANDFILLS
Introduction
A major method for the disposal of pesticides, pesticide containers,
and pesticide related waste is to take them to the local landfill or dump.
Industrial manufacturing plants also use chemical landfills for disposal of
pesticide wastes(3). And yet, very little is known about the fate of these
chemicals after they have entered the landfill. Some States have realized
the need to control this indiscriminate dumping of pesticides and have
established strict criteria for landfills which are to be designated to
accept hazardous materials(15). These sites (secured or specially designated
landfills) are required to be designed or located such that the leachate will
not enter any water system, or in any other way pollute the immediate
environment.
There are several potential advantages to using landfills for disposal
of pesticides. First, there is already a collection system established,
some of which might be convertible to secured landfill sites. Second,
approved, secured landfills are capable of accepting pesticide containers
as well as bulk pesticides(4,10). Third, all classes of pesticides can be
deposited in such landfills, and it is one of the cheapest disposal procedures
available.
63
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There are, though, disadvantages to using landfills for pesticide
disposal. First, not all landfills can safely accept hazardous materials
due to possible surface or groundwater contamination and handling hazards,
etc. The ratio of secured landfills to general landfills is relatively low,
thus creating an availability problem. Secondly, the stabilization time for
a landfill which contains hazardous materials may be longer than a conventio
landfill, and thus the reclaimed landfill may have restricted use. Also,
for many chemicals, burial in a landfill, in reality, means underground
storage and no detoxification at all. A comparison of landfill disposal
methods to chemical, incineration, and biological methods is presented in
Appendices I and II.
In comparison to the amount of research conducted on municipal waste
disposal matters, pesticide landfill disposal research is very minimal.
Very little research has actually been conducted to study the fate of
concentrated pesticides in landfills. Therefore, most of the basic
research information reported here is taken from projects related to
other primary landfill research goals. A listing of agencies active in
landfill pesticide disposal problems and research is given in Table 11,
and abstracts of some of the research work discussed are included at the
end of this section.
64
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Table 11
Agencies active in the field of pesticide
disposal in landfills
1. California State Solid Waste Management Board, Sacramento, Ca.
2. Federal Working Group on Pesticides, Washington, D.C.
3. National Agricultural Chemicals Association, Washington, D.C.
4. Hazardous Waste Management Division, Office of Solid Waste
Management Programs, U.S. EPA.
5. State of Montana, Bureau of Solid Waste Management.
6. University of Illinois, Urbana, Illinois.
7. U.S. Army Medical Research and Development Command, Edgewood
Arsenal, Maryland
8. U.S. Department of Interior, U.S.G.S. Water Resource Division,
9. U.S. Army Corps of Engineers, Champaign, Illinois.
65
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Basic Research Findings
The major environmental hazard associated with landfilling of
pesticides occurs when the chemicals or metabolites begin to move from
the disposal site, primarily downward and into the saturated zone below.
This involves a dynamic situation where the pesticide in the leachate
moves downward, while chemical, physical, and biological forces detoxify
the pesticide. Thus, the pesticide's mobility and its half-life in the
soil environment are important data in establishing criteria for site
selection. Several review articles on biological metabolism of pesticides
in soil(2,8) describe the effects soil moisture, oxygen concentration,
temperature, pH, and organic matter have on the persistence of a pesticide.
Other projects have studied the generation and characteristics of leachate
from landfills(14), and methods for its confinement and reduction or
neutralization. An excellent review article by SHWRL, NERC, Cincinnati(14),
discusses in great detail the composition, movement, and characteristics of
municipal waste leachate.
Several groups have established procedures and guidelines for chemical
landfill site selection(5,15). These guidelines include recommendations on
how to dispose of various wastes as well as list criteria which are needed
to evaluate the geological data for a given site. Since most present
technology gaps of the landfill research have not been specifically concerned
with pesticides, there is much to be learned in regard to disposal of pestici
in landfills. Selected research areas which need to be further investigated
are described below.
66
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Present Technology Gaps
General Areas For Landfill Haste Disposal Research
1. How far above groundwater.does a site need to be to be considered
a specially designated landfill site?
2. In areas with high water tables, can a landfill be designed which
is sealed off from this groundwater?
3. What effects do the various soils have on attenuation of pesticides
in the leachate?
4. What methods can be used to successfully encapsulate hazardous
wastes, and what wastes need encapsulation?
5. Is it more advisable to have percolation with leachate recirculation,
or inhibit leachate production and percolation?
Specific Pesticide/Landfill Research Areas
1. What effect do pesticides have on the stabilization times for
landfills?
2. Should pesticides be entered separately from municipal wastes or
mixed together for best detoxification results?
3. At what concentrations should the pesticides be placed into the
landfill?
