A
EPA
United States
Environmental Protection
Agency
Hazardous Waste Engineering
Research Laboratory
Water Engineering Research
Laboratory
Cincinnati OH 45268
EPA/600/9-86/001
January 1986
Research and Development
Proceedings:
Research Workshop on the
Treatment/Disposal of
Pesticide Wastewater
-------
-------
EPA/600/9-86/001
January 1986
PROCEEDINGS: RESEARCH WORKSHOP ON THE TREATMENT/DISPOSAL
OF PESTICIDE WASTEWATER
by:
James S. Bridges ;
Hazardous Waste Engineering Research Laboratory
and
Clyde R. Dempsey
Industrial Waste and Toxics Technology Division
Water Engineering Research Laboratory
Office of Research and Development
Cincinnati, Ohio 45268
HAZARDOUS WASTE ENGINEERING RESEARCH LABORATORY
WATER ENGINEERING RESEARCH LABORATORY
OFFICE OF RESEARCH AND 'DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
-------
DISCLAIMER
The abstracts submitted as part of these proceeding;; describe work
that has not been funded by the! U.S. Environmental Protection Agency and
therefore the contents do not necessarily reflect the views of the Agency and
no official endorsement should be inferred.
i
The proceedings, other than the abstracts, have been reviewed in
accordance with the U.S. ' Environmental Protection Agency's peer and
administrative review policies and approved for presentation and publication.
-n-
-------
FOREWORD
The U.S. Environmental Protection Agency is charged by Congress with
protecting the Nation's land, air, and water systems. Under a mandate of
national environmental laws, the agency strives to formulate and implement
actions leading to a compatible balance between human activities and the
ability of natural systems to support and nurture life. The Clean Water Act,
the Safe Drinking Water Act, and the Toxics Substances Control Act are three
of the major congressional laws that provide the framework for restoring and
maintaining the integrity of our Nation's water, for preserving and enhancing
the water we drink, and for protecting the environment from toxic substances.
These laws direct the EPA to perform research to define our environmental
problems, measure the impacts, and search for solutions.
The Water Engineering Research Laboratory is that component of EPA's
Research and Development program concerned with preventing, treating, and
managing municipal and industrial wastewater discharges; establishing
practices to control and remove contaminants from drinking water and to
prevent its deterioration during storage and distribution; and assessing the
nature and controllability of releases of toxic substances to the air, water,
and land from manufacturing processes and subsequent product uses. This
publication is one of the products of that research and provides a vital
communication link between the researcher and the user community.
The research workshop on the treatment/disposal of pesticide
wastewater was developed in order to better understand how to deal with the
on-site management/disposal of dilute pesticide wastewaters. It was organized
and conducted by the Agricultural Research Service, USDA and the Environmental
Protection Agency, and these proceedings were prepared to document the results
of this effort. It is hoped that the content of these proceedings will
stimulate action that will reduce pollution from the agricultural application
of pesticide wastewater.
Francis T. Mayo, Director
Water,Engineering Research Laboratory
-m-
-------
ABSTRACT
A research workshop on the treatment/disposal of pesticide wastewater
generated by the agricultural application of pesticides was held at the U.S.
Environmental Protection Agency's Andrew W. Breidenbach Environmental Research
Center in Cincinnati, Ohio on July 30-31, 1985. The purpose of this workshop
was to address issues regarding the effectiveness of current state-of-the-art
capabilities, identification of emerging techniques or technologies that may
be applicable along with technologies being applied in other areas, and the
need for research efforts capable of providing results in a 3 to 5 year time
frame as they pertain to the treatment/disposal of dilute pesticide wastewater.
The format of the two-day workshop included the sixty-one invited
participants representing an appropriate cross-section of interests and
expertise attending at their own expense. Participants were mostly
individuals actively involved in related research as well as adequate repre-
sentation from the user and regulatory community to assure that the problem
and candidate solutions were kept in proper perspective. The first-day
plenary session addressed twelve technologies as follows: (1) pesticide
rinsewater recycling, (2) granular carbon adsorption, (3) UV-ozonation, (4)
small-scale incineration, (5) solar photo-decomposition, (6) chemical
degradation, (7) evaporation, photodegradation and biodegradation in
containment devices, (8) genetically engineered products, (9) leach fields,
(10) acid and alkaline trickling filter systems, (11) organic matrix
adsorption and microbial degradation, and (12) evaporation and biological
treatment with wicks. The second day divided tne participants into two
workgroups. Workgroup A was entitled, "Physical/Chemical Treatment and
Recycling" and Workgroup B was entitled, "Biological Treatment & Land
Application".
This publication is a compilation of the sixteen speaker's abstracts,
both workgroup results and a conclusion with recommendations. Workgroup A and
Workgroup B were each divided into six sub-work groups to review and assess
their respective technology(s). The conclusion and recommendations developed
as Section 2 of these Proceedings represent the results of these sub work-
groups. These collective appraisals were the basis of research
recommendations.
i
The results of this research workshop will be of particular interest
at the 1986 National Workshop on Pesticide Waste Disposal in addition to
recognizing immediate research needs.
-IV-
-------
CONTENTS .
FOREWORD .................... iii
ABSTRACT iv
ACKNOWLEDGMENT . . vi
1. Introduction . 1
2. Conclusions and Recommendations 5
3. Abstracts . 7
4. Work Group Results. 26
APPENDICES
A. Most Commonly Used Pesticides in American Agriculture . ... . 41
B. List of Attendees 42
C. Agenda for July 30, 1985 47
D. Agenda for Work Group A on July 31, 1985 . 49
E. Agenda for Work Group B on July 31, 1985 50
F. Work Group A, Physical/Chemical Treatment & Recycling ..... 51
G. Work Group B, Biological Treatment & Land Application 52
H. Sub-Work Group Summary Sheet 53
-v-
-------
ACKNOWLEDGMENT
The workshop was sponsored by the following organizations:
American Farm Bureau Federation
Association of American Pesticide Control Officials, Inc.
U.S. Department of Agriculture, Agricultural Research Service
U.S. Environmental Protection Agency, Office of Research and Development
A special note of appreciation is extended to the research workshop
participants who presented the specific related research at the plenary
session. The presentation and discussions of all the attendees/participants
during the workgroup sessions involved each individual and this action
accounts for the success of the workshop. Dr. Philip C. Kearney, Chief of
USDA's Pesticide Degradation Laboratory and Mr. Francis T. Mayo, Director of
EPA's Water Engineering Research Laboratory did an excellent job of moderating
the sessions and kept the meeting on a timely schedule. Thanks also go to Mr.
Raymond F. Krueger and Mr. Matthew Straus for their participation in
discussing the regulatory aspects of pesticide wastewater. Of course, nothing
actually gets done without administrative and typing support and we are
grateful to Mrs. Jane DeMaris for all of her tremendous hard work.
-VI-
-------
SECTION 1
INTRODUCTION
BACKGROUND
Regulation of pesticide waste disposal at the federal level is a
relatively recent development. The 1972 amendments to the Federal
Insecticide, Fungicide and Rodenticide Act (FIF.RA) specified that the label
statement must include recommendations for disposal. More recently, under
authority of the Resource Conservation and Recovery Act (RCRA) and the RCRA
amendments, the Environmental Protection Agency (EPA) has promulgated a
complex and dynamic set of regulations that are intended to control the
management of hazardous wastes (some of which are pesticides) from cradle to
grave.
Compliance with RCRA as-well-as other State and local pesticide disposal
regulations will require significant involvement by the agricultural pesticide
applicator as in many cases he will be defined as a hazardous waste generator.
1985 NATIONAL WORKSHOP ON PESTICIDE WASTES DISPOSAL
On January 28 and 29, 1985 a National Workshop on Pesticide Wastes
Disposal was held in Denver, Colorado. The objective of this workshop was to
provide a national forum for Federal and State agencies, pesticide user
groups, pesticide producers, agricultural organizations and academia to
jointly assess:
1. Waste disposal needs of pesticide users.
2. Pesticide waste disposal technology.
3. Requirements for making selected technology available to pesticide
users.
4. Applicable Federal, State and local regulations.
5. Recommendations and future actions. ;
This workshop was co-sponsored by numerous national associations and
government agencies representing the agricultural chemicals industry,
agricultural, interests, state and local pesticide control agencies, U.S.
Department of Agriculture (USDA) and EPA. An original attendance estimate at
100 to 150 people blossomed to approximately 400 people representing a broad
spectrum of State and Federal agencies, pesticide applicators, chemical
manufacturers, universities, farmers, waste disposal consultants and
contractors, pesticide retailers and trade associations.
-1-
-------
Three categories of problems were identified:
1. Disposal of dilute pesticide wastewater.
2. Disposal of pesticide containers. |
3. Management of soil and residuals contaminated with pesticides.
Review and evaluation of the 1985 workshop by the coordinating committee
identified the immediate need for a follow-up effort to better understand how
to deal with the on-site management/disposal of dilute pesticide wastewaters.
It was emphasized many times during that workshop that there was a need to
identify, develop and demonstrate; practical, effective and economical methods
for treating and disposing of pesticide wastewater which can be operated at or
near (within a 50 mile radius) the farm. The 1984 "small generator"
amendments to RCRA make this a matter of special importance to pesticide
applicators with on-site rinsate management problems. ,
i ,
Sources of these wastes include:
1. Waste from the mixing, loading and cleaning operations.
2. The washing of application equipment including the outer skin of
aircraft and the exteriors of ground equipment.
3. Rinsate generated by the triple rinsing of pesticide containers.
There was agreement on the need to (1) appraise the effectiveness of
current state-of-the-art capabilities, (2) identify emerging techniques .or
technologies that may be applicable along with technologies being applied in
other areas, and (3) identify information gaps which can be filled through
research efforts in a 3 to 5 year time frame. The first two items are
necessary for current regulatory development and implementation. However, it
is recognized that the regulatory process is an iterative process which must
be based upon the best available information at the time but which also must
be reviewed and revised periodically as new information is generated.
Furthermore it was perceived that after the state-of-the-art capabilities,
emerging technologies and technology transfer opportunities were assessed that
data gaps would be identified that can only be addressed through research
efforts (i.e., item #3).
RESEARCH WORKSHOP
Discussions between representatives of the Agricultural Research Service
(ARS), USDA and the EPA concluded that a cooperative effort in addressing
these issues would fall under the umbrella of the recent Memorandum of
Understanding between EPA and the USDA.
-2-
-------
A specific cooperative ARS/EPA proposal was; developed to hold a Research
Workshop to address these issues by an invited group of 40-60 participants.
For purposes of this workshop, "on-site disposal" included near vicinity
collection and disposal of limited volumes of wastewater, but not long
distance transport to more distant waste disposal facilities.
While there are approximately 680 active pesticide ingredients used in
American agriculture, this workshop was to focus on the treatment and disposal
of wastewater contaminated with the most commonly used formulated pesticides
with emphasis on those that are identified as hazardous constituents under
RCRA. (See Appendix A).
FORMAT
The Research Workshop was held in Cincinnati, Ohio at the Andrew W.
Breidenbach Environmental Research Center on July 30 and 31, 1985. Sixty-one
invited participants (see Appendix B) representing an appropriate
cross-section of interests and expertise attended at their own expense.
Participants were composed principally of individuals actively involved in
related research. However, there was also adequate representation of the user
and regulatory community to assure that the problem and candidate solutions
were kept in proper perspective.
The first day (see Appendix C) was taken up by sixteen 20 minute
presentations and discussions on specific subject areas at a plenary session.
Abstracts of these presentations are given in Section 3. Each presenter was
asked to address as appropriate for his subject the following three aspects:
1. State-of-the-art capabilities.
2. Emerging technology and/or technology transfer opportunities.
3. Research needs with a 3-5 year payout.
In addition, each presenter was asked to explain the following features of
his topic as it applies to the on-the-farm treatment/disposal of dilute
pesticide wastewater.
1. Current applications.
2. Perceived and potential difficulties.
3. Cost.
4. Ease of use (i.e. mobility, technically uncomplicated, failproof,
etc.).
5. Size.
6. Shortcomings (durability, reliability, range of use, etc.).
-3-
-------
I
7. Key points from both the user and regulator viewpoints.
The morning of the second day (see Appendices D and E) was devoted to two
concurrent work group sessions dealing with the following types of treatment
and management techniques:
Work Group
A
B
Subject area
Physical/Chemical
Treatment & Recycling
Biological Treatment
& Land Application
The objective of these work group sessions was to develop collective
appraisals of needs and opportunities and develop recommendations for
follow-up action. The afternoon of the second day was used for presentation
of a report by each of the groups and a short overview session.
