WATER POLLUTION CONTROL RESEARCH SERIES
12020 FYE 01/72
   THE PESTICIDE MANUFACTURING
INDUSTRY-CURRENT WASTE TREATMENl
      AND DISPOSAL PRACTICES
 U.S. ENVIRONMEN 1 AL PROTECTION AGENCY

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    WATER POLLUTION CONTROL RESEARCH SERIES
The Water Pollution Control Research Series describes the
results and progress in the control and abatement of pollution
in our Nation's waters.  They provide a central source of
information on the research, development, and demonstration
activities in the water research program of the Environmental
Protection Agency, through inhouse research and grants and
contracts.with Federal,  State, and local agencies, research
institutions, and industrial organizations.
          f
Inquiries pertaining to Water Pollution Control Research
Reports  should  be directed to the  Chief, Publications  Branch
(Water), Research Information Division, R&M, Environmental
Protection Agency, Washington, B.C.  20460.

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     THE PESTICIDE MANUFACTURING INDUSTRY -

CURRENT WASTE TREATMENT AND DISPOSAL PRACTICES
                          by


                   Patrick R. Atkins
               The University of Texas
                Austin, Texas  78712
                        for the


          iOffice of Research and Monitoring

        ENVIRONMENTAL PROTECTION AGENCY
                  Project #12020 FYE
                     January 1972
         For sale by the Superintendent of Documents, U.S. Government Printing Office
                   Washington, D.C., 20402 - Price $1.80

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                 EPA Review Notice
This report has been reviewed by the Environmental
Protection Agency and approved for publication.
Approval does not signify that the contents neces-
sarily reflect the views and policies  of the Environemntal
Protection Agency, nor does mention  of trade names  or
commerical products constitute endorsement or recom-
mendation for use.
                          11

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                            ABSTRACT
       Numerous pesticides and pesticide manufacturing processes are
in use in the United States. The wastes produced are varied and possess
characteristics which make them unique. This study was undertaken to
determine the State of the Art of the waste treatment practices  utilized by
the industry to  manage these wastes. A literature search was  conducted
and the data  obtained was supplemented with interviews conducted at
twenty pesticide manufacturing plants.

       Since pesticide manufacture is an extremely sensitive area at
the present time, much of the information obtained is incomplete.  How-
ever, the  data presented should be of considerable use to those planning
waste treatment facilities. The report contains information on current and
predicted  pesticide production trends, a description of typical pesticide
manufacturing^processes, a review of the literature which describes  pes-
ticide chemistry and  waste treatment  practices, a detailed summary of the
waste treatment systems discussed in the plant interviews,  and cost
estimates.

       The report is  designed to be a basic  reference document containing
information on the spectrum of treatment and disposal methods in current
use.  No attempt was made to prove  or disprove statements made in the
literature  or the plant interviews.  Areas of  needed research are discussed
in the recommendations section.
                                 iii

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                          CONTENTS
Chapter                                                      Page

I       Conclusions                                             1

II      Recommendations                                        9

III     Pesticide Production and Use                            15
           Definition of Pesticides                 .            15
           Trends in Production and Use                        15
           Recent Production and Sales Data                    17
           Forecasts in Production and Use                     26

IV     Pesticide Manufacture                                   31
           Producers of Pesticides                             31
           Manufacturing Processes and Waste Generation       31
               DDT                                           32
               Carbaryl                                      33
               Parathion and  Methyl Parathion                  3^
               2,4,5-T, 2,4-D and MCPA Herbicides            35
               Diolefin-based Insecticides                     36

V      Pesticidal Waste Treatment Techniques: Removal,
       Detoxification, Degradation and Decomposition            ^1
           Chemistry of Pesticides                             4l
               Natural Insecticides                            ^1
               Carbamates                                    ^1
               Organophosphorus Insecticides                  kl
               Chlorinated Hydrocarbons                       k2
           Treatment Methods                                  hk
               Chemical Oxidation                            Wv
               Coagulation                                    52
               Adsorption                                     55
               Photochemical Degradation                      TO
               Liquid-Liquid  Extraction                        70
               Biological Degradation                         7^
               Foam Fractionation                             85
           Disposal Methods                                   85
               Combustion                                    85
               Burial                                         89
                                 v

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CONTENTS (Continued)

Cha pter                                                      Page

                Ocean Dumping                                93
                Deep Well Disposal                            95

VI     Treatment and Disposal Practices Presently Employed      99
           In-Plant Control                                    99
           Neutralization and  pH Adjustment                   100
           Chemical Treatment                               101
           Physical Treatment                                108
           Biological Treatment                               113
                Basic Requirements
                    Temperature
                    pH
                    Nutrients                                 119
                    Degradability                             119
                Trickling Filters                               121
                Activated Sludge                              122
                Aerated Lagoon                               125
                Stabilization Ponds                            126
           Incineration                                       127
           Burial
VII     The Cost of Waste Treatment                           137
           Photochemical Degradation                         137
           Activated Carbon                                  138
           Chemical Treatment                                139
           Biological Treatment                               139
           Incineration                                       1^7
           Burial                                            148
           Ocean Disposal                                   150

VTII    Acknowledgments                                      153

IX     References                                            155

X      Appendices                                            163
                                 VI

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                           FIGURES
                                                            Page

 1       Classification and Relative Importance of
        Pesticides (Anon.,  Chem. Engr. , 1969)                 16

 2       Past and Projected Pesticide  Production in the U.S.
        (Neumeyer, et ah , 1969)                              27

 3       Oxidation of 2,4-DCP with Potassium Permanganate
        (Aly and Faust,  1965)                                  46

 4       Removal of Lindane by Treatment with Potassium
        Permanganate (Buescher, et a_l. , 1964)                  V[

 5       Removal of Lindane by Aeration and Ozonation
        (Buescher, et al., 1964)                               kQ

 6       Removal of Aldrin by Aeration and Ozonation
        (Buescher, et al. , 1964)                               14.9

 7       Removal of Dieldrin by Aeration and Ozonation
        (Buescher, et al. , 1964)                               50

 8       Effectiveness of Chlorine Treatment of 0.1  mg/1
        Rotenone Solution (Cohen,  eta]..,  1960)                53

 9       Contact Time and Chlorine Dioxide Required to
        Detoxify 0.1 mg/1 Rotenone (Cohen, et al., 1960)       5^

10       Carbon Dosage  Curves for Removal of Fish Poisons
        (Cohen, et a].. , 1960)                                 62

11       Removal of DDT from  Solution as a Function of
        Contact Time (Whitehouse, 1967)                       63

12       Removal of Aldrin from Solution as a Function
        of Contact Time (Whitehouse, 1967)                     6k
                                 Vll

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 FIGURES (Continued)                                        Page

13      Removal of Dieldrin from Solution as a Function
        of Contact Time (Whitehouse,  1967)                    65

14      Removal of Dieldrin from Solution as a Function
        of Carbon Dosage (Whitehouse,  1967)                  66

15      Removal of Aldrin from Solution as a Function of
        Carbon  Dosage (Whitehouse, 1967)                     67

16      Removal of DDT from Solution as a Function of
        Carbon  Dosage (Whitehouse, 1967)                     68

17      Photochemical Degradation Rates for Aldrin, Dieldrin,
        and Endrin (2537 A source)  (Bulla and Edgerly, 1968)    71

18      Dilution Effect on Respiration Rates
        (Ford and  Gloyna, 1967                                76

19      Batch Aeration of 2,4-D & 2,4,5-T Acid Wastes
        (Ford and  Gloyna, 1967)                               77

20      Anaerobic Degradation of Lindane in Sludge Containing
        1.5% Dry  Solids at 35C (Hill and McCarty, 1969)       79

21      Anaerobic Degradation of Lindane in Active and
        Poisoned Sludge at 35C (Hill and McCarty, 1967)       80
22      Anaerobic Degradation of Single Pesticides in 3500 ml
        of 7.2% Total Solids Sludge at 35C (Hill and Mccarty,
        1967)                                                81

23      Anaerobic Degradation of Pesticide Mixtures in
        Thick Sludge at 35 C (pesticides without extractable
        degradation products) (Hill and McCarty, 1967)         82
24      Anaerobic Degradation of Pesticide Mixtures in
        Thick Sludge at 35C  (pesticides with extractable
        degradation products)  (Hill and McCarty, 1967)         83

25      Pesticide Degradation in Dilute Sludge at 20C
        (Hill and McCarty,  1967)                              8^
                              viii

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 FIGURES (Continued)                                        Page

26      Schematic Diagram of a Waste Injection Well
        Completed in Competent Sandstone
        (Warner, 1965)                                        97

27      Ozonation Test Results of Dehydrochlorination (DHC)
        Wastewaters (Ford and Eckenfelder, 1968)             10?

28      The Effects of Temperature on BOD Removal
        from Soluble Industrial Wastes (Ford,  1971)            118

29      Capital Cost Relationship - Neutralization
        (Ford and Gloyna ,  1970)

30      Capital Cost Relationship - Activated  Sludge
        (Ford and Gloyna,  1970)

31      Capital Cost Relationship - Trickling Filters
        fEPA Report 12020  2/70, 1970)

32      Capital Cost Relationship - Aerated Lagoon
        (EPA Report 12020  2/70, 1970)

33      Capital Cost Relationship - Lagoons
        (EPA Report 12020  2/70, 1970)

34      Capital Cost Relationship - Incineration
        (EPA Report 12020  2/70, 1970)

35      The Cost of  Solid Waste Disposal in
        Sanitary Landfills (Heaney, _et.al. ,  1970)              151
                                  IX

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                            TABLES
 No.                                                        Page

 1       Decrease in Inorganic Pesticide Usage in the U.S.
        (Anon.,  Chem. Engr. , 1969)                            17

 2       Production Decline of Chlorinated Pesticides in U.S.
        (Anon.,  Chem. Engr., 1969)                            18

 3       U.S. Pesticide Production
        (Anon.,  Chem. Engr., 1969)                            19

 4       Synthetic Organic Pesticides: Volume and Value
        of Sales by Classes, U.S., 1966-1969
        (Anon.,  U.S. Tariff Commission, 1969)                 21

 5       Pesticides and Related Products: U.S. Production
        and Sales  (Anon., U.S. Tariff Commission,  1969)        23

 6       Principal Products - Dominant Pesticide Products
        (Neumeyer, et aj.. , 1969)                              28

 7       Waste Characteristics of Chlorinated Herbicide
        Wastes  (Ford and Gloyna, 1967)                        37

 8       Effects of Oxidants on Pesticides in Aqueous
        Solution (Buescher,  et al. , 1964)                       51

 9       Summary of Cumulative Pesticide Removal at
        10-ppb Load from Raw River Water
        (Robeck, et al. ,  1965)                                 57

10       Efficiency of Adsorption and Recovery from Carbon
        (Faust and Suffet, 1966)                               58

11       Effect of Activated Carbon on Herbicides and
        Insecticides (Sigworth, 1965)                          59

12       Carbon Dosages  Required to Reduce  the Concentration
        of 2,4-D Compounds (Aly and Faust, 1965)              6l
                                   x

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 No.                                                        Page

13      Carbon Dosages Requirec to Reduce the
        Concentration of 2,4-DCP (Aly and Faust,  1965)         6l

14      Liquid-Liquid Extraction Systems and Percent
        Recoveries (Faust and Suffet, 1966)                    72

15      Cumulative Pesticide Removed - Foam Foundation
        (Whitehouse,  1967)                                   86

16      Percent Loss  on Combustion of Commercial
        Formulations  of Pesticides at Five  Temperatures
        (Kennedy, et  al. , 1969)                               88

17      Relative Mobility of Pesticides  in Soils
        (Working Group on Pesticides, 1970)                   91

18      Chemical Treatment (Author, 1971)                     103

19      Ozonation of  Dehydrochlorination (DHC)
        Wastes (Ford and Eckenfelder, 1968)                  106

20      Chemical Treatment (Anon. , National Agr.
        Chemical Association, 1965)                         109

21      Physical Treatment  (Author,  1971)                     110

22      Biological Treatment (Author, 1971)                   115

23      Incineration (Author, 1971)                           129

24      Costs for Various Degrees of Treatment for
        Different Combinations of Waste Characteristics
        (Barnard,  1970)                                      1^5

25      Estimated Marine Disposal Cost for 1968
        (Witt,  1971)                                         152
                                   xi

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                          CHAPTER  I

                         CONCLUSIONS
       Based on the information gathered during this  study, the following
conclusions have been formulated:

       1.   Pesticide usage in the United States will continue to grow in
the future.  The increasing demand for food and fiber  and the spiraling
cost of labor both act to insure the need for pesticides in the form of
insecticides, fungicides and herbicides to make farm production more
efficient. Legislation restricting the use of certain types of pesticides
will have an impact on various phases of the pesticide industry, but in
the main, pesticide production and use will continue  to increase at the
present rate or  an accelerated rate.

       2.   Certain classes of pesticides may decrease in actual usage
and will  be  replaced by other compounds which do not possess the char-
acteristics which could make them potentially harmful to the environment.
For example, long-lived DDT and related isomers will no doubt decrease
in usage  with a subsequent increase in the use of other broad spectrum
pesticides from the organo-phosphate and carbamate classes.

       3.   As  the total pesticide production and usage in  the United States
continues to grow, shifts  in the use  of certain classes of pesticides will be
significant. The herbicide usage is  increasing more rapidly than insecticide
and fungicide usage and this trend will probably continue.  Herbicides now
occupy approximately 33.5% of the pesticide market and this percentage will
increase  as farm labor costs continue to spiral.  The  chlorinated hydrocarbon
type herbicide  usage has decreased  but substitute compounds have more
than made up for this decrease. The present projections of pesticide usage
in the United States indicate an annual growth rate  of approximately 16%.
Herbicide usage is expected to increase at perhaps 20% per year.  The use
of alternate pest control methods including sterile insects, insect attract-
ants, and insect traps may also effect the pesticide market.  It is impossible
at this time to  predict the effect that these emerging techniques may have.

       4.   Because of the high cost of development, testing and marketing
new pesticidal  compounds  (3-6 million dollars per product), few entirely
new types of pesticides will  probably be marketed in the near future.  Even

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though there is a trend toward shifting from the chlorinated hydrocarbon
classes of pesticides, new  substitute compounds will be few in number.
Most of the replacement compounds will be existing pesticidal compounds
or modifications of these existing compounds.

       5.   Many of the patents on major  pesticides will expire within
the next five years.  This will open these compounds to the com-
petitive market and will perhaps influence the price and usage rate of
several major pesticidal compounds.  Therefore, it is difficult to  project
the total pesticide usage and the percent of the market that will be occupied
by the various types of pesticides beyond 5-10 years.

       6.   A large amount of information  is available on the manufacturing
processes  involved in producing most pesticidal compounds. However,
much of the success of a given reaction is based on a certain amount of
rrart" that cannot be described in the literature.  These variations in pro-
duction practices affect the quantity and quality of the waste streams
resulting from the manufacturing process.   For this reason, detailed  data
concerning wastewater characteristics, toxicity, treatability and  volumes
is almost impossible to obtain.  Generalizations can be made and are
included  in this report.   However, wide variations in wastewater  quality
can occur and these variations may require entirely different treatment
systems for plants that are involved in producing the same type of basic
compounds.

       7.   Wastewater streams from  pesticide manufacturing generally
contain total dissolved solids in excess of 10,000  mg/1, low suspended
solids, high COD and some BOD, a small  amount of toxic product and
pH values that may range from very acid to highly  basic. The  wastes may
resemble a number of typical industrial waste streams in many ways, but
the presence of active pesticidal agents,  solvents, high dissolved solids,
and wide pH fluctuations pose unusual problems which must be considered
when waste treatment and disposal systems are planned. Many of the
treatment problems arise as a result of the high total dissolved solids or
the wide pH fluctuations which  can occur rather than from the organic
components of the waste stream.

       8.   A large number of methods are being or have been used in
treating pesticide manufacturing wastes.  Much of the data is  sketchy and
incomplete.  Since this  is an area that receives wide-spread public atten-
tion, most  manufacturers are hesitant to release information on any waste
streams that contain pesticidal  compounds, no matter how dilute the  toxic

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components may be.  For this reason, much of the information on pesticide
removal from waters arises from studies or processes designed to treat
drinking water.  Many of these processes appear to be applicable for
handling waste treatment streams but others cannot be used for industrial
wastes since the pesticidal wastes often contain extremely high dissolved
solids,  organic solvents,  and acid or basic compounds.

       9.   Treatment methods including chemical oxidation with chlorine,
chlorine dioxide, potassium permanganate, ozone and peroxide have been
studied  and shown to be capable of removing in excess of 95% of the active
compounds from some types of pesticide manufacturing waste  waters.
Coagulation with alum and various polymers has been attempted with some
success.  Adsorption on activated carbon, saturated clays, humic acid,
muck soils,  bentonites, cation exchange resins, aluminum silicate and
hydrous magnesium aluminum silicate have shown some promise as  methods
to remove  small quantities of pesticides from  aqueous systems.  Photo-
chemical degradation has  also been successfully demonstrated as a  method
of treating waters containing  small quantities of pesticidal compounds.
Liquid-liquid extraction studies show that processes such as  benzene
extraction are effective in removing DDT from manufacturing wastes.

      10.  Biological degradation studies have been attempted by a large
number of workers, but the unanswered questions  concerning biological
degradation of pesticidal wastes are still numerous  and much work needs
to be done in this area.  Aerobic and anaerobic studies have been conducted
under both laboratory, pilot and full-scale conditions.  In many cases the
biological system is  quite effective in treating  the pesticide waste. How-
ever, since the  pesticide  waste may be quite  unique in characteristics,
detailed laboratory studies or pilot studies should be conducted before  any
large-scale treatment system is designed and built.  Aerobic and/or
anaerobic organisms  appear to be capable  of degrading compounds such as
2,4-D,  2,4,5-T, malathion,  parathion, lindane, heptachlor and  silvex.
Compounds such as dieldrin appear to be relatively bio-resistant, although
some soil microbes have been reported to be active in degrading  this
particular pesticide.

      11.   Combustion is one of the most popular disposal methods for
concentrated waste streams,  semi-solids, and  solid wastes.   Many man-
ufacturers indicate that the combustion process can effectively destroy most
organic compounds (liquid and gaseous) but that problems arise because of
other components in the wastes that are burned.  The high salts may produce

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feed system and burner'maintenance problems, rapid corrosion and plume
opacity; high burning temperatures  produce oxides of nitrogen; sulfur and
phosphorus compounds in the waste may be converted to sulfur dioxide
and phosphorus pentoxide, which can cause downwind air pollution prob-
lems; compounds  containing heavy  metals such as lead, mercury and
arsenic produce dangerous aerosols and require special precautions
before incineration can be used safely.

       12.   Burial of pesticides is  a common practice because of its
relatively low cost.  This method is practiced by almost all the  pesticidal
manufacturing operations  that were  visited during the course of this  study.
With the exception of one plant, no detailed  studies were being  conducted
to determine the amount of horizontal or vertical movement of the materials
buried at the landfill or pit disposal sites.  The literature indicates  that
in general pesticide compounds move very little in a soil system.  How-
ever, if the soil is not homogeneous or if groundwater  intersects the burial
zone,  pesticidal migration is possible.

       13.   Ocean disposal is a convenient method of  pesticide  manufacturing
waste  disposal for manufacturing plants located near the oceans or the
Gulf of Mexico.  Concentrated liquid and semi-solid wastes are carried
by barge in bulk form or in containers to dumping sites  several miles to
several hundred miles offshore.  This type of system can be relatively
inexpensive if conducted  on a large scale.  However,  present regulatory
authorities indicate  that in the near future severe restrictions will be
placed on this method of waste disposal. Therefore, long-term  commit-
ments  to this type of disposal practice should be discouraged.

       14.   During this study a large number of pesticide manufacturing
plants were visited and their waste treatment practices were discussed.
The information obtained during these interviews is included in this
report.  The results  of these interviews indicate that:

              a.  In-plant control  of wastewater discharges entering the
       effluent stream can be an effective method of reducing the volume
       of wastewater and concentration of pollutants to be treated.  Con-
       siderable  interest in this method of water pollution abatement has
       been generated in the petrochemical industry.  However, the belief
       is held by  several operators that in the case of  some pesticidal
       wastes, if large-scale reuse is employed, the resulting  stream may
       be too concentrated to be amenable to treatment by many chemical
       and biological systems.

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       b.  Continuous monitoring equipment on waste streams at
several places in a plant has proven to be useful as a warning
system to prevent toxic "slugs" from spills or upsets from
reaching and possibly damaging chemical or biological treatment
systems.  A monitoring network plus diversion and storage  facil-
ities make it possible to contain and eventually treat these "slugs"
rather than allowing them to pass through the system.

       c.  Neutralization and pH adjustment are  necessary for
most of the waste streams resulting from pesticide manufacturing.
This neutralization may be needed for corrosion control, biological
organism protection and receiving water protection. Limestone
trenches, slaked lime feeders and neutralization  basins are com-
monly used but many other chemical neutralization agents are
employed as well.  It has been found by at least  one plant oper-
ator that a significant reduction in chemical costs (caustic) can
occur if waste acids are  mixed with the lighly basic wastes only
after the low pH stream has been subjected to limestone trench
treatment.

       d.  Several chemical treatment methods were in use to
reduce wastewater  problems at plants visited during this study.
The chemical treatment methods varied widely in cost, applica-
tion and effectiveness.  The characteristics of the waste waters
from pesticide manufacturing included such a broad spectrum of
values that each chemical method had to be designed for the  par-
ticular waste in question.  Often these designs were made with
little or no information on reaction rates, final reaction products,
mixing requirements, etc.

       e.  Physical treatment methods in use at the various  plants
visited include carbon adsorption, sedimentation, filtration, heating,
dilution and total evaporation.  These types of treatment systems are
very similar to those found in most  petrochemical operations  and dif-
fer very little from  the standard design.  However, extra care must
be taken to reduce  the probability of accidental  spills and  leakages
because of the relatively high toxicity of some of the wastes.

       f.  Biological treatment systems are used extensively in
treating  pesticide manufacturing wastes.  During this study several
types of biological systems were in evidence, including trickling
filters, activated sludge systems, aerated lagoons and stabilization

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ponds.  BOD removals in the 80-95% range were reported for
some trickling filter,  activated sludge and aerated lagoon sys-
tems, and stabilization ponds achieved as much as 50% BOD
reduction.  Phenol and active pesticide removals were some-
what lower in most cases,  but some systems including speci-
ally designed activated sludge systems achieved removals
reported to be in excess of 99%.  Most operators seem pleased
with the biological units and the effluents  produced.  The high
operating costs and the vulnerability of the systems to upsets
were areas of major concern.  Design criteria and operating
parameters are included in  the report if they were made avail-
able by the plant operators.

       g.  Several cities accept waste streams from petro-
chemical and pesticidal manufacturing plants, dilute these
wastes with municipal sewage, and treat them in conventional
municipal treatment systems.  Oftentimes the pesticidal com-
ponents in the industrial waste stream pass through the plant
without complete degradation.  Preliminary studies in the
Delaware River Basin  indicate that high concentrations of  DDT
and DDT degradation  products have accumulated in  sediments
below outfalls from municipal treatment plants accepting indus-
trial wastes. The effect of these compounds on the treatment
plant itself is unknown and the effect on receiving waters and
the benthal deposits in these receiving waters is yet to be
determined.

       h.  Incineration practices in most of the plants visited
indicate that a well-operated incinerator  can be  an extremely
useful  pesticidal waste disposal device.  In  no cases did any
plant operator indicate that problems resulted from incomplete
combustion of the pesticidal or organic components of the
waste stream.  Most  problems appeared to be associated with
the inorganic and corrosive components of  the waste streams
rather than the organic or pesticidal components.  Particulate
and gaseous  pollutants escaping the combustion chamber and
entering the effluent stream of the incinerator have  caused
significant air pollution problems.  This type of problem has
resulted in the abandonment of at least one large-scale incin-
eration facility for pesticide wastes.   Evidently, little is
known about the characteristics of the particulates and gases
in the exhaust streams of incinerators  burning the liquid
wastes associated with pesticide manufacturing.

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              i. Almost every pesticide manufacturing plant contacted
       during this study utilized 'Some form of burial as a method of dis-
       posal of at least a portion of their processed waste.  In most
       cases little  study of the migration rate of the toxic components
       of the waste to be  buried had been undertaken.  Since many of
       the plants utilized contract disposal services,they felt little
       responsibility for studying the effect of the compound  on the sur-
       rounding underground environment.  Therefore, very few problems
       associated with burial practices were reported.  Perhaps the most
       often mentioned problem concerning burial as a disposal method
       was sloppy handling techniques at the burial site.  In some cases,
       poor handling  resulted in blowing dust, spilled liquids, and sur-
       face runoff contamination during rainy  periods.

              j. Ocean disposal and deep well injection are two
       methods that are being used in the  pesticide manufacturing
       industry.  These methods are discussed in the report but are not
       recommended as practices to be considered in the future. Uncer-
       tainties associated with these disposal methods have  caused con-
       siderable pressure to be placed on regulatory agencies.  As a
       result these methods will  probably be severely restricted in the
       future.