4. What is the ultimate fate of a pesticide in a landfill?
67
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Recommendations
Since few research projects have been solely concerned with the fate
of concentrated pesticides in the landfill environment, many questions remain
unanswered in this area. The following research proposal topics are aimed
at helping to fill in these technology gaps.
1. Conduct laboratory and field research to determine
conditions for optimum rate of pesticide degradation
in a landfill.
2. Conduct research to determine how far a pesticide
will move down a soil column in comparison to its
half-life.
3. Determine how to treat pesticides in leachate that
is to be collected and recycled.
4. Determine if pesticides in conventional landfills
are polluting water systems currently, or will in
the future. Also, if pesticides in old landfills
are causing pollution, how can this be remedied?
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Abstracts of Research on Landfill Disposal of Pesticides
University of Illinois, Urb'ana, State Water Survey,
Dr. W.H. Walker. EPA Project No. 803216, 1DB064.
Awarded in 1974 for a two-year period. No specific
pesticide. Field verification of industrial hazardous
waste migration from land disposal site.
Abstract:
Although this project has just started, one area of research will be
to monitor the environmental contamination from a chlorinated pesticides
manufacturing plant's disposal site in Illinois. Preliminary results show
that chlorinated pesticides were found in high concentrations in rainwater
puddles downhill from the disposal site. Wells will be drilled to determine
the movement of these chemicals(16).
Montana Department of Health and Environmental Services,
Helena, Montana, Kit Walther, EPA Contract WA74-R448,
awarded in 1974 for an 18-month period of performance.
Pesticide Disposal Demonstration Project. 2,4-D,
2,4,5-T, Diallate, Lindane, DDT, Aldrin, arsenic
pesticides, sodium fluorosilicate, and others.
Chemical, landfill, and soil incorporation methods
of disposal.
Abstract:
Montana previously collected on a Statewide basis excess pesticide
formulations and stored them in an ammunition bunker in northeast Montana.
With this project, the State will conduct another Statewide campaign to
collect pesticide containers and then dispose of all in a chemical landfill.
69
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In conjuction with this chemical landfill, a soil incorporation technique
will be studied to determine the feasibility of using the soil as a system
for the detoxification of large amounts of certain pesticides and container
residues. The pesticides will be entered at various concentrations, and the
degradation rate monitored over an 18-month period(ll).
U.S. Army Construction Engineering Research Lab. Corps
of Engineers, Champaign, Illinois. In-house. 1974.
DDT. Laboratory soil leachate columns, 6 ft diameter.
Abstract:
High levels of DDT (250 mg/kg soil) were placed into a ten foot soil
column and the movement and persistence of DDT was monitored. Water was
applied at a rate of 35 inches per year after adjusting for water runoff
for a properly capped and crop covered landfill site. Very little research
data are available at this time due to failure to have proper analytical
equipment; a progress report is forthcoming(12).
U.S. Department of the Interior, USGS, Water Resources
Division. In-house. Date reported, August 1967.
Manufacturing wastes from endrin, heptachlor and
heptachlor expoxide. Investigation of environmental
contamination from a chemical landfill.
70
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Abstract:
Velsicol Chemical Company established a chemical landfill for its
pesticide manufacturing wastes in Hardeman County, Tennessee. Due to
fear that the environment was being contaminated by this chemical dumping,
the U.S. Geological Survey was requested to investigate the disposal
site and determine the extent of damage. The general results were that the
pesticides had moved into the water aquifers below (90 ft) and that there
was also surface spread of the pesticides and contamination of an adjacent
stream.
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Reference - Landfill
1. Davidson, J.M. et al. (Oklahoma State University). Use of soil parameters
for describing pesticide movement through soils. Washington, U.S.
Environmental Protection Agency, May 1975. 149 p. (Distributed by
National Technical Information Service, Springfield, Va., as PB-242 859.)
2. Lichetnstein, E.P. Environmental factors affecting fate of pesticides.
^Degradation of synthetic organic molecules in the biosphere; natural,
pesticidal, and various other man-made compounds. Proceedings of a
Conference, San Francisco, California, June 12-13, 1971. Washington,
National Academy of Sciences, 1972. p. 190-205.
3. Klein, S.A., et al. (University of California at Berkeley, Sanitary
Engineering Research Lab). An evaluation of the accumulation, trans!ocat
and degradation of pesticides at land wastewater disposal sites; final
report 15 May 73-31 Aug. 74. Washington, U.S. Army Medical Research and
Development Command, Logistics Division, Nov. 1974. 235 p. (Distributed
by National Technical Information Service, Springfield, Va., as AD/A-006
551.)
4. Information available on disposal of surplus pesticides, empty containers
and emergency situations. Washington, Safety Panel (FWGPM), 1970.
58 p. (Distributed by National Technical Information Service, Springfield
Va., as PB-197 146.)
5. Ground disposal of pesticides: the problem and criteria for guidelines.
Washington, Safety^Panel (FWGPM). 1970. 62p. (Distributed
by National Technical Information Service, Springfield, Va., as
PB-197 144.)