-4-
-------
: SECTION 2
CONCLUSIONS AND RECOMMENDATIONS
Based .upon information generated during the, 1985 National Workshop on
Pesticide Wastes Disposal, it is clear that the 'applicators percieve an urgent
need to identify and prove effective and economical technologies for managing
dilute pesticide wastewater. .
During this Research Workshop, twelve different technologies were
identified as possible methods for this purpose which could be operated at or
near the farm. Of these, only four were considered proven technologies for
this application which are readily available. These are:
1. Recycling Pesticide Rinsewater.
2. Granular Carbon Adsorption. '
3. Evaporation, Photodegradation and Biodegradation in Containment
Devices.
i
4. Leach Fields.
It was the general consensus that applicators should plan their operation
so as to minimize the quantity of wastewater that must be managed. This
involves mixing only the volume of material needed for the spray operation and
using rinseates from containers where possible and where approved for further
spray operations. It appears that reusing rinsewaters for subsequent sprays
is widely practiced to various extents by many appplicators. Elxpanding and
maximizing this technique offers a very promising and cost effective method
for solving a major portion of the problem. However, implementation of this
expansion requires that a number of questions be;resolved via research efforts.
While granular carbon adsorption is considered a proven technology, it has
been utilized on a very limited basis for pesticide wastewater. In addition,
there are a number of questions that need to be answered to take maximum
advantage of this technology.
Universities and other research facilities have been employing
evaporation, photodegradation and biodegradation in containment devices (often
referred to as "pits") to treat pesticide wastewaters for over fifteen years.
However, this method is not widely utilized for several reasons. These
include such unknowns as the potential for the treatment to further produce
hazardous wastes, uncertainty of the science and the product results and lack
of understanding of the treatment process on specific pesticides.
Leach fields are being used by many small fruit farms in New York.
However, additional information is needed to fully assess the groundwater
pollution potential posed by this system.
-5-
-------
Two of the technologies (UV-Ozonation and Chemical Degradation) were
considered technology transfer opportunities. UV-Ozonation is being used to
remove toxic pollutants from water in Europe and chemical degradation is
currently used for industrial waste clean-up and spills. The remaining six
technologies are all emerging technologies which require significant research
and development before they could be made available for widespread use.
Insufficient information is available at this time to rank these
technologies and it is recognized that the optimum method of managing this
wastewater will probably involve the utilization of a combination of
technologies. However, it is clear there is an immediate need to initiate a
research effort to:
i.
i
1. Address those research needs identified for the currently available,
proven technologies such that utilization of these methods can at
least be maximized on an interim basis. i
2. Conduct preliminary assessments of the effectiveness of the
technology transfer and emerging technology opportunities and rank
them for further development. Consider the | combination of
technologies as part of this effort.
3. In priority order, address the identified research needs for the
technology transfer and emerging technology opportunities.
-6-
-------
SECTION 3
ABSTRACTS
PRACTICAL SYSTEM TO TREAT PESTICIDE-LADEN ; WASTEWATERS GENERATED BY
APPLICATORS1
The treatment system described is based on recirculation of
pesticide-contaminated wastewater through a bed of granular activated
carbon(GAC) and was developed for use at a residential pest-control facility
at Fort Eustis, VA. This in-house research program was conducted by the U.S.
Army Medical Bioengineering Research and Development Laboratory, Fort Detrick,
Frederick, MD. Testing demonstrated that a mixture of seven pesticides could
be removed from 400 gal of water with 45 Ib of GAC. The most challenging test
purified 400 gal of water containing 400 ppm of each pesticide. The process
has a mathematical basis and thereby is predictable. The system is
inexpensive and simple to operate, and the spent carbon has a very low
leaching rate. Now that the utility of this system has been demonstrated for
chemicals used to control residential pests, we plan to evaluate it for onsite
use by agricultural pesticide applicators.
PESTICIDE RINSEWATER TREATMENT2
The disposal of sediments and rinsewater from agricultural spraying by
aerial applicators and land-based operations has become a large cost component
in the use of these materials. The problem has been magnified by the RCRA
reauthorization that prohibits the use of adsorbents to solidify otherwise
liquid rinsewaters. Canonie Engineers was requested by the Western
Agricultural Chemical Association (WACA) to develop a rinsewater treatment
system that could be easily maintained and would not require large capital
expenditures for equipment. The criteria for the system were as follows.
The equipment should be small enough to be placed on concrete pads
currently in use for the rinsing of equipment by applicators. A lined sump
should be part of the facility so that rinsewater can be collected preparatory
to treatment. The system should be capable of sediment removal, and it should
be able to handle both oil- and water-based formulations. The system should
minimize operator contact through the treatment process and be capable of
treating to a level that would permit the process rinsewaters to be reused in
future formulations.
1 David W. Mason, Robert H. Taylor,,Jr., Daniel R. Coleman, Southern
Research Institute, Birmingham, AL 35255. William H. Dennis, Jr.,
Consultant, Braddock Heights, MD 21714.
2phillip E. Antommaria, Canonie Engineers, Inc., Chesterton, IN 46308.
-7-
-------
To accomplish these ends, Canonle developed the treatment train shown in
Figure 1. The first step in the treatment is passage of sediments
containing pesticides to a cyclone separator for the removal of coarse
solids. Solids from this process are discharged to a 55-gal drum, and
liquids inherent in the, process are returned to the sump for future
treatment. Once coarse sediments are removed, smaller particles are removed
using a diatomite filter. A diatomite filter was selected because of its
low cost and ability to remove certain pesticides. In addition, the
diatomite filter requires very small volumes of backwash water. The treated
water then goes to a pretreatment tank from which it is pumped to a Calgon
Clean-Sorb unit. Clean-Sorb, which contains activated alumina, can break
oil-water emulsions and will remove any oil-based material from the
streams. After treatment in the Clean-Sorb unit, the effluent is passed to
two or more Calgon Vent-Sorb units that contain activated carbon for final
treatment of the pesticide rinse. The rinsewater then goes to a treated
water storage tank where it can either be used for future rinsing of
equipment and vehicles or for the reformulation of pesticides for
application.
Total capital cost for this system is $20,000. The California
Department of Agriculture has funded a 1-year study for the installation of
two systems in the State of California and the requisite analytical work as
a proof of process design. The State of California has waived the
permitting as a treatment facility under RCRA to permit this experimental
system to go forward. The U.S. Environmental Protection Agency has
concurred with this action. The systems are currently being installed by
one aerial and one ground-based applicator. Data on this operation will be
available within the year.
TREATABILITY STUDIES OF PESTICIDE WASTEWATERS BY GRANULAR ACTIVATED CARBON,
HYDROLYSIS, CHEMICAL OXIDATION, AND UV-PHOTOLYSIS3
Compliance with existing effluent guidelines and with those being
prepared for pesticide wastewaters will require the investigation of
physical-chemical methods for treatment of process effluents and final
discharge. Although granular activated carbon (6AC) has been well
established as a treatment method, a limited data base exists on its
effectiveness for reducing pollutant concentrations of specific pesticides
to discharge levels. Conventional performance testing of 6AC generally
requires the use of pilot columns and is time-consuming and expensive.
Performance data or other physical-chemical treatment methods are also
limited. However, many of these methods have the potential for
cost-effectively meeting the discharge requirements by decomposing the
pesticide. ' ,
3L.J. Bilello, Environmental Science & Engineering, Inc., Gainesville,
FL 32602, and Shri Kuhlkarni, Radian Corporation, Research Triangle
Park, NC 27709.
-8-
-------
Figure 1. Pesticide rinsewater treatment system.
-9-
-------
Environmental Science and Engineering, Inc. (ESE) and Radian were asked
by EPA to assess available treatment methods, to select potentially
effective methods for bench-scale studies, and to develop and demonstrate
bench-scale treatment methods for screening these selected alternatives.
Following an extensive literature and industrial user survey* chemical
oxidation, hydrolysis, and UV-photolysis were recommended for bench-scale
methods development.
As a follow-up before 6AC development studies, ESE was to demonstrate
the use of the dynamic mini column adsorption technique (DMCAT) as a means
of rapidly evaluating GAC performance.
This presentation discusses the rationale and methods used in selecting
the technologies for study and the results of laboratory investigations.
Four pesticides, 2,4,-D, Linuron, Prometron, and Methomyl, were evaluated in
the laboratory using the procedures developed to evaluate the technologies.
The objectives of these experiments were twofold: 1) to assess the validity
of the experimental protocol, and 2) to determine the decomposition rates of
each of the pesticides at various conditions to determine whether the
technology was effective and the conditions preferred. Hydrolysis studies
were performed at pH 3, 7, and 9 and at temperatures of 50° and 30°C.
Hypochlorous acid, hydrogen peroxide, and ozone were used as the chemical
oxidants. UV-photolysis experiments were conducted to determine the effect
of light intensity, exposure time, pH, temperature, and the pressure of
inhibitors or additional oxidants on the decomposition rates of each of the
pesticides.
DMCAT is a rapid GAC evaluation method that provides data on pollutant
breakthrough, GAC usage rates, order of pollutant breakthrough, and
determination of the limiting pollutant. DMCAT pumps wastewater through a
2-mm column packed with pulverized GAC. Samples are collected routinely
through a closed sample system.
The experimental plan consisted of validation of DMCAT procedures,
comparison with side-by-side pilot columns, and comparison with operating
full-scale systems. Wastewater containing Atrazine and toluene was used in
this experimental program. Additional DMCAT tests were ; performed to
evaluate GAC performance on Terbacil.
PESTICIDE RINSEHATER RECYCLING SYSTEMS4
During the 1984 spray season, Growmark, Inc., and the Illinois
Environmental Protection Agency researched the concept of recycling
pesticide rinsewaters by mixing them into succeeding spray solutions as an
alternative to treatment and/or disposal. Wastewater management systems at
13 commercial agrichemical facilities were examined. j
4-A.G. Taylor, Illinois Environmental Protection Agency,
Springfield, IL 62706 i
-10-
-------
The basic design of the wastewater collection and recycling systems
includes a wash pad and receptacle for rinsewater;containment. The wash pad
component is typically a reinforced, 18- by 36-ft'concrete slab that catches
water generated in the washing and rinsing of most spray equipment,
drippings from hoses, and foamovers that occur while loading.
The most efficient device for collecting rinsewater draining from the
wash pad is a 1000-gal concrete tank. A pre-cast tank or a poured tank made
of high-density, 6000-psi concrete is used for this purpose. The collection
tank set up varies depending on the scope of the operation. At a minimum,
one tank is required for containment of rinsewater and incidental spillage.
Two tanks are used to segregate corn and bean chemical rinsate.
A basic unit including the wash pad, tanks, plumbing, and pumps can be
installed for less than $10,000.
To study the feasibility of recycling rinsewater, water samples were
collected from the containment facilities at the 13 agrichemical sites and
analyzed for the pesticides introduced into each respective system.
Concentrations in the rinsewater mixtures were compared with those in
standard spray solutions to assess potential contamination problems and to
determine dilution factors for reuse.
The results indicate that the addition of rinsewater to fresh spray
solutions of the commonly used corn and soybean herbicides at a 5-percent
rate by volume will very slightly influence the total active ingredient
concentrations. In each case, the total amount falls well within the limits
allowed for the primary active ingredient when used alone, which tends to
support the reuse concept (Table 1). '
TABLE 1. RINSEWATER EFFECTS ON SPRAY SOLUTION CONCENTRATIONS
Standard Spray Recycle
Solution Allowable Variation with
Herbicide Concentration* Rate Variation** 5% Rinsewater
(ppm)(+/-ppm)
Atrazine
Cyanazine
Metalochlor
Alachlor
Metribuzin
Linuron
Pendimethalin
Butyl ate
Trifluralin
14,100
15,000
12,000
16,300
2,600
1,870
7,500
21,300
4,500
1,500
3,000
1,500
3,000
375
375
1,500
2,300
750
10
20
12
18
14
20
20
11
17
0.60
.56
.70
.52
3.23
4.49
1.12
.39
1.87
*Based on median recommended application rates applied with water at
20 gal per acre.
**Based on manufacturers' label recommendations.
-11-
-------
Blending of the rinsewater into the spray solutions does raise some
questions, particularly for regions where more .diverse and sensitive
specialty crops are grown. The main concerns rise from tank mixing of
pesticides not labeled for such use. Trace amounts of these pesticides
could be phytotoxic to the crop, and the potential exists for residues in
excess of established tolerances. Follow-up studies are proposed to address
these issues.