      15.  The cost associated with the  treatment of  pesticide manufac-
turing wastes is difficult to determine on a generalized basis. It can be
assumed that the cost associated with treating pesticide manufacturing
wastewaters biologically will be somewhat higher than the treatment of
most petrochemical wastewaters of similar organic loading.  Longer
detention times are generally required  to insure  accurate degradation of
the toxic components.  Chemical  and physical treatment methods must
be highly effective and are usually expensive.   These systems should be
designed for the particular waste  involved and the cost will vary widely
depending on the toxicity  of the waste and its resistance to chemical and
physical treatment.  The costs of incineration are a function of the volume
of the waste that is to be  burned, the corrosive  nature of the waste and
its fuel value as well as the air pollution control equipment required to
prevent atmospheric contamination.  Little detailed cost information
could be obtained for  the incineration units presently in use.  Burial and
ocean disposal costs  can  be estimated quite easily and some figures are
included in this  report.  It appears that in the short term these two methods
can be very inexpensive if conducted on a relatively large scale.  However,
increased regulatory constraints will no doubt have some effect on  these
costs.

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      16.  Without more information on waste stream quality, toxicity
and flows, it is impossible to isolate areas of the pesticide industry where
the problems  may be more pressing.  From the information compiled during
this study, it is evident that progress is being made in the area  of pesti-
cide manufacturing  waste treatment, but severe problems still remain.
The most enlightening facet of this study was  that in several cases, the
people involved did not or would not realize that a problem did exist.
Therefore,  to say that one type of pesticide or manufacturing process
poses a more severe problem than another would be misleading.  With
proper process  design,  plant control and waste treatment, most, if not
all, pesticide manufacturing wastes  can be discharged safely.  Plant
operators must  be made aware of the need for  proper waste management
and the control measures which can be beneficial.  Many  manufacturers
in all phases of pesticide production have realized this and  have been
successful in reducing environmental contamination from  pesticide man-
ufacturing wastes.  Others have not.

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                          CHAPTER II

                      RECOMMENDATIONS
       1.  Pesticide manufacturing wastes are composed of a wide variety
of compounds, some of which are active as  pesticidal agents and many of
which are not.  In order to gain a more complete understanding of the  prob-
lem, all  pesticide manufacturers should be required to periodically submit
detailed  analyses of all waste streams discharged from their plants.   Con-
venient forms should be designed to permit computer logging, retrieval,
and analysis of the submitted data.  The analytical requirements should
be specified to insure that the manufacturer is aware of the composition
of his waste discharges and the potential each component has for produc-
ing environmental stress. These analyses  should not be limited to liquid
wastes but should also include incinerator off-gases and the semi-solids
and solids which are buried.

       2.  Often plant operators indicated  that the composition of indi-
vidual waste streams from single units or small areas of the plant was
unknown.  It is recommended that all plant managers be encouraged to
examine  the individual waste streams before they are combined. In some
cases a portion of the wastewater produced  in the plant may be easily
treated or recycled  before it is contaminated with acids, solvents, active
pesticidal compounds, etc.  In addition, careful study may show that one
waste stream may be useful in treating another.  As an example, it was
found that a substantial reduction in chemical requirements for neutraliza-
tion occurred if a caustic rinse stream was mixed  with an acid waste  after
the acid  stream passed through a limestone  trench rather than before trench
treatment.

       3.  Conversely, water reuse and waste  stream separation should
be studied carefully before steps are taken to institute such practices.
The effects of concentrating the waste stream on its treatability and poten-
tial for causing environmental stress should be considered.

       4.  Pesticide manufacture and pesticide manufacturing waste treat-
ment are sensitive  areas.  Due to the increasing public and governmental
attention directed  toward pesticides,  many  manufacturers are hesitant to
discuss  these matters outside the company.  Therefore, it is recommended
that a detailed study of waste treatment practices be initiated through
an industry-sponsored organization that would have ready access to design

-------
data, operational parameters, cost information, treatability data and
treatment efficiency information.  The detailed design and operational
data could be published in the form of a manufal similar to but more
detailed than the manual Waste  Disposal,  published by the Agricultrual
Chemical Association in 1966.

        5.   Since most chemical and  biological waste treatment systems
are sensitive to rapid changes in wastewater quality, continuous moni-
toring equipment should be installed at strategic points through  a plant
to detect unusual conditions indicative of spills or upsets which might
produce toxic "slugs" in the wastestream.  Diversion and storage facil-
ities should be provided  to protect the treatment systems.  Research is
needed  to facilitate the development and production of reliable detectors
capable of providing the  desired response to  changes in waste stream
quality.  This type of protection may  be partially attainable with a large
holding pond before the treatment  system,  but in the use of some highly
toxic compounds, even large ponds may prove to be inadequate.

        6.   Most pesticide  removal work has been  conducted  using low
levels of active compounds  in drinking water.  Similar studies should be
conducted to determine the effectiveness of removal processes such as
chemical coagulation,  clay adsorption, carbon adsorption, foam fraction-
ation, ozonation, etc. on waste streams containing relatively high con-
centrations of active pesticides, high concentrations of organics and high
concentrations of dissolved solids.

     .".-  7.   Many pesticide manufacturing aqueous  waste  streams contain
high concentrations of dissolved solids.  These solids may cause signifi-
cant problems in chemical and biological treatment  systems, incinerators,
deep wells and evaporation  ponds. In-depth studies of the problems asso-
ciated with the high  salt concentrations (10,000 -  100,000 mg/1) typical
of pesticide manufacturing wastes should be  conducted to determine  the
feasibility of "conventional" industrial waste treatment systems.
                                                               i
       8.   Kinetic data  on  physical and chemical  treatment processes for
pesticidal wastes are limited.  Investigations of reaction  rates and dose-
time-effectiveness relationships for commonly used chemical agents in
typical pesticide manufacturing  wastewater streams should be conducted.
The kinetics of the reactions and the  end products  of the reactions should
be determined.
                                  10

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       9.  Neutralization is required for most pesticide manufacturing
liquid wastes.  These highly buffered acidic or basic streams often require
massive chemical doses to produce desirable pH  levels. At these dose
levels a thorough understanding of reaction  rates, product formation and
possible interference with further reaction,  mixing requirements, and mass
transfer are of importance.  Engineering designs could include the consid-
eration of these factors if research into the  application of the basic  neu-
tralization theory was conducted to obtain usable design data.

      10.  The effect of neutralization chemicals on subsequent chemical,
physical or biological treatment schemes  may  also be significant. Inves-
tigations of the effects of various  neutralization agents on the wastewater
quality and treatability should be conducted.  In  addition,  the large sludge
volumes resulting from these massive chemical doses can produce signifi-
cant solid  waste problems which should be considered.  The  toxicity,
stability, and leach rates of these sludges should be investigated.

      11.  Biological waste treatment appears to be a reasonable scheme
for handling many types of pesticidal wastes.   However, design criteria
and operational data for waste streams containing active pesticidal agents
are sketchy.  Full-scale or  pilot studies should be  conducted to better
determine parameters such as loading rates, detention times, allowable
"toxic"  concentrations, MLVSS, oxygen r-equiremenLs, etc.,  which are
necessary  to  achieve optimum efficiency with  representative  waste streams,
In addition, the presence  or absence of potentially  harmful degradation pro-
ducts should  be investigated for "high rate" biological systems treating
complex pesticidal  waste  streams.

      12.  The rate of removal  of soluble organics by a biological waste-
water treatment system appears  to be significantly affected by the waste-
water temperature.  Detailed investigations of the temperature dependence
of pesticidal  compound degradation (as well as other soluble organic
materials)  should be conducted to  insure that  systems are designed with
adequate capacity to handle the pesticidal and organic loads during  the
winter months when biological activity is reduced.   This temperature
effect is not  limited to pesticide manufacturing wastes but affects biolo-
gical systems for any industrial wastewater containing a high percentage
of soluble  organic material.

      13.  Incineration appears to be an effective waste disposal method
for pesticide  manufacturing  wastes, but several problem areas should  be
investigated. These include:

                                  11

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              a.  The gaseous and particulate emissions resulting from
       incineration of wastes which have been treated with various neu-
       tralization agents should be characterized.  Detailed analysis of
       the flue gases  produced under field conditions should be conducted
       for "typical" wastes burned in several types of multichamber,
       vortex, and fluidized bed units.

              b.  Methods of minimizing undesirable gases and
       particulates through combustion control, air flow control,
       incineration design, waste stream modification and exhaust
       cleaning should be studied for pesticidal waste streams.

              c.  Visible  plumes often result from  the high temperature
       burning of  pesticide wastes. These persistent fogs  might be
       reduced or eliminated by proper  burning and particulate removal.
       Studies should be conducted to determine ways by which these
       visibility problems can be reduced when wastes  containing high
       levels of dissolved solids are burned.  The  particle  size, size
       distributions, mass emission rates, nucleating potential, etc.
       should be determined.

              d.  In general ash disposal from incineration was not
       considered a problem, but research should be conducted in this
       area to determine the possible effect of this ash on the envi-
       ronment, and the potential for recovery of usable products from
       this waste material.

      14.  Some pesticide manufacturing wastes are discharged into
conventional municipal waste treatment facilities.  Often a  portion of
the active compounds passes through the system.   Studies  should be
conducted to determine the effect of conventional treatment  systems on
the diluted wastes and the effect of the pesticide compound on the
conventional system.

      15.  Many pesticide manufacturing operations are  a part of a
large  petrochemical complex and the pesticidal wastes are  mixed with the
other  petrochemical waste  streams for treatment in a common system.
The effectiveness of these industrial waste treatment systems on the
active pesticidal compounds  should be determined.
                                  12

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      16.  Many long-lived pesticides tend to concentrate in certain
areas of the environment. For example, DDT in a wastewater discharge
will result in a build up of DDT and its degradation products in the sedi-
ments near the discharge point.  The sediment concentrations may be
several orders of magnitude  higher than the concentration of pesticides
in the water.  Therefore, it is recommended that studies of the distri-
bution of various long-lived compounds in environmental systems be
investigated to determine those compounds which may pose significant
threats, even  at low initial concentrations.

      17.  If rapid  progress is to be made in reducing the  amount of
pesticidal wastes discharged, information on present practices and  prob-
lems must be made  available to researchers, plant operators, and control
agencies.  More discussion and more rapid exchange of information will
be required if  the complex problems associated with airborne and water-
borne pesticidal agents are to be understood and solved.
                                 13

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                           CHAPTER III

                  PESTICIDE PRODUCTION AND USE
Definition of Pesticides

       Pesticides are chemical compounds used to destroy organisms
that are considered by  man to be "pests".  They are  usually classified
(according to the target organism) as insecticides, herbicides, fungi-
cides, rodenticides, miticides, acaricides, and nematocides.  Figure
1 shows the relative importance of the types of pesticides; heavy arrows
for  herbicides and insecticides indicate that they are more widely  used
than the other pesticides.

       Pesticides include both organic and inorganic materials. Examples
of inorganic pesticides include compounds of lead, arsenic, mercury,
chlorine, Paris Green (Arsenical),  lime-sulfur washes, hydrogen cyanide,
lead arsenate,  sodium  arsenite,  metal salts (copper, zinc, chromium,
and thallium), and toxic compounds of fluorine and sulfur. Examples of
naturally occurring organic pesticides  are rote none,  pyrethrin, red squill,
sabadilla, nicotine, and petroleum derivatives.  Examples of  synthetic
organic pesticides are  DDT (dichloro diphenyl trichloroethane),  BHC
(benzene hexachloride), chlordane, methoxychlor, aldrin, dieldrin, para-
thion, malathion,  toxaphene, 2,4-D (2 ,4-dichlorophenoxyacetic acid),
2,4,5-T (2,4,5-trichlorophenoxyacetic acid),  captan, zineb,  and  barbaryl
(Sevin).  A more complete list of widely used pesticides  is contained in
Appendix A.
Trends in Production and Use

       The extent to which the pesticide industry has  changed over the
years can be readily grasped by considering that more  than 80% of this
industry's output now comes from organic chemicals, while in the 1940's
the industry depended almost entirely on inorganic materials.   The  shift
is illustrated by the decrease in output of lead arsenate and calcium
arsenate which were the backbone of the pre-war pesticide industry.

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   RAW  MATERIALS:
    90% ORGANIC
   (95% SYNTHETIC)
   FUNGICIDES
ORGANO- METALLIC
                  HERBICIDES


TOTAL  KILLERS      SELECTIVE  KILLERS
PRE-EMERGENT

           POST- EMERGENT
                    RAW MATERIALS:
                    10% INORGANIC
                    (5% NATURAL)
                                                        RODENTICIDES
                  'ACARICIDES
              NEMATOCIDES
               \    \



INSECTICIDES       \      STERILANTS
  KILLERS
                                           ES       L
                                           \     <
      ATTRACTANTS

REPELLANTS
                                SYSTEMIC
  GROWTH   REGULATORS
            CONTACT
        Figure 1.  Classification and Relative Importance of Pesticides
                 (Anon. , Chem. Engr. .  1969)

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       Table 1.  Decrease in Inorganic Pesticide Usage in the U.S.

            Year	1940   1960   1965   1967    1968

Lead arsenate (million pounds)        75     10     7      6      9

Calciumarsenate (million pounds)     50      7     4      2      3


Source: Anon. ,  Chern. Engr., 1969.
Highly chlorinated organic compounds have followed the same trend (Table
2).  BHC (benzene hexachloride), for instance, has been gradually dis-
placed by the dieldrin-heptachlor class of compounds which are more
specific and effective.  In contrast, the production of DDT has fluctuated
erratically and is now below its peak of the early 1960's, but may continue
to be used in significant quantities (Anon., Chem. Enqr., 1969).

       With the appearance of resistance to DDT by a number of organisms,
a large group of  new pesticides has appeared (first the organophosphates,
then the carbamates, and others).  There are now in the  U.S. some  900
active pesticidal chemicals formulated into over 60,000  preparations (Mrak,
et. al_., 1969).  Recent regulations limiting or banning the use of DDT under
certain conditions may have a marked effect on its future production, as
well as the production  of "replacement compounds." However, the  high
costs involved in developing and testing  new pesticides for marketing have
risen to 3-6 million dollars per product and will tend to reduce the number
of new chemicals reaching the market.
Recent Production and Sales Data

       Production of the major pesticides for 1960-1969 is given in Table
3.  Trends in pesticide usage are obvious. As indicated more clearly in
Table 4, changes are occurring in the popularity of certain pesticides.
Since 1966 the percentage of pesticides classified as fungicides (on a
weight basis) has dropped from 14.4 % to 13.3% in 1969 and the  insecti-
cide percentage has decreased from 58.7% of the market to 53.2%.
Herbicide use during the same period  increased from 26.9% of the market
to 33.5%.  The chlorinated hydrocarbon type herbicide usage has
decreased, but the  substitute compounds have more than made up for
the decrease.
                                   17

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     Table 2.  Production Decline of Chlorinated Pesticides in U.S.
Annual Production, Million Lbs.
Year
1952
1954
1956
1958
1960
1962
1964
1966
1967
1968
1969
BHC
85
77
85
31
37
12
<6
<6



DDT
100
97
138
145
164
167
124
141
103
139
123
Others*
	
45
87
98
91
106
105
119
120
116
110
Total
185
219
310
274
292
285
240**
260**
223**
255**
233**
 *Dieldrin, aldrin, toxaphene, heptachlor, chlordane, endrin, terpene
  polychlorinates.
**Estimate.
  Source: U.S. Tariff Commission Statistics, Chem. Enqr. ,  1969.
                                    18

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Table 3.  U.S. Pesticide Production (Annual Production - Thousand Lb.)
Compound
Calcium arsenate
Lead arsenate
Copper sulfate
Aldrin toxaphene
group
Benzene
hexachloride
DDT
Methyl bromide
Parathion
Ferbam
Nabam
Zineb
1960
6,
10,
116,
99,
37,
164,
12,
7,
2,
2,
-
590
062
000
671
444
180
659
434
529
978

1962
4,
9,
79,
. 106,
12,
167,
12,
8,
2,
4,
-
660
990
968
276
022
032
757
786
966
216

1964
6,958
9,258
83,768
105,296
	
123,709
16,994
12,768
1,838
2,251
6,664
1965
4,192
7,098
94,656
118,832
	
140,783
14,303
16,607
2,384
2,489
5,075
1966
2,890
7,328
103,416
130,470
	
141,349
16,345
19,444
1,379
2,053
4,721
1967
2,040
5,952
80,256
120,183
	
103,411
19,665
11,361
2,331
1,361
3,055
1968
3
9
87
115
-
139
20
-
1
-
3
,398
,016
,568
,974

,401
,454

,900

,081
1969
	
	
101,136
	
	
	
	
	
	
	
	

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       Table 3.  (Continued)
ro
o
Compound
2 , 4-D acid
2,4, 5-T acid
Methyl parathion
Other organic
pesticides
1960
36,185
6,337
11,794
227,229
1962
42,997
8,369
16,156
348,967
1964
53,714
11,434
18,640
437,943
1965
63,320
11,601
29,111
477,148
1966
68,182
15,489
35,862
577,816
1967
77,139
14,552
33,344
663,261
1968
79,263
17,530
38,163
694,421
1969
47,077C
	
17,938
	
       alncludes the chlorinated compounds aldrin, chlordane, dieldrin, heptachlor, and toxaphene.




        Gross production (gamma isomer content was 7.7 million pounds in 1961,  3.4 million pounds in 1962,

        and 1.8 million pounds in 1963); no data since 1963.




       Preliminary




       Source:  U.S. Tariff Commission Statistics, 1969.

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ro
  Table 4.  Synthetic Organic Pesticides:  Volume and value of sales by classes, U.S. , 1966-1969


                                    VOLUME OF SALES


                       1966                1967                 1968                 1969

Class           Amount  % of Total  Amount % of Total   Amount  % of Total   Amount  % of Total

                1000 Ibs             1000 Ibs            1000 Ibs            1000 Ibs

Fungicides       118,397    14.4     120,413   13.4     129,961    13.5     124,418    13.3

Herbicides &
 plant hormones 221,502    26.9     287,582   32.1     318,554    33.2     311,158    33.5

Insecticides,
 fumigants,
 rodenticides
 and soil
 conditioners     482,357    58.7     489,368   54.5     511,116    53.3     493,088    53.2


Total            822,256   100        897,363  100        959,631   100        928,663   100

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      Table 4.  (Continued)
                                           VALUE OF SALES
      Class
                      1966
                Amount  % of Total
       1967               1968
Amount  % of Total   Amount  % of Total
       1969
Amount  % of Total
ro
ro
                      $1000
      Fungicides
Herbicides &
 plant hormones  257,635
      Insecticides,
       fumigants,
       rodenticides
       and soil
       conditioners
                                    $1000
                 53,275     9.1      56,333    7.2
                                 44.1    429,980   54.6
                272,892    47.3     300,730   38.2
                    $1000
                     62,061     7.3
$1000
 61,174     7.2
                    483,330    56.9     495,670    58.2
                    303,849    35.8     294,322    34.6
      Total
                583,802    100      787,043  100
                    849,240   100
851,166   100
      Source:  U.S. Tariff Commission Statistics, 1969.

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                    Table 5.  Pesticides and Related Products:  U.S.  Production and Sales, 1969



      [.Listed below are all pesticides and related products for which any reported data on production or sales

       may be published.  (Leaders are used where the.reported data are accepted in confidence and may not

       be published or where no data. were reported.)  I
                                *                  J
u>


Product


Grand Total 1 ,
PESTICIDES AND RELATED PRODUCTS , CYCLIC
Total
Fungicides , total
3 , 5-Dimethyl-l, 3 , 5-2H-tetrahydrothiadiazine-
2-thione (DMTT)
Mercury fungicides, total
Phenylmercuric acetate (PMA)
Phenylmercuric oleate
Other mercury fungicides
Naphthenic acid, copper salt
Pentachlorophenol (PCP)
8-Quinolinol (8 -Hydrozyquinoline) , copper salt
All other fungicides


Production
1,000
pounds
104,381

819,748
100,748

1,074
1,475
534
407
534
1,545
45,988
88
50,578


Quantity
1,000
pounds
928,663

666,038
84,384

1,102
1,298
351
381
566
1,529
40,566
205
39,684
Sales

Value
1,000
dollars
851,166

697.167
34,557

517
6,792
2,467
1,126
3,199
438
5,946
285
20,579

Unit
Value
per
pound
$0.92

1.05
.41

.47
5.23
7.03
2.96
5.65
.29
.15
1.39
.52

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      Table 5.  (Continued)
ro
Product Production
1000
pounds
Herbicides and plant hormones, total 324,221
l,2-Dihydropyridazine-3 , 6-dione
(Maleic hydra zide) (MH)
Phenozyacetic acid derivatives:
2,4-Dichlorophenizyacetic acid (2,4-D)
2,4-Dichlorophenozyacetic acid esters
and salts, total
2 , 4-Dichlorophenozyacetic acid ,n-butyl ester
2 , 4-Dichlorophenozyacetic acid , sec-butyl ester
2,4-Dichlorophenozyacetic acid,
dimethylamine salt
2,4-Dichlorophenozyacetic acid, iso-octyl ester
All other (2,4-D) esters and salts
. . 2,4,5-Trichlorophenozyacetic acid (2,4,5-T)
2 ,4 ,5-Trichlorophenozyacetic acid esters
and salts , total
2,4, 5-Trichlorophenozyacetic acid ,
n-butyl ester
2,4, 5-Trichlorophenozyacetic acid ,
iso-octyl ester
All other (2,4,5-T) esters and salts
2-(2,4,5-Trichlorophenozy) propionic acid (Silvex)
2,771

47,077

56,998
3,403
4,992

22,403
11,093
15,107
4,999

11,626

258

4,187
7,181
1,597
All other cyclic herbicides and plant hormones 199,153

Quantity
1000
pounds
250,069
  _

18,786

46,057
2,675
	

20,270
8,384
14,728
	

5,697

524

2,974
2,181
	
179,547
Sales
. Value
1000
dollars
445,275
_ __

5,224

14,627
1,200
	

6,347
2,449
4,631
	

5,963

452

3,393
2,118
	
419,461

Unit
Value
per
pound
1.78
 _ _

.28

.32
.45
	

.31
.29
.31
	

1.05

.86

1.14
.97
	
2.34

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      Table 5.  (Continued)
ro
Product


Insecticides and rodenticides , total
Aldrin-toxaphene group
a -Bis (p-chlorophenyl) -B, B , B -trichloroethane
(DDT)
Organophosphorus insecticides, total
0, 0-Dimethyl 0-p-nitrophenyl phosphorothioate
(Methyl para th ion)
All other organophosphorus insecticides
All other insecticides and rodenticides
PESTICIDES AND RELATED PRODUCTS, ACYCLIC
Total
Fungicides , total
Dimethyldithiocarbamic acid, ferric salt(Ferbam)
Ethylene bis (dithiocarbamic acid) , disodium salt
(Nabam)
All other acyclic fungicides
Herbicides and plant hormones
Production
1000
pounds
394,467
	

123,103
92,458

50,572
41,886
178,906

284.945
39,805
	

1,938
37,867
69,085

Quantity
1000
pounds
331,585
110,366

80,305
70,361

32,818
37,543
70,553

262,625
40,034
1,771

1,989
36,274
61,088
Sales
Value
1000
dollars
217,335
50,228

11,032
73,190

15,794
57,396
82,885

153.999
26,617
645

880
25,092
50,395

Unit
Value
per
pound
.66
.46

.14
1.04

.48
1.53
1.17

.59
.66
.36

.44
.69
.82
      Source:  U.S. Tariff Commission Report, 1969.

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Forecasts in Production and Use

       The production and use of pesticides in the U.S. is expected to
continue to grow at an annual rate of approximately 16%.  Predictions are
that insecticides will more than double in use  in five years and herbicides
will increase at a more accelerated pace  (perhaps 20% annually).  The
foreign use of pesticides will likewise continue to increase with the
organochlorine and organophosphorus insecticides continuing to repre-
sent a significant part of the foreign market (Mrak , _et al., 1969).

       Sales predictions based on a survey of  13 of the industry's leading
producers (companies which account for well over half of the pesticide
sales in the U.S.) show a $187 million increase in U.S. sales of techni-
cal synthetic organic pesticides in 1970 and a  $651 million jump by  1975.
These manufacturers project the $1.5 billion pesticide market in  1975 will
be as follows:  fungicides, $75 million; insecticides,  $526 million;
herbicides, $950 million (Anon. ,  Industry and Business, 1970).  Figure
2 graphically shows past and predicted pesticide production (including
exports) in the U.S.  Presently 32 of the major pesticides account for
more than 50% of the total sales of unformulated pesticides.  The pro-
jected growth of these market leaders is given  in Table 6.
                                   26

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<0
o
   2400
I; 2200
 H-
 o
 n
 o
 o
 o:
 o.

 UJ
 o

 o


 
 UJ
 Q_

 u_
 o

 UJ
 u
2000


1800


1600


1400


1200


1000


 800


 600


 400


 200
TOTAL  UNFORMULATED

    PESTICIDES
        '62    '64    '66
                        '68    '70

                        YEAR
                               '75
 Figure 2.  Past and Projected Pesticide Production in the U.S.



 Source: Neumeyer, _et al.. , 1969.

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                   Table 6.  Principal Products
                   Dominant Pesticide Products
Products, annual sales
  Projected
Sales Growth       Type
  Chemical
Classification
$25 million & over
Atrazine
Treflan
Sevin
Amiben and Related Products
Malathion
2, 4-D
$10-25 million
Aldrin
Ramrod, Randox &
Related Products
Diazinon
Toxaphene
DDT
Methyl Parathion
Parathion
Guthion
Planavin
Endrin
Dithiocarbamates
Captan
Chlordane
Heptachlor
$5-10 million
2, 4, 5-T
Tordon
Methyl Bromide
Knoxweed (EPTC, 2, 4-D)
Disyston
Thimet

5-10%
15-20%
5-10%
15-20%
10-15%
5-10%

0-5%

10-15%
5-10%
0-5%
decline
0-5%
decline
10-15%
20%+
0-5%
0-5%
5-10%
10-15%
decline

10-15%
15-20%
decline
10-15%
10-15%
10-15%

Herb.
Herb.
Inst.
Herb.
Inst.
Herb.