72
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6. Fields, T., Jr., and A.W. Lindsey. Landfill disposal of hazardous
wastes: a review of literature and known approaches. Environmental
Protection Publication SW-165. (Washington), U.S. Environmental
Protection Agency, June 1975. 36 p.
7. Lehman, J.P., Chairman. Task Force on excess chemicals; final report.
Washington, U.S. Environmental Protection Agency, Office of Solid
Waste Management Programs, Aug. 24, 1973. 1 v. (various pagings.)
(Unpublished report.)
8. Kearney, P.C., et al. Decontamination of pesticides in soils. ln_
F.A. Gunther, ed. Residue reviews; residues of pesticides and
other foreign chemicals in foods and feeds, v. 29. New York,
Springer-Verlag, 1969. p. 137-149.
9. Floyd, E.P. Occurrence and significance of pesticides in solid wastes;
a Division of Research and Development open-file report (RS-02-68-15).
(Cincinnati), U.S. Department of Health, Education, and Welfare, 1970.
34 p. (Restricted distribution.)
10. Ottinger, R.S., et al. (TRW Systems Group). Recommended methods of
reduction, neutralization, recovery or disposal of hazardous waste.
v. 5. National disposal site candidate waste stream constituent
profile reports—pesticides and cyanide compounds. U.S. Environmental
Protection Agency, Aug. 1973. 144 p. (Distributed by National
Technical Information Service, Springfield, Va., as PB 224 584.)
11. Personal communication. K. Walther, Helena, Mont., to D. Munnecke,
Office of Solid Waste Management Programs, Aug. 22 and 23, 1974.
73
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12. Personal communication. H. Ridge and D. Baker, U.S. Army Construction
Engineering Research Lab., Champaign, 111., to D. Munnecke, Office of
Solid Waste Management Programs, Oct. 17, 1974.
13. Rima, D.R., et al. Potential contamination of the hydrologic
environment from the pesticide waste dump in Hardeman County,
Tennessee. Washington, U.S. Geological Survey, Water Resources
Division, 1967. 41 p. (Unpublished Open File Report to the Federal
Waster Pollution Control Administration.)
14. Brunner, D. Gas and leachate from land disposal of municipal solid
waste; summary report. Cincinnati, U.S. Environmental Protection
Agency, Solid and Hazardous Waste Research Division. (In preparation;
to be distributed by National Technical Information Service, Springfieli
Va.)
15. Guidelines for hazardous waste land disposal facilities. Sacramento.
California Department of Health, Vector Control Section, Jan. 1973.
44 p.
16. Walker, W.H. Field verification of industrial hazardous material
migration from land disposal site. Cincinnati, U.S. Environmental
Protection Agency, Solid and Hazardous Waste Research Division.
(In preparation; to be distributed by National Technical Information
Service, Springfield, Va.)
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Appendix I. Comparison of Incineration and Biological Methods for
Disposal of Waste Pesticides and Pesticide-Related Wastes
INCINERATION
BIOLOGICAL
Disposal capacity.
100-200 gal/hr
Pesticide concentration up to 100%
accepted.
Economics:
initial cost.
operating costs.
Reliability of system.
Percent detoxification.
Effluent hazard.
Technology requirements.
Staff needed.
Availability of system.
Applicability:
Excess pesticides.
Small quantities.
Pesticide containers.
$30K-$80QK
$50-$2007ton
good
99.9% plus
0-150 Ib/day/MGD
System.
limited by pesti-
cided water solubility,
system agitation.
variable
$30-1200/GGD
subject to shock,
cold temperature.
up to 100%,
generally 60-85%
effluent gases discharged must be
scrubbed
sophisticated
normal
restricted
excellent
good
possible
general biological
treatment equipment.
normal
limited
poor
excellent
poor
75
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Appendix II. Comparison of Landfill and Chemical Methods for
Disposal of Waste Pesticides, and Pesticide-related Wastes
LANDFILL
CHEMICAL
Disposal capacity.
Pesticide concentration
Economics:
initial cost.
operating costs.
Reliability of system.
Percent detoxification
Effluent hazard
Technology requirements.
Staff needed.
Availability of system.
Applicability:
Excess pesticides.
Small quantities.
Pesticide containers,
tons/day
can accept any
concentration
varies with system
$1.50-$32/ton
good
very low to none at
all in short time
period
varies with system
mg to tons
can accept any
concentration
varies with system
$16.00/ton and up
good-fair
0-100%, though
generally incomplet
leachate is potentially still a toxic
hazard. Volatility problem.
specially designated
landfill technology
normal
restricted to
specially designated
landfills
good
good
good
general to highly
sophisticated
chemistry
normal
restricted to
engineered faciliti
fair
good
good
ya!3'
SW-5
76
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