PESTICIDE WASTE DISPOSAL5
The Louisiana Department of Agriculture began enforcement of pesticide
waste disposal regulations on January 1, 1985. These regulations pertain to
all commercial pesticide applicators. Basically, they require that
applicators have facilities to clean the equipment spray tank, spray system,
mixing tanks, and pesticide containers without contaminating the soil,
groundwater, or other bodies of water.
,
Water used to wash the spray system can be disposed of in several ways.
Approximately 35% of the aerial applicators plan to rinse the aircraft over
the field being treated. This process involves returning the aircraft to
the loading area and loading 50 to 60 gal of clean water. The aircraft is
then returned to the area being treated, and the washwater is sprayed over
the field. The aircraft then returns to the loading area for a second load
of 50 to 60 gal of clean water. This second load of clean water is then
applied to the area being treated. This process is repeated until the
residue remaining in the spray system has a very low pesticide concentration.
Aircraft normally have 5 to 8 gal of residue in the spray system at the
end of a spray operation. Adding 60 gal of clean water to the spray system
will reduce the concentration to 10% to 12% of normal field strength. This
washwater can normally be applied to the field being treated without
exceeding the label rate. This concentration can be reduced by about 40% if
the spray system is modified to remove all pesticide from the spray tank.
The general consensus is that it will cost less for applicators who fly
fewer than 300 hrs per year to triple rinse the aircraft over the field
rather than to construct facilities for recycling washwater.
In other cases, the applicator can change pesticides without washing the
aircraft. As an example, most applicators can switch from soybean
herbicides to soybean insecticides to soybean fungicides without cleaning
the aircraft. This can be accomplished without exceeding the label rates or
violating the label of the pesticides involved. For example, when mixed
with 300 gal of water, the residue in the aircraft will have a concentration
of less than 3% of normal field strength.
5Darryl Rester, Louisiana State University Agricultural Center
Baton Rouge, LA. 70308-
-12-
-------
About 60% of Louisiana's aerial applicators have built wastewater
recycling facilities. These facilities consist of three to five wastewater
containment tanks. Each tank will hold 200 to 500 gal of pesticide waste.
After the completion of a spray job, the aircraft will be washed to remove
the residue from inside the spray system. The washwater and pesticide
residue will be collected and pumped into the desired containment tank. In
most cases, this washwater will contain pesticide waste at less than 10% of
normal field strength. This washwater will then be used as a dilution agent
on the next job where compatible chemicals are used. As an example, most
,applicators will have a tank for cotton herbicides and insecticides, soybean
herbicides and insecticides, rice herbicides, and other pesticides, as the
situation dictates.
In most situations, the applicator will use 1 part pesticide washwater
with 4 or 5 parts of fresh water. This step reduces the pesticide waste to
less than 2.5% of normal field strength. This is an inexpensive technique
for recycling the wash water and thus insuring rapid disposal. Using very
dilute wastewater (less than 2.5% of normal field strength) will reduce the
possibility of illegal residue on and damage to crops, and it still insures
rapid disposal of the washwater.
About 80% of Louisiana's aerial applicators are based on rented land.
Most applicators are reluctant to build wastewater processing facilities on
rented land. Financing is often difficult to obtain for building a facility
of this nature on rented land.
Use of a wastewater recycling system requires very careful management.
Filtration of the wastewater to remove solid contaminants can be difficult.
This problem can be reduced by removing the wastewater from the containment
tanks as soon as possible. Also, modifying ; the aircraft to pump the
washwater from the spray system to the containment tank will greatly reduce
contamination.
Several applicators have taken steps to modify the aircraft and remove
the pesticide from the aircraft in flight. These applicators have extended
the pump intake inside the spray tank. This will reduce the volume of
pesticide remaining in the aircraft by approximately 40%. A few applicators
have added remotely operated valves to the outer end of each spray boom.
This allows removal of pesticide residue from;inside the spray system in
flight. In most cases, less than half a gallon of pesticide will remain in
the aircraft. The applicator then uses a fresh water wash tank on board the
aircraft to wash the remaining residue from inside the spray system while in
flight. This system works extremely well for aerial applicators who change
pesticides several times per day; it also works well for applicators who use
several air strips during the course of a normal :day.
Louisiana aerial applicators feel that they can comply with existing
regulations and still apply pesticides in an economical manner. However,
they are very concerned about the possibility of having to contain the
washwater from the exterior of the aircraft. Containing exterior washwater
will increase the amount of contaminant that must be removed. If exterior
washwater is contained, it will not be feasible to modify the aircraft for
cleaning in flight.
-13- :
-------
ULTRAVIOLET-OZONATION IN PESTICIDE WASTEWATER DISPOSAL: STATE-OF-THE-ART,
TECHNOLOGY TRANSFER, AND RESEARCH NEEDS6 ;
The use of large-scale ultraviolet-ozonation(UV-03) , units holds
promise for on-the-farm treatment of pesticide wastewaters. : Its greatest
potential will be in combination with microbial metabolism, either as a pre-
or post-treatment step, with indigenous or engineered organisms. The major
advantages are onsite destruction, mobility, low cost, ease of operation,
and versatility in oxidizing a potentially large number of organic
pesticides.
I
The state-of-the-art capabilities of UV-Oa for pesticide disposal have
been reported only in a few studies to date. One onsite demonstration with
a 66 lamp UV unit successfully degraded formulated Atrazine (4480 ppm) and
2,4-D (1086 ppm). Paraquat (1500 ppm) destruction required the addition of
acetone to accelerate the process. None of the degraded products isolated
and identified to date are halogenated.
I
The emerging technology of genetic engineering for selected degradative
strains in combination with UV-03 offers a number of new opportunities for
destroying pesticide wastes in situations where either process alone may be
only partially successful. A recent example is a two-step pretreatment of
the insecticide Coumaphos [0,0-diethy 0-(3-chloro-4-methyl-2-oxo-2H-benzo-
pyran-7-yl)phosphorothioate], taken directly from .an animal dip vat opera-
tion. Because of the turbidity and extraneous organic material present in
these solutions, the rates of UV-03 were too slow to be effective as a
disposal option. A Flavobacterium sp. rapidly hydrolyzed the phosphoro-
thioate linkage to yield chlorferon (3-chloro-4-methyl-7-hydroxycoumariri)
and diethylthiophosphoric acid. The reaction is catalyzed, by an enzyme
known as phosphotriesterase. The microorganism could not cleave the ring
product. UV-03 of tnis solution rapidly fragmented the ring and killed
the microorganism. This latter effect has important implications in
preventing the release of engineered microorganisms into the environment.
The DNA fragment encoding phosphotriesterase has been isolated and
characterized. The phosphotriesterase has a broad substrate specificity for
other organophosphorus insecticides; therefore, experience with Coumaphos
can be readily transferred to other waste situations. An Acromobacter sp.
that rapidly hydrolyzes several methyl carbamate insecticides has recently
been reported from our group. This microbe could be used in the two-step
pretreatment process to include an even larger group of insecticides.
i
A number of research needs must be met over the next 3 to 5 years before
the process can be fully implemented. A reasonably priced UV-03 unit must
be developed to make this an economical process. One estimate is that a
production line unit could be manufactured for less than $20,000. The
mobility of the unit makes cost-sharing between a large number of potential
users over several years an attractive economic consideration. Second, the
rates and products for each of the major pesticides or pesticide classes
must be determined. Currently, this information is being developed for the
20 leading pesticides that comprise more than 90% of the U.S. market.
Finally, the process(es) must be optimized for time and cost per gallon
processed.
Kearney, U.S. Dept. of Agriculture, Beltsville, MD 20705.
i
-14-
-------
DESCRIPTION OF A SMALL, AUTOMATED, FLUIDIZED-BED COMBUSTOR SYSTEM AND ITS
POTENTIAL FOR THE INCINERATION OF PESTICIDE WASTE and WASTEWATER7
Incineration is a viable method for the disposal of pesticides if it is
properly carried out. In general, this means controlling the amount of
oxygen for combustion, the temperature level, and the time of exposure. Two
incineration guidelines that have been developed to date are:
1) A dwell time of 2 sec at 1200°C with 3% oxygen, or
2) A dwell time of 1.5 sec at 1600°C with 2% oxygen.
These guildeines have been developed for incineration systems using two
separate burner sections: a rotary kiln and a secondary burner system.
Recent work using fluidized-bed technology suggests that complete
destruction can be achieved at much lower temperatures.
In 1981, the Ohio Agricultural Research and Development Center (OARDC)
began construction of a small, efficient (22 kW/hr) fluidized-bed combustor
(FBC) using corncobs as a fuel source (Keener, H.M., J.E. Henry and R.J.
Anderson, 1982. Corncob burner prototype developed and tested. Ohio Report
67(4):71July-August. OARDC, Wooster, OH). The burner is made up of a
6-in. diameter stainless steel pipe as the combustion chamber and a unique
fluidized-bed-to-air heat exchanger system. The burner produces a clean,
high-temperature output (800°C) air stream for process and space heating
purposes, and possibly for generation of electricity.
In the fall of 1982, an automatic control system was added to the unit
to complete the developmental phase. Results of the 1982 tests showed that
the OARDC-FBC burns corncobs cleanly, delivers clean, heated air
efficiently, and requires minimal maintenance over long periods of time when
properly operated (Keener, H.M., J.E. Henry and R.J. Anderson. 1983.
Controllable fluidized-bed direct combustor produces clean high temperature
air. Presented at Montana State University, Bozeman, MT, June. ASAE Paper
No. 83-3037, American Society of Agricultural Engineers, St. Joseph, MI).
Success has been demonstrated in burning other fuels. Coal burns
especially well in this FBC, though no attempts have yet been made to deal
systematically with coal-burning pollution problems. A second prototype of
44 kW thermal capacity is now under construction.
Adoption of this system to the incineration of aqueous pesticide waste
appears quite feasible. Figure 2 is a schematic showing one possible
arrangement for such a unit fired with corncobs. With this system, some
heat recovery is desirable to minimize fuel usage. By burning 9.1 kg/hr of
corncobs (5 % moisture, wet basis) it is estimated that up to 50 !
-------
wastewater could be incinerated (5.5 kg water/kg of fuel); Without heat
recovery, only 16 kg/hr could be handled. Operating 24 hr a day, 312 days a
year, this small portable system could possibly handle 375,000 kg (100,000
gal) of aqueous pesticide waste per year. '
However, questions that need to be answered before such a system is
viable are (1) which pesticide materials can be successfully destroyed at
800° to 900°C, (2) how long a residence time is needed in this FBC if
material goes into the burner section as a vapor, (3) what excess oxygen
levels are required, (4) what fuel additives are needed to control corrosion
and/or emissions, and finally, if viable, (5) what are the economic factors
for fixed and operating costs.
Figure 2. Schematic of OARDC burner system coupled to an evaporator for the
incineration of aqueous waste. I
-16-
-------
REMOVAL OF PESTICIDE WASTES BY MEANS OF SOLAR PHOTODECOMPOSITION8
A proposed new approach to the treatment and removal of pesticide wastes
involves solar photodecomposition of the organic pollutants. In this
scheme, photocatalytic semiconductor powders and colloids are suspended in
contaminated wastewater; under solar irradiation, the photocatalytic
semiconductor particles drive photoredox reactions on the particle surface.
These redox reactions convert organic compounds to CO? and
The approach is based on the fact that semiconductor particles can
absorb sunlight to produce electron-hole pairs that separate, move to the
surface, and promote oxidation-reduction reactions. This process will occur
either because of built-in electric fields at the semiconductor-liquid
interface (space charge layers), preferential trapping or reaction of the
electron or holes, or because the particle is small enough to permit carrier
diffusion to the surface with subsequent charge transfer to solution before
bulk electron-hole recommendation occurs. For some reactions involving slow
intermediate steps, the process can be greatly enhanced by depositing
catalytic metals on the semiconductor surface.
Initial experiments were performed at the Solar Energy Research
Institute using undoped TiOg (anatase) powders (0.4 g/L) suspended in
aqueous solutions containing model toxic compounds (chlorotoluene and
phenol). Under illumination with simulated sunlight, nearly complete
removal of 78 ppm phenol and 53 ppm chlorotoluene was achieved within about
4 hr. Additional results of other researchers are presented on removal of
4-chlorophenol, chloroethylene, cyanide, toluene, and PCB's. Problems and
future research areas required for practice implementation of the
photoelectrochernical solar approach are discussed.