Inst.

Herb.
Inst.
Inst.
Inst.
Inst.
Inst.
Inst.
Herb.
Inst.
Inst.
Inst.
Inst.
Inst.

Herb.
Herb.
Fum.
Herb.
Inst.
Inst.

Chi. Hyd.
Syn. Org.
Carb.
Chi. Hyd.
O.P.
Chi. Hyd.

Chi. Hyd.

Chi. Hyd.
O.P.
Chi. Hyd.
Chi. Hyd.
O.P.
O.P.
O.P.
Syn. Org.
Chi. Hyd.
Carb.
Chi. Hyd.
Chi. Hyd.
Chi. Hyd.

Chi. Hyd.
Chi. Hyd.
Syn. Org.
Carb.
O.P.
O.P.
                                  28

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Table 6.  (Continued)
                             Projected                     Chemical
Products,  annual sales      Sales Growth       Type       Classification
Pentachlorophenol
Methyoxychlor
Kelthane
Bux-Ten
Cyprex
Paraquat
Banvel
0-5%
5-10%
0-5%
15-20%
10-15%
0-4%
15-20%
Fung.
In st.
In st.
In st.
Fung.
Herb.
Herb.
Chi. Hyd.
Chi. Hyd.
Chi. Hyd.
Garb.
Syn. Org.
Syn. Org.
Chi. Hyd.
Source: Neumeyer , _et al_., 1969.

Legend:

Garb.       =  carbamate
Chi.  Hyd.  =  chlorinated hydrocarbon
Syn. Org.   =  synthetic organic
O. P.       =  organophosphorus
                                 29

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                          CHAPTER IV

                   PESTICIDE MANUFACTURE
       This chapter will include brief discussions of the manufacturing
processes utilized to produce several of the major types of pesticides.
Since many of these processes are presently covered by patents, infor-
mation of kinetics, yields, waste products and product purity is limited.
General process descriptions taken from various  literature sources will
be given and waste stream characteristics as reported by manufacturers
will be included without modification.
Producers of Pesticides

       Dow Chemical and E.I. duPont de Nemours, followed by Union
Carbide, are the largest producers of pesticides in the U.S.  Next in
sales volume are American Cyanamid, Rohm and Haas, Stauffer Chemical,
Velsicol Chemical,  and Chemagroall of which have  specialized in a
particular area.  For instance, Chemagro produces a complete line of
phosphate insecticides and miticides developed by Bayer in West Germany.
FMC Corp., which acquired Niagara Chemical, is typical of many other
companies that entered the pesticide business by acquisition. Oil com-
panies such as Standard Oil of California (Ortho brand products)  and Shell
(Vapona brand), and drug companies such as Geigy and Elanco also produce
significant quantities of pesticides (Anon. , Chern., Engr. , 1969).
Manufacturing Processes ajnd Waste Generation

       The patent literature contains valuable information on the numerous
processes for the manufacture of pesticides.  A collection of processes for
84 important pesticides is found in Pesticide Production Processes (Sittig,
1967).  However, in many cases a certain amount of "art"  that cannot be
described in the literature is required to produce a pure product or achieve
90% reaction rather than 60%. Therefore, product quality and waste stream
characteristics will vary significantly, even for the same product and process,

       The basic manufacturing processes for some of the more widely-used
pesticides are described in the following discussion.
                                31

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DDT

       DDT (Dichloro-diphenyl-trichloroethane) is a name that covers 27
possible isomers,  the most active of which is l,l,l-trichloro-2, 2-bis
(chlorophenyl) ethane.  DDT was one of the first pesticides  manufactured
on a large scale and easily holds the record for the greatest volume of
any organic pesticide ever produced.  Its manufacture is relatively simple;
it is made by condensing monochlorobenzene  and chloral in the presence
of concentrated sulfuric acid (Sittig / 1967).

       The reaction can be represented by the following equation:
                +CC1-CHO
The biggest problems in DDT manufacture are in the recovery of unconverted
ingredients and in steering the reaction toward production of the desired
isomer.  The reaction is kept below 30  C and  takes place at atmospheric
pressure in a stirred batch reactor system.

       DDT recovery (according to U.S. Patent 2,932,672,  Diamond
Alkali) is by crystallization. Impure DDT crystals are washed with a
caustic solution, and unreacted  monochlorobenzene is removed by
melting the crystals and bubbling steam through the melt. The purified
crystals  are then dried and flaked  (Anon. , Chem. Enqr. ,  1969).

       The wastes resulting from the process  include spent  acids
(hydrochloric and sulfuric), monochloral benzene,  sodium monochloral
benzene  sulfonate, chloral, NaOH caustic washwaters,  chlorobenzene,
sulphonic acid,  and some product.  The waste streams may contain DDT
in the 1-5 ppm range with  DDE and other related compounds present in
amounts  up to four times the DDT level.  The pH of the waste is low and
the salt content  is high.   Information on DDT waste stream characteristics
including BOD, COD, toxicity, TDS, flow, etc. were not made available
by any of the manufacturers contacted during this study.
                                 32

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Carbaryl (Sevin)

       The largest volume carbamate insecticide is  1-naphthyl, N-methyl
carbamate.  According to Union Carbide,  carbaryl (Sevin) is manufactured
from alpha-naphthol, phosgene, and methylamineall of which are readily
available.  There are three reaction steps.  Alpha-naphthol reacts with
sodium 1-naphthoxide, which in turn, is reacted with phosgene; the result-
ing chloroformate is reacted  with methylamine as follows:
                               OCONHCH3
                                       + CH NH HC1
                                           O   
The carbamate which crystallizes is easily separated (U.S. Patent
2,903,478).  Excess amine must be added to remove the hydrochloric
acid formed in the reaction.  Considerable care, through the use of
special scrubbers and by enforcing safety precautions,  must be taken
to ensure that phosgene does not escape to the atmosphere.  Wastewaters
contain high total solids, but almost no suspended solids and little pes-
ticidal compounds.  A typical waste stream from carbamate manufacture
will contain:

              COD                             10,000mg/l
              BOD5                            Nil
              Total Solids                      40,000
              PH                              7-10
              Suspended Solids                 Nil
              Sodium                           8,000
              Chlorides                        100
              Phosphates                       Nil
              Organic Nitrogen                 500
                                 33

-------
               Sulfates                    20,000
               Product                     Nil
               Toxicity                    Low
               Flow per pound of product    Not available
Parathion and Methyl Parathion

       These materials are both manufactured from sodium p-nitrophenolate;
methyl parathion is formed by reaction 0,0-dimethyl  phosphorothiochlor-
idate with the sodium compound,  and parathion, from the reaction of the
equivalent 0,0-diethyl compound.

       There are three steps involved in the synthesis of both parathion
and methyl parathion:  one common method involves the reaction of the
appropriate alcohol (methyl or ethyl alcohol) with phosphorus penta-
sulfide,  followed by chlorination.
               2 ROH + PS       2(RO)2 PSH + H  S
               ROPSH+C1       (RO)  PCI + HC1 + S
                 Ct        L+          Ct

The phosphorothoro-chloridate is then reacted with sodium  p-
nitrophenoxide, forming the final product
               (RO) PCI + NaOC  H NO0  (RO) POC H NO0 +NaCl
                  2           o 4   2     2    o  4   Z

(Anon. , Chem. Engr. ,  1969)

       The waste streams from parathion manufacture may contain sulfur,
HC1,  sodium chloride, sodium carbamate, trimethyl theophosphate,  and
other  organics including paranitrophenol and small amounts of product.
A typical waste stream can be characterized by:

               COD                3,000 mg/1
               BOD                   700
               Total Solids        27,000
               pH                      2.0

-------
              Acidity              3,000
              Sodium              6,000
              Chlorides           7,000
              Phosphates            250
              Nitrates                20
              Sulfates             3,000
              Parathion              20
              Calcium               High

Gaseous emissions from parathion production contain significant amounts
of mercaptans including hydrogen sulfide.  Concentrated residues and
tank bottoms must also be handled since  they contain large amounts of
intermediates and some  product.  This portion of the  waste may be a
slurry with a paste-like consistency which poses severe handling prob-
lems (Stutz, 1966), but  seldom enters the wastewater stream.
2,4.5-T. 2,4-D and MCPA Herbicides

       The major aromatic-based herbicides are 2,4,5-T (2,4,5-
trichlorphenoxyacetic acid); 2,4-D (2 ,4-dichlorphenoxyacetic acid),
and MCPA (2-methyl, 4-chlorophenoxy acetic acid).  Their synthesis
begins with the reaction of monochloracetic acid with a  phenol group.
The phenoxy group, which is produced  in this reaction,  appears in
these three herbicides in a 2,4-DEP  ("Falone"), and many other her-
bicides. .The general reaction of monochloracetic acid with phenol is
via sodium phenate.  The process used for 2,4-D, the most widely sold
product of the chlorinated herbicide manufacturing process, is typical.
Monochloracetic acid is condensed with the dichlorphenate in an alkaline
solution at atmospheric pressure and 60 to 80C for six  to eight hours
in a jacketed stirred reactor; no catalyst is necessary.  The reaction may
be described by:
              Cl                           Cl
                 ONa                         OCH COOH
                  + C1CH  COOH  	-   ||f          + NaCl
                                       cr
                                  35

-------
When the reaction is complete, excess 2,4-dichlorophenoxide is decomposed
by acidifying the mixture to pH 5. The 2,4-dichlorophenol is removed by
steam distillation and recycled.  By  reducing the pH to about 1, the 2,4-D
acid precipitates from the reaction mixture and can then be filtered, washed
and dried. Esters of the 2,4-D acid are used as herbicides.  The other
chlorinated herbicides are produced in a similar  manner.

       For 2,4,5-T manufacture, a solvent is added to the reaction system
to produce the required reaction temperature of 100-180C, and the rate  of
reaction  is faster than that for 2,4-D production. MCPA is made by chlor-
inating methyl phenoxyacetic acid which comes from the reaction of mono-
chloracetic acid with the sodium  salt of ortho-cresol.

       The waste stream from chlorinated  hydrocarbon herbicides includes
large amounts of sodium chloride, hydrochloric acid,  some caustic, and
organics  including solvents, phenols, chlorophenols and chlorophenoxy
acids.  These wastes arise from acidification, washing steps,  phase sep-
aration steps, incomplete yields and chlorination of the phenolic compounds.
A typical waste  stream can be characterized by:

              COD                 8,300 mg/1
              BOD5                6,300
              Total Solids       104,000
              Suspended Solids     2,500
              pH                     0.5
              Chlorides          52,000
              Chlorophenols         112
              Chlorophenoxy Acids   235
              Nitrogen              Low
              Phosphorus            Low
              Flow                  30 # COD/ # Product

The chlorinated herbicide wastes can vary considerably from plant to
plant and even in the same plant as indicated by the  data in Table 7.
Diolefin-based Insecticides (Aldrin,  Dieldrin, Endrin, Chlordane and
Heptachlor)

       This group of insecticides is  derived from cyclopentadiene, and
from hexachlorocyclopentadiene.  Hexachlorocyclopentadiene can be
                                 36

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                        Table 7.  Waste Characteristics of Chlorinated Herbicide Wastes
Analysis
PH
COD (mg/1)
BOD 5 (mg/k)*
Chlorides (mg/1)
Total Solids (mg/1)
Total Volatile
Solids (mg/1)
Suspended Solids (mg/1)
Volatile Suspended
Solids (mg/1)
Total Kjeldahl Nitrogen
(mg/1)
Ddors

2, 4, 5-T Acid Waste
Sample #1
7.5
21,700
16,800
96,300










Sample #2
7.9
25,700
*
69,000
172,467

18,150
700

242

40
Not
Offensive
Sample #3

19,600
2 , 4-D Acid Waste
Sample #1
8.5
27,500
13,400 16,700











144,000










Sample #2
9.5
23,600
*
72,000
167,221

22,100
348

83

45
Not
Offensive
Sample #3

22,700
13,000











JO
       *16,680 mg/1 using 50-50 dilution of 2,4-D and 2,4,5-T and acclimated seed (below toxic levels)




       Source:  Ford & Gloyna  "Confidential Report" 1967.

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produced from a reaction of n-pentane and chlorine as described by J.
T. Fatten, et al. in U.S. Patent 2,960,543.  Cyclopentadiene may be
produced by vapor phase cracking of naphtha.  Aldrin (1,2,3,4,10-
hexachloro-1,4,4a,5 ,8-hexahydro-l ,4-endo-exo-5 ,  8 dimethano-
naphthalene) may be produced under slight pressure and elevated
temperatures by the reaction of hexachlorocyclopentadiene with
bicycloheptadiene, according to the equation:
           H
Toluene may be used as a solvent in the reaction.

       Dieldrin may be produced by epoxidizing aldrin with a per-acid:
                                            H
       Chlordane (1,2,4,5,6,7,8,8-octachlor-2,3,3a,4,7,7a-hexahydro-
4,7-methanoindene) is produced by the reaction of hexachlorocyclopentadiene
and chloropentadiene according to the Diels-Alder condensation at atmos-
pheric pressure and 70-85C:
       H
H
Cl
Cl
                                   38

-------
Chlorination of chlordene produces chlordane:
                         H
                              + Cl
        Cl
                                             Cl
       Heptachlor may be formed by chlorination of chlordene in a
benzene solution, resulting in substitution chlorination rather than
addition chlorination:
                            + CL
                                                        H
                    + HC1
       A typical waste stream from a diolefin based chlorinated
hydrocarbon pesticide manufacture will include:
               COD
               BODr
                   \J
               Total Solids
               Suspended Solids ,
               PH
               Chlorides
               Nitrates
               Phosphates
               Product
               Toxicity
               Flow
  500 mg/1
   50
1,000
  100
    2
  High
  100-300 ppb as Endrin
  High
  0.375 gallons treated
    wastewater/#product
               (This does not include concentrated liquids, tank
               "bottoms", spent catalysts, etc., which are normally
               landfilled.)
                                    39

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                           CHAPTER V

             PESTICIDAL WASTE TREATMENT TECHNIQUES:
             REMOVAL, DETOXIFICATION, DEGRADATION,
                         and DECOMPOSITION
       This chapter is included to provide a summary of the information
contained in the technical literature which deals with the  treatment and
disposal of pesticides and  pesticide wastes.  The amount of work reported
on this subject is limited and many studies are incomplete.  However, all
available data were evaluated and are included in as usable form as possible,
Chemistry of Pesticides

       Natural insecticides such as rotenone and pyrethrins  (plant extracts)
are susceptible to hydrolysis, oxidation,  and photodegradation.  Rotenone
is readily detoxified by the action of light and air. Deterioration also takes
place with heat (at 100C, 76% of the rotenone is lost in 2 hours and at 40
C,  4.6% is lost in 30 hours).  Pyrethrins are easily hydrolyzed in a basic
medium to nontoxic products (Frear,  1955).

       Carbamates such as carbaryl (Sevin) are susceptible to hydrolysis
in alkaline media.  The reaction is rapid at  pH  levels of 9 or more.  The
product of alkaline hydrolysis is naphtol. For disposing of small volumes
of carbaryl suspended in water, caustic treatment in settling tank may be
sufficient.  For each 5 pounds of carbaryl actually carried into the tank,
addition of 2 pounds of flake caustic will provide a 50% excess of the
minimum required to react with the carbaryl. (Flack,  1966 and Anon. ,
Natl.  Agr. Chem. Assn., 1965).

       Orqa no phosphorus insecticides such as TEPP (tetraethyl pyro-
phosphate) and parathion are susceptible  to hydrolysis.  Parathion hydrol-
ysis is accelerated in an alkaline  media.  Malathion can be hydrolyzed
and oxidized.  The decomposition  is catalyzed  by iron salts.  Hydrolysis
is faster under alkaline conditions.  This is illustrated by the following
pH study:  at a pH of 12,  malathion  is hydrolyzed almost instantaneously,
at pH of 9, 50% is hydrolyzed in about 12 hours and no hydrolysis occurs
at pH 5-7 in 12 days (Whitehouse,  1967).  In water solutions TEPP is
rapidly hydrolyzed even in the absence of alkali.  At 25C the half-life
of the  compound in neutral water is 6.8 hours and at 38C it is 3.3 hours.
The presence of alkalis also increases their hydrolysis rate greatly.  The
product of hydrolysis is diethyl phosphoric  acid which is non-toxic.

-------
       Chlordane in the presence of an alkali dehydrochlorinates to form
nontoxic products; this  reaction is catalyzed by traces of iron and some
other metals  (Whitehouse,  1967).

       Heptachlpr is not affected by acid or alkaline condition and is
stable against hydrolysis; however, it is subject to catalytic decompo-
sition by metals such as iron.

       Aldrin is stable  chemically and is not decomposed by alkaline
materials  (Whitehouse,  1967).  Aldrin in aqueous solutions is readily oxi-
dized by chlorination, potassium permanganate, ozone and aeration; per-
oxides have no measurable effects.  Catalytic decomposition of aldrin
results when it is mixed with inert diluents  for dusts  (Fleck,  1966, Frear,
1955,  Buescher, et al. , 1964,  and Whitehouse, 1967).  If oxidation is
used,  care must be taken to insure complete reaction. The first step in
the oxidation of aldrin leads to dieldrin rather than to a nontoxic product
Like heptachlor, aldrin  is subject to catalytic decomposition if active
metals are present.

       Dieldrin, like aldrin, is chemically  stable and is not decomposed
by alkalis and mineral acids; however, it is subject  to catalytic decompo-
sition (Frear, 1955).

       Isodrin  (a stereoisomer of aldrin) is  slowly decomposed when
heated above 100C.  Like aldrin, isodrin is not decomposed by alkalis
(Frear, 1955).

       Endri.n is not decomposed by alkalis, but acids cause a rearrangement
into a compound which does not demonstrate insecticidal activity.

       Toxaphene  is dehydrochlorinated by  heat (at temperatures above
155C), UV light,  and alkalis.

       Benzene Hexachloride  (BHC)  -  The isomers of BHC are stable to
light,  heat, air,carbon dioxide, and strong acids (Whitehouse, 1967).
In the presence of alkalis the alpha, gamma, delta,  and  epsilon isomers
are readily dehydrohalogenated. The beta isomer is  decomposed slowly
by alkali at room temperature, but it is readily broken down at higher
temperatures under the same conditions.  Approximate second order rate
constants for dehydrochlorination at 20C are (Cristol, 1947):

-------
       k  (alpha-isomer)
0.169 liters sec   mole
       k, (beta-isomer)     =

       kj (gamma-isomer)  =

       k, (delta-isomer)   =
where
       C  H Cl  +  OH"
         666
       C  H Cl  +  OH"
         65   5
       C  H Cl  +  OH
         644
3 x 10~6   "

0.045

0.110

not determined
C6H6C15 +   H2
C H Cl   +   HO  + Cl
 644       2
C  H Cl   +  HO  + Cl
 633       2
       DDT- In the presence of alkali DDT is dehydrochlorinated to form
dehydrochloro-DDT (l,l-dichloro-2 ,2-bis (p-chlorophenyl) ethylene).
This reaction is readily catalyzed by traces of iron, aluminum, and chro-
mium salts.  Pure DDT is quite stable in the presence of heat and does
not decompose  below  195C, but the technical material decomposes at
about 100C due to the presence of impurities such as iron.  The products
of thermal decomposition are not pesticidal.  DDT is also decomposed by
UV light and  some  investigations have revealed considerable decomposi-
tion by exposure to sunlight. DDT in solvents containing chloro- and
nitro-groups, such as mono- and dichlorobenzenes, ethylene chloride,
and nitrobenzene,  is readily decomposed by these materials.  DDT  is also
decomposed by basic  organic compounds such as methylamine and dimethyl-
amine(Anon. , Chem. Enqr. ,  1969, Mrak,  et aK ,  1969).  DDT, however is
not subject to hydrolysis since it is almost completely insoluble in water.

       TDE or DDD - Its physical and chemical properties are similar to
those of DDT.  It is dehydrochlorinated in alkali at a slower rate than DDT.
It is not affected by exposure to UV under conditions which decomposed
DDT, but it is dehydrochlorinated in the presence of ferric chloride at 300C.

-------
       Methoxychlor has generally the same physical and chemical
properties of DDT, but it is somewhat more resistant to decomposition
in the presence of alkalis.  It slowly dehydrochlorinates in strong alkalis.

       DFDT - Like  DDT, it is easily dehydrochlorinated by alkali.

       Q, p.'-DDT - It is dehydrochlorinated by alcoholic alkali like the
p, p1 isomer, but at  a much slower rate (Frear, 1955).

       Dilan - Like  DDT, this compound is unstable in the presence of
alkalis.  It is also oxidized rather easily (Frear, 1955).

       Chlorobenzilate - Being an ester,  it is decomposed by strong
acids and alkalis (Frear, 1955).

       Aramite - Being an ester,  the  material is readily decomposed by
alkalis.  It is also slowly decomposed by sunlight.

       Phenolic herbicides may be oxidized with Fenton's reagent (hydrogen
peroxide and ferrous ammonium sulfate catalyst: Fe(NH )  (SOJ2) and with
hypochlorite  (chlorine oxidation).  Fenton's reagent oxidizes phenol opti-
mally when one mole of ferrous salt and three moles of hydrogen peroxide
per mole of phenol are used. Aeration increases the reaction rate and drives
the reaction further to completion.  Phenolic herbicides, which are substi-
tuted phenols, may be oxidized with Fenton's reagent (the greater the degree
of substitution, the  slower the reaction rate).  PGP (pentachlorophenol) is
not oxidized by Fenton's reagent.  Oxidation with hypochlorite works for
phenol and may work for substituted phenols (Eisenhauer, 1964).  The
chemistry of these compounds is similar to that of an intermediate strength
organic acid.  They readily form the esters, amides and salts  under proper
conditions.  They also form relatively water-insoluble salts of divalent
cations. Strong solutions of. acid  , amine and other salts of 2,4-D and
2,4,5-T can be precipitated with calcium or magnesium salts to reduce the
quantity of pesticides in a gross manner (Fleck, 1966).

Treatment Methods

       Chemical Oxidation

       Several studies have been  conducted on the effects of  oxidants on
pesticides (Robeck,  at ah , 1965, Aly and Faust, 1965,. Bueschler,_et ah ,

-------
1964, Brower, undated. Cohen, filai. ,  1960).  The following are lists of
oxidants commonly used, pesticides tested, and some results of the studies.

       Oxidants:      Chlorine (Cl ); chloride dioxide, potassium permanganate
                      (KMnO  ); ozone (O ); and peroxide (HO, Na O ).
                           fz          0                   Lt     * 

       Pesticides:     DDT; lindane; parathion; dieldrin; 2,4,5-T ester;
                      endrin;  aldrin; rotenone; toxaphene; powdered cube
                      root; sulfoxide;  2,4-DCP; and 2,4-D compounds
                      (sodium salt and esters).

       Results:        1)   Parathion is oxidized by chlorine and ozone to
                          a more toxic product which is known as  paraoxone
                          (Robeck, et ah , 1965).

                      2)   2,4-DCP (parent compound of 2,4-D) is readily
                          oxidized by potassium  permanganate (see Figure
                          3)  (Aly and Faust, 1965).

                      3)   In  general, unsaturated organic compounds are
                          more susceptible to ozone oxidation than satu-
                          rated compounds.  Buescher, e_t a_l. (1964) found
                          that lindane in aqueous solution is  readily
                          decreased by ozonation and only partially affected
                          by potassium permanganate.  Treatment with chlor-
                          ination, peroxides, and aeration has no measurable
                          effects  (see Table  7, Figure 4, and Figure 5).

                      4)   Aldrin in aqueous solution is readily attached by
                          chlorination, potassium permanganate, ozone and
                          aeration (see Figure 6 and Table 8); peroxides
                          have no measurable effect (Buescher,  e_t ah ,
                          1964).  According to Brower (Sc.D.  Dissertation,
                          1967), the  ozonation products of aldrin are less
                          toxic than aldrin itself.

                      5)   Dieldrin concentration  in aqueous solution is
                          decreased by aeration as shown in Figure 7
                          (Buescher,  etaL , 1964).

-------
        100
         80
    c
    
-------
   40
O 30
UJ
IE
UJ
o
ir
UJ
o_
   20
10
                                                     40 mg/l
                                                     32 mg/l

                                                     20 mg/l
                                                     I6mg/l-
                              9       12       15       18
                           CONTACT   TIME  (hours)
                                                              21
                                                                  24
             Figure 4. Removal of lindane by treatment with potassium
                      permanganate. The initial concentration was
                      approximately 8 mg/l lindane in distilled  water.
                      Lines and values represent the concentration of
                      KMnO4 added.
             Source:   Buescher, e_ta_l., 1964.

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                     AERATE.D	
                           COMPRESSED  OR
                             AT  STP
Figure 5 .y R'emovl -of liridane by aeration and ozonation.
        '.-The iri'itfal concentration of lindane was
        ', ;a"pprdximately 8 mg/1 in distilled water.  The
        ; '-ozone .^n^entration was 3.9% by weight in
       " '. ai.r'inj^cited at a rate of 0.3 1/m through a
       .-  ..2.5 l-'r^fector.  10% ozone absorption was achieved
Source:    Buescher, etaL , 1964.

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  100
   90
   80
   70
O  60
UJ
Cd
UJ
UJ
a.
                 OZONATION
   50
   40
    30
    20
    10
                   o
                /  AERATION
 /
/
              I
                   I
I
I
      0      10
         LITERS
           20     30    40    50
          OF  AIR,  COMPRESSED  OR
        OZONATED  AT  STP
   Figure 6.  Removal of aldrin by aeration and ozonation.
            The initial concentration of aldrin was approx-
            imately  .02 mg/1 in distilled water.  The ozone
            concentration was 3.9% by weight in air injected
            at a rate of 0.3 1/m through a 2.5 1 reactor.  10%
            ozone absorption was achieved.
   Source:   Buescher, .eta!-/ 1964.