DISPOSAL OF DILUTE PESTICIDE WASTES BY EVAPORATION AND BIODEGRADATION USING
CONCRETE PIT* SYSTEMS9
All agricultural spray operations generate variable quantities of dilute
pesticide wastes as surpluses in spray tanks, rinsates from spray equipment
and containers, and from outdated or leftover materials. Well planned and
managed operations minimize the quantity to be disposed of and the
possibility of environmental pollution.
Pesticide applicators should (1) mix only the volume of material needed
for the spray operation, (2) apply the mixture to the area for which it was
approved, (3) use rinsates from containers where possible and where approved
for further spray operations, and (4) triple rinse and properly dispose of
all containers.
A.J. Nozik and J.Cooper, Solar Energy Research Institute, Golden,CO 80401.
9Char;les V. Hall, Iowa State University, Ames, lA 50011-
*The term pit used in this abstract meets the technical definition of a tank
as described by RCRA.
/
-17-
-------
For the past 15 years, a pesticide disposal system that involves
containment, evaporation, and biodegration has been used successfully and
safely at the Iowa State University Horticulture Station near Ames.
Residual wastes from more than 50 pesticides have been deposited in the
evaporation pit, with an average of approximately 6000 gal being evaporated
annually. The evaporation pit is a reinforced concrete structure 12 x 30 x
4-ft deep, filled with 1-ft layers of gravel (3/4 x 1 1/2-in.) and a field
soil with 3% organic matter (gravel-soil-gravel). The pit has a tile system
underneath for sampling and monitoring leakage, and it has an automated
movable cover to exclude rainfall.
The pit is connected with the pesticide building, which is used for
storage of chemicals and spraying equipment. All washwater from the mixing
operations is pumped from a sump into the evaporation pit. |
i ;=.
The safety and success of this system was confirmed by a 3-year study
sponsored by the U.S. Environmental Protection Agency from 1976-78, results
of which were published by the National Technical Information Service in
1981 (P.B. 81-797-584). This report shows that no leakage had occurred,
aerobic soil bacterial activity was about normal, and the capacity for
evaporation exceeded that required for the operation. Also, pesticide
degradation by biological activity and chemical action prevented the buildup
of any hazardous problems.
In 1983, a small model with
Horticulture Station. This model
hinged fiberglass cover. Both
Chemical Society Symposium Series
the same components was installed at the
is 4-ft in diameter, 4-ft deep, and has a
systems are described in the American
259, 1984. I
i
The Iowa State University system has served as a model for farmers,
chemical companies, other research stations, and commercial applicators.
The following modifications from the original system are recommended:
1
2.
Include a 30-mil-plus,
concrete pit.
nonphotodegradable membrane liner inside the
3.
4.
5.
Install a rigid, raised, hinged cover with (1) sufficient air
circulation space to maximize evaporation, and (2) adequate
overhang to prevent rainfall from entering. Also, a wire enclosure
should be installed on the support posts to preyent children,
animals, and debris from entering. !
i
Provide a collector for dumping into the pit.
Provide a sampling system underneath the pit i for leakage
detection. In areas where there is danger of flooding, the pit
should, be erected above ground level and sufficiently bermed to
prevent the danger of rupturing by freezing.
Provide a recirculation spray system to enhance evaporation in more
humid areas.
-18-
-------
6. Provide an enclosed equipment wash rack with drain connected from a
sump into the pit.
The design criteria may differ for various geographic areas, but in all
cases, it should be practical for use.
One area that should be vital to future recommendations and the basis
for disposal regulations is a study of the effectiveness of systems
currently in use. Such a study should result in a manual of acceptable
methods and instructions for use.
DISPOSAL OF AQUEOUS PESTICIDE WASTES AT UNIVERSITY OF CALIFORNIA
AGRICULTURAL FIELD STATIONS10
The University of California Agricultural Field Stations have been
disposing of pesticide wastes in lined evaporation beds for many years. The
sources of the wastes have been primarily rinsates from pesticide containers
and application equipment. All of the beds located throughout the state
have the same basic design in that the rinsates are supplied to the bed from
underneath the soil surface through PVC leach lines located at the bottom.
The leach lines are covered over with a couple of inches of rock followed by
up to 24 in. of soil. Starting in 1980, the beds were sampled and analyzed
for pesticide content, and those beds that were considered heavy users were
sampled at least annually. Soil core samples were taken from quadrants
inside the bed at depths of 0 to 1, 1 to 6 and 6 to 12 in. Air samples were
also taken along the edge of the bed starting in 1981. Results from these
investigations showed that the beds do not generally build up high levels of
pesticides and that the levels found in the air were quite low. Pesticide
concentrations were generally much higher at the 0 to 1 in. sampling, which
means that the pesticides rise to the surface by mass transport. This
discovery has initiated some studies for determining some simple but
effective degradation practices to incorporate into the beds .for enhancing
degradation of the pesticides. Recent laboratory studies regarding the
effects of various soil factors and amendments on the degradation of
pesticide mixtures in waste disposal systems has shown that of all the
variables studied, pesticide concentration was the single most important
factor in determining degradation rate. This result may be attributed to at
least three processes-- that is, (1) limitation in the availability of
active sites involving soil surface catalyzed reactions, (2) low water
solubility of the pesticides studied (thereby making them rate-limiting),
and (3) inhibition of microorganisms in large pesticide concentrations
(thereby reducing microbial degradation). The other factors examined in
combination with each other were pH, organic matter amendment, soil .type,
soil moisture, and soil sterilization..
10Wray Winterlin, University of California, Davis, CA 95616.
-19-
-------
As a result of these studies and recent California.legislation, a type
of evaporation bed has been proposed that contains and degrades pesticide
rinsates without threatening the environment. The system involves an
above-ground, double-lined evaporation bed located on top of an impervious
liner covered with an inert material such as sand or rock and surrounded by
a berm. Visible monitoring for leakage or damage between the liners is part
of the design,, and the components of the bed are essentially above ground,
including the wash pad where the materials are originally.deposited. The
design also contains a storage and supply tank where the rinsates are
initially desposited and where they can be pretreated before being
transferred into the bed. The proposed bed contains soil and amendments
similar to that found in our present system.
ONSITE PESTICIDE DISPOSAL AT CHEMICAL CONTROL CENTERS11 ,
In cooperation with the U. S. Department of Agriculture Soil
Conservation Service (USDA-SCS), chemical control centers have been
installed on many small fruit farms in the 20:- to 300-acre range. These
facilities consist of a water source, catch basin, leach Tines, and
pesticide storage; they help minimize danger to the worker and damage to the
environment in the mixing and filling stages; of pesticide spraying
operations. In this study, surface water and deep soil i samples were
analyzed to detect any migration or runoff of waste pesticides from typical
chemical control centers. Both a 1-, and a 5-year-old facility were
monitored for 13 months with no evidence of leaching>into surrounding water
sources or into soil within 18 in. of the leach lines. Entomological
evaluation of soil biota and monitoring of dermal exposure to pesticides of
mixer-applicators took place throughout the 1980 season. No adverse effects
were detected.as a result of the chemical control centers.
These centers are currently operational. Though financial assistance is
no longer being made available for installations on individual farms, the
USDA-SCS is providing information to farmers wishing to construct them.
They are a practical, economical alternative to pond or streamside pesticide
handling, and they have had good user, acceptance. More thorough evaluations
of chemical migration should be undertaken if this method is to be
considered for widespread usage. . ; ; '.
11Terry D. Spittler, Cornell University, Geneva, NY 14456.
-20-
-------
BIOLOGICAL AND CHEMICAL DISPOSAL OF WASTE PESTICIDE SOLUTIONS1?
Pesticide applicators and dealers are faced with a waste disposal
problem that may vary according to the size and -type of operation.
Wastewater from vehicle washing, spray or nurse tank rinsewater, haulback
solutions, facility runoff, spilled materials, obsolete or unidentifiable
chemicals, containers, and incompatible mixtures are all recognized sources
of waste pesticide solutions.
Various methods of treatment and disposal of waste pesticide solutions
have been proposed and evaluated. Such methods include land disposal (land
cultivation, soil mounds and pits), evaporation .basins and lagoons, chemical
treatment, physical treatment (adsorption and reverse osmosis), biological
treatment (trickling filters and activated sludge), and incineration. In a
report to the U.S. Environmental Protection Agency the SCS Engineers stated
that soil mounds could be the most readily implementable disposal method for
dilute pesticide solutions.
The objective of this study is a continued assessment of a biological
and chemical treatment system for wastes and spilled pesticide solutions.
Specifically, the study assesses the reliability of an acid and alkaline
trickling filter system that can economically treat and dispose of pesticide
wastewater. The population of pesticide-decomposing microorganisms has been
monitored over time and correlated with pesticide activity (bioassays). The
collected information provides preliminary data for a long-term goal: To
develop a relatively inexpensive, reliable, and convenient disposal system
for waste pesticide solutions that is suitable for use by the chemical
applicator or dealer.
DISPOSAL OF DILUTE AND CONCENTRATED AGRICULTURAL PESTICIDE FORMULATIONS
USING ORGANIC MATRIX ABSORPTION AND MICROBIAL DEGRADATION13
Studies are proposed to provide information on disposing of dilute or
concentrated pesticide solutions. These studies will include laboratory and
field studies. If these prove successful, on-the-farm demonstrations of
this process will be provided and offered as a means for disposing of
pesticides asssociated with U.S. Agriculture. The disposal process will
involve absorption .of selected pesticides onto an organic matrix
(concentration and containment phase) followed by degradation using
microorganisms in a nutrient-enriched composting environment
(degradation/product neutralization phase). Preliminary work done in our
laboratory has shown that under appropriate conditions, absorption of
pesticide solutions (Diazinon) onto selected organic media can be quite
significant. For example, the Diazinon level in a 200-ml solution
containing 10,000 mg/kg was reduced to 55 mg/kg when exposed to (mixed with
or filtered through) 5 g of peat moss for only 24 hr. The Diazinon
12B. Klubek, C. Schmidt and J. Tweedy, Southern Illinois University,
Carbondale, IL 62901.
13Donald E. Mullins, Roderick W. Young and Glen H. Hetzel, Virginia
Polytechnic Institute and State University, Blacksburg, VA 24061.
-21-
-------
was concentrated onto the peat moss by a factor of 19 (10,000 tng/kg in the
initial solution concentration, resulting in a level of 190,000 mg/kg peat
moss). Other forms of organic media, including activated carbon, could
possibly be used in the concentration and containment phase.
We have demonstrated both in laboratory studies (using radio-labeled
Diazinon) and in field studies that Diazinon can be degraded quite rapidly
in a nutrient-enriched microbial system (composting environment). For
example, in field studies, it was found that when Diazinon was applied at
moss), this level was reduced,to 61 mg/kg in
mg/kg in 18 weeks. Based on the results of
studies, more extensive experimentation is
high levels (32,000 mg/kg peat
8 weeks and subsequently to 7
these experiments and other
warranted with other pesticides.
If adequate funding is made available to support further work on this
process, it is quite possible that delivery of a safe, simple, inexpensive,
and effective system for dealing with specific pesticides could be made to
the agricultural industry within 3 to 5 years. This would obviously require
a coordinated effort between research (laboratory/field), extension
(demonstration), and regulation agencies.
TOXIC SUBSTANCE SOLVENT EVAPORATOR^14
j
This paper presents the concept of the toxic substance solvent
evaporator (TSSE). The state-of-the-art capability, emerging technology
and/or technology transfer opportunities, and further research needs are
discussed. The TSSE is an off-shoot of the biological incinerator that was
developed to first biodegrade organic contaminants using thermophilic
bacteria in an aerated, closed container and concurrently evaporate the
water by saturating the air, which is discharged through a stack. By
wicking the pesticide waste material onto a large surface area, evaporation
is greatly accelerated. Since the solid component of these pesticide wastes
is less than 0.1%, evaporation creates a major volume reduction. In fact,
the very dilute nature of the pesticide waste residues being considered
reduced the necessity for also biodegrading the waste in some cases.
A pilot unit has been operated in New Orleans and provided data from
which to make evaporation rate predictions. Because of the simplicity of
the concept, a do-it-yourself Kit can be supplied to the applicators to keep
the costs of the evaporator very low. Methods exist for accelerating the
evaporation rate through mechanical means, but the basic system derives its
energy from the sun and is operable over most of the United States during
the growing season. ;
14Robert W. Claunch, New Orleans, LA 70114.
-22-
-------
Various configurations of the evaporation/biological metabolism
combinations are available as a function of waste volume, strength, and
composition. The wick provides a large surface area for immobilizing
microorganisms, and it provides a combination of anaerobic and aerobic
metabolism when used in conjunction with a closed container.
The TSSE is aimed primarily at helping the small hazardous waste
generator, and it applies to all chemical waste streams containing dilute
quantities of a toxic material. However, this technology could have
applications in almost any liquid waste treatment scenario, including the
enhancement of biological processes. The simplicity of the concept and the
hardware makes the TSSE a candidate for use in third world countries.
Further research is required to determine the resulting biological
metabolites or the physical and chemical properties of the residues left on
the wick. Also, the physical integrity of the system and the choice of
materials need further development.
MICROBIAL DEGRADATION OF PESTICIDES15 :
Microbial degradation of pesticides may be classified into several
categories. By far the most important class of microbial metabolism is
incidental metabolism, where pesticide degradation is coincidental to basic
carbon and energy utilization of the microorganisms. In such cases,
microbes grow freely without pesticides. Two radically different subclasses
exist within this class of metabolism. They are wide-spectrum and analog
metabolism. The former reactions are usually carried out by enzymes that
have a wide enough substrate spectrum to degrade pesticides. A good example
is the case involving hydrolases. Malathion degradation at carboxylester
bonds by varieties of Trichoderma viride clearly depends on the nonspecific
hydrolases this species produces.
By contrast,, analog metabolism involves enzymes that are rather
specific, requiring normal induction (acclimatization) through the use of
specific carbon sources. For instance, it is possible to select out some
PCB-degrading microorganisms by an enrichment approach with biphenyl or
monochlorobiphenyl as sole carbon sources. These microorganisms acquire
specific enzyme systems to degrade biphenyl-type chemicals (e.g.,
dioxygenase), which in some cases happen to metabolize chlorinated analogs
as substrates. Wide-spectrum and analog metabolism may be distinguised on
several accounts. First, wide-spectrum metabolism may be directly
correlated with indicators for general microbial activities such as biomass,
ATP production, etc., whereas analog metabolism is not. Second, the
addition of general nutrients such as glucose, mannitol, etc. increases the
wide spectrum but decimates the analog activities.
io Matsumura, Michigan State University, East Lansing, MI48824.
-23-
-------
The second major class of pesticide metabolism is catabolism, a process
in which microorganisms derive energy by metabolizing pesticides. In many
instances, the second and third addition of a pesticide in the same locality
have been reputed to increase rm'crobial degradation of a pesticide. Note
that such activities should include cases in which microorganisms use only
part of a pesticide molecule as long as they derive energy lay doing so.
Metabolic use of mexacarbate is a good example. Catabolism differs from
incidental metabolism in that it requires high levels of pesticides in a
given locality to sustain the microbial activities. In incidental
metabolism, the pesticide levels are not vital and are usually very low,
since pesticides are not the normal substrates to those enzymes.
The third major class of metabolic activities is resistance metabolism.
In such cases, microorganisms actually spend energy to detoxify pesticides
for their own survival. By definition, such pesticides must be toxic to the
metabolizing microorganisms (e.g., antibiotics, fungicides, etc.).
PHANEROCHAETE CHRYSOSPORIUM: ITS POTENTIAL USE IN THE BIOLOGICAL
DEGRADATION AND DISPOSAL Oh AGRICULTURAL CHEMICAL WASTES lb
I
Phanerochaete chrysosporium, an example of a white rot fungus, is able
to degrade a broad spectrum of structurally diverse organopollutants.
Pesticides of interest that are degraded by P. chrysosporium include DDT,
DDE (a DDT metabolite), Dicofol, Lindane and Toxaphene. Evidence suggests
that this ability is due to the lignin-degrading system of this
microorganism. Studies using DDT as a model compound have shown that both
lignin and DDT degradation (as measured by 14C02 evolution) were
promoted by nutrient nitrogen starvation, whereas degradation was suppressed
in nutrient-nitrogen-sufficient cultures. Similarly, the temporal onset and
disappearance of Co2 from 14C_DDT and i4c_iignin appeared to
coincide. Waste treatment systems inoculated with £_. chrysosporium may
prove to be a useful and economical process for the small-scale disposal of
agricultural wastes. For example, aerobic composting or the use of rotating
biological contactors are two waste treatment processes that may oe
economical, easy to operate, and otherwise suitable for onsite use.
Although biological treatment is a potentially attractive method for
chemical waste disposal, there are a number of research areas that must be
explored for this process to be applied in pesticide disposal systems, borne
of these research areas are as follows: 1) Studies must demonstrate what
conditions are most favorable for growth of the introduced microorganisms
and what conditions favor biodegradation. For example, P. chrysosporium
requires nutrient nitrogen starvation and acidic pH for growth and
biodegradation. 2) Conditions that discourage competition by undesired
microorganisms may have to be examined.
n A. Bumpus and Steven D. Aust, Michigan State University,
East Lansing, MI 48824-1319.
-24-
-------
3) The relative toxicity of pesticides for pesticide-degrading
microorganisms must be determined. 4) The rates of certain pesticides
undergoing degradation must also be studied with the objective of enhancing
these rates. 5) Other lignin-degrading fungi should be studied to determine
their relative suitability for use in such systems.
-25-
-------
SECTION 4
WORK GROUP RESULTS
INTRODUCTION : . ,; '
Work groups A (Physical/Chemical Treatment _&_RecyQling) -ancl'" B
(Biological Treatment &= Land Application) were each:-su&-cl1yided into "six
sub-work groups. Appendices F and "6 provide the titles and membership of
these sub-work groups.
Each work group was asked to review and assess !its respective
technology(s) in a consistent manner. To~facilitate this, a form (Sub-Work
Group Summary Sheet, Appendix H) was ^developed and used by each sub-work
group to report its findings and this provided the basis for (the information
reported in this Section.
i
Among other things each technology(s)-was placed in one of the following
three categories: ' i
i
1. Technology 15 currently being utilized on a commercial basis to
treat and dispose of dilute pesticide wastewater. (i.e., proven
technology).
2. Technology is being utilized commercially to treat other types of
waste and offers promising opportunities for pesticide wastewater.
(i.e. technology transfer opportunities). ~[
3. Technology is not being utilized commercial but experimental data
indicates it is a promising candidate technology, for pesticide
wastewater, (i.e., emerging technology). I
i
Table I summarizes the results of this categorization for both work
groups.
WORK GROUP A, PHYSICAL/CHEMICAL TREATMENT AND RECYCLING
Pesticide Rinsewater Recycling -------
Pesticide rinsewater recycling systems are various wastewater volume
reduction techniques used in combination with a containment facility for
collecting rinsewater, incidental spillage and leftover spray; solution which
are subsequently recycled into new spray rni.xtures. , .-... !- "-'----.--
-26-
-------
TABLE 1. CATEGORIZATION OF TECHNOLOGIES
CATEGORY
Technology
Physical/Chemical
Treatment & Recycling
1. Pesticide Rinsewater
Recycling
2. Granular Carbon
Adsorption
3. UV-Ozonation
4. Small-scale
Biological Treatment
& Land Application
1. Evaporation, Photo-
degradation & Bio-
degradation in
Containment Devices
2. Genetically Engineered
Products
3. Leach Fields .
4. Acid & Alkaline
Trickling Filter Systems
5. Organic Matrix Adsorption
& Microbial Degradation
6. Evaporation & Biological
Treatment with Wicks
Proven
Technology
X
X
Technology
Transfer,
Emerging
Technology
5.
6.
Incineration
Solar Photo-
Decomposition
Chemical Degradation
X
X
X
X
X
X
-27-
-------
Current Applications
This technique is practiced to various extents by both ground and aerial
commercial applicators. During 1984 a broader utilization of this approach
was evaluated in Illinois and about 60% of Louisiana's aerial applicators have
built wastewater recycling facilities. While some
recycling procedures, there may be potential conflicts
illegal tank mixing and 2.) application of chemicals to
states have approved
with FIFRA such as I.)
non-targeted areas.
Advantages, Disadvantages and Key Points --
The advantages of recycling are that it is economical, technically
uncomplicated, provides total containment, may be adapted to specific site
situations and minimizes the amount of wastewater that must be treated and
disposed.
The disadvantages are that it may result in phytotoxic problems, illegal
residues and yield suppression ;if segregation of chemicals is not practiced.
It may not be feasible where a large number of chemicals are used on a variety
of crops.
The key point of this .technique is that it eliminates adverse
environmental consequences resulting from site runoff; minimizes quantity of
waste that must be disposed; is compatible with loading, mixing and washing
operations and requires less specialized monitoring and treatment skills than
other treatment options.
Status and Cost
This technique is currently available. Its capacity is based on the scope
of the operation. Capital cost range from $5,000 to $10,000 and operating
cost are minimal.
Research Needs
1. Determine the acceptable concentration of chemicals in rinse
solutions that can be recycled without causing phytotoxicity, crop
residues or yield suppression.
2.
3.
4.
Design volume reduction systems to minimize quantities of rinsewater,
i.e., injection systems and flush systems.
Define criteria for system utilization, including the identification
of concentrations of pesticides acceptable for reuse.
Develop a "quick test" to analyze rinse solutions on-site.
5. Develop engineering design specifications. '
6. Develop user education and training materials and programs.
-28-
-------
Granular Carbon Adsorption
Wastewater contaminated with pesticides is passed through a bed of
granular carbon, and the pesticides are removed through adsorption onto the
carbon. Some pretreatment is usually required to1 remove suspended solids and
break oil-water emulsions.
Current Applications --
This technology ha's been used to remove organics from a variety of
wastewaters. Of particular interest, the Army is;employing a system based on
the recirculation of pesticide - contaminated wastewater through a bed of
granular activated carbon to treat wastewater generated by the residential
pest-control facility at Fort Eustis, VA. i
In addition, two systems (located at one ground based and one aerial
applicator's site) have recently been installed in California for evaluation.
The state of California waived the permitting of this treatment facility under
RCRA to allow this experimental system to go forward. The U.S. EPA concurred
with this action. :
Advantages, Disadvantages and Key Points
This is a proven technology for treating other types of wastewater and
when properly designed it is almost foolproof. Other advantages include the
possibility for system mobility and this technology is accepted, convenient
and uncomplicated.
The presence of solids and emulisifiers may cause operating problems if
not properly handled in the pretreatment step. In addition, pesticides that
are not adsorbable must be removed by some other process.
Status and Cost
This technology is available and its capacity is unlimited. Capital cost
range from $100 to $400 per gallon per minute and operating cost are
approximately two dollars per pound/of carbon used which includes the cost of
disposing of the spent carbon as a hazardous waste..
Research Needs
1. Evaluate biodegradation on the carbon filter alone or with other
materials.
2. Evaluate powdered carbon.
3. Prepare isotherms for the most commonly used pesticides as formulated.
4. Evaluate biological treatment (composting) of the spent carbon.
-29-
-------
UV-Ozonation . '_'.']
Pesticide "laden wastewater is subjected to ultraviolet (UV) light and
ozone. This alters the pesticide molecule to make it more polar, less toxic
and more biodegradable. Normally, this technology should be utilized in
combination with microbial metabolism, either as a pre- or post- treatment
step. i
Current Applications
It is currently being used for water purification on a commercial basis in
Europe to remove toxic pollutants. Experimental studies , have reported
successful degradation of formulated Atrazine (4480 ppm) and 2,4-D (1068
ppm). The possibility of combining UV-ozonation and engineered organisms
holds promise.
No known permits have been issued for this technology to treat pesticide
wastewater.
Advantages, Disadvantages & Key Points --
The advantages of this technology include the fact that it destroys the
pesticides (i.e., as opposed to concentrating them) and can treat all organic
pesticides as formulations. In addition, it can be mobile (i.e., many users)
and is easy to handle. , * .
i .
However, degradation products are not known and there has been limited
testing for this application.
Key questions , that must be answered from both the user and regulator
viewpoint include: 1.) what percent conversions will be required, 2.) what
residue levels will be permitted in the soil and 3.) what follow-up research
will be required.
Status and Cost
This technology is in the experimental stage for pesticide wastewater
treatment. Capacity ranges from .3 to 20 gallons per hour;. Capital and
operating costs are approximately $20,000-and 7g!/hr., respectively.
Research Needs
1. Development of a monitoring system on the unit to determine product
conversion. i
i
2. The identification of degradation products.
3. Evaluate the economics and co-treatment opportunities.
-30-
-------
Small-scale Incineration
When exposed to adequate temperatures for a minimum period of time and
with the appropriate amount of oxygen, the pesticide molecule is destroyed.
Current Application -- .