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        LITERS  OF AIR,  COMPRESSED OR
                 OZONATED  AT  STP
Figure 7. Removal of dieldrin by aeration and ozonation.
         The initial concentration of dieldrin was approx-
         imately 0.2 mg/1 in distilled water.  The ozone
         concentration was  3.9% by weight in air injected
         at a rate of 0.3 1/m through a 2.5 1 reactor.  10%
         ozone absorption was achieved.

Source:   Buescher,  e_t al. , 1964.
                       50

-------
  Table 8.  Effects of Oxidants on Pesticides in Aqueous Solution
                                                             13
Oxidant
C12
H22
Na22
KMnCD
4
Oxidant
Dosage
(mg/1)
40
40
40
40
Pesticide
Lindane
Negligible
Negligible
Negligible
Positive
Studied
Aldrin
Positive
Negligible
Negligible
Positive
Ozone
3.9% by.wt.
of ozonized
air at 0.3 1/m
Positive
Positive
Source:   Buescher> et al.  (1964)
                                   51

-------
                      6)  Rotenone and rotenoid compounds;  Cohen,  et al.
                         (1960)  state that chlorine and chlorine dioxide are
                         effective against these compounds, but some
                         means must be provided for removing the sub-
                         stantial  amount of residual chlorine as shown in
                         Figures 8 and 9.
       Coagulation
       Alum coagulation studies by Robeck,_et al. (1965), Cohen, et al.
(I960), and "Whitehouse (1967) have been conducted on several pesticides.
The following  is  a list of pesticides studied and some results of the
studies.

       Pesticides:     DDT; Lindane; Parathion; Aldrin; Dieldrin; Captan,
                      BHC; Malathion;  and fish poisons (rotenone,
                      toxaphene,  cube  root,  sulfoxide).

       Results:        1) DDT is easily removed by alum coagulation at
                        doses typical  of conventional water treatment.
                        Efficiencies of removal are 98% for a 10 ppb load
                        and  97%  for a  25 ppb  load (Robeck, _et al, ,  1965).

                      2) Lindane and parathion have low efficiencies of
                        removal by conventional alum coagulation and
                        sand filtration.  For a load of 10 ppb, the removal
                        efficiency is 10% for lindane and 20% for parathion
                        (Robeck ,_et al. . 1965).

                      3) Fish poisons (rotenone, toxaphene, cube powder,
                        and commercial formulations) are not removed by
                        alum coagulation.  Treatment of these compounds
                        with as much as 100 mg/1 alum produces no sig-
                        nificant reduction in concentration (0.1 mg/1
                        initial concentration of rotenone and toxaphene;
                        2.0 mg/1 initial concentration of cube powder and
                        commercial formulations) (Cohen,_et_aL , 1960).

                      4) Aldrin, Dieldrin, Captan, BHC, and Malathion
                        have low efficiencies of removal by chemical
                        coagulation.   Aldrin (0.2 mg/1),  Dieldrin (.05
                        mg/1), Captan (.556 mg/1), and BHC (.0178 mg/1)

-------
v_n
UJ
UJ
(T

LU
Z
o

UJ
H
O
(T
                  100

                   80

                   60

                   40



                   20
10
 8
 6
                      -ONE-HALF  OF  96-hr TLm VALUE  = 0.003 mg/l
                     0    5   10   15   20  25  30  35  40  45


                          CHLORINE  APPLIED  (mg/l)


                       Figure 8. Effectiveness of Chlorine Treatment of 0.1 mg/l
                                Rotenone Solution

                       The data in Table 5 have been plotted to provide, by
                       extrapolation, an estimation of the  amount of chlorine
                       required to reduce the toxicity of 0.1 mg/l rotenone to
                       one-half the 96-hr TL  (median tolerance limit).
                                          m

                       Source:  Cohen,_et al_. , 1960.

-------
O
<

z
O
O
   200
  100

-  80


^  60


K  40
20
     10
              I
                 I
1
1
I
      0.4    0.5    0.6    0.7    0.8    0.9    1.0

        CHLORINE  DIOXIDE  APPLIED (mg/l)
   Figure 9 .  Contact Time and Chlorine Dioxide Required to

            Detoxify 0.1 mg/l Rotenone.

   The temperature of the solution was 25C; the pH, 7.5.
   Source:  Cohen, et al. . I960.

-------
                     were treated with alum (Aluminum sulfate, 0.02
                     to 1.0 grams per liter).  The hardness of the
                     samples was 10, 100, and 250 mg/1 (CaCOg).
                     The percent removal was approximately 6% for
                     Aldrin,  13% for Dieldrin, 3% for BHC , and 2%
                     for Captan. Neither the alum dosage nor the
                     hardness variation seems to affect the removal
                     to any great extent.  Malathion (100 to 180
                     mg/1) was  treated with alum, ferric sulfate
                     (72% Fe~(SC- ) ), and alum plus coagulant aids.
                     The percent removal was approximately 10% for an
                     alum dosage of 250 mg/1.  Ferric  sulfate removed
                     about 10% of the malathion for a dosage of 400
                     mg/1.  Coagulant aids had little effect upon
                     alum removal of malathion.
       Adsorption
       Many adsorption studies (Robeck, _et aL,,  1965, Aly and Faust, 1965,
Cohen, _et ah,  I960, Whitehouse, 1967, Sigworth, 1965,  Coffey, 1967,
Faust and Suffet, 1966, MacNamara, 1968) have been conducted on a large
number of pesticides.  The following are a list of adsorbents used, a list
of pesticides studied, and some results of the studies.

       Adsorbents:   Activated carbon; saturated clay systems (H/A1,  Ca
                     Mg, K); humic acid, New Jersey soils, muck soil
                     (organic soil); bentonite clay; cation exchange
                     resin; anion exchange resin; EPK (Edgar Plastic
                     Kaolin from the EPK Company); hydrous aluminum
                     silicate; USP (Fisher Scientific Company); and
                     Diluex (hydrous magnesium aluminum silicate).

       Pesticides:    DDT,DDD; lindane; parathion; dieldrin; endrin;
                     aldrin; chlordane; malathion; captan; BHC; 2,4-D
                     derivatives; 2,4-DCP; 2,4,5-T ester; toxaphene;
                     rotenone; CIPC; DCPA; DNBP; trifluralin; diphenamide;
                     amiben;  paraquat; and linuron.

       Results of studies on activated carbon:

                      1)  Activated carbon studies on herbicides and
                         pesticides (Sigworth, 1965) have shown that
                                   55

-------
    it is successful in reducing the concentration
    of these toxic compounds.  Investigations have
    included such widely used  herbicides and insec-
    ticides as BHC, DDT,  2,4-D, toxaphene, dieldrin,
    aldrin, chlordane, malathion, and parathion (see
    Table 9).

2)   Activated carbon studies on the removal of fish
    poisons (Cohen, et_ah_, 1960) have shown that
    rotenone,  toxaphene, and the solvents and emul-
    sifiers present in all the commercial fish poison
    formulations are removed.  This broad activity
    also eliminates odors.

3)   A study by Whitehouse (1967) on the removal of
    malathion, 2,4-D, aldrin,  dieldrin,  and DDT (by
    means of adsorption  on activated carbon) showed
    that substantially 100% removal could be obtained
    for  all levels of pesticide used.

4)   Activated carbon adsorption studies on herbicides
    have shown that the  amount of adsorption as
    measured by the reduction in biological activity
    was as follows:

    CIPA >trifluralin > 2,4-D >diphenamide >DCPA >
    DNBP >amiben (Coffey, 1967).  CIPC and tri-
    fluralin which were the most  readily adsorbed
    by activated carbon were desorbed the least.
    2,4-D was readily desorbed from both activated
    carbon and bentonite clay.

5)   Table 9 shows  that activated carbon easily removes
    DDT, lindane, parathion, dieldrin, endrin, and
    2,4,5-T ester (for initial concentrations  of 10 ppb).

6)   Table 10 shows high efficiency of adsorption for
    BHC, chlordane, DDT, aldrin, DDD, and endrin.

7)   Table 11 gives the effects  of activated carbon on
    parathion,  BHC, malathion,  2,4-D, chlordane, and
    DDT.

-------
      Table 9.  Summary of Cumulative Pesticide Removal at 10-ppb Load from Raw River Water
                                                  Pesticide Removed-per cent
Process
 DDT     Lindane  Parathion  Dieldrin 2,4,5-T
	                             Ester
                             Endrin
Chlorination5ppm chlorine
  (Batch test-90 minute contact)
Alum coagulation and sand .filtration

Carbon:

    Slurry- Slow mixing
                 _3
      5 ppm (2x10   #/# carbon) .
                                       98
                                                          751
                    80*'
           55
       65***
             30
>99
    ';:2rQ ppm (5x10

     Bed0:5
             55    >99

            ' ao,   >99

            >99    >99
75     80

85   v
35
                                                                                      ,.80
 * * Oxidized to paraoxon, which-i'S-more toxic than parathion.
 **A value of 20% is reported by Robeck, et al.. 1965.
***A value of 63% is reported by Robeck, et al.. 1965.
Source:   Robeck, e^ ai. , 1965.

-------
Table 10.  Efficiency of Adsorption and Recovery from Carbon
Insecticide
BHC
Chlordane
DDT :
Aldrin
DDD :
Endrin 

Adsorbed
99
99
98-100
97
96-100
91
Percent
Recovered
80
75
76
85
82
86
BHC - 8 liters of 5 ppm emulsion were passed through 12 grams of carbon.
Chlordane - 8 liters of 5  ppm emulsion were  passed through 12 grams of
            carbon.
DDT - 200 liters of 2.5 ppm emulsion were passed through 30 grams of
       carbon.
Aldrin, DDD, Endrin -  No data reported.

Source: Faust and Suffet, 1966.

-------
                     Table 11.  Effect of Activated Carbon on Herbicides and Insecticides
vn
Pesticide
Parathion
BHC-37, gamma
Malathion, 50 per cent
2,4-D, 23.5 per cent
2,4-D, 11.7 per cent
Chlordane, 6 percent
DDT, 50 per cent
Concn.
Treated
With
Carbon
(ppm)
10
25
2
6
1
50
5
Carbon
Dosage
Used
(ppm)
10
5
10
20
10
10
2
Threshold Odor Threshold Concn. Afte
Values Odor Units Calcd.
Before
50
70
50
50
70
50
70
After
4
6
4
3
2
1.4
4
Removed
per ppm
Carbon
4.6
12.6
4.6
2.4
6.8
4.9
33
From Odor
Reduction
( Units)
0.8
0.22
0.08
0.085
0.005
0.084
0.15
r Treatment
Detd. by
Chemical
Anal.
(ppm)
2.6
0.08
0.25
1.38
L*
L*
L*
        * Concentrations were to low to determine by available test methods.
        Source:  Sigworth,  1965

-------
 8)  Tables 12 and 13 give the carbon dosages
    required to reduce the concentrations of 2,4-D
    compounds and 2,4-DCP (the parent compound
    of 2,4-D).  Various amounts of the carbon
    (activated) were added to 1 liter volumes of
    fixed concentrations of the  sodium salt and the
    isopropyl, butyl, and  isooctyl esters of 2,4-D
    and 2,4-DCP.  These  suspensions were stirred
    rapidly at room temperature 25C +, 2C for 30
    minutes. Then the carbon was removed rapidly
    by vacuum filtration through filter paper. As
    the data in Table 12 indicates, large carbon
    dosages are required for good removal, making
    the process expensive if large volumes of
    wastewater are involved.

 9)  Figure 10 gives  the  carbon dosages required for
    removal of fish poisons.  The final concentration
    of the poisons desired is  half the  96-hour TLM -
    medium  tolerance limit (Cohen, e_ta_l., 1960).

10)  Figures  11, 12, and 13 show the results of
    tests of the removal of DDT, aldrin,  and dieldrin
    as a  function of contact time.  The experimental
    procedure consisted of placing 200 ml of pesti-
    cide  mixture into a flask containing 60  mg of
    activated carbon (300  mg/1).  Seven flasks, each
    containing 300 mg/1 of carbon in a pesticide
    mixture, were then placed on a Burrell wrist
    action shaker and agitated for specified times
    of 15 minutes, 30 minutes,  45 minutes, 1 hour,
    1.5  hours, 2 hours, and 3 hours.  Figures 14, 15,
    and 16 show the results of tests of the  removal  of
    dieldrin, aldrin and DDT as a function carbon
    dosage (Whitehouse,  1967).  The  experimental
    procedure consisted of placing 200 ml of pesti-
    cide  mixture into flasks which contained a  spe-
    cific concentration of carbon (5 mg/1, 25 mg/1,
    50 mg/1, 100 mg/1,  300 mg/l, 500 mg/1, 700  mg/1,
    or 900 mg/1).  The flasks were then placed  on the
    shaker and mixed for the optimum  time.
              60

-------
      Table 12.  Carbon Dosages Required to Reduce the Concentration
                         of 2, 4-D Compounds *
Initial
Concn.**
(mg/1)
10
5
3
1

Sodium
Salt
306
153
92
31
Carbon
Isopropyl
Ester
150
74
44
14
Dosage (mg/1)
Butyl
Ester
165
82
49
15

Isooctyl
Ester
179
89
53
16
 *Final concentration 0.1 mg/1.
**Expressed as the acid equivalent.
Source:  Aly and Faust, 1965.
           Table  13.  Carbon Dosages Required to Reduce the
                     Concentration of 2,4-DCP*
Initial
Concn.
(ug/l)
100
80
50
30
Carbon
Dosage
(mg/1)
5.9
4.7
2.9
1.7
# Removed
# Carbon
1.66xlO~2 **
1.33xlO~2 **
1.65xlO~2 **
1.64xlO~2 **
 *Final Concentration 2.0 |jg/l.
**Not in original table,  calculated by author.

Source:  Aly and Faust, 1965.
                                    61

-------
                 0       0.4       0.8       1.2       1.6       2.0

            INITIAL  FISH  POISON  CONCENTRATION, C0  (mg/l)



          Figure 10. Carbon Dosage Curves for Removal of Fish Poisons

From these curves, the amounts of carbon required to reduce any concentration of
fish poison to the selected permissible residual concentration can be determined.

Curves A, B, C, and D refer to the following poison formulations:

       Formulation A: active ingredients 2% rotenone and 7% toxaphene

       Formulation B: active ingredients 5% rotenone and 15% other cube extractives

       'Formulation C:  active ingredients 2.5% rotenone, 5% cube extractives,
                      and  2.5%  sulfoxide

       Formulation D:  active ingredients 5% rotenone and 10% other cube extractives

       Cube root - A fish poison

Source:  Cohen,  et_aL/ I960.

                                    62

-------
g   30
A  BARNEBY-CHENEY  XH-2  (WOOD  CHARCOAL)
  FISHER  COCOANUT
                                     I
                             I
                0.5
        1.0
       CONTACT
 1.5       2.0
TIME  (hours)
2.5
3.0
                      Figure 11.  Removal of DDT from Solution
                               as a Function of Contact Time

                      Initial DDT Concentration = 0.0044 ppm
                             Carbon Dosage = 100 ppm
                                   pH = 6
                      Source:  Whitehouse, 1967.

-------
   A  BARNEBY-CHENEY  XH-2  (WOOD  CHARCOAL)
   o  FISHER  COCOANUT
                                1
0.5        1.0        1.5        2.0

          CONTACT  TIME (hours)

      Figure 12.  Removal of Aldrin from Solution
                as a Function of Contact Time

      Initial Aldrin Concentration = 0.0066 ppm
            Carbon Dosage = 100 ppm
                   pH = 6
2.5
3.0
       Source: Whitehouse, 1967.

-------
ON
VJl
BARNEBY-CHENEY  XH-2  (WOOD  CHARCOAL)
FISHER  COCOANUT
                                              I
                          I
                                   1.0        1.5        2.0       2.5

                                  CONTACT  TIME  (hours)
                             Figure 13. Removal of Dieldrin drom Solution
                                      as a Function of Contact Time

                             Initial Bieldrin Concentration = 0.0040 ppm
                                  Carbon Dosage = 100 ppm
                                        pH = 6
                                              3.0
                             Source:  Whitehouse, 1967.

-------
ON
CTs
       Q
       UJ

       O

       UJ
       cr
   100


    90


    80


    70


    60


    50
E   40
tr
Q
uj   30

Q
    20


    10


     0
                         A  BARNEBY-CHENEY XH-2  (WOOD  CHARCOAL)

                             FISHER  COCOANUT
                       50        100       150       200       250

                                CARBON  DOSAGE  (mg/l)

                            Figure 14. Removal of Dieldrin from Solution
                                     as a Function of Carbon Dosage

                            Initial Dieldrin Concentration = 0.0040 ppm
                                  Contact Time = 1 Hour
                                       pH  = 6
                                                                   300
                            Source: Whitehouse, 1967.

-------
          100
o\


^_^
Q
UJ
O
:E
UJ
cc
z:
cc
Q

90
80
70
60

50
40
30
20
            0

            0
                          A  BARNEBY-CHENEY  XH-2  (WOOD CHARCOAL)
                          o  FISHER  COCOANUT
                       50        100       150       200       250

                                CARBON  DOSAGE  (mg/l)

                             Figure 15. Removal of Aldrin from Solution
                                      as a Function of Carbon Dosage
                             Initial Aldrin Concentration = 0.0066 ppm
                                    Contact Time = 1 Hour
                                          pH = 6
300
                             Source: Whitehouse, 1967.

-------
ON
Co



""
0
UJ
o
5
Ul
oc
\-
o
o

100
90
80
70
60
50
40
30
20
          10

           0
                            BARNEBY-CHENEY  XH-2 (WOOD CHARCOAL)
                            FISHER  COCOANUT
                      50        IOO       150      200       250

                               CARBON  DOSAGE  (mg/l)

                            Figure 16. Removal of DDT from Solution
                                     as a Function of Carbon Dosage

                            Initial DDT Concentration = 0.0044 ppm
                                   Contact Time = 1 Hour
                                         pH = 6
300
                            Source: Whitehouse, 1967.

-------
Results of studies on clays, resins, and other adsorbents:

              l) The adsorption of linuron, malathion, diphenamide
                 and DDT was studied using H/A1, Ca, Mg, and
                 K saturated clay systems and humic acid.  Adsorp-
                 tion by homoionic clays and humic acid was in the
                 order of malathion > diphenamide > linuron with
                 the exception of negative adsorption of diphenamide
                 in H/A1 and Mg kaolinite and H/A1 illite clays.
                 Potassium homoionic clays generally adsorbed more
                 linuron, diphenamide and malathion than did other
                 clay systems.  DDT clay systems indicated almost
                 total removal of the insecticide (MacNamara, 1968).

              2) An adsorption study of herbicides by Coffey (1967)
                 showed  that the biological activity of paraquat, a
                 cationic herbicide,  was not reduced by bentonite
                 clay and cation exchange resin.  DNBP (4,6-
                 dinitrophenol-O-sec butylphenol) was also
                 shown to be more strongly adsorbed by an  anion
                 exchange resin than by activated carbon.

              3) An adsorption study by Whitehouse (1967)  indicated
                 partial adsorption of aldrin, dieldrin, DDT, 2,4-D,
                 BHC,  captan,  and 2,4,5-T by clays. The clays
                 used were:  EPK - Edgar Plastic Kaolin, hydrous
                 aluminum silicate obtained from  the Edgar  Plastic
                 Kaolin Company; Bentonite, U.S.P. obtained from
                 the Fisher Scientific Company; and Dilvex, a
                 hydrous magnesium  aluminum silicate obtained
                 from the Floridan Company.

              4) In an adsorption study with ion-exchange resins,
                 Aly and  Faust  (1965) showed that strongly  basic
                 anion exchange resins can be used for partial
                 removal (about 30 to 40%) of high concentrations
                 of 2,4-D (120 mg/1 sodium salt, 10 tng/1 Butyl
                 Ester) and 2,4-DCP (10: mg/1) similar to those
                 that may result from the discharge of industrial
                 wastewaters into natural waters.

-------
       Photochemical Degradation

       Photochemical degradation studies by Bulla and Edgerly (1968),
Smith and Grove (1969),  and Crosby (undated) have been conducted on
several pesticides and pesticide groups.  The pesticides and  pesticide
groups studied included aldrin,  dieldrin,  endrin, guthion,  chlorinated
herbicides,  carbamates, and diquat.  Some results of the studies were:
                                             o
                      1)  Irradiation by a 2537 A energy source decreases
                         the toxicity of aldrin to some fish.  Figure  17
                         gives  photochemical degradation curves for
                         aldrin, dieldrin and endrin (Bulla and Edgerly,
                         1968).

                      2)  Smith  and Grove (1969) reported  that in dilute
                         solution radioactively labeled diquat is rapidly
                         degraded by filtered radiation from a mercury
                         vapor  lamp and  also by natural sunlight to give
                         identical photochemical decomposition products.

                      3)  UV irradiation of some  pesticides and  pesticide
                         groups had the following effects  as  reported by '
                         Crosby (1969):

                         Pesticide (group)

                         Dieldrin                 Isomerization
                         Chlorinated compounds   Reduction
                         Guthion                 Reduction
                         Chlorinated herbicides   Replacement of aromatic
                                                  halogens by hydroxyl
                         Carbamates              Elimination

       Liquid-Liquid Extraction

       An extensive study by Faust and Suffet (1966) was  made on  liquid-
liquid extraction of pesticides with various solvents.  Table 14 summarized
the results of this study.  Most extractions show high percent recoveries.
Another study by Shrivastava (1967) on liquid-liquid extraction shows that
benzene  is very effective in removing DDT from manufacturing wastes.
                                   TO

-------
   100
    90
-7  80
 en
   70
c
I 60

-------
Table 14.  Liquid-liquid Extraction Systems and Percent Recoveries
          1:1 Solvent to Aqueous Phase Volume Ratio
Desticide(s)
DDT

3arathion

Dieldrin and
metabolites
DDT , toxaphene ,
aldrin, dieldrin,
BHC
3arathion and
diazinon
2,4-D, MCPA,
2,4,5-T
2,4-D
5 Phenoxyalkyl
acids , + dalapon
Solvent (s)
3:1 Ether and
n-hexane
1:1 Benzene &
n-hexane
n-hexane

1:1 Ether-pet.
ether or CHC1

1:1 Ether-pet.
ether or CHC1
O
CHC13
1: 3 Ether and
CHC13
Ether

No. of
Extractions
4

Cont.

4

5


5

3
3
4

Sample
Volume
(Liters)
1.5

200

0.1

1.0


1.0

0.3
0.25
0.1

PH
4.0-5.0

___

	

	


	

2.0
2.0
2.0

Mean
Recovery (%)
(Total)
88a, 61b

97

90-95

88


90

93
102a,
10 if
99'.9d
966

Reference
Berck (1953)

Sumiki and
Matsuyama (1957)
Cueto and
Hayes (1962)
Teasley and
Cox (1963)

Teasley and
Cox (1963)
Erne (1963)
Aly and Faust
(1963)
Abbott _et al.
(1964)

-------
Table 14.  (Continued)
Pesticide (s)
6 C\2 -hydrocarbons
8 Cl -hydrocarbons

Dipterex and DDVP
2,4-D, dieldrin,
perthane
8 Triazine
herbicides
Organophosphates
and C12-
hydrocarbons
Sol vent (s)
Pet. ether
n-hexane
Ethyl acetate
Pet. ether
Dichloromethane

n-hexane

No. of
Extractions
Cont.
2
2
Cont.
2

1

Sample
Volume
(Liters)
20
1
0.05
18
0.2

1

pH
	
	
8.0
	
9.0

Acid

Mean
Recovery (%}
97
98
94.5
93, 87, 93
92. 5f

90

Reference
Kahn and
Wayman (1964)
Lamar et al .
(1965)
El-Refai and
Giuffrida (1965)
Sanderson and
Ceresia (1965)
Abbott et al.
(1965)
Warnick and
Gaufin (1965)
 Interferences absent.
 Interferences present.
Interferences present; 2,4-D measured by a colorimetric method.
Interferences present, 2,4-D measured by ultraviolet absorption.
eMean value for the six herbicides.
 Mean value for the eight herbicides.
Source: Faust & Suffet, 1966.

-------
       Biological Degradation

       Biological degradation studies by Stutz  (1966), Mills (1959),
Randall (1963), Chacko, e_t al_. (1966), Matsumura, ejt 1. (1967), Loos
(1967), Bounds and Colmer (1965), Newland, et al. (1969),  Hill and
McCarty (1967) have been conducted on several pesticides.   These
studies involve the activated sludge treatment method as well as micro-
bial degradation under aerobic and anaerobic conditions.  The following
is a list of the pesticides tested, a list of the microbes used, and some
results of the  studies.

       Pesticides:    Parathion; methyl parathion; DDT; PCNB; dieldrin;
                     2,4-D; 2-CPA; 4-CPA; MCPA; silvex;  fenac; delapon;
                     CDAA; CIPC; 2,4,5-T; heptachlor epoxide; lindane;
                     haptachlor; endrin; DDD; and aldrin.

       Microbes:     Actinomycetes; filamentous fungi; soil micro-
                     organisms; bacterial enzymes; and  streptomyces.