Approximately 250 incinerators are in operation in the U.S. that are
currently being used to destroy a variety of organic wastes. However, these
incinerators are typically very expensive (capital cost is approximately
$35,000,000) and very, very large compared to the volumes of waste being
considered.
Experimental work has been conducted with a small-scale, -fludized,-bed
combustor utilizing corncobs as a fuel. The potential exists to modify this
system for the disposal of dilute pesticide waste either with a mobile system
or on a regional basis.
Permits and test burns would be required for each site, although a class
permit might be a possibility. This requirement would represent a significant
effort and a special problem for these small-scale systems.
Advantages, Disadvantages and Key Points
The advantages of this approach include the system can be mobile, it
destroys the pesticide and other on-the-farm. waste (i.e., corncobs) could
provide the fuel source.
However, the heavy metals in some pesticide presents a special problem.
The cost of permitting, construction and operation would be relatively high
and the potential for mechanical breakdowns exists.
The key point of this technology from the user viewpoint is that it offers
the potential of acceptable disposal within a reasonable distance to the
generated waste. However, class permitting would likely be necessary for its
practical utilization.
Status and Cost
This system is in the experimental stage and could possibly be made
available in 2 to 3 years following successful research and development. The
capacity of the current test unit is 10 to 15 gal/hr. Capital cost are
estimated at $20,000 to $50,000 and operating cost are not available.
Research Needs
1. Determine the minimum dwell time and temperature.
2. Evaluate the economics of a mobile system versus a regional facility.
-31-
-------
3. Evaluate the destruction efficiency for representative pesticide
wastewater including the sampling for POHC's and PIC's.
4. Test and evaluate other small-scale designs.
5. Evaluate the impact of co-firing with other wastes.
Solar Photodecomposition
Photoactive (photocatalytic) semiconductor pesticides ranging in size from
100 K to ly, are suspended in wastewater and subjected to solar illumination.
The pesticides absorb sunlight and photo catalytically degrade organic
pesticides into C02, H20, and HC1. Air is bubbled through the water to
enhance the rate of degradation.
Current applications --
Using model compounds such as phenol and chlorinated hydrocarbons, this
technique of pesticide degradation has only been studied in a laboratory
environment with application oriented towards energy conversion
technology would be subject to RCRA if used under certain conditions
with underground ponds. There is a possibility that above ground
would not be subject to RCRA. This technology could also be,used
photoreactor to treat pesticide wastes within a very short time.
This
such as
treatment
with a solar
Advantages, Disadvantages, and Key Points --
The advantages of this technology are that it is relatively simple,
passive system with high quantum efficiency that can sensitize to visible
light using simple no toxic photocatalysts (Ti02 & Fe203),. There are no
intermediate residues as it takes the pesticide waste all the way to C02.
This technology can be used in present holding ponds and may be combined with
artificial UV sources.
The disadvantages include a lack of knowledge on the effect of dirt and
the effectiveness for insoluable pesticides. Also unknown are the
consequences of cloudy and/or rainy,days on the process of degradation.
One application is to incorporate heterogenous photo catalysts into
existing holding/evaporation ponds. From the user's viewpoint this approach
would be a relatively non-complex approach as an add-on to existing
holding/evaporation pond technology. ;
Status and Cost .
This technique is currently in the research stage but could be implemented
without a great deal of difficulty. The capitol and operating costs are
unknown however expected to be very low. If this technology is used as an
add-on to existing holding/evaporation pond, the cost may be negligible.
-32-
-------
Research Needs -
1. Conduct lifetime studies of photocatalysts.
2. Conduct laboratory studies using real pesticides.
3. Study the effects of mixed semiconductors.
4. Study the effects of artificial UV (lamps) in UV-ozonation system.
5. Study the effects of particle size with technique.
6. Develop a scale-up project for demonstration.
7. Determine pesticide degradation rates in existing systems.
8. Study the effects of turbidity in ponds using this technology.
Chemical Degradation
Several chemical means are used for degradation of pesticide wastes.
These chemical techniques are used to either detoxify or decompose the
selected waste and may also serve as a pretreatment for further pesticide
waste . Existing chemical degradation technology include: gas phase methods,
liquid phase methods, chemical fixation, and catalytic liquid phase methods.
The methods/techniques described at the workshop were UV-Photolysis, chemical
oxidation, hydrolysis and activated carbon.
Current Applications
Few applicators use this technology because of the considerable capital
expense required for those specific techniques which have been researched.
All of the chemical methods appear to be more expensive than physical
treatment or/and disposal. These methods are being used for industrial waste
clean-ups and spills. This technology may be acceptable to EPA under RCRA
permits for treatment.
Advantages, Disadvantages, and Key Points
This technology is chemically predictable with some data available on
certain pesticide wastes. Other advantages are easily monitored, technically
simple, mobile, can .rapidly degradate wastes, and relatively foolproof in
operation.
Disadvantages are that the technology is not applicable to all pesticide
wastes (particularly mixed wastes), treatabiIity .needed, and directions must
be cookbook style for the user. Reactions can be violent and chemicals and
sludges may be hazardous. This technology may not be an ultimate disposal and
products may be toxic.
-33-
-------
The user must be educated in the use and the system must be safe and user
friendly. A key viewpoint for the user and regulator is that an ultimate
disposal must be arranged.
Status and Cost
This technology is available, however, the costs are generally greater
than the small quantity pesticide user can economically | afford. Less
expensive chemical treatment technique may be developed which will be more
suitable to pesticide waste rinseates from the farm.
i
Research Needs --
1. Determine destruction specifications for each pesticide.
2. Address practices for the disposal of sludges and treated effluent.
3. Develop cost and user data at existing site demonstration.
4. Develop a user's manual for education of technique, cost estimation
and equipment information. !
5. Evaluate as a pre-treatment step.
WORK GROUP B, BIOLOGICAL TREATMENT AND LAND APPLICATION '
Evaporation, Photodegradation and Biodegradation in Containment Devices
This technology is described as the treatment of dilute pesticide
rinsewaters by evaporation, photodegradation and/or biodegradation. Treatment
is conducted in containment devices, either above ground or in-ground. The
treatment process of evaporation has the objective of reducing the liquid and
solid pesticide waste to a sludge for ultimate disposal by the conversion of
much of the waste into a vapor. In connection with or through separate
treatment, photodegradation treats the pesticide wastes by means of radiant
energy, especially light. Evaporation and photodegradation occurs on or near
the surface of the wastes, however the biodegradation can occur throughout the
treatment process as the chemical breakdown of pesticides by microorganisms,
enzymes, plants and other subcellular systems. Reactions such as oxidation,
reduction and hydrolysis result to degrade waste pesticides to the ultimate
products of carbon dioxide, water and salts.
Current Application
This technology is being used by universities and ;other research
facilities to treat wastes, but it is not widely practiced. Several reasons
for this lack of application are the unknowns such as the potential for the
treatment to further produce hazardous wastes, uncertainty of the science and
the product results and lack of understanding of the treatment process on
specific pesticides.
-34-
-------
Advantages, Disadvantages and Key Points --
The advantage to these treatment options is these technologies are passive
and should not require heavy economic investment.
A major disadvantage considering the use of various containment sites is
the potential for leakage which may require .considerable monitoring to comply
with RCRA.
Status and Cost --
The technology is readily available, but the extent of use depends on
regulatory acceptance. Capacity of the containment system depends on physical
dimensions, climatic conditions, and the pesticides involved. Capital costs
of $10,000 plus were projected with minimal operating costs. However, lower
capital cost would be required for smaller scale systems.
Research Needs
1. Develop improved structural designs and containment facilities.
2. Study the wastes characteristics during the chemical, physical and
biological processes.
3. Identify chemical degradation products.
4. Determine methods for enhancement of evaporation.
5. Study the optimization of degradations by the addition of
supplements; research of volume, surface areas, media, etc.
Genetically Engineered Products
Genetically engineered products are described as including (1) recombinant
microorganisms (living) and their products (non-living) (2) naturally
occurring organisms manipulated by man, and (3) microorganisms and plasmids
produced by any methods other than DMA recombinant techniques.
Current Applications
Most of the genetic engineering options are in various stages of
theoretical, experimental, and developmental processes.
Advantages, Disadvantages, and Key Points
This technology is not yet a practical option because of its
unavailability; however, expected advantages include flexibility., uniqueness,
and economical aspects.
The disadvantage in the case of living transformants is that their
environmental fates are not known. At this point there is too much unknown
for reproducibility and practical applicability. To be acceptable as an
option, there needs to be public education to generate confidence and better
clarification on the nature of genetically engineered products.
-35-
-------
Status and Cost
Costs and capacity are not - available yet in some cases the technology
should be economical. For non-living products and naturally occurring
organisms, availability may be 1-3 years away. For living transformants
utilization, expected availability is over 5 years away.
Research Needs j
1. Address envrionmental fates.
2. Address environmental and laboratory stability.
3. Develop methods for containment and destination of organisms.
4. Determine innovative application of genetic engineering technology.
5. Evaluate environmental hazards.
Leach Fields
This field-sited method is currently being utilized on an individual basis
to treat and dispose of dilute pesticide wastewater. Rinses and spills are
channeled into a leach field rather than collected for other treatment or
allowed to runoff into surrounding surface water. Leach lines are generally
two to four feet below grade and within the field operations.
Current Applications j
This technology is widely used .by small fruit farms in the state of Mew
York.
Advantages, Disadvantages, and Key Points
This technology is of low cost to the operator and is currently being used
as an easily maintained multipurposed method to collect and treat pesticide
wastewater. I
The obvious disadvantage of this technology is that its operation is not
isolated from the groundwater. The soil conditions, site choices, drainage,
and climate are very critical to the successful operation and the site is not
mobile.
Status and Cost .
This technology is available and can be ready for use within 1 - 2 weeks,
serving continuously depending on weather and spraying operations. The
capital cost is minimal with the operating cost being negligible.
-36-
-------
Research Needs --
1. Demonstration of safety and efficiency by monitoring existing systems.
2. Gather of existing data.
3. Evaluation of fate and transport according to various site conditions.
Acid and Alkaline Trickling Filter Systems
Pesticide wastewater is recirculated through either an acidic or alkaline
filtration medium and the pesticide is treated by a combination of chemical
and biological methods. The acidic or alkaline filtration medium facilitate
chemical hydrolysis, and microorganisms attached to the medium biodegrade the
pesticide.
Current Applications --
Trickling filters are a proven technology for treating a variety of
municipal and industrial wastewaters. However, the proposed modification to
enhance hydrolysis of pesticide is a new concept in the experimental stage.
Facilities for conducting this research have been installed on the Southern
Illinois University - Carbondale campus. Dilute and concentrated solutions of
wastewater containing triazines, dinitroanilines and methyl-carbonates have
been studied in both filtration systems with encouraging results.
Advantages, Disadvantages and Key Points
This system is projected to be relatively inexpensive and uncomplicated.
Operators could be easily trained and the system can be sized according to
need. Research to date indicates the system would effectively treat the most
commonly used herbicides and insecticides in Illinois and no further
disposition of residue is required. The system probably has a wide range of
use.
However, there has been a persistance of triazines in the alkaline systems
and the infiltration rate through the acidic medium is low. The recirculating
pumps must be constructed of non-corrodable material and products of
degradation and pump life are unknown.
The key points of this technology is the alkaline system is easy to
maintain while the acidic system is somewhat more difficult. This technology
has the potential of a wide range of use and space requirements are directly
related to the volume of wastewater generated.
Status and Cost
This is an emerging technology which could be available in 3 to 5 years
following successful research and development. Capital and operating cost are
estimated at $6,000 and 2,500/year, respectively.
-37-
-------
Research Needs
1. Identify products of degradation. \
2. Characterize and quantify emissions. ,
3. Evaluate the treatment of a broader spectrum of pesticides.
Organic Matrix Absorption and Microbial Degradation
The pesticide contaminate is absorbed onto an
concentration and containment phase) which is
nutrient-enriched composting environment (phase
neutralization).
organic matrix (phase 1,
then biodegraded in a
2, degradation/product
Current Applications '
This combination of technologies is not presently being employed.
However, the elements are being used to treat pesticide wastewater to some
extent. As discussed earlier, granular carbon adsorption is being used by the
Army and is being evaluated in the State of California. This is pertinent
since activated carbon would be a possible alternative for the organic matrix
adsorption phase.