       Results:      1) Pilot plant tests made on parathion wastes
                        combined with domestic wastes  show that para-
                        thion wastes can be treated successfully in
                        municipal activated-sludge treatment plants
                        (Stutz, 1966).  Full-scale plant operation by
                        Monsanto (Coley and  Stutz, 1966;  Stutz, 1966)
                        has shown that parathion process wastes can
                        be treated at the plant without dilution. Neu-
                        tralization, pH control, and nutrient addition
                        precede activated sludge treatment. Seven to
                        ten days aeration was employed, with  100  to
                        150% sludge return.  Suspended solids levels
                        were  maintained at 15,000 - 18,000 mg/1  (30%
                        volatile).  The  COD was reduced from  3,000 to
                        100 mg/1 and suspended solids in  the effluent
                        were  60 mg/1.  BOD reduction was  near 90% and
                        the phenol content was  near 0.1 mg/1.  Parathion
                        degradation was not reported.   The clarified
                        effluent plus waste solids were  sent by sanitary
                        sewer to a conventional municipal  plant for final
                        treatment.

                     2) A study on 2,4-D wastewater shows that it can be
                        successfully treated by  the activated-sludge pro-
                        cess  provided that dilution and nutrient requirements

-------
   are satisfied (dilution factor of 3.40 was used for
   industrial effluent containing up to 3,000 ppm of
   2,4-D; the nutrient requirements  were satisfied  by
   mixing settled  sewage with industrial effluent in a
   ratio of 1:600)  (Mills, 1959). Treatability studies
   of 2,4-D and 2,4,5-T acid wastes (Ford and Gloyna,
   1967)  indicate  that wash wastewaters had to be
   diluted twenty  to one with tap water before bio-
   logical treatment could be used (Figure 18).  The
   waste concentration had to be less than 1,800 mg/1
   (as COD) for effective treatment (Figure 19).  Sig-
   nificant COD and BOD removal were accomplished
   if proper seed and sufficient dilution were  provided.
   Recently, a detailed full-scale study indicated
   that 2,4-D and 2,4,5-T wastes can be  treated in
   an aerated lagoon system when diluted  at least
   thirty to one with municipal sewage. After three
   days in the aeration basin and several weeks
   detention in a stabilization pond, 87 to 94%  removal
   of chlorophenols and 49 to 80% removal of  chloro-
   phenoxy acids  were achieved (EPA Report 12130
   EGK 06/71).

3)  A malathion degradation study by Randall (1963)
   showed that the activated sludge  process is  highly
   effective in removing malathion from solution.  It
   also showed that daily applications of  malathion
   to an activated sludge  system do  not result in an
   increasing buildup of malathion residue.

4)  A study made on microbial degradation  of DDT,
   PCNB (pentachloronitrobenzene),  and dieldrin
   showed that actinomycetes,  filamentous fungi,
   and streptomyces degrade PCNB and that several
   actinomycetes dechlorinate DDT  to DDD but no
   microorganisms tested  degraded dieldrin (Chacko,
   etaL , 1966).  However,another study shows
   that a few soil microbes (unspecified) are  very
   active in degrading dieldrin  to various  metabolites
   (Matsumara, eta]..,  1967).

5)  A study made on microbial degradation  of 2,4-D
   2-CPA, 4-CPA, and MCPA showed that bacterial
             75

-------
a\
   100

   90

   80

   70

CD  60

X  C^
O  50

~  40

   30

   20

   10

    0
             WASTE =  I : I  MIXTURE OF 2, 4-D
                 AND  2, 4, 5-T  ACID   WASH
                 WASTEWATERS.  (DILUTIONS
                 MADE WITH TAP WATER)
SEED + 10% WASTE
                                                '  SEED + 5 %  WASTE
                                                  _A
                                                   SEED + 2%  WASTE
                                                 	P	
                                               r / y ^^i li^ L^  I  *
                                               W////////,
                                                   SEED ONLY
                                                         >IO% WASTE
          5   10  15   20  25  30  35  40  45  50  55  60 65  70  75

                         REACTION TIME  (hours)

                       Figure 18. Dilution Effect on Respiration Rates.

                       Source: Ford and Gloyna, 1967.

-------
2100
 1800
                                      I         I
                                  BOD,  2,4,5-T
                         	COD ,  2,4, 5-T
                         	BOD,  2, 4-D
                         	  COD,  2, 4-D
                     2345
                        AERATION  TIME  (DAYS)
                Figure 19. Batch Aeration of 2,4-D and 2,4,5-T Acid Wastes.
                Source: Ford and Gloyna, 1967.

-------
   enzymes  catalyze the degradation of these
   pesticides (Loos, ea_l. , 1967).  Extracts
   from organisms cultured in media containing
   phenoxyacetate herbicides converted these
   compounds rapidly to phenols when added to
   solutions containing the herbicides.

6)  A study of Bounds and Colmer (1965) made on
   detoxification of herbicide by streptomyces
   gives positive results for 2,4-D,  silvex, fenac,
   and dalapon.  It also gives negative results
   for CDAA, CIPC, and 2,4,5-T.

7)  A study made on the  degradation of  T- BHC
   (lindane) in  simulated aerobic and anaerobic
   lake impoundments shows  that anaerobic
   degradation  is considerably more rapid than
   aerobic degradation.  It also  shows that degra-
   dation leads to detoxification (Newland, _et aj.. ,
   1968).

8)  On the degradation of selected chlorinated
   hydrocarbon  pesticides, Hill and McCarty (1967)
   showed that many of these pesticides are degraded
   under suitable biologically active, anaerobic
   conditions.  It also showed that anaerobic degra-
   dation is faster than aerobic degradation for most
   of the chlorinated hydrocarbon pesticides studied
   (exceptions  were heptachlor epoxide and dieldrin
   which were very persistent in both environments).
   It indicates  that extractable  degradation products
   are  more  common under anaerobic  than under cor-
   responding aerobic conditions.  It ranks the
   pesticides studied and their extractable degrada-
   tion products in the following approximate order
   of increasing persistence under anaerobic condi-
   tions:  lindane, heptachlor,  endrin, DDT, DDD,
   aldrin, heptachlor epoxide, and dieldrin.  Figures
   20-25 show  the anaerobic  degradation rates for
   the  pesticides studied under a variety of conditions,
            78

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  100
                                LINO/WE  ADDED
       0     2     4     6      8     10     12     14
        DAYS  AFTER  PESTICIDE  INJECTION
Figure 20.  Anaerobic Degradation of Lindane in Sludge containing
          1.5% dry solids (56% volatile).  The pesticides were
          dissolved in acetone injected into one-gallon reactors
          and the systems were agitated on shakers.

Source:    Hill and McCarty, 1969.
                            79

-------
E
Q.
Q.
<
2
LJ
LU
Z
9    4
                 40        80        120       160

              DAYS  AFTER  PESTICIDE  INJECTION
200
       Figure 21.  Anaerobic Degradation of Lindane in Active and

                 Poisoned (4 g/1 cobaltous and mercury salts)

                 Sludge at 35 C.  10 ppm  Lindane Added Initially.


       Source: Hill and McCarty, 1967.
                             80

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CO
H
                                              T
                                   I  ppm   DDT  ADDED
                                 T
AA
                                       LEGEND

                                       0   MEASURED  CONCENTRATION OF
                                           INJECTED  PESTICIDE
                                           MEASURED  CONCENTRATION OF
                                           APPARENT  DEGRADATION  PRODUCT
                                                      i
                                         1
                        40               60
             AFTER  PESTICIDE  INJECTION
     200
                                                                              300
            Figure 22.


            ^egend:

            Source:
Anaerobic Degradation of Single Pesticides in 3500 ml of 7.2% total
solids (48% volatile) sludge at 35 C.  Similar studies on heptachlor
and aldrin were reported by the authors.

o   Measured Concentration of Injected Pesticide
A   Measured Concentration of Apparent Degradation Product
Hill and McCarty, 1967.

-------
Q.
a.
e>
1 1
1 1 1
40  ppm   LINDANE  ADDED
                           POISONED
                           ACTIVE  i  a  n
                           THICK  SLUDGE
                               I
                         I
I
              10      20      30     40      50
           DAYS   AFTER   PESTICIDE   INJECTION
                                        60
 Figure 23.  Anaerobic Degradation of Pesticide Mixtures in Thick
            Sludge at 35C (pesticides without extractable degradation
            products).  Poisoned with 0.5 g/1 mercurous chloride as
            mercury. One-gallon sludge units containing 7.2% solids
            (thick sludge) or 4% solids (Active I,II, and Poisoned)
            were used.  Similar studies on aldrin,  heptachlor, epoxide,
            and dieldrin were reported by the authors.

 Source:     Hill and McCarty, 1967.
                           82

-------
           E
           Q.
           O.
00
uo
UJ
CC

CO

O

O
O
a:
a.
    100
          Z   80
               60
               40
          id

          Q   20
          O
          I-
          cn
          UJ
          a_
                       DDT   PRODUCT ( DDD)
THICK  SLUDGE


       -ACTIVE  I
                                  -POISONED

                             ACTIVE I
                            10
                            20
               30
40
50
60
                            DAYS   AFTER  PESTICIDE   INJECTION
            Figure 24
            Anaerobic Degradation of Pesticide Mixtures in Thick Sludge at 35  C

            (pesticides with extractable degradation products). Poisoned with

            0.5 g/1 mercurous chloride as mercury.  One-gallon sludge-units

            contain 7.2% solids (thick)"-or 4% solids (Active I and Hand Poisoned)

            were  used.  Similar studies  on heptachlor, heptachlor products, endrin,

            and endrin products were reported.
            Source:
            Hill and McCarty, 1967.

-------
oo
g
ex
OL
     <
     2
     UJ
            60
            50
     I     40|
            30
      UJ
      o

      o     201

      CO
      UJ
      a.

            10
                                      CUMULATIVE
CUMULATIVE

ADDED

DDT
                                                             AEROBIC  SLUDGE  (DDT)
CONCENTRATION
                                                               AUTOCLAVED   GLASS  BEADS

                                                                          (DDT)
                                                       NAEROBIC  SLUDGE (ODD)
                     INSET

                  ANAEROBIC UNIT
                                 DAILY

                                 INJECTIONS

                                 ENDED AT

                                 57 DAYS
                                                            ANAEROBIC  SLUDGE  ( DDT)
                     10
                     20     30    40    50
                                 60
                      70     80    90    IOO    110    120
       Figure 25
       Source:
                         DAYS  AFTER  INITIAL  PESTICIDE  INJECTION


            Pesticide Degradation in Dilute oludge at 20C (daily injection units). Quantity injected

            to give incremental increase of 1 ppm.  Five-gallon sludge units were used.  The sludge

            was digested wastewater sludge diluted  19:1 with tap water.  Similar studies on hepta-

            chlor, epoxide, aldrin, and lindane were reported.

            Hill and McCarty, 1967.

-------
                     9) An aerobic study made on malathion shows that
                        the reduction of malathion concentration in
                        water is greatly increased by increasing the
                        rate of aeration.  It also shows that activated
                        sludge may be acclimated to daily feedings of
                        malathion at a level of 100 mg/1 (Randall, 1963).

       Foam Fractionation

       A foam fractionation study by Whitehouse (1967), was conducted
on aldrin and dieldrin.  The following is a list of the surface active agents
used and the results of the  study.

       Surface active agents:
                     cationic (Aerosol C-61)
                     anionic (alkyl benzene sulfonate)
                     nonionic (Dowfax 9N9)

       Results: This study showed that the cationic surface agent,
Aerosol C-61, removes aldrin and dieldrin more effectively than the
anionic and the nonionic surface active agents tested.  It also showed
that repeated dosing is more effective than  a single dose of the same
total quantity.  Table 15 shows the  cumulative pesticide removed with
three repeated doses of  10  mg/1 of Dowfax 9N9,  10 mg/1 of ABS (Alkyl
benzene sulfonate), and 2.5 mg/1 of Aerosol C-61. Pesticide solution
samples of 500 ml were  used.

Disposal Methods

       Most disposal methods used for pesticidal  wastes are closely
related to the wastewater treatment  methods previously discussed.  How-
ever,  there are some disposal methods  which may  not directly involve
treatment; these include combustion, burial, disposal at sea, and deep-
well injection. Such methods may be used  solely  as alternatives to
treatment or they  can be utilized in  conjunction with treatment processes.
A brief discussion of these  methods follows:

       Combustion

       Incineration is a popular disposal method for concentrated waste
streams.  Most organic  compounds  (liquid and gaseous) can be effectively
destroyed by the method, but other  components  of  the waste streams often

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    Table 15.  Cumulative Pesticide Removed - Foam Foundation
Dose No. (Equal dos
per treatment)
Surface Active
Agents (dose size)
10 mg/1 of Dowfax
9N9
10 mg/1 of ABS
2 . 5 mg/1 of
Aerosol C-61
Cumulative
Aldrin
-12 3
37% 57% 64%
53% 65% 71%
65% 80% 83%
Cumulative
Dieldrin
1 2 3
40% 75% 86%
52% 77% 89%
83% 95% 97%
Each Sample  = 500 ml
Aldrin Dose   = 0. 02 mg/1
Dieldrin Dose = 0.035 mg/1
                    i
Source:  Whitehouse, 1967.
                                 86

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cause significant problems. Nitrogen compounds present in combustion
air and in many pesticide manufacturing wastes invariably produce oxides
of nitrogen (NO, NC^, etc.) when burned.  Since these gases are of
importance in the atmospheric  re3ctions which produce photochemical
smog, regulations against their production are often severe and will no
doubt become more restrictive  in the future.   Sulfur-bearing compounds
may  produce significant quantities of sulfur dioxide and sulfuric acid as
reported by Tabor (1970).  Regulations restricting SC>2 emissions are
already in effect in almost  all  states.

       Compounds containing  heavy metals including lead, mercury, and
arsenic should be burned only  if proper precautions are taken to control
atmospheric emissions. Lead  and mercury salts as well as arsenic can
escape the combustion chamber and travel great distances, contaminating
large areas.  Low levels of these compounds  may produce  recognizable
effects in plants or animals as well as people.  Compounds containing
chlorine produce hydrochloric  acid, which can cause serious corrosion
problems in the incinerator and in some  cases significant downwind pol-
lution problems.

       These problems make it difficult but not impossible to burn many
pesticide wastes. Temperature control, excess air control, fuel and waste
feeding techniques, and proper incinerator design can all reduce the mag-
nitude of the emission problems.  A well-designed and operated air clean-
ing device  (which will normally constitute a major capital investment) can
remove many of the gaseous pollutants and eliminate virtually all of the
particulates.  These  devices should be included in the original design of
the incineration equipment  and not merely added at a later date  when air
pollution problems become  obvious.

       Table 16 summarizes results of a combustion study made by
Kennedy, e_t a_l. (1969) on nineteen  pesticide  formulations  at five differ-
ent temperatures.  Most pesticides  showed a high percent loss  on com-
bustion.  However,  the data shown indicate that care must be taken to
provide adequate  combustion temperatures and contact times for complete
disposal.   The tests  were made in controlled  temperature chambers where
adequate oxygen was available.   Commercial formulations of the pesti-
cides were burned rather than  waste streams.  The data indicate that most
pesticide compounds are destroyed  effectively by burning at 800C to
1000C.  Exceptions are atrazine, zineb, bromocil, dalapon, DSMA, and
sevin.
                                  87

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  Table 16. Percent Loss on Combustion of Commercial Formulations of
                   Pesticides at Five Temperatures
Commercial
Formulation
Picloram
Atrazine
Nemagon
Trifluralin
Ma lath ion
2,4,5-T
Zineb
Vernam
Paraquat
Dicamba
Bromacil
Dieldrin
DDT
Dalapon
2,4-D
Diuron
DNBP
DSMA
Sevin
Loss (%) at
600C
90.8
87.8
99.6
99.7
95.3
99.9
70.1
99.6
98.3
98.6
88.8
99.1
99.2
64.3
99.8
94.6
99.8
80.6
88.7
700UC
91.8
88.1
99.6
99.8
96.0
99.9
71.3
99.6
98.6
98.7
89.1
99.4
99.3
64.3
99.9
95.0
99.8
80.7
88.8
800C
95.6
88.8
99.6
99.8
96.3
99.9
71.5
99.6
99.0
98.9
89.4
99.5
99.7
67.8
99.9
95.4
99.8
80.7
88.8
900C
98.7
88.9
99.6
99.8
96.4
99.9
72.7
99.6
100.0
99.0
90.5
99.5
99.9
73.8
99.9
95.5
99.8
81.2
89.1
1000C
99.2
89.0
99.6
99.8
96.7
99.9
72.8
99.6
100.0
99.4
91.3
99.5
100.0
91.0
99.9
95.7
99.8
81.2
89.5
Source:  Kennedy, _et al_. , 1969.

                                 88

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       In a combustion chamber, the toxic compounds may undergo
decomposition by oxidation, pyrolysis, isomerization or polymerization.
If the combustion temperature is too low,  the residence time in the
chamber is too  short, adequate air is not  present, or the waste is not
well dispersed  to expose a large amount of surface area, then complete
destruction of the toxic compounds  may not occur.  In  the case of organo-
phosphate insecticides, toxic isomers of  the original compound may be
produced (Smith and Ledbetter, 1970).

       Many of the major problems associated with incineration of
pesticide  wastes in the past resulted from failure to consider the con-
stituents of the waste other than toxic materials.  Pilot studies should
always be conducted to provide information on  effluent gas and particulates
from the incinerator exhaust.  In a well-designed,  well-operated inciner-
ator,  phosphorus-containing compounds produce ^2^5  anc^ phosphoric acid,
which can result in a heavily-persistent white  plume visible for long per-
iods of time. High potassium or sodium levels in a waste can produce
hygroscopic salt nuclei that cause visibility  problems  in humid atmos-
pheres (Marks,  1965).  In addition, the salt  particles  may be air pollu-
tants of consequence,  especially in agricultural areas.

       Burial

       Burial of pesticide wastes is a common practice.  Solid, semi-solid
and liquid wastes are often buried in landfill or placed in open pits.  The
liquid and semi-solid wastes are usually  sealed in containers for transport
to land fill sites or placed in the open pit areas in bulk.  Therefore, the
two methods  differ considerably and will be discussed separately.

       The land fill type disposal method normally involves opening a
trench, often fifteen feet or more in width and up to twelve feet deep,
depositing the waste material in the trench, compacting  the material
(thus rupturing  any  containers present) and covering the  waste daily with
a minimum of six inches of compacted earth.  The final fill cover should
be at least 18 inches deep in order to isolate the waste material.  Where
topography permits,  the waste material can be  used to fill low areas
without opening a trench. Borrow pits are necessary to provide the neces-
sary cover material. However, if this procedure is used, special measures
must  be taken to provide for surface drainage around the fill site.

       Subsurface pesticide movement is  possible and should be considered
especially in highly permeable soils.  In  tight, clay meterial and high
                                   89

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organic content soils, most pesticides will move slowly as rainwater and
landfill leachate  pass through the soil.  Studies indicate that chlorinated
hydrocarbons including dieldrin (Eye, 1968) and aldrin migrate only a few
feet in natural  soils over periods of years.  The U.S.G.S. (Rima, et a_l. ,
1967) reports little horizontal movement of dieldrin, endrin, heptachlor
and heptachlor epoxide from a landfill located at a  site underlain by a
nearly horizontal strata composed of deposits of sand,  silt and clay.
However, it was  reported that the subsurface disposal had produced a
zone of contamination directly  beneath and  peripheral to the landfill.
Laterally the limits of the zone of contamination appeared to be confined
to 25  feet or less from the trench margins.  The depth of the zone, however,
extended nearly to the water table, 90 feet  beneath the land surface.  In
addition,  surface waters in a nearby stream contained traces of the four
pesticides, probably from surface runoff.

       Organophosphate pesticides also move  slowly in soils, as shown
by King and McCarty (1966). In a gravelly  sand soil (5% clay) six to eight
feet of eluted water was required to move 25% of the applied thiamate
through one and one-half inches of soil.  In a heavy clay soil (37% clay),
after 28 feet of elute water, only 5% of the  same pesticide had moved
through the soil.

       These studies indicate  that, if proper care is taken, landfill area
can be a suitable disposal method. The soil type  should be such that
waste migration is minimized (i.e. , high clay or high organic content).
The water table should not be near the disposal site (a  minimum of 10
feet between trench bottoms and the water table should be maintained).
Surface flow should be controlled  to prevent erosion and surface water
contamination.  Site management should be strict enough to prevent spills,
leaks and improper dumping or  covering.  A monitoring program should be
instituted which would include surface water sampling, ground water
sampling below the fill, and water sampling at any nearby drinking water
sources.  Table 17  shows in generalized fashion the relative mobility of
various pesticides in "typical" soil.

       It should  be  realized that a natural soil system  is never a simple
homogenous medium that can be modeled with assurance.  Undetected
layering,  faults and fractures,  and drainage channels to ground water can
cause unforeseen problems.  Since the rate of travel of chemicals in a
soil-water system is dependent on the solubility and sorption character-
istics of the pollutant and the physical characteristics  of the aquifer,
detailed study and sampling should be conducted before a fill site is
chosen.
                                   90

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      Table 17.  Relative Mobility of Pesticides in Soils*
Immobile
Aldrin
Chlordane
DDT
Dieldrin
Endrin
Slightly Mobile
Atrazine
Simazine
Prometryne
Azinophosmethyl
Carbophenthion
Mobile
2;4-D
2,4,5-T
MCPA
Picloram
Fenac
Heptachlor

Toxaphene

TDE

Lindane

Heptachlor Epoxide

Trifluralin
Diazinon

Ethion

Methyl Parathion

Lindane

Heptachlor Epoxide

Parathion

Phorate

Diuron

Monuron

Linuron

CIPC

IPC

ERTC

Pebulate
*Mobilities are based on soil thin-layer chromatography - mobile compounds
 move between Rf 1.0-.65,  slightly movile  .64-.10, and immobile .09-.00.
 (Rr = "relative to fructose").

Source: Working Group on Pesticides , 1970.
                                91

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        Pesticides buried in a landfill may be degraded biologically or
chemically.  Unsaturated,  branched chain compounds of high molecular
weight are less susceptible to degradation than the saturated short chain
compounds.  Aromatics are also resistant to degradation in soils.  The
principal factors  that govern the stability of pesticides  and related halo-
genated and phosphorylated compounds include soil texture,  humus con-
tent,  temperature, moisture and pH.  The half life of these materials  may
vary from  a few weeks to several years (Witt, 1971).  A listing of a number
of representative pesticides and their persistence in "typical" soil is given
in Appendix A.

       The open  dump, or open pit disposal method, is also  used by  many
pesticide  manufacturers.  The pit disposal method consists of placing
wastes in an open pit or trench without compaction or cover.   The wastes
are exposed to the elements until the pit is filled.  When full,  the pit is
covered with earth and abandoned.  These methods are used  because  of
their relative cost.  Landfill operation requires labor and equipment costs
of at least $1.00 per ton of waste  plus the cost of haul.  Pit  disposal can
be accomplished  for almost no cost if the pit is located on or near the
plant site.

       Pit disposal  can produce the same types of contamination as a
landfill.  Since abandoned sand and gravel pits, rock quarries and other
naturally occurring topographic features are often utilized as disposal
pits for reasons of availability and economy, the probability  of large
scale subsurface contamination is increased.   In general, the problems,
both real and aesthetic, associated with pit disposal make it undesirable.
Odors, volatile toxic gas  releases , and  increased likelihood of water
contamination are potential problems.  In addition, the  probability of
accidents near the pit is high, since haphazard dumping is usually
employed. Even  after final cover,  the disposal site is subject to  sig-
nificant settlement,  cracking, and  perhaps surcharge  during  heavy rains.
For these  reasons, the Working Group  on  Pesticides recommends that
"this method of pesticide waste disposal  should be discouraged except
under extremely favorably geologic conditions and where the  site is very
remote from producing wells"  (Working Group on Pesticides,  1970).

       Burial practices are receiving close scrutiny by  various regulatory
agencies.  The degree of control and severity of the regulations will con-
tinue to increase and care must be  taken when  choosing  the method as a
long term  disposal practice.  A regulation to control waste burial proposed
by the State of California is included in this report as Appendix C since
it is typical of regulations  which may be expected in the future.
                                  92

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       Ocean Dumping

       A disposal method currently used for some manufacturing wastes
generated at locations near oceans  or the Gulf of Mexico is ocean dump-
ing.  This practice is now receiving much attention and will probably be
subject to highly restrictive legislation in the near  future.  Presently, con-
centrated  liquid  and  semi-solid wastes are carried by barge in bulk form or
in containers to  dumping sites several miles to several hundreds of miles
offshore.  There the  wastes are discharged overboard in the wake of the
barge.   Containers are weighted to  insure that they sink or are pierced
after dumping.  In 1968, approximately 330,000 tons of pesticide wastes
were dumped in this  manner (Anon., Chem. and Engr. News, 1970).
Dumping costs average  slightly less than $4.00 per ton (Witt, 1971).

       Presently, regulatory  activity and authority  is confusing and
inadequate.  "States do not exercise control over ocean dumping and
generally  their authority to regulate ocean dumping  is also largely con-
fined to the territorial sea.  The Coast Guard enforces several federal
laws regarding pollution, but has no direct authority to regulate ocean
dumping.  The authority of the Federal Water Quality Administration (now
WQO of the EPA) does not provide for issuance  of permits  to control ocean
dumping"  (Council on Environmental Quality, 1970).  However, this prac-
tice is changing.  The State of New Jersey is considering  ocean dumping
regulations which can apply to pesticidal wastes.  (Appendix D contains
a statement by Governor Cahill of New Jersey on this subject).  Indica-
tions are that regulations restricting ocean dumping will also be forth-
coming from the  Congress. These  regulations will require that strict
criteria be followed in selecting dumping sites  and  performing dumping
operations.