Biodegradation is an important mechanism for treating pesticide wastewater
in containment devices which have been operated at Iowa State University and
the University of California Field Station for many years. Composting is a
proven technology for treating other types of wastes, particularly municipal
waste. :
Advantages, Disadvantages and Key Points
This system could be divided into two modules (one from each phase). The,
module for the phase 1 process could be moved from site to site with the
concentrated pesticide on the organic matrix being treated at a central
location (phase 2). In addition, it is compatible with certain other
treatment alternatives such as engineered organisms and granular carbon
adsorption (i.e., disposal of spent carbon). It is expected to.be relatively
uncomplicated and foolproof.
However, this system is in the early development stage and needs to be
evaluated and proven before it could be applied to the treatment of dilute
pesticide wastewater.
The key points of this system is it would be capable of treating a wide
range of pesticide concentrations, the required operating skills could be met
by people mormally employed by certified applicators, the cost are expected to
be relatively low and the system promises to effectively contain and destroy
the pesticide contaminant. I
-38-
-------
Status and Cost --
The system is an emerging technology which could be available in 3 to 5
years following successful research and development. Capital and operating
costs are not available.
Research Needs ' ,
1. Evaluate the bioclegradability of pesticides in a composting
environment and identify the products of degradation.
2. Compare below and above ground composting pits.
3. Evaluate candidate organic matrices.
4. Conduct bench- and pilot-scale studies with real wastewater
containing mixtures of pesticides'.
5. Perform field demonstration studies.
6. Develop field monitoring techniques.
Evaporation and Biological Treatment With Hicks
Wastewater is wicked onto a large surface area and treated by a
combination of biological degradation and evaporation.
Current Applications
Wicks are currently being used to absorb oil for oil spill control and
incineration of wicks has been tested. Wicks are not currently being used for
wastewater treatment.
Advantages, Disadvantages and Key Points
The advantages of this system include extreme simplicity (there are no
mechanical parts), very low capital and operating costs, zero discharge, ease
of operation, above ground operation (minimizes groundwater contamination
potential) and mobility.
However, further development is required to protect this system from
extreme weather and rainfall. Evaporation might have to be assisted by
mechanical means in some geographical regions and it requires a relatively
large area which might be considered unsightly by some. The wicks would have
to be replaced on some frequency and expended wicks might have to be disposed
as hazardous waste.
The key points of this approach is it is very simple to operate. There
are no effluents to monitor and no permanent structures or underground tanks
are required. The system can be designed for aerobic and/or anaerobic
degradation of the pesticide.
-39-
-------
Status and Cost '
This technology is in the experimental stage and availability will depend
upon the rate at which this research is pursued. The capacity ranges from 1
to 3 gal per day per square yard of wick material. However, this can be
increased through the use of fans and heat. Capital and operating cost are
not available. However, operating cost are expected to be; very low and the
wick material cost ranges from 1 to 2 dollars per square yard,.
Research Needs -- i
1. Determine wick life. I
.
2. Assess air emission.
' .?'>* :
3. Determine degree of biodegrad'ation achieved on the wick.
4. Evaluate disposal options for expended wicks.
5. Evaluate system performance via pilot-scale studies.j
-40-
-------
APPENDIX A
MOST COMMONLY'USED PESTICIDES IN AMERICAN AGRICULTURE
TABLE A-l. MOST COMMONLY USED INSECTICIDES IN AMERICAN AGRICULTURE
1.
2.
3.
* 4.
* 5.
6.
7.
8.
* 9.
10.
Common Name
carbaryl
carbofuran
chlorpyrifos
methyl parathion
parathion
phorate
synthetic pyrethroids
turbufos
toxaphene
malathion
Trade Name
Sevin
Furadan
Dursban
Penncap
Foil do!
Thimet '
many
counter
Alltox
Cythion
TABLE A-2. MOST COMMONLY USED HERBICIDES IN AMERICAN AGRICULTURE
1.
2.
3.
4.
5.
6.
* 7.
8.
9.
10.
Common Name
alachlor
atrazine
butyl ate
trifluralin
metolachlor
cyanazine
2,4-D
metribuzin
i propanil
bentazon
Trade Name
Lasso
AAtrex
Sutan
Tref 1 an
Dual
Bladex
many
Sencor, Lexone
Stam
Basagran
*Identified as a hazardous constituent by RCRA
-41-
-------
APPENDIX B
LIST OF ATTENDEES
1. Mr. ,Ray J.;Anderson
Assistant Director
Natural Environmental Res. Div.
American Farm Bureau Fed.
225 Touhy Avenue
Park Ridge, IL 60068
(312) 399-5783
2. Dr. Phillip Antommaria*
Executive Vice President
Canonic Engineering
1408 North Tremont Rd.
Chesterton, IN 46308
(219) 926-8651
3. Mr. Louis J. Bilello*
Environmental Science &
Engineering, Inc.
P.O. Box ESE
Gainsville, FL 32602
(904) 322-3318
4. Mr. Calvin Blystra
World Wide Waste Treatment, Inc,
3278 Colby Rd.
Whitehall, MI 49461
(516) 894-2645
5. Mr. James S. Bridges
U.S. EPA, AWBERC
26 W. St. Clair Street
Cincinnati, OH 45268
(513) 684-7502
6. Mr. Mark Bruce
University of Cincinnati
Chemistry Department
Cincinnati, OH 45221
(513) 475-4481
7. Dr. John A. Bumpus*
Department of Biochemistry
Michigan State University
East Lansing, MI 48824
(517) 353-0807
8. Mr. Hyung-Yu'l Cho
Research Associate
University of Illinois
1102 S. Goodwin Ave.
Urbana, IL 61801
(217) 333-0596
9. Mr. Robert w|. Claunch*
2920 Westchester
New Orleans,: LA 70114
(504) 394-2620
10. Mr. Daniel R. Coleman
Head, Biotechnology Div.
Southern Research Institute
2000 9th Avenue, South
Birmingham, AL 35255
(205) 323-6592
11. Mr. Harold M. Collins
Executive Director
National Agricultural
Aviation Association
115 D. Street, S.E., Suite 103
. . Washington, D.C. 20003
(202) 546-5722
12. Mr. Clyde R, Dempsey
Chief, Chemicals & Chemical
Products Branch, WERL,EPA
26 West St. Clair Street
Cincinnati, OH 45268
(513) 684-7502
13. Dr. William|H. Dennis, Jr.
Consultant
P.O. Box 51
Braddock Heights, MD 21714
(202) 351-5695
14. Mr. Roy R. Detweiler
Consultant to DuPont Company
Chadds Ford,Enterprises, Inc.
Box 3K
Chadds Ford; PA 19317
(215) 388-1234
* Presenter
-42-
-------
15. Mr. Kenneth A. Dostal
Chemical & Chemical Products Branch
Industrial Wastes & Toxics Technology
Division, WERL, EPA
26 W. St. Clair Street
Cincinnati., OH 45268
(513) 684-7502
16. Dr. Charles Earhardt
Vice-President of Manufacturing
Services
United Agricultural Products
P.O. Box 1286
Greeley, Colorado 80632
(303) 355-4400
17. Mr. Orlo R. Ehart
Chief, Pesticide Use & Control
Wisconsin Dept. of Agric. Trade
£ Consumer Protection
801 W. Badger Road
P.O. Box 8911
Madison, WI 53708
(608) 266-7135
18. Mr. Tom Ewing
Publisher-Editor
Cincinnati Environment
P.O. Box 19356
Cincinnati, OH 45219
(513) 271-1178
19. Mr. Larry Fradkin
Environmental Scientist
U.S. EPA, ECAO
26 W. St. Clair Street
Cincinnati, OH 45268
(513) 684-7531
22. Dr. Richard 0. Hegg
Dept. of Agricultural
Clemson University
Clemson, S.C. 29631
(803) 656-3251
Eng,
20. Mr. Thomas J. Gilding
Director of Environmental
National Agricultural
Chemicals Assoc.
1155 15th Street, N.W.
Suite 900
Washington, D.C. 20005
(202) 296-1585
21. Dr. Charles V. Hall*
Dept. of Horticulture
Iowa State University
Ames, IA 50011
(515) 294-2751
Aff.
23. Dr. Glenn H. Hetzel
205 Seitz Hall
Agricultural Engineering Dept.
Virginia Polytechnic Institute
& State University
Blacksburg, VA 24061
(703) 961-5978
24. Dr. William T. Keane
Arizona Aerial Applicators
803 North 3rd Street
Phoenix, AZ 85004
25. Dr. Philip Kearney*
Chief
, Pesticide Degradation Lab.
Building 050 - Room 100
BARC West
U.S. Dept. of Agriculture
Beltsville, MD 20705
(202) 344-3533
26. Dr. Harold Keener*
OARDC
Ohio State University
Wooster, OH 44691
(216) 263-3859
27. Dr. Brian P. Klubek*
Department of Plant & Soil Sc.
Southern Illinois University
Carbondale, IL 62901
(618) 453-2496
28. Mr. Raymond F. Krueger
U.S. EPA - TS 769C
Office of Pesticide Programs
401 M. Street, S.W.
Washington, D.C. 20460
(202) 557-7347
29. Dr. Shri Kulhkarni
Senior Scientist
Radian Corporation
P.O. Box 13000
Research Triangle Park
North Carolina 27709
(919) 481-0212
-43-
-------
30. Mr. David W. Mason
Biotechnology Division
Southern Research Institute
2000 Ninth Ave. S.
P.O. Box 55305
Birmingham, AL 35255
(205) 323-6592
31. Dr. Fumio Matsumura*
Pesticides Research Center
Michigan State University
East Lansing, MI 48824
(517) 353-9430
32. Mr. Francis T. Mayo
Director
Water Engineering Research
Lab. EPA, AWBERC :
26 W. St. Clair Street
Cincinnati, OH 45268
(513) 684-7951 ;
33. Ms. Joan McCaffery
OSWER, EPA
401 M. Street, S.W.
Washington, D.C. 20460
(202) 382-4515
34. Mr. Robert W. Morgan
Dow Chemical Company
Agricultural Products Dept.
P.O. Box 1706
9008 Building
Midland, MI 48640
(517) 636-6642
35. Dr. Donald E. Mullins*
Department of Entomology
Virginia Polytechnic Institute
and State University
Blacksburg, VA 24061
(703) 961-5978
36. Mr Richard F. Murphy, Jr.
President
Fred J. Murphy Co.
Society of American Florists
10826 Kenwood Road
Cincinnati, OH 45242
(513) 791-6732
37. Mr..Ronald E. Ney, Jr.
U.S. EPA
Waste Management £ Econ. Div.
Office of Solid Waste
401 M. Street, S.W.
Washington, D.C. 20460
(202) 475-8859,
38. Dr. A.J. Noiik*
Solar Energy Research Inst.
1617 Cole Boulevard
Golden, CO 80401
(303) 231-1000
39. Mr. Donald A. Oberacker
U.S. EPA, HWERL.
AWBERC
26 W. St. Clair St.
Cincinnati,'OH 45268
(513) 684-7696
40. Dr. James V. Parochetti
Program Leader
Pesticides, Applicator
Training & Weed Science
U.S. Dept. of Agriculture
14th & Independence Ave., S.W.
Washington,,D.C. 20250
(202) 447-6506
41. Mr. Donald L. Paulson, Jr.
CIBA-GEIGY Corporation
Agricultural Division
P.O. Box 18300
Greensboro, NC 27419
(919) 292-7100
42. Dr. Ian L. Pepper
Soil £ Wateir Science Dept.
College of Agriculture
University of Arizona
Phoenix, AZ|
43. Mr. Jim Pritchard
Vice President
World Wide Waste Treatment
2278 Colby Rd.
Grand Rapid, MI 49461
(616) 894-2645
-44-
-------
44. Mr. Edward W. Raleigh
Registration Manager
E.I. duPont de Nemours
and Company, Inc.
Barley Mill Plaza
Walker's Mill Bldg.3-158
Wilmington, DE 19898
(302) 992-6022
45. Dr. George W. Rambo
Director, Research Education
and Technical Resources
National Pest Control Assoc.
8100 Oak Street
Dunn Loring, VA 22027
(703) 573-8330
46. Mr. Dennis B. Redington
Monsanto Agricultural Prod. Co.
800 N. Lindbergh Blvd.
St. Louis, Missouri 63167
(314) 694-4956
47. Mr. Darryl Rester*
Louisiana Cooperative Extension
Service
Louisiana State University
Agricultural Center
Baton Rouge, LA 70308
(504) 388-4141
48. Ms. Catherine Schmidt
Researcher
Southern Illinois University
Carbondale, IL 62901
(618) 453-2496
49. Dr. James N. Seiber
Department of Environmental
Toxicology
University of California
Davis, CA 95616
(916) 752-1142
50. Mr. Eugene Speck
Associate Director
Agricultural Field Stations
University of California
Davis, CA 95616
51. Dr. Jerry D. Spittler*
NYSAES
Cornell University
Geneva, NY 14456
(315) 787-2283
52. Mr. Matthew Straus
Chief
Waste Identification Branch
Office of Solid Waste
401 M. Street, S.W.
Washington, D.C. 20460
(202) 475-8551
53. Mr. Don Tang
U.S. EPA - RD-681
Senior Staff Engineer
Office of Research & Devel.