       If  ocean  dumping continues  to be utilized for waste disposal,
certain factors must  be  carefully considered to insure minimum environ-
mental degradation.  Site selection is important, and consideration of
tidal action, water depth, currents, proximity to shore, island or fishing
grounds, bottom characteristics, etc.,  must be included.  In addition,
detailed assessment of  the possibility of the following factors should be
conducted.
        1.   Surface  Slicks
       2.   Depletion of Dissolved Oxygen
       3.   Acute Toxicity
       4.   Long-Term Toxicity Effects

-------
       Estimates of dilution can be based on models such as one
developed by Pearson (1968) and Ketchum and Ford (1952) and modified
by Smith (1969):
       where:

       C
       ~  =  average dilution along the axis of the waste plume at time,t,
              after passage of the barge
       d   =  assumed mixing depth (ft)
       K   =  eddy diffusivity (ftVsec)
       t   =  time elapsed after passage of the barge (sec)
       V   =  barge velocity, relative to plume (fl/sec)
       Q   =  waste discharge rate (gallons per hour)
       K   =  0.001 L4/3
       L   =  depth of the water at the dumping site

       Using these equations and assuming a water depth (and mixing
depth)  of 300 feet,  barge velocity of 5 knots and a discharge rate of
120,000 gallons per hour, the estimated dilution along the plume center
line would be:

       Distance behind barge    Time after passage    Dilution factor
                  (ft)                   (min)
                    100                 0.19             30,000
                  1,000                 1.95             94,000
                 10,000                19.50            300,000

Recent studies (Smith, 1969) indicate that at least in one case,  the above
equations overestimate the dilution factor by a factor of four or five. Even
so, this brief analysis indicates that rapid dilution of both BOD and toxic
components occurs  in the barge wake. However, studies of the effects of
low-level concentrations of waste materials should be  conducted before
indiscriminant dumping occurs.

       In addition, special detail should be given to wastes sealed in
drums.  These drums may be weighted and allowed to sink or they may be
pierced after dumping. In either case, these drums will release wastes

-------
below the surface in relatively still waters where mixing is limited.
Severe local problems may result from the contents of these containers.

       Deep Well Disposal

       Subsurface, and particularly deep subsurface, disposal of waste
is receiving increased attention from  industry and regulatory agencies
alike as  plant production increases with its proportionate increase in
waste effluent.  In order to prevent the cost of waste disposal from reach-
ing astronomical proportions,  subsurface disposal has been utilized by
several plants having large quantities of concentrated water-borne wastes.

       It is estimated that about 240 municipal and industrial deep wells
have been installed in the  U.S. since 1950 (Anon. ,  Industrial Waste,
1971).  However, increased concern over the  fate of the injected wastes
has lead to some questions concerning the safety of this practice,  and
future regulations controlling deep well disposal promise to be restrictive.
The U.S. Geological Survey has been  of assistance in determining the
geologic structure of the areas considered  for subsurface disposal.  The
wells must be  located over deep permeable rock formations which have
suitable  hydrologic properties to receive and contain the volume  of waste
injected. Extreme care must be exercised  in the construction of  the well
to prevent any possible contamination of the fresh water zones.  The
required  depth of the well is dependent upon a number of factors  including
the slope of the aquifer being  considered for injection, the salinity and/or
purity of the water in the aquifer, ease or difficulty in drilling, and the
ability of the formation to accept the  additional liquid material.

       The detailed geological data for the area should be collected to
locate and define the extent of the disposal formation and  to trace  the
pollutional movement.  Extensive studies should be conducted to test the
wastewater and  formation water compatibility.  The State of Texas  requires
a detailed record of the subsurface  geologic data covering a  2-1/2 mile
radius around a  proposed disposal well before a permit will be issued. In
addition, all unplugged wells  in the vicinity of the disposal  well must be
Jogged.  The Injection Well Act of the State of Texas is included in this
report as Appendix B.

       The well itself should  be constructed  by capable drilling  contractors
in accordance with the requirements of the governing regulatory agencies.
The well should be designed to protect all fresh water formations and other
formations which may yield future natural resources. It should be  constructed
                                   95

-------
of corrosion-resistant materials of reliable quality.  Disposal well
failures have been associated with inadequate construction or poor
materials more often than with improper operation or incompatibility
of the waste fluid with the formation.  Figure 26 shows a diagram of
a completed liquid waste injection well (Anon.,  National Agricultural
Chems. Assn., 1965 and Warner,  1965).

       Since deep well disposal places the waste in a remote location
where its ultimate fate cannot be adequately determined, the practice  of
subsurface injection is receiving critical review in many agencies.  The
uncertainties associated with this type of disposal can make it question-
able, especially  for long-lived pesticides and pesticidal wastes.

-------
                                                  PRESSURE  GAGE
                                                  WELLHEAD  PRESSURE
FRESH- WATER- BEARING  ' . 0 '- 'i '. \ * '
SURFACE SANDS AND     '.',  ;! j'-A ' . ' '.:'.
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                                                 INNER CASING SEATED IN OR
 PERMEABLE
 BEARING
 INJECTION
\
4
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	 	 _


E SALT-WATER-'".^ . '.': ''^ ''/'.
SANDSTONE .'': '.''. .' '": ' '..
HORIZON ,-'; -.' '; - '. ' '"'
i , .  ,"'i'- r
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*+

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CEMENTED TO S

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NONCORROSIVE
	 PACKERS TO Pf
* CIRCULATION IN

~ " " ADFM UAI F f*f\

'. " \ *" ' . ' ' " '  '
'"". "- ' * . ".

                                                               FLUID
  Figure 26.  Schematic Diagram of a Waste Injection Well Completed
              in Competent Sandstone.

  Source:  Warner, 1965.
                                       97

-------
                         CHAPTER VI

    TREATMENT & DISPOSAL PRACTICES PRESENTLY EMPLOYED
       A number of major pesticide manufacturing plants and several
formulating operations were visited and their treatment facilities were
observed.  The information presented in the following discussion is
based on the results of these site visits.  It is impossible to present
detailed design and operational data applicable to all types of pesticidal
wastes.  In many cases such information is not known and in other cases
the data cannot be released for manufacturing  process  security reasons.
Therefore,  the information presented of necessity will  be general in
nature, but should be useful as a basis for preliminary decision-making
and initial  design requirements for waste treatment facilities.
In-Plant Control

       One of the most obvious methods of minimizing pollution from
pesticide manufacture is to institute control techniques that will reduce
the loss of raw material, solvent and product.  Good housekeeping mea-
sures have proved beneficial in several pesticide manufacturing plants.
Automatic monitoring and alarm equipment installed at various locations
in the waste collection system of at least one major pesticide and petro-
chemical manufacturer has given the treatment system operators the capa-
bility to 1) detect toxic slugs  and route them to holding basins, and 2)
to determine which plant processes are responsible for excessive waste
discharges.  Thus process managers can be held responsible for spills
and poor housekeeping practices.  The monitoring  system has been instru-
mental in reducing the waste load on the treatment plant and has prevented
toxic slugs  from reaching the biological treatment  systems.

        Process areas in pesticide manufacturing plants should be  sealed,
diked and drained to a collection system to prevent contamination  from sur-
face run-off.  Sumps in the drain system can concentrate heavy materials
and often reduce  the organic and toxic load to the  treatment system.  A
major chlorinated herbicide manufacturer presently uses  a sump system
and a portable sump pump (pulled by a tractor) which periodically collects
the sump contents and transports it to the incinerator feed tank for burning.
                                   99

-------
       Several plants, especially those involved in formulating, wash
their spills, both liquid and powder, into  sewers for collection and treat-
ment.  However,  one major formulator has instituted a vacuum system for
dust collection in the dry formulation area.  A cyclone is used to concen-
trate the collected dust which is ultimately buried in a landfill.  The elim-
ination of the waterborne waste has proved beneficial since this was a
major source of pesticide contamination in the plant effluent.  No prob-
lems of equipment malfunction or excessive airborne emissions were
reported.

       Attempts to conserve or reuse water in pesticide manufacture have
proven cost effective for some manufacturing processes,  especially where
ultimate disposal by deep well injection,  burial, or ocean dumping is
employed.  However, if biological treatment is utilized,  water conserva-
tion and reuse may result in wastes too concentrated with organic material,
dissolved inorganics or toxic compounds for treatment.  In several plants,
dilution of the waste stream is necessary  before treatment can be accom-
plished.  Therefore,  water conservation schemes should  be critically
reviewed in light of the proposed waste treatment plans.
Neutralization and pH Adjustment

       In almost all cases, pesticide manufacturing wastes require some
pH adjustment before treatment or discharge.  The process waste streams
invariably contain highly acidic and/or alkaline components.  The term
neutralization implies the adjustment of the wastewater stream pH to values
near 7 (neutral).  This  step is required for:

              a)  corrosion control
              b)  reaction control on many chemical treatment processes
              c)  protection of stream organisms if direct discharge is
                  employed
              d)  protection of microorganisms in biological treatment
                  systems.

       The most widely used neutralization agent in the pesticide industry
is lime.  In some cases, acid waste streams are  merely passed through a
lined trench which contains piles of 2-1/2" limestone or dolomite.  As the
waste flows through and over the limestone, the acids  are neutralized and
the  calcium ions go into solution.   pH levels as high as 5.3 and 5.5 may
be achieved in these types of trenches.  The pH of the trench effluent is
dependent on limestone purity, residence time, waste acidity, etc.
                                  100

-------
Following the trench treatment, automatic pH monitoring and slaked lime
feeding can be used to raise the pH level to the desired value.

        Most plants have some caustic streams which are often mixed with
the strongly acid streams before treatment.  However,  several operators
have found that substantial chemical savings can occur if the caustic wastes
are metered into the waste water stream after the  limestone trench treat-
ment rather than combining the waste streams ahead of the trench.  Thus
the caustic waste can replace the expensive slaked lime and the associated
feeding equipment as the final pH adjustment agent.  Excess caustic wastes
may be  added prior to the limestone pit if caustic waste storage is a problem.

        In some cases, where excessive total dissolved solids  may cause
problems (incineration, deep well, etc.)  neutralization agents such as
anhydrous ammonia  are used.  This chemical is expensive but produces a
neutralized stream with a much lower potential for air pollution from incin-
eration  or solids precipitation in a deep well stratum.  The  ammonium ion
is combustible producing gaseous nitrogen oxides which cause  no direct
visibility problems,  whereas sodium, calcium,  and potassium salts pro-
duce submicronic crystals when burned and form persistent  plumes in,humid
atmospheres.  However, proposed regulations concerning ambient NO
levels indicate that NO emissions will be curtailed  in the  near future.
This may require that ammonia not be used without proper air cleaning
equipment on the incinerator.

        Mixing in the neutralization basin may be critical.  Care must be
taken to insure adequate mixing and detention for the neutralization reac-
tions  to reach completion, to reduce the effect of shock loads  on biological
or chemical systems following neutralization and to prevent sludge build-up
in the neutralization basins.  The latter factor is of prime importance with
parathion and some  chlorinated  hydrocarbon wastes,  since calcium  salts
often  precipitate when  lime neutralization is used.  Continuous vertical
paddles were recommended by several plant operators who used small
rectangular neutralization basins.
Chemical Treatment

       A variety of chemical treatment processes have been used to
detoxify pesticide manufacturing wastes.  Limited laboratory data are
currently available on reaction rates, chemical doses and efficiencies.
Most existing neutralization systems have been overdesigned to insure
                                  101

-------
effectiveness.  Table 18 summarizes the information on current chemical
treatment practices gained from interviews with plant engineers and operators.

       Ozone in concentrations of 4,000 to 6,000 mg/1 can oxidize chlor-
inated hydrocarbon wastes effectively if adequate contact time is available.
A study by Ford and Eckenfelder (1968) of DHC wastes from a dehydro-
hlorination unit showed that ozone dosages in excess of 4,000 mg/1 were
required  for COD removals of 80% or more.  However, their data indicated
that ozone absorption efficiency Legins to decrease rapidly when  the ozone
concentration exceeds 4,000 mg/1.  The data are summarized in Table 19
and Figure 27.  The wastes from the dehydrochlorination unit are similar to
the phenolic  wastes that result from some chlorinated herbicide manufac-
ture,  and the effectiveness of ozone treatment of DHC waste should  be
similar to ozone treatment of herbicide wastes.

       Potassium  permanganate can effectively be used as an oxidizing
agent for some pesticide compounds.  Organophosphate wastes (up to 7%
organic)  undergo substantially complete breakdown of the toxic compounds
if held at 180F for 20 minutes in a strong potassium permanganate solu-
tion.  This reaction is carried out in a  sealed, glass-lined vessel.  The
system is capable  of treating an average flow  of 14 gpm on a batch basis.

       Acidification with HC1 to pH of 2 or less will deodorize organo-
phosphate wastes. The mercaptans (odorous compounds containing sulfur)
are effectively destroyed if the acidified wastes are held at 215F for 30
minutes or more.   However, little reduction in toxicity occurs. Aldrin,
dieldrin and endrin are susceptible to rapid dehydrochlorination in solu-
tions  with a pH below 3; but are stable  in alkaline solutions.  Often acid
addition  is the only treatment method used to detoxify wastes  containing
these pesticides.

       Highly alkaline conditions  can detoxify certain pesticidal compounds.
Caustic soda is often used for pH adjustment to bring about hydrolysis of
some  chlorinated hydrocarbon and organophosphate manufacturing wastes.
For example, 20%  caustic added in an amount  equal to one part caustic
solution  to 30 parts waste from an  organophosphate plant is sufficient to
produce complete hydrolysis in 1.5 hours  when held at 200F. An enclosed
glass-lined vessel is used as a reaction unit.  It has been found  in at
least  one plant that relatively rapid hydrolysis of organophosphate wastes
occurs at a pH of 9 at slightly elevated temperatures.  For example,  it was
reported  that at a temperature of 38C,  the half-lives of the toxic  phosphate
compounds vary from 4 to 96 hours.  DDT, toxaphene,  and related compounds
undergo hydrolysis in strongly alkaline  solutions but are relatively stable in
                                  102

-------
                                    Table 18.  Chemical Treatment
O
U)
Type of
Product
Chlorinated
Herbicides

Chlorinated
Herbicides






Chlorinated
Insecticides
Chlorinated
Insecticides





Waste Pretreatment Chemical
Flow Treatment
50 gpm Limestone Slake Lime
Trench Slurry

None Low grade
Ca (OH)
and Inci-
nerator
Scrubber
Water
Flash
Mixed
None Lime Ad-
dition
75 gpm None Caustic
Scrubber
Water and
Ammonium
Hydroxide
added as
needed
Effectiveness
pH raised from
5.2 to 7.2

pH raised to
8






pH raised to
6.5
pH raised to
9 for hydrol-
ysis




Post -
Treatment
Aerated
Lagoon

Sedimenta-
tion






Incinera-
tion
"Total"
Evapora-
tion




Remarks
No preci-
pitation
occurs
Effluent
toxic at
300:1 di-
lution




Some preci-
pitation
Rapid hy-
drolysis
occurs





-------
       Table 18.  (Continued)
Type of
Product
Organo-P
Insecticides
Organo-P
Insecticides
Waste
Flow
500 gpm
100 gpm
Pretreatment
Limestone
Trench
None
Chemical
Treatment
Process
Waste ,
Caustic
added as
needed
Lime Ad-
dition
Effectiveness
pH raised
from 5 . 2 to
7.5 or 8
pH raised from
<1 to 4.2
Post -
Treatment
Activated
Sludge
None
Remarks
Higher pH
required
for methyl
parathion
Biological
treatment
o
       Organo-P
       Insecticides
40 gpm   None
20% caus-
tic solu-
tion, 200
F for 1.5
hours;
strong HC1
215F for
5 hours;
potassium
permanga-
nate,  180
F for 20
minutes
Hydrolysis
"Total"
Evapora-
tion
                                                            Odor Control
                                                            Organic
                                                            Oxidation
possible but
not satis-
factory

Treatment in
sealed
reactors

-------
       Table  18.  (Continued)
o
VJ1
Type of
Product
Organo-P
Insecticides
Carbamates
Triozone
Insecticides
Chlorinated
Waste Pretreatment Chemical
Flow Treatment
25 gpm None Caustic
Addition
? None Caustic
Addition
None Acid Pond
holdings
300 gpm None Limestone
ditch
neutral-
ization
Effectiveness
pH to 6 for
corrosion
control
pH to 7 for
corrosion
control
pH < 2
for 8 or
more hrs .
pH 5.5
Post-
Treatment
Ocean
disposal
Ocean
disposal
pH adjust-
ment with
lime
None
Remarks
No
alternative
solution
Incineration
contemplated


       Source:  Plant Interviews.

-------
                       Table 19.  Ozonation of Dehydrochlorination (DHC)  Wastes
Sample
Designation
1-18
1-06
1-14
1-12
1-15
1-11
1-17
Ozone passed Ozone absorbed Ozone
Wastewater pH through soln.
(m-moles) m-moles
DHC 12.2
DHC Unadj.-12.6
DHC
DHC
DHC
DHC adj. - 7.0
Wash Belt -7 . 8
2.
5.
8.
10.
12.
6.
2.
07
52
33
05
50
36
07
2.
5.
8.
9.
11.
5.
1.
07
28
18
66
26
62
08
Absorption
(mg/1) Efficiency
f/\
(/o)
994
2530
3920
4640
5400
2700
518
100.
95.
98.
96.
90.
88.
52.
0
6
1
1
1
4
1
COD
raw waste
(mg/1)
3340
3340
3340
3340
3340
3340
3072
COD COD
effluent reduction
(mg/1) (%)
1410*
900
745*
450
314*
1460*
900
57.8
73.0
77.5
86.5
90.5
56.5
70.1
*Sample analyzed immediately following ozonation.
DHC = Wastes from Dehydrochlorination Unit.
Source: Ford and Eckenfelder, 1968.

-------
   100



    90



    80



~   70



Q   6
UJ

O   50

UJ

K   40
Q
O
0   30



    20



    10



     0
                   OZONE

                   ABSORPTION

                   EFFICIENCY
          COD  REMOVED
  NOTE'  NO  WASTE WATER
         pH  ADJUSTMENT



I    I     I    I     I    I
                                1
00


90


80


70


60


50


40


30


20


10
                                      O

                                      UJ

                                      O

                                      u_
                                      u.
                                      UJ
                                      I-
                                      Q.
                                      t
                                      O
                                      CO
                                      CD
                                           Ul

                                           O
                                           N
                                           O
        2000     4000     6000     8000

        OZONE  ABSORBED  (mg/l)
Figure 27.  Ozonation Test Results of Dehydrochlorination
         (DHC) Wastewaters.


Source:    Ford and Eckenfelder, 1968.
                  107

-------
acid mediums.  Catalysts such as ferric chloride greatly increase the
hydrolysis rates.  The stability of several major pesticides in alkaline
mediums-is given in Table 20.

       In many plants caustic or waste caustic from other operations is
used only for pH adjustment, prior to biological waste treatment or chem-
ical coagulation.  Chemical degradation occurs to some extent, but the
pH levels remain too low and the detention time in the mixing basins is
normally too short for detoxification to safe levels.  For example, chlor-
incated hydrocarbon waste neutralized in a limestone trench and held at
a pH of 7.2 in an equalization basin for  an average of 12 hours showed
little reduction in active compounds.  Similarly, a plant engineer reported
that pH of 7.8 to 8.3 in a neutralization basin preceding biological treat-
ment reduced the concentration of organophosphate insecticides by less
than 5% during the two hour detention period.

       The addition of sodiumhypochlorite solution or gaseous chlorine  to
herbicidal wastes until a residual chlorine level is achieved can effectively
degrade the aqueous stream. The pH levels  should be low (3) and the design
contact time should be at least 10 minutes at high temperatures (85 F) or
longer at lower temperatures.  An industry using this technique reports sat-
isfactory results and no major equipment problems to date.  Chlorine to
phenol ratios in excess of 50:1 may be required to complete the oxidation.
Physical Treatment

       Table 21 summarizes the information obtained during plant site
interviews. Since pesticide wastes include a broad spectrum of water
quality parameters, the physical treatment schemes are quite varied.
Design and operating criteria were not available in most cases.

       Suspended solids offer little problem in most pesticide  manufacturing
operations. These operations produce waste streams containing elemental
sulfur bicarbonates, sulfates, phosphates, nitrates and other inorganic ions.
In general, the salts produced will remain in solution.  However,  the addi-
tion of lime for neutralization can produce insoluble compounds which will
precipitate. This  sedimentation may occur in the mixing basin if adequate
turbulence is not supplied.  Often dead spaces occur in mixing tanks and
invariably cause problems from sludge bank buildups.  If effective sedi-
mentation is desired, long detention times are necessary since the floe
produced in typical pesticide wastewater  settles slowly.  For example,
                                  108

-------
                                 Table 20.  Chemical Treatment
            Pesticide
                         Acid
Alkali
Chlori nation
o
VD
Aldrin



Dieldrin



Endrin



DDT



Toxaphene



Organic Phosphates



Carbaryl (Sevin)



IPC



Chloro  IPC



Phenoxy Herbicides
                                     Reaction-HCl



                                     Reaction-HCl



                                     Reaction-HCl



                                     Stable



                                     Stable
Stable



Stable



Stable



Decomposes



Decomposes



Break Down



Decomposes



Decomposes



Decomposes
No Reaction
                                                                            Decomposes
            Source:  Waste Disposal Manual ,  National Agr. Chemical Association,

                    Washington, D.C.

-------
                                        Table 21.  Physical Treatment
H
H
O
Type of Waste Pretreatment Physical Effectiveness Post-
Product Flow Treatment Treatment
Chlorinated 30 gpm pH adjust- Carbon 95% Phenol Trickling
Herbicides ment to 3 w/ Adsorption 80% BOD Filter
H9SO. in packed removal Activated
tower Sludge
Chlorinated 1500- Lime Sedimen- 60% suspended None
Insecticides 3000 gpm addition tation solids removal
Pesticides
Remarks

100-300 ppm
chlorinated
hydrocarbons
in effluent
       Chlorinated
       Insecticides
       Chlorinated
       Insecticides
       Formulated
       Chlorinated
       Insecticides
       and
       Herbicides
Low
          None
          Filtration
None
Filtration
Diatoma-
ceous earth
Activated
Carbon

< 2 ppm as
DDT in
effluent
< 0. 5 ppm
as DDT in
effluent
Activated
Carbon

Sanitary
Sewer

Sedimenta-
tion of
Clay
Carrier
Total
evaporation
                                                         Concentrated
                                                         wastes only


                                                         Concentrated
                                                         wastes only
Solids
recycled

-------
Table 21.  (Continued)
Type of
Product
Organo-P
Insecticides

Organo-P
Insecticides


Triazine
Herbicides

Organo-P
Insecticides


Metallic
Carbamates
Waste Pretreatment
Flow
100 gpm Lime
addition

Low None



Low HC1 added
to pH < 1

None



High None

Physical
Treatment
Sedimenta-
tion , 2 day
detention
5.25%
sodium
hypochlorite
2:1 dose
Heat to
150F for
2 hours
Sedimenta-
tion, three
day deten-
tion
Sedimenta-
tion, short
Effectiveness
10% Suspended
solids
reduction
100%
hydrolysis


?


Effluent
S.S.=900mg/l


Solids
reduced to
Post-
Treatment
None


None



pH adjust-
ment

None



Sanitary
Sewer
Remarks
Milky white
effluent
pH = 4
30 minutes
at 212F
24 hours at
90F



Pilot studies
underway for
biological
treatment
High Na SO4
and other
                                                    1200 ppm from
                                                    1600 ppm
metal surf ate s

-------
Table 21.  (Continued)
Type of
Product
Waste
Flow
Pretreatment
Physical
Treatment
Effectiveness
Post-
Treatment
Remarks
Dithiocarbamate  28 gpm
Pesticides
None
Formulated
Chlorinated &
Organo Phos-
phorous
Pesticides
                 20 gpm   None
Dilution by
discharge
during high
flow periods

Solar
evaporation
                                                                       None
                                            None
To be
discontinued
in the near
future

Low sludge
production
Dredging
landfilled
periodically
Chlorinated 48 gpm None
Sulfur
Fungicide
Solar
evaporation
None Design rate
2 . 0 gpm per
acid
S ourc e:  P lant I nte rview s.

-------
lime added to one organophosphate pesticide waste produces a milky white
suspension in the waste.  Only 30 percent of this material can be removed
in a lagoon with three days detention.  Conversely a chlorinated herbicide
plant obtains relatively good removal (up to 30%) of 2,4-D and 2,4,5-T
acids,  amines and other salts with lime floe.  pH adjustment to 6.5 and
12 hours sedimentation is required. The esters are not removed by this
technique .

       Sludge removal can be accomplished with mechanical scrapers if
the sedimentation basin has a regular geometric shape, or it must be done
manually if the basin is an irregular pond.  Manually cleaned basins are
most often used since sludge production rates are small.  However, in
some cases,  sludge volume buildup has been underestimated and the sed-
imentation basin quickly becomes useless without frequent cleaning.
Therefore, accurate estimates of sludge production are important.  For
example, if lime (Ca(OH)9) is used to neutralize a waste containing sulfuric
acid, 1.39 pounds of calcium sulfate will be  produced for each pound of
sulfuric acid  neutralized.
                        +  Ca(OH)2 - >  CaSO4  +

                 1 pound + 1.35 pounds        1.39 pounds

If this material concentrates to a 5% solids sludge in the sedimentation or
neutralization tank, it will occupy a volume equal to 28.5 ft 3 per ton.
Therefore, one million gallons of waste containing 415 mg/1 H-SO, (2000
pounds per million gallons) will produce 2780 pounds of sludge when neu-
tralized with 100% reactive lime. This sludge will occupy 40 cubic feet
in the sedimentation basin.  If less reactive limestone is used, the sludge
production rate is of course higher.
Biological Treatment

       Biological treatment of aqueous wastes from pesticide manufacturing
processes can be an economical method of reducing toxicity, organic con-
tent, and suspended materials.  The biological systems used must be care-
fully cultured in the proper environment to produce specialized organisms
capable of utilizing the waste components as food sources, and these
organisms must be protected against shock loads, rapid pH changes and
poisonings from  plant upsets,  spills, etc.  In order to design and
operate a successful biological system, the waste stream characteristics
                                  113

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and the limitations of the organisms cultured must be considered.  The
following discussion will deal with some of the special design consider-
ations that should be included,  and design and operating parameters from
several existing treatment facilities will be cited.  Table 22 summarizes
the information on current biological treatment practices obtained during
the plant site interviews.
Basic Requirements

        Biological populations can be utilized to rapidly and efficiently
remove organic materials from waters if a suitable environment is provided,
For aerobic (full oxygen based) biological proliferation,  adequate food,
oxygen, nutrients and proper pH and temperature conditions are required.

        Temperature:  The temperature effects on biological systems are
significant, even at ambient levels around the United States.   During the
hot summer months, biological activity is accelerated and oxygen solu-
bility is decreased, presenting the critical design situation for aeration
equipment.  During the winter months biological activity decreases with
temperature as does the removal rate  of organic  material.  Therefore,
winter conditions should be used as the initial design situation for
determining the size of the oxidation  reactors.  Figure 28 indicates the
magnitude of the effect that normal winter temperatures  may have on sol-
uble industrial wastes. These studies conducted in the  Northeastern
United States show that temperature effects should be considered in a
treatment system design.  Even though biological systems operate most
efficiently  at temperatures in the 30 to 35C range (40 to 45C for
certain thermophilic bacteria),  systems to maintain temperatures near the
optimum level are not usually feasible for industrial wastes because of
the added expense.  The system size and detention time is usually
increased to compensate for reduced biological activity during cold
weather.

        pH;  Biological systems may operate reasonably well in the pH
range from  5 to 9  if adequate acclimation time is allowed and rapid pH
changes do  not occur.  Most biological systems are designed  to operate
in the  6 to  8 pH range.  Rapid pH changes are extremely detrimental to
biological systems and must be prevented.  The aeration system acts as
a well mixed equalization tank capable of reducing the effect of shock
loads, especially if the power level is high enough to insure complete
mixing in the basin, but the system capabilities can be exceeded.  The
                                  Ilk

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      Table 22.  Biological Treatment
Type of
Product
Chlorinated
Herbicides
Waste
Volume
2 mgd
Pretreatment
pH adjust-
ment 5: 1
Biological
System
Trickling
filter
Design
Parameters
2 . 5#Phenol
1000 ft3 /day
Effectiveness
(Reported)
70% phenol
removal
Post- -
Treatment
Activated
sludge
dilution
with cooling
water -
nutrient
addition
H
I-1
VJl









Chlorinated
Herbicides




Chlorinated
Herbicides



2 mgd 5:1
dilution
nutrient
addition
& trickling
filter
85,000 30:1
gpd dilution
with
sanitary
sewage
Activated
sludge




Trickling
filter (one
third of
diluted
flow only)
675 gpd/ft'
                          6 hr./aera-
                          tion MLVSS =
                          600 mg/1
                          3300 gpd/fr
                          25#BOD/1000
                          ft3/day; 0.5#
                          phenol/1000
                          ft^day (oper-
                          ated at less
                          than design
                          loading
                 95% phenol
                 removal
None
                 70% BOD,
                 55% phenol,
                 0% phenoxy
                 acid removal
Aerated
lagoon and
stabilization
pond

-------
Table 22,  (Continued)
Type of
Product
Chlorinated
Herbicides
Chlorinated
Herbicides
Chlorinated
Herbicides
Chlorinated
Hydrocarbons
Waste
Volume
85,000
gpd
85,000
gpd
43,000
gpd
43,000
gpd
Pretreatment
30:1
dilution +
1/3 of flow
passes
through
trickling
filter
30:1
dilution
aerated
lagoon
Carbon
adsorption
and pH
adjustment
Carbon
adsorption
& trickling
filter
Biological
System
Aerated
lagoon
Stabili-
zation pond
Trickling
filter
Activated
sludge
Design
Parameters
3 days
detention,
2500 #BOD/
acre/day
23,900#O2/
day,MLVSS=
200 mg/1
30 days
detention,
30 #BOD/
acre/day
30 gpd/ft2
.07 #BOD/
1000 ft /day
16 hr. aeration
2 pounds BOD/
1000 ftVday
Effectiveness
(Reported)
70% BOD ,
75% phenol,
55% phenoxy
acid removal
50% BOD ,
50% phenol,
25% phenoxy
acid removal
90% phenol
removal ,
70% BOD
removal
46% phenol
44% BOD
removal
Post-
Treatment
Stabilization
pond
None
Activated
sludge
None

-------
Table 22.  (Continued)
Type of
Product
Organo-P
Insecticides




Waste
Volume
720,000
gpd




Pretreatment
pH
adjustment
with lime



Biological
System
Activated
sludge




Design
Parameters
6 days
aeration, 27~
tfCOD/lOOOft /
day MLVSS
6000 mg/1
D.O. > 2
Effectiveness
(Reported)
99% BOD
96% COD
99% OP
removal


Post-
Treatment
Municipal
Sewer




Carbamate        High
Insecticides
pH           Aerated
adjustment   lagoon
Good
Some toxic
wastes bypass
lagoon and are
barged to sea
Source:  Plant Interviews

-------
H
CO
1 V/V/
2 90

5 80
y 70
iZ 60
u_
 50

_J
 40
O
5 30
UJ
o:
20
in
Q
O 1 0
CO
0


A
n
 n
A D o
A
^ n
DO

A DRBC
O CHEMICAL
D CHEMICAL



I 1 1 1 1

0 5 10 15 20 25
32 41 50 59 68 77








. PLANT "A"
. PLANT "B"



1

30 (C
86 (F
                                          TEMPERATURE
     NOTE
      I.  ALL  LOADINGS 3 0.5 Ib BOD5  applied / day / Ib MLVSS.
      2.  ACTIVATED  SLUDGE  TREATMENT  OF WASTEWATERS  DISCHARGED  FROM CHEMICAL  PLANTS
      3.  GOOD SLUDGE  SETTLING  OBSERVED AT  COLDER  TEMPERATURES.

                    Figure 28.   The Effects of Temperature on BOD Removal from
                                Soluble Industrial Wastes.

                    Source:  Ford, 1971.

-------
natural buffering capacity (perhaps as high as 0. 7 pounds of alkalinity
equivalent per pound of COD removed)  is not sufficient to protect the
system against large strongly basic slugs of waste and offers no protection
against acid slugs.  The CO produced in carbon bio-oxidation can affect
the pH of the system.  CO? tends  to cause slightly acid conditions in
high rate  systems.  In addition, biological systems can produce acid
byproducts such as H2SO4/ HNO3, and H3PO4 from the oxidation of
pesticidal components such as  ethyl parathion.  Adequate buffer capa-
city must be provided to prevent significant pH changes.

       Nutrients:  In addition to organic substrate, biological populations
require inorganic nutrients for cell synthesis, including nitrogen, phos-
phorus, iron, silica,  and others.  Most of the required trace elements are
present in sufficient quantities  in  pesticide manufacturing wastewater
streams, with the exception of  nitrogen and/or phosphorus in some  cases.
In general, a carbon to nitrogen to phosphorus ratio of 100:5:1 is adequate
to allow unrestricted biological growth.  If these nutrients are lacking,
they should be added to the waste stream.  Ammonia or soluble nitrates
and nitrites can be added to overcome nitrogen deficiencies, and soluble
phosphates can be added as a source of useable phosphorus.  These addi-
tions will seldom be needed for pesticide manufacturing wastes, and when
they are,  waste streams from other plant operations can often by used to
supply the needed nutrients.

       Degradability:  Almost every  organic compound can be broken down
biologically if_ proper environmental  conditions are maintained and  suffi-
cient time is provided.  Organisms must be allowed adequate time to develop
the enzymes necessary to stabilize the waste components for energy and
cellular building material. After acclimation, the organisms will consume
the wastes at a rate dependent  on  many factors.  If this utilization  rate is
slow, the waste may be considered non-biodegradable for practical treat-
ment purposes.  Compounds such as tertiary aliphatic alcohols, ethers,
benzene,  trichlorophenols and pentachlorophenols fall into this refractory
group and present problems  in pesticide waste treatment.  Some of  the
factors which affect biodegradability are:

       1.  Solubility and availability:  Compounds in emulsified or
           chelated forms are not readily available to micro-organisms
           and are slowly removed.  A prime example is DDT and many
           of its isomers which are extremely insoluble in water.
                                   119

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       2.  Molecular size: The  physical size of complex molecules often
           limits the approach of enzymes and reduces the rate at which
           organisms can  break down the compound.  Many pesticide com-
           pounds  and their isomers are of large and  complex structure
           making  them  resistant to degradation.  Some carbamates and
           carboxylic acid based compounds are examples.

       3.  Molecular structure:  Aliphatic (straight and cyclic) compounds
           are in general more degradable than aromatic compounds.  Thus
           some pesticide compounds and parts of some molecules can be
           degraded  easily while other parts cannot.   In some cases,  par-
           tial degradation will occur, but the pesticidal activity of the
           waste stream may  not be reduced significantly if the toxic
           components of  the compound are bioresistant.

       4.  Substitutions:  The substitution of elements other than carbon
           in the molecular chain often make the compound more  resistant.
           Esters and epoxides,  salts, etc.  are  more resistant than the
           base pesticidal compound.

       5.  Functional Groups: Halogen substitution  to an aromatic compound
           renders it less  degradable.  The number of substitutions and the
           location are  of importance.  Chlorophenols are an excellent
           example of increasing resistance with increasing  substitution.
           Amino and hydroxyl substitutions often increase degradability.

       Most  pesticide manufacturing wastes  are susceptible to some degree
of biological  treatment,  but in special cases  10 to 15  days of contact are
required to achieve  significant removal.  Therefore, a detailed  study of the
waste properties, and biodegradation tests are necessary before a biological
treatment method is chosen and designed.

       The biological methods commonly used in  pesticide manufacturing
waste treatment include:

       1.  Trickling  filters; normally high rate systems used as roughing
           filters.

       2.  Activated sludge;  usually highly active biological solids,
           extended  contact systems.
                                 120

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       3.  Aerated lagoons; long detention lower biological activity
           basins equipped with surface aeration equipment.

       4.  Stabilization ponds; long detention low biological activity
           basins with no aeration facilities.  These systems are usually
           facultative.  They are most often used as polishing devices
           to remove small amounts  of organic material. The suspended
           solids in the effluent are usually higher than the influent sus-
           pended solids since biological floe and  algae are present in
           the effluent.
Trickling Filters

       Trickling filters are often used in industrial waste systems because
of their ability to handle fluctuating waste loads and toxic "slugs" without
longterm upset.  These systems are used as "roughing filters"  or load
leveling devices.  After passage through the filter, the waste stream
organic load is reduced (up to 85%  BOD reduction for some one-pass
systems) and shock loads or toxic slugs are attenuated by mixing.  If
recirculation is employed,  further organic removal and load  leveling is
achieved.

       The  typical filter system consists of a bed 8-10 feet deep composed
of 2-4" diameter stones.  Biological slimes attach themselves  to the rock
surfaces and consume  the soluble wastes as the wastewaters trickle  over
the stones.  Natural draft or forced air ventilation from the  underdrains
through the  bed, counter current to  the wastewater flow, is  required to
keep the system odor free. Improved operation can be achieved in special
cases  if synthetic polyethylene media are used instead of rock. Well-
designed media reduce the possibility of plugging and increase ventilation,
thus allowing very deep trickling filters to be  used.   Filters carrying syn-
thetic  media in excess of twenty feet thick are now being used effectively
for some wastes.

       As the soluble  components of wastes are utilized by the organisms
in a filter bed, the slime layer builds up and eventually sloughs off.  If a
toxic slug reaches the filter, the outer layer of organisms will  contact the
toxic material and will die. The dead material will slough, exposing new
and active organisms which will continue to utilize the waste once the  toxic
material has passed  through the system.  If the system is overloaded, the
excess organic material will also pass through the system,  not affecting
                                  121

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the biological processes.  Thus the trickling filter is a good pretreatment
device  (roughing filter) for the types of loads which can occur in pesticide
manufacturing.  If recirculation is employed, wastes with high organic
loads can be treated.

        Normally hydraulic loadings on trickling filter systems should not
exceed 0.5 gallons of waste per minute per square foot of filter  surface.
For "roughing filter" operation, organic loading is relatively unimportant.
However, the loading  should be high enough to efficiently utilize the organ-
isms for waste removal. A chlorinated herbicide plant reports that loadings
of 25 pounds BOD per  day per 1000 ft of filter volume at flow rates of 0.11
gpm/ft   resulted in 70% removal of phenol wastes and  80% reduction of BOD
for a one pass roughing filter system.  In this system the wastes were
mixed (l to 6) with cooling waters for dissolved salts and phenol dilution
before treatment.  After one pass through the filter the phenol wastes
received final treatment by activated sludge.

        Similarly, a conventional trickling filter treating chlorinated
herbicide wastes diluted approximately 30:1 with municipal sewate showed
72% reduction of BOD  and 54% reduction of chlorophenols,but no removal
of chlorophenoxyacids.  This  filter was operated at a hydraulic loading of
0.24 gpm/ft and an organic loading of 45 #/1000 ft3/day.

        New, high rate filters with synthetic media may be utilized for
pesticide waste treatment in the future.  However, since some dilution
is required for many pesticide manufacturing wastes to reduce toxicity
and dissolved salts before biological treatment, the resulting organic
concentration is too low to sustain high rate filters.  For this reason these
systems should be considered only in specialized cases.
Activated Sludge

       Activated sludge treatment is the biological oxidation of wastes in
a fluidized reactor containing a concentrated biomass supplied with organic
waste and oxygen in correct proportions to stimulate efficient utilization of
the waste by the organisms for energy and microbial cell synthesis.  After
sufficient contact, the wastewater (mixed liquor) is drawn off and the
bacteria  are allowed to coagulate and settle in a clarifier.  The settled
"sludge" is returned to the  system to maintain a high bacterial population
in the aeration basin, or wasted when the sludge production exceeds the
system's requirements.  The clarified water is released. In this process,
                                  122

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suspended and dissolved organic material is converted to biomass which
can be removed by sedimentation. Most organics can be utilized by the
bacteria,  including pesticides, pesticidal isomers, solvents and organic
by-products under proper conditions.  The utilization rates are different
for each compound so removal efficiencies can differ for the various types
of compounds  in the system.

       Activated sludge systems for the treatment of pesticide manufacturing
wastes may carry unusually high  solids (bacterial) concentrations in the
aeration basin.  A conventional activated sludge system for municipal
sewage will usually maintain a mixed liquor suspended solids loading of
2000 to 2500 mg/1 in the aeration tank. Pesticide waste systems may
maintain suspended solids loadings as high as 18,000  mg/1 with perhaps
1/3 of these solids active.  If lime is used for neutralization, calcium
carbonate, calcium sulfate, and calcium phosphate will form a major por-
tion of the fixed solids.

       In one organophosphorus pesticide plant, the waste is treated by a
modified activated sludge process.  The waste is held  in an aeration basin
for six days to achieve  95 to 99% reduction of pesticidal compounds. BOD
removals in excess of 99% are also achieved.  Mixed liquor volatile solids
levels of 5000 to 6000 mg/1 (total solids often exceed  15,000 mg/1)  are
maintained and dissolved  oxygen levels of 2 mg/1 or more in the aeration
basin are provided by an automatic oxygen monitoring system which  con-
trols the blowers. The  waste and returned sludge are introduced into the
aeration tanks at several points  to help provide good mixing.  This  in
conjunction with an adequate mixing power level serves to protect the
system design.  COD loading of 12,000 pounds per day (0.08 #COD/day/
#MLVSS) and air flows up  to 24,000 cfm are used as operating parameters.
Efficiencies of 99% BOD removal, 96% COD removal and 99% organophos-
phorus removal are reported.  The system is extremely  sensitive to  the
organic loading rate and operates poorly if the proper COD loading is not
maintained. Sludge production of 300 pounds of dry solids per day  (.025 #/
#COD removed)  is typical.  The clarified effluent and excess biological
solids are sent to conventional activated sludge municipal treatment plant
for final treatment.

       An activated sludge system presently used to treat  a chlorinated
hydrocarbon herbicide waste is of a more conventional nature.  The process
waste is first  diluted  5:1 with low BOD, nontoxic cooling waters and
ammonia is added to satisfy nutrient requirements.  The waste stream is
then passed through the "roughing filter" .  After one pass, the filter
                                  123

-------
effluent flows into an aeration basin for six hours of contact with a
biological culture maintained at 600 mg/1 mixed liquor volatile suspended
(MLVSS)  solids.  The waste is introduced at the head of the basin only,
since the filter serves to prevent shock loads.  The initial phenol levels
in the aeration basin often approach 30 mg/1 and 95 to 99% removals are
reported. The total MLSS level is maintained at 900 mg/1 and approxi-
mately 2/3 of the solids are classified as volatile. The  settling character-
istics of the  sludge produced by this system are good.  The sludge is
removed  in the  clarifier, partially de-watered and disposed of by deep
well injection into an unusually permeable underground formation.  The
system operates well but is subject to periodic upset when unusual toxic
compounds enter the system via spills or process upsets.  A large holding
basin is  available into which wastes may be bypassed if toxic components
are suspected.  The  bypassed wastes can then  be metered into the treat-
ment system  slowly so that dilution will reduce the effect of toxic compo-
nents on the  organisms.

       Many pesticidal wastes which can be diluted  at the manufacturing
plant are discharged directly into municipa1- sewers.  Often little pesticide
removal occurs.  DDT discharged into a large northeastern U.S. municipal
plant appears to pass through the system with less than 25% removal.  The
activated sludge system accounts  for little actual biooxidation since most
of the removal occurs in the primary sedimentation basin.  The DDT content
of the effluent is high but sediment samples obtained below the outfall
contain relatively large amounts of DDD but little DDT.  Thus it appears
that little degradation of DDT occurs during the short contact period in
the activated sludge plant, but some biological oxidation occurs slowly
in the river sediments.

       Studies conducted in England also show that some pesticide removal
occurs in a municipal treatment system, but that high effluent concentration
can also occur. The following statements are obtained from "Notes on
Water Pollution Research"  (March  1967), published by the Water Pollution
Research Laboratory, Stevenage, England:

       "The  Laboratory has carried out a limited survey of pesticides
       entering and  leaving the works mentioned above,  which treats,
       by biological filtration, sewage from an area containing a
       factory at which pesticides are formulated. Dieldrin,  ct-BHC,
        T-BHC, and DDT were all present in the crude sewage.  The
       number of results was not sufficient for the calculation of a
       materials balance but it is clear from the results that all four
                                 124

-------
       pesticides tend to concentrate in the primary and filter
       sludges.  For example, the concentrations of y-BHC in
       composite samples of sewage for five consecutive days
       varied from 1.3 to 64 |ag/l but on the same days the con-
       centration in the primary  sludge  was of the order of 300
       }jg/l.  A similar relationship was found for dieldrin.  DDT
       was present in the crude  sewage but during sewage treat-
       ment it was largely broken down to DDE and IDE, both of
       which  were present in the primary sludge. Pesticides were
       present in the filter sludge (total solids content approximately
       four percent)  at concentrations of some hundreds of micro-
       grams  per litre and in three samples  the amounts of DDE
       were greater  than 1 mg/1.

       "The final effluent contained about 1 (jg/l of r-BHC
       throughout the period but the other pesticides were
       present at markedly reduced concentrations.  Fish kept
       in a cage within the effluent channel remained alive
       during the seven-day period of the experiment."
Aerated Lagoon

       In situations where land is available and a low maintenance, low
operational expense system is desirable, the aerated lagoon is an attrac-
tive treatment method. Aerated lagoons are not generally effective for
treating highly concentrated wastes, i.e. , COD >700 mg/1.  The system
normally employs surface aeration equipment  on a 6 to  10 foot deep  basin
with several days detention.  No  sludge return is employed, so that sus-
pended  solids levels (biological solids) are low, thus necessitating long
detention requirements for  pesticidal wastes. Aerated lagoon loadings
of 25  to 50 pounds of BOD per acre per day are low enough to prevent
anaerobic conditions in a well aerated and well mixed system, and may
be design criteria usable for pesticidal wastes if the toxic compounds
are not  extremely bioresistant.

       In one system operated on an experimental basis, a chlorinated
hydrocarbon herbicide waste was  diluted 30 to 1 with municipal sewage
and fed at an average BOD  rate of 615 pounds per acre  per day,  and 70%
BOD removal was obtained. Twenty-three thousand nine hundred pounds
of oxygen transfer capacity per day were provided by four surface aerators
(125 horsepower).   Phenolic loadings of 29 pounds per  acre per day  (1/3
                                 125

-------
phenol, 2/3 phenoxy acids) were maintained and the system achieved
80-90% phenol removal and 56 to 72% phenoxy acid removal. The average
detention time was slightly more than three days.  Low biological solids
levels were noted in the basin.  During one four month sampling period
(summer), effluent suspended solids averaged 108 mg/1 and the settleable
solids averaged 5.3 ml/1.  Effluent BOD levels averaged 26 mg/1 and
phenol levels were 0.2 mg/1. Phenoxy acids were unreported but probably
approached  1. 7 mg/1 in the effluent.

       In general effluent  quality from  an aerated lagoon is poor because
the biological solids present in  the overflow exert a BOD.  However, the
breakdown of toxic organics may be nearly complete with almost no pesti-
cidal agents in the effluent (EPA Report in press, Grant #  12130 EGK 06-71)
To accomplish this, long detention times will be required due to the
inherently slow biological  utilization of complex hydrocarbons.  One par-
ticularly difficult waste  (a combination of pesticidal and petrochemical
process effluents) is presently being treated by aeration in a lagoon,
having a detention time of  seventeen days.  Pesticide  levels in the
effluent are low,  but COD  and color remain high.  Plant officials feel
that if more air can be supplied  to the  system, higher organic removals
can be capable of maintaining dissolved solids levels  of approximately
2. 0 mg/1 in the entire  system.   Higher D.O. levels do not significantly
increase oxidation rates, but D.O.  levels  less than 0.5 maybe  inhibitory
(Ford, 1971).
Stabilization Ponds
       An additional biological treatment system which is used as a
polishing device in most instances and a complete system in some cases,
is the stabilization pond.  The pond acts as a reactor where biological
oxidation is allowed to proceed at natural rates.  The ponds are normally
designed to be facultative, with aerobic conditions near the surface and
anaerobic conditions in the bottom waters.  The anaerobic organisms can
successfully metabolize many relative resistance compounds but often
produce odors in the process.  Therefore, the aerobic conditions must be
maintained in the surface waters to reduce or elimate the odors which are by-
products of anaerobic digestion.

       The success of treatment is dependent upon the proper balance of
bacterial and algal activity in the  system since the former utilize organic
wastes for energy and the latter produce oxygen in the presence of sun light.

-------
Excessive organic loadings, low temperatures, rapid or severe  pH
changes, toxic compounds and high concentrations of sulfur-containing
compounds can cause significant reductions in treatment efficiencies.

       The long detention times normally utilized in stabilization pond
design gives microorganisms the time to degrade relatively resistant com-
pounds.  If organic loadings are low enough to insure aerobic conditions,
at least in the surface waters, good BOD and COD reductions can be
achieved in relatively short  time periods (1-3 days) but phenols,  phenolic
acids and complex hydrocarbons will remain.  The operators of  an existing
pond with a 20-day detention period claim the BOD is reduced from  120 to
near 0 mg/1 (sic),  the sulfides are reduced from  15 to near 0 mg/1 and
total phenols are reduced from 17 to approximately 7 mg/1 under summer
conditions.  It is unusual for stabilization  pond  effluents to have such
low BOD levels since the algae and bacterial solids in the effluent  will
exert a BOD.  Biological oxygen demands in excess of 10 mg/1  are more
typical.  In another system an existing  polishing pond following an aerated
lagoon reduces chlorophenols from average levels of .33 to .12 mg/1 and
phenoxy acids from 1.62 to 1.27 mg/1 in a  30-day detention period. BOD
reductions from 23.1 to  14 mg/1 are typical in this system.

       Since algal growth is of major importance in a system of this type,
wastes with high color content, high turbidity or emulsions cannot be
treated effectively.  The light penetration may be so reduced by these
conditions that good algal growth (and the associated oxygen production)
is impossible.  Likewise high sulfur containing wastes often result in
the proliferation of dark bacterial cultures which effectively prevent light
transmissions and reduce removal efficiencies (FWPCA Report,  1970).

       As indicated earlier, a properly  designed pond  can produce good
effluents.  Detention times of 20 days or more are typical. Organic load-
ing should be relatively low for pesticidal wastes, perhaps in the range of
20 to 30 pounds of BOD  per acre per day. Care must be taken to  eliminate
algal toxins, high sulfur wastes and excessive turbidity.  If possible pilot
scale units  should be run to obtain usable design information on a parti-
cular waste before the pond  system is constructed.
Incineration

       High temperature incineration is the waste disposal method preferred by
the majority of plant managers interviewed. A well-designed, well-operated
                                  127

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system can handle a wide variety of wastes without upsets and produce a
residue that is  small in volume (if present at all),  and void of pesticidal
components.  Gaseous, liquid and solid pesticidal wastes may be burned
in incinerators. Table 23 contains a summary of the information on incin-
eration techniques gained during the site interviews.