, 401 M. Street, S.W.
Washington, D.C. 20460
(202) 382-2621
54. Mr. A.G. Taylor*
Agriculture Adviser
Illinois EPA
' 2200 Churchill Rd.
Springfield, IL 62706
(217) 785-5735
55. Mr. Richard Taylor
Pesticide & Toxic Chemical
News
, 1101 Penn Ave., S.C.
Washington, D.C. 20003
(202) 546-9191
56. Mr. John Ward
Environmental Protection
Specialist, U.S. EPA
26 W. St. Clair Street
Cincinnati, OH 45268
(513) 527-8365
57. Mr. David Watkins
Chemicals & Chemical Products
Branch, IWTTD, WERL, EPA
AWBERC
26 W. St. Clair Street
Cincinnati, OH 45268
(513) 684-7502
-45-
-------
58. Mr. Brian Westfall
HWERL, EPA, AWBERC
26 W. St. Clair Street
Cincinnati, OH 45268
(513) 684-7795
59. Mr. Wray WinterTin*
Department of Environmental
Toxicology
University of California
Davis, CA 95616
(916) 752-1142
60. Dr. James Worley
Monsanto Agricultural
Products Company
800 North Lindbergh Blvd.
St. Louis, MO 63167
(314) 694-5267
61. Dr. Roderick Young
Biochemistry & Nutrition Dept.
Virginia Polytechnic Institute
& State University
Blacksburg, VA 24061
(703) 961-6532
-46-
-------
APPENDIX,C
AGENDA FOR JULY .30, 1985
RESEARCH WORKSHOP ON THE TREATMENT/DISPOSAL
OF PESTICIDE WASTEWATER GENERATED
BY THE AGRICULTURAL APPLICATION OF PESTICIDES
Auditorium, AWBERC, Cincinnati, Ohio
AGENDA.
Time
8:00
8:30
8:40
9:00
9:00
9:20
9:40
10:00
10:15
10:35
10:55
Description
8:30 Registration
8:40 Welcome
9:00 Status of Regulatory Development
for the Treatment/Disposal of Dilute
Pesticide Wastewater
-11:55
- 9:20
-9:40
-10:00
-10:15
-10:35
-10:55
-11:15
SESSION A, PHYSICAL/CHEMICAL TREATMENT
AND RECYCLING
Practical System to Treat Pesticide-
Laden Wastewater Generated by Applicators
Pesticide Rinsewater Treatment
Presenter
Mr. Francis T. Mayo
Mr. Raymond F. Krueger
Treatability Studies of Pesticide Waste-
waters by Granular Activated Carbon,
Hydrolysis, Chemical Oxidation, and UV-Photolysis
Dr. Philip C. Kearney
Mr. David W. Mason
Dr. Phillip Antommaria
Mr. Louis J. Bilello
BREAK
Pesticide Rinsewater Recycling Systems
Pesticide Waste Disposal
UV-Ozonation in Pesticide Wastewater
Disposal State-of-the-Art, Technology
Transfer and Research Needs
Mr. A.G. Taylor
Mr. Darryl Rester
Dr. Philip C. Kearney
11:15 -11:35
11:35 -11:55
Description of a Small Automated Fluidized Dr. Harold M. Keener
Bed Combustor System and its "Potential"
for the Incineration of Pesticide Waste/Wastewater
Removal of Pesticide Wastes via a Photo-
electrochemical Solar Approach
Dr. A,,J. Nozik
-47-
-------
11:55 - 1:15 LUNCH
1:15 - 4:10 SESSION B, BIOLOGICAL TREATMENT £ LAND' Mr. Francis T,. Mayo
APPLICATION ; ' ; i
1:15 - 1:35 Disposal of Dilute Pesticide Wastes by Dr. Charles V. Hall
Evaporation and Biodegradation Using Con-
crete Pit Systems
1:35 - 1:55 Disposal of Aqueous Pesticide Wastes at Mr. Wray Winterlin
University of California Agricultural Field ;
, Stations :
1:55 - 2:15 On-Site Pesticide Disposal at Chemical Dr. Terry D.Spittler
Control Centers
2:15 - 2:35 Biological and Chemical Disposal of Waste Dr. Brian P.^Klubek
Pesticide Solutions
2:35 - 2:50 BREAK
2:50 - 3:10 Disposal of Dilute and Concentrated Agri- Dr. [Donald E.'Mullins
cultural Pesticide Formulations Using . | \
Organic Matrix Absorption and Microbial ;),
Degradation '
3:10 - 3:30 Toxic Substance Solvent Evaporator Mr. Robert W. Claunch
3:30 - 3:50 Microbial Degradation of Pesticides Dr. iFumio Matsumura
3:50 - 4:10 Phanerochaete Chrysosporium: Its Potential Dr. John A. Bumpus
Use in the Biological Degradation and i
Disposal of Agricultural Chemical Wastes '
4:10 - 4:30 Explanation of Next Day's Agenda Mr. Francis T. Mayo
4:30 - 5:00 Questions and Answers Concerning the Mr. Raymond F. Krueger
Regulatory Aspects of Pesticide Waste- . and
water Mr. Matthew Straus
5:00 ADJOURN '
-48-
-------
APPENDIX D
AGENDA FOR WORKGROUP A ON.JULY 31, 1985
PHYSICAL/CHEMICAL TREATMENT & RECYCLING
(Room 120/126, AWBERC, Cincinnati, Ohio)
Time Description Presenter
8:15 - 8:30 Finalize Sub-Work Group Members and Dr. Philip C. Kearney
and Leaders, Explain Objectives, and Convene
in Sub-Work Groups
8:30 - 9:30 Sub-Work Group Meetings, Development of Sub-Work Group
Initial Findings and Recommendations Leaders
9:30 - 9:45 BREAK
9:45 -11:45 Presentation, Discussion and Approval of Dr. Philip C. Kearney
Sub-Work Group Findings and Recommendations and
to Each Work Group Sub-Work Group
Leaders
11:45 - 1:00 LUNCH
WORK GROUPS A & B RECONVENE TOGETHER IN AUDITORIUM AT 1:00 P.M.
1:00 - 1:30 Summary of Work Group A Findings and Dr. Philip C. Kearney
Recommendations
1:30 - 2:00 Summary of Work Group B Findings and Mr. Francis T. Mayo
Recommendations
2:00 - 2:15 Conclusions & Adjournment Dr. Philip C. Kearney
and
Mr. Francis T. Mayo
-49-
-------
APPENDIX E
,
AGENDA FOR WORK GROUP B ON JULY 31, 1985
BIOLOGICAL TREATMENT & LAND APPLICATION
(Room 130/138, AWBERC, Cincinnati, Ohio;)
Time
Description
Presenter
8:15 - 8:30 Finalize Sub-Work Group Members .and Leaders, Mr. Francis T. Mayo
Explain Objectives, and Convene in Sub-Work . ;
Groups ;
8:30 - 9:30 Sub-Work Group Meetings, Development of Sub-Work Group
Initial Findings and Recommendations Leaders
9:30 - 9:45 BREAK
9:45 -11:45 Presentation, Discussion and Approval of Mr. Francis T. Mayo
Sub-Work Group Findings and Recommendations and
to Each Work Group Sub-Work Group
Leaders
11:45 - 1:00 LUNCH . ! . .
WORK GROUPS A & B RECONVENE TOGETHER IN AUDITORIUM AT 1:00 P.M.
1:00 - 1:30 Summary of Work Group A Findings and
Recommendations
1:30 - 2:00 Summary of Work Group B'Findings and
Recommendations
2:00 - 2:15 Conclusions & Adjournment
Dr. Philip C. Kearney
Mr. Francis T. Mayo
Mr. Philip C. Kearney
|" and
Mr. Francis T. Mayo
-50-
-------
APPENDIX F
WORK GROUP A, PHYSICAL/CHEMICAL TREATMENT & RECYCLING
Sub-Work" Group
1. Pesticide Rinsewater Recycling
2. Granular Carbon Adsorption
3. UV OZonation
4. Small-Scale Incineration
5. Solar Photodecomposition
6. Chemical Degradation
Members '
A.6. Taylor*
Donald Paulson
Eugene Speck
Darryl Rester
Phillip Antommaria*
Joan McCaffery
Kenneth A. Dostal
Hyung-Yul Cho
George W. Rambo
Phillip C. Kearney*
Mark L. Bruce
James N. Seiber
Shri Kuhlkarni
William Keane
Harold Keener*
Donald Oberacker
Ray Krueger
James Bridges
Roy Detweiler
A.J. Nozik*
Phillip C. Kearney
Shri Kuhlkarni
Mark L. Bruce
James N. Seiber
Lou Bilello*
Jim Pritchard
Cal Blystra
Ed Raleigh
*Sub-Work Group Leader
-51-
-------
APPENDIX 6
WORK GROUP B, BIOLOGICAL TREATMENT &. LAND APPLICATION
Sub-Work Group
1. Evaporation, Photodegradatiori and
Biodegradation in Containment
Devices
2. Genetically Engineered Products
3. Leach Fields
Acid and Alkaline Trickling
Filter Systems
Organic Matrix Absorption
and Microbial Degradation
6. Evaporation & Biological
Treatement with Wicks
Members
Charles Hall*
Matthew A. Straus
John A. Bumpus
Wray Winter!in
Harold Collins
Thcimas Gilding
Dennis Redington
i
Fumio Matsumura*
Ian L. Pepper
Don Tang
Richard Taylor
Orlo Ehart
James V. Parochetti
Terry D. Spittler*
Ronald Ney
Robert Morgan
Brian P. Klubek*
Catherine Schmidt
Donald E. Mull ins*
David Watkins
Charles Earhart, Jr.
Jimmy W. Worley
Roderick Young
Richard Hegg
Glen H. Hetzel
R.W. Claunch*
Clyde R. Dempsey
-52-
-------
APPENDIX H
SUB-WORK GROUP SUMMARY SHEET
Instructions
Sub-Work Groups have been organized- by technology or groups of
technologies to develop initial recommendations concerning the application of
that technology(s) to the treatment/disposal of dilute pesticide wastewaters
which can be operated at or near the farm. These recommendations will then be
presented to the full Work Group for discussion, modification and approval.
Each Sub-Work Group is to summarize their recommendations for each
technology on this form.
Briefly Describe Technology:
Check Most Appropriate Box:
Technology is currently being utilized on a commercial basis to treat
and dispose of dilute pesticide wastewater.
Technology is being utilized commercially to treat other types of
waste and offers promising opportunities for pesticide wastewater.
Technology is not being utilized commercially but experimental data
indicates it is a promising opportunity for pesticide wastewater.
State-of-the-Art Capabilities
Current Application(s):
Regulatory Status (i.e., Indicate where this technology has received state
approval to treat pesticide wastewater): .
-53-
-------
Capacity:
Capital Cost:
Operating Cost:
Availability or Expected Availability (i.e., delivery date):
Advantages (i.e., mobile, technical uncomplicated, fail proof,
_
etc.):
Disadvantages (i.e., environmental shortcomings, durability, reliability,
range of use, etc.):
Key Points From Both the User and Regulator Viewpoint:
Research Needs
- - I
Identify the data gaps that need to be addressed for this technology to be
utilized for the treatment and disposal of dilute pesticide wastewater. Limit
consideration to those questions that can be answered in a 3 to 5 year time
frame:
-54-
-------
Sub-Work Group Members:
Leader
Members:
U.S. GOVERNMENT PRINTING OFFICE- 6 4S-01 4/20027
-55-
-------
-------
-------
3? °
(D -*.
"
cu o
01
m
CO
O
O
m
-o
crv
o
CD
t
oo
o
o
'. < =
5 5 E
So o
5 o §
III
§n
2 o -.
"» O CD
^ < O
CD CD
O ;j
CD O
a. m
o- °
3 -^
H x
LO 3
|l|
Is
-i CD
CD O
o a,
> m c
to 3 3
D -T CD
ooo.
5 ^
^ §
2 ^
Q) CR
T)
o
o
o'
o =r o
= 4, CD
o ° 2
§1%
o
3=
3
(D
(D
Q)
------- |