       Incinerator design is important in insuring  that complete
destruction of pesticides and related compounds occurs.  The burning
chamber must be designed to provide:

       a.  Adequate residence time in the flame
       b.  Adequate mixing to insure  contact of the waste with the
           necessary  amount of oxygen
       c.  Adequate oxygen in the burning  chamber for complete
           combustion plus a small amount of excess air for safety
       d.  Adequate temperature to insure complete destruction of
           the organic compounds.

       Several types of incinerators are available  which can provide the
proper burning conditions.  These include multi-chamber types,  tan-
gentially fired vortex type burners,  baffled chamber burners,  and fluid-
ized bed  burners.  Each type has  some advantages and disadvantages
for various types of wastes.  Some general considerations will be dis-
cussed below.

       The residence time in the  flame can  be controlled by properly
sizing the primary  burning chamber and the fuel and air flow rates.  The
chamber should provide a  minimum of 0.3 to 0.5 second residence time
at normal burning temperature of 1400 to 1800F.  At higher temperatures,
oxidation occurs more rapidly and shorter residence times can be tolerated,
                                                                j
       Mixing  is controlled by the air-fuel  injection into the chamber.
High pressure nozzles  and baffle  plates are often used to disperse liquid
and gas streams into the primary combustion air.  Moving jets which
oscillate spraying  the waste against a dispersion plate have also been
used successfully. If  auxiliary fuel is used to maintain  high burning
temperatures, the fuel  stream can be used to aid in dispersing the
incoming waste stream. At high temperatures  many relatively noncor-
rosive fluids  become highly  corrosive (i.e.  toluene) and  the nozzle and
baffle plate design should consider this factor.
                                  1P8

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                                           Table 23.  Incineration
\0
Type of
Product
Organo-P
Insecticides



Organo-P
Insecticides


Chlorinated
Pesticides





Organo-P
Insecticides




Waste Pretreatment
Burned
All liquid None
wastes; 4%
organic s
1.5%
organo-P
Gaseous None
wastes
only -
Mercaptans
Tank and None
still bottoms -
high chlorine
wastes



Gaseous None
wastes,
concentra-
ted liquid
semi -solid
wastes
Incinerator
Type
Atomizer
Burner
Natural
gas fuel

Thermal
Oxidizer,
Natural
Gas Fuel
Vortex
burner,
Natural
gas fuel
available
but not used

Atomizer
Burner ,
Natural gas
fuel


Operating
Characteristics
1600F




1800F
For odors
only

1400F






1600F
For odors &
liquids



Air
Pollution
Control
None




None



23 foot
packed
tower
scrubber
carrying
2" saddles,
500 gpm
Caustic
spray
fiber-glass
demisters


Remarks
P25
particulate
and high
SO 2 present

No detectable
odor. High
fuel costs

Persistent
white plume
resulting from
sodium chloride
aerosol. Scrubber
water contains
300-400 ppm HC1
Persistent
white plume
from P<35;
SO 2 present



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       Table 23.  (Continued)
OJ
o
Type of
Product
Chlorinated
Herbicides







Carbamates
Urea Based
Insecticides

Chlorinated
Insecticides


Waste Pretreatment
Burned
Concen- Blending
trated
chlorinated
wastes and
general
petro-
chemical
process
wastes
All Blending
process
wastes

Concen- Screening
trated and
chlorinated blending
residues
Incinerator
Type
High
pressure
atomizer,
natural gas
available




Low
pressure
spray against
baffle plate
Down flow
primary
burner

Operating
Characteristics
Horizontal
combustion
chambers
1800F





1400F



1000-1400F
Steam injected


Air
Pollution
Control
Venturi
scrubber
18" drop






None



Carbon
block
packed
scrubber
Remarks
Very
satisfactory
services
reported





No problems
reported


Primary air
preheated
by exhaust


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Table 23.  (Continued)
Type of
Product
Chlorinated
Insecticides



Urea
Herbicides
Chlorinated
Surfur
Fungicide








Waste Pretreatment
Burned
Gaseous None
wastes-
methyl
chloride

Veracil None

Toluene & None
Methanol
waste
stream
containing
some
product &
off gas
stream from
product
drying
Incinerator
Type
Low
Pressure
natural
gas burner



High
pressure
stream
atomizer,
natural
gas aux.
fuel




Operating Air
Characteristics Pollution
Control
1500F Dilute
caustic
packed
tower
scrubber
None

1700F Packed
tower
caustic
scrubber
for HC1






Remarks
99% removal
of HC1





A dense white
water vapor
plume is formed.
Particulates
seldom exceed
Ringelmann
No. 1




Source: Plant Interviews.

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        The oxygen supply to the primary burning chamber is of prime
importance.  Underfire air,  or air which enters the flame area, influences
mixing, oxidation and burning temperature.  Too much air causes a cooling
of the flame and reduced residence time;  too little air produces incomplete
combustion,  inadequate mixing and, at times, excessive temperatures.
Secondary air,  or air introduced beyond the  primary flame area, is required
to insure complete oxidation of the gases as they leave the flame area.
The exhaust temperature can be  controlled by the secondary air rate.  Pre-
liminary studies indicate  that, for best burning of typical pesticidal wastes,
primary air rates  should exceed  the secondary air rates  to provide exhaust
gases with the  least amount of toxic components, including SC>2 and CO.

        Most operators agree the combustion temperature in the incinerator
should be maintained in the 1400  to 1800 F range.  In  some special cases,
high temperatures may be required, but most wastes  will be destroyed  at
these temperatures.   The  combustion temperature may be controlled in  a
number  of ways.  Good insulation will increase the combustion tempera-
ture of a furnace; proper air-fuel control  and proper primary to secondary
air ratios will increase burning temperatures; auxiliary fuels can be used
to increase burning temperatures; steam injection and preheating of com-
bustion air or the waste stream itself will raise burning temperatures.
Although high burning temperatures insure better oxidation of the waste
stream, excessive temperature levels are not recommended.  As the burn-
ing temperature increases, the resistance to oxidation of the materials
used  to construct the furnace decreases, and incinerator costs increase.
Noxious gases, notably oxides of nitrogen,  increase markedly in concen-
tration as the combustion temperature increases. In addition, inorganic
salts, including NaCl and P^Or, are produced in smaller and  smaller sized
particles as the temperature increases.  These aerosols may act as nuclei
for droplet formation and produce persistent white fogs when humid condi-
tions  exist.  Even complete combustion will not eliminate aerosol  forma-
tion,  but the severity and persistence  of the resulting plumes  can  be reduced
with proper burning.

        Pesticide  wastes containing sulfur compounds, chlorine, chlorides,
phosphorus, flourides and heavy metals will produce airborne  emissions
that require  the use of air pollution control devices.   In order  to burn com-
pounds  containing the constituents listed above without violating federal
or state emission standards, incinerators are normally equipped with a
scrubber.  These  devices are widely accepted because they can be used
to control acid gases and particulates, they are corrosion resistant and
reliable.
                                 132

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       Scrubbers may be grouped in two basic categories, low energy
and high energy devices.  Low energy scrubbers include packed towers,
spray towers,  and plate towers.   Packed towers consist of deep beds of
inert packing material through which air and scrubbing liquids flow.  In
the counter current type tower, scrubbing liquid flows downward and the
exhaust gases flow upward contacting the  large wetted areas  of the pack-
ing. This type of device is excellent for soluble gas removal and effective
in removing large particulates.  Small particulates such as  NaCl crystals
are not removed well.  A twenty-three foot  packed  tower carrying 1-1/2"
ceramic packing  is used to scrub  exhaust gases from a chlorinated hydro-
carbon waste burner.  Water flows up to 500 gpm are used to  remove the
HC1 resulting from the  combustion of 2-3 gpm of concentrated waste.  The
scrubber water collects 300-400  ppm HC1 in one pass through the  tower.
The scrubber water is neutralized before discharge into a receiving stream.
The tower, however, is ineffective in removing sodium chloride from the
air stream.

       Spray scrubbers produce showers of fine droplets  with a series  of
nozzles and the exhaust gas to be cleaned  is passed upward  through the
spray.  Particulates are swept out of the air stream, and  some soluble
gases are removed.  Collection efficiencies are low.  A spray tower used
for organophosphate insecticide wastes was found  to be ineffective for
aerosol collection (2 5) until a fiberglass demister was installed. The
demister has made the  spray scrubber system capable of 99%+ removal  of
particulates and acid gases when a mild caustic is used as the  scrubbing
liquid.

       High energy scrubbers are  more efficient as gaseous and particulate
removal devices, but they are more expensive  to operate.  The venturi  scrub-
ber is an example of the high energy type of scrubber.  The gases are forced
through a throat at high velocity and allowed to expand rapidly.  Water is
injected in the high velocity, high turbulence section, where  impaction,
condensation, and absorption result in efficient gaseous  and  particulate
removal.  A venturi scrubber presently is used to clean the  exhaust from
a chlorinated hydrocarbon incinerator.  The plant engineer reports that  it
operates well at 18 inches  of water pressure drop.   No particulate  or odor
problems have occurred since the scrubber  was put into operation.   Corro-
sion has produced some difficulties, but replacement with acid  resistant
materials has  evidently solved these problems.  The acidic scrubbing water
is mixed with  the process waste  stream before neutralization  and biological
treatment.
                                 133

-------
       One additional problem associated with most scrubber systems is
the quenching section.  When a gas stream enters a scrubber, it is cooled
considerably by the scrubbing liquid.  However,  in the quenching area,
both hot gases and the cool liquid contact the chamber walls causing
severe stresses in the lining materials.  Therefore, considerable thought
must be given to quench section design and choice of firebrick.

       Tall stacks have often been used  to disperse incinerator gases
rather than clean them.  However,  stringent air pollution laws in effect
or proposed in almost all states will require gas cleaning,  giving  no
credit for tall stacks.  In most cases, tall stacks successfully disperse
contaminants, preventing high concentrations from reaching ground level.
However,  there  are instances when stacks do not work well, especially
if the plant is located in a valley area or  an area of frequent atmospheric
stagnation.  The plume may persist and reach ground level in concen-
trated form, rather than being dispersed as  expected under normal mete-
orological conditions.   If the plume contains SC^, HC1 mist, phosphoric
acid mist or heavy metals, problems can result.  Therefore, air  cleaning
devices are recommended on all pesticide waste incinerators. Scrubbing
devices usually saturate the exhaust  stream with water vapor producing
a plume containing condensed water.   These droplets tend  to hinder dis-
persement and further decrease the effectiveness of tall stacks.
Burial as a Disposal Method

       Almost every pesticide manufacturing plant contacted during this
study utilized burial as a method of waste disposal for some portion of
their process waste.  In some cases, liquids and semi-solids are buried
in containers, but most plants utilize burial for solid wastes only, and
cover burial is used in most cases.  Several  plants employ private dis-
posal companies to collect, transport, and bury their wastes off the plant
property.  With the exception of one plant (Rima, 1970), no manufacturer
had investigated the migration rate or pollution potential of the buried
waste.  In most cases, care was taken to choose burial sites in relatively
impermeable soil,  away from ground water and  surface water supplies; but
actual follow-up studies and site monitoring  are not being  conducted.
However, one plant indicated that they were  investigating  the possibility
of incorporating their lagoon sludge into  an asphalt mixture before landfill
burial to reduce the possibility of leaching.

       Burial rates ranged from 3-4 tons per  day of semi-solids contained in
55-gallon steel drums,  to hundreds of tons of dredging from a sedimentation

-------
lagoon buried over a three day period. All the plants which utilized
lagoons had plans to remove the solids from the lagoon when necessary
and dispose of them by landfill.  No information on drying times, trans-
portation problems or landfill operations  was available  since records
were seldom kept or available for this report.  Disposal costs ranged
from $6.50 per 55-gallon drum (approximately $32.50 per ton) to near
zero costs for on site pit disposal of  lagoon sediments.  It is virtually
impossible to cite typical costs or to describe the effectiveness and
safety of a "typical" burial operation.

       In general,  it is recommended that extreme caution be used
when pesticidal waste burial is  necessary. Even if  a soil analysis is
performed and reasonable distances to ground and surface waters are
maintained, the possibility of contamination still exists.  Pesticide
movement in a heterogeneous soil system is a complex  phenomenon that
is not completely understood.  Therefore, adequate design parameters
cannot be cited with certainty for all  pesticides under all conditions.

       In addition, a well-designed and well-constructed landfill is
only safe if operated properly.   Sloppy waste handling at the site is a
significant problem.  Several plant managers mentioned poor landfill
operation as a major point of concern. Leaky transfer equipment,  rup-
tured or poorly sealed drums,  blowing dust and wet weather operation
were mentioned as reasons for possible surface contamination at the
burial sites.
                                 135

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                           CHAPTER VII

                 THE COST OF WASTE TREATMENT
       Cost is a major factor considered in waste treatment and disposal
system design. However, since equipment requirements, labor costs,
operating costs and maintenance expenses are a function of the type plant
involved,  the housekeeping practices of the plant and the geographic
location, the economic parameter is most difficult to qualify.   The fol-
lowing discussion will deal in general terms with the economics of sev-
eral of the major treatment and disposal methods discussed in the literature
and specific data from  private interviews will be included where possible.

       Pesticide manufacturing wastes are  basically organic chemical
wastes which may be treated in a variety of ways.  The toxic components,
usual pH range and  high dissolved solids levels of pesticide wastes may
cause special problems which can increase costs,  but in general the
treatment costs should parallel those required for other chemical wastes
of similar organic loading.  Therefore,  the generalized cost estimates
included in this discussion which are based on municipal and petro-
chemical treatment history should be viewed as rough estimates which
may be somewhat in error.
Photochemical Degradation

       "Using experimental data for the photochemical degradation of the
compounds at 10 cm depth, a cost estimation has been made for a 50%
degradation.  The estimates are based on power consumption using a
cost of $0.015 KWH.  Because these cost figures are extrapolated from
an experimental situation, actual field application might function less
expensively. Attention should be directed to the geometric and reflection
aspects of ultra-violet radiation for a more economical process design.

       Compound                         Cost/Mil Gal

       Aldrin                             $24.00

       Dieldrin                           $73.00
       Endrin                            $57.50
                                 1ST

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Activated Carbon

       A method of predicting the cost of activated carbon treatment
has been developed by Dorr-Oliver, Inc.  Treatment cost for low
organic wastes, based upon a two-stage counter-current absorption
process, can be predicted by the following equations:

       Capital Cost:

               Log (cost) =  -.839-0.495 Log (influent flow)

       Operating Cost:

               Log (cost) = 0.45 Log (influent flow) + 1.06

       Total Cost:

               Log (cost) = 0.396 Log (influent flow) +0.83

       where

               Cost = Cents/1000 gal.

               Influent Flow = 1000's of gallons

The assumptions behind the development of these equations include:

       1)  Carbon dosage = 300  mg/1

       2)  Carbon cost 7 cents per Ib.

       3)  Power cost 1 cent/KWH

       4)  Steam cost 1 dollar/million BTU

       5)  Polyelectrolytes cost 1 dollar/lb.

       6)  Average carbon loss = 5% per cycle

       7)  Influent flow =10   gal/day

       8)  Average waste stream COD = 40 mg/1
                                 138

-------
       9)  Maintenance was assumed at 3% of fixed capital investment

      10)  Amortization was for 20 years at 4% interest.

Cost  estimates by this method will probably be lower than those which
will be found in most industrial situations since relatively low carbon
costs, carbon losses, and interest  rates were assumed.  Ford (1971) has
estimated that costs near 25 cents per 1000 gallons are more typical.


Chemical Treatment

       Chemical treatment costs  for pesticide wastes cannot easily be
quantified because of the widely differing waste characteristics, the
large  number of chemicals that can  be used and the degree of treatment
required.  However, some data are  available on neutralization  since
it is a common practice in many industries.  Figure 29 shows actual costs
for  typical neutralization facilities  for petrochemical wastes receiving
lime treatment.  Chemical costs for the plants surveyed in this study
ranged from $0.50 per ton for waste lime sludge used by one chlorinated
hydrocarbon manufacturer to $16.00 per ton for  slaked lime used after
limestone trench treatment of a similar chlorinated herbicide waste stream.
Lime trench treatment can be performed at considerably less cost since
large  contact basins are not needed.  Limestone costs varied from  $0.50
per ton for low parity stone to $5.50 per ton for high quality stone.

       Estimates of total chemical  treatment costs  for pesticide waste
treatment at plants visited during this study include $400,000 per year
for  three stage chemical treatment of  a  14 gpm organophosphorus waste
stream.  Eventually, thermal evaporation will also be employed at the
organophosphorus  plant increasing  the costs somewhat. A second plant
indicated that 25% of the capital cost of the facility was allocated to
pollution control equipment.


Biological Treatment

       Most published data on biological treatment processes deal with
municipal sewage systems or industrial streams with similar characteristics.
Figures 30-33 show typical costs that can be expected from various bio-
logical waste treatment unit processes.  Table 24 contains a summary of
generalized cost data for several treatment schemes used  for industrial
                                  139

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160  -
140   -
                            FLOW  (MGD)



            Figure 29. Capital Cost Relationship - Neutralization,



            Source:  Ford and Gloyna, 1970.
                              iko

-------
   10'
eo
 O

 *I03
 CO
 O
 O
 2
 O
    10
     CXI
1.0
10.0
100.0
               VOLUME  OF AERATION  BASIN (MG)


              Figure 30. Capital Cost Relationship - Activated Sludge .


              Source: Ford and Gloyna, 1970.

-------
      I04
Q
O
O
x
CO

CO
O
O

      I02
                               .INFLUENT  BOD5
                                 I960 mg/l

                             INFLUENT  BOD

                             150-700 mg/l
0.1                        1.0



                 WASTE  FLOW (MGD)

       Figure 31. Capital Cost Relationship - Trickling Filters.

       Source: EPA Report, 1970.
                                                           10.

-------
   I04
-S10
 o
 o
 Q.

 <

 O
    10'
    10
      O.I
        1.0              10.0



VOLUME  OF  AERATION  BASIN  (MG)



Figure 32. Capital Cost Relationship - Aerated Lagoon.


Source: EPA Report, 1970.
100.0

-------
z
o
   500
   400
o

tr

to 300
o
o
CO
o
o
   200
100
                         I
                                      I
I
                         10                20               30


                                   SURFACE   AREA  (ACRES)

                        Figure 33. Capital Cost Relationship - Lagoons.


                        Source: EPA Report, 1970.
                                                                        40

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                                Table 24

               COSTS FOR VARIOUS DEGREES OF TREATMENT FOR

           DIFFERENT COMBINATIONS OF WASTE CHARACTERISTICS

                              Waste BOD in mg/1
WASTE
FLOW 1 . 0 MGD
Pre or Primary
Activated sludge
Sand filtration
Carbon adsorption
Ion exchange
Anaerobic ponds
Aerated lagoon
WASTE
FLOW 0.5 MGD
Pre Primary
Activated sludge
Sand filtration
Carbon adsorpt.
Ion exchange
Anaerobic ponds
Aerated lagoons
3000
Cost*
0.32
1.93
2.40
6.54
7.17
2.36
1.61

0.19
1.13
1.42
4.02
4.36
0.81
0.97
Effl.
BOD
2700
25
15
1

200
100

2700
25
15
1

200
100
1000
Cost*
0.32
1.13
1.61
3.91
4.54
0.63
0.51

0.19
0.66
1.00
2.50
2.83
0.36
0.51
Effl.
BOD
900
25
15
1

200
100

900
25
15
1

200
100
500
Cost*
0.32
0.85
1.05
2.18
2.18
0.43
0.58

0.19
0.50
0.81
1.50
1.84
0.24
0.35
Effl.
BOD
450
25
15
1

200
100

450
25
15
1

200
100
*Costs are given as total capital costs in millions of dollars.
Source:  Barnard, 1970.

-------
wastes.  From these data it can readily be seen that no single system
can be considered the most economical for a variety of cases.  Effluent
requirements, flow volume, waste load, etc. must be considered.  For
example, as Table 24 shows,  high flow, high BOD wastes may be treated
more effectively and more cheaply with activated sludge than anaerobic
ponds, but low flow, low BOD wastes  are more cheaply (but less effici-
ently) treated with anaerobic ponds. In general, toxicity or pesticidal
component removal will parallel BOD and COD reduction if the compound
is biodegradable.  Therefore,  the same type of  cost-effectiveness analysis
used for industrial waste treatment should hold for pesticide wastes.

       An alternate method of estimating the cost of waste water treatment
is to determine the charges assessed by municipal treatment plants which
accept industrial wastes.  The idea of a city assessing surcharges on
industry is gaining wide acceptance.   However, pending legislation in
the United States Congress will probably set pretreatment requirements
for all industries discharging wastes into publicly owned treatment facil-
ities which have received federal funds.  These pretreatment requirements
will have some effect on the present practice of industrial treatment in
municipal plants, but until the legislation is approved in its final form,
the magnitude of the effect cannot be estimated.

       If the surcharge rates presently used are established to allow  the
the city to recover the  added cost of treating the industrial waste , they
should be indicative of  treatment costs for large scale plants.  Unfortu-
nately, the rates established by municipalities can vary widely.  Excessive
charges are sometimes used to discourage industrial contributors that could
overload a system, and conversely,  low charges are sometimes set to
encourage industries to use facilities that are experiencing financial dif-
ficulties.  Therefore, examples of high average and low rates should be
examined.

       a)  Low - Many large cities apply the same rates to any industrial
          discharge as they do domestic customers.  Charges are usually
          set at some  fixed percentage of water costs and range from
          $0.03 to 0.12 per 1000 gallons.  The cities normally require
          that the wastewater characteristics be determined and the
          discharge must be shown treatable prior to acceptance.

       b)  Average - A  small municipality in a North Atlantic state with a
          30 MGD plant, charges an organic chemical plant $0.40 per
          1000 gallons for flows up to 0.75 MGD.  No  surcharge based
          on organic loading or treatability is included.
                                 146

-------
       c)  High - A major North Atlantic city charges $0.70/1000
          gallons  for flows less than 0.03  MGD and decreasing amounts
          to $0.44/1000 gallons for flows exceeding 0.57 MGD.

       Various schemes exist for sewage charge determinations in
cities which feel that the additional cost incurred for testing, monitor-
ing a-nd reporting wastewater  characteristics is worthwhile.  The City
of Philadelphia assesses a surcharge of $0.15 per pound of BOD above
350 mg/1 or suspended solids above 400 mg/1.  Their studies show that
it presently costs $0. 06/1000 gallons to provide primary and secondary
treatment and from $0.036 to  $0.04/1000 gallons to provide primary
treatment only to mixed industrial and municipal wastes.   (Water Dept.-
City of Philadelphia,  1970).  The City of Chicago charges industry unit
prices of $0.21 per 1000 gallons of flow plus $0.014 per pound of BOD5
plus $0.024 per pound of suspended solids  for large discharges (Malin,
1971).  This system requires  extensive self-monitoring and reporting
from the industry plus a large amount of spot sampling conducted by the
city  crews.

       The City of New York  has developed an ordinance which allows
an industrial surcharge, D, to be assessed, based on the  formula:

              D = C F V  f(SS - 350) + (BOD -  300) ~|

       where D = the amount of surcharge in dollars
             C = actual cost per pound for removing pollutants
             F  = a conversion factor (mg/1 to ft/million gallons)
             V  = waste discharge volume in ft^
            SS  =  suspended  solids concentration
           BOD = Biochemical Oxygen Demand

       The figures,  350 and 300, are the concentrations of suspended
solids and  BOD, respectively, below which there is no charge to industry,
The cost factor C is  recalculated each year and is currently set at $0.025
per pound (Malin,  1971).
Incineration

       Liquid, semi-solid and solid wastes from pesticide manufacturers
are burned in several types of furnaces.  The multiple-chamber spray
injection furnace is the type most often used. Natural gas or fuel oil

-------
is used as auxiliary fuel to insure proper combustion. The total
incineration costs are dependent on the capacity requirements,  BTU
value of the waste be to burned, operating temperature, waste injec-
tion method and gas cleaning requirements.  Figure 34 summarizes a
large amount of data on liquid waste incineration.

        Vortex furnaces for high BTU liquid wastes and fluidized bed
incinerators for solid wastes are being investigated by pesticide man-
ufacturers.  The total cost of these units is high because of increased
maintenance and operating costs.  Capital costs may be somewhat lower
than more conventional units since the higher heat rates and  heat transfer
capabilities reduce the required size of the units for a given  waste volume.
Few vortex units are in operation to date so meaningful cost data are  not
available. However, European experience with fluidized  bed  units indi-
cates that capital costs should range from $60 to $120 per pound per hour
of capacity, and operating costs should  be near $5.00 per ton for small
units (1600 #/hr) to less than $1.00 per  ton for 8000 pounds per hour  and
larger units (Witt, 1971).

        A major cost factor that must be included in incinerator feasibility
studies is the cost of the required air cleaning equipment. In order to meet
present and proposed air control regulations  (Ringelmann #1 plume opacity,
SO2 and particulates based on  process weight, NOX based on BTU rating)
precipitators,  filters  (for particulates only) or flue gas scrubbers must be
employed. The capital and operating costs for these devices  can exceed
the costs of small incinerator units and may represent as  much as 25% of
the total cost  of very large installations.  Water treatment requirements
for the scrubber blowdowns also represent a  significant cost  factor. As
a rule of thumb, for incinerator units with capacities greater  than 1000
pounds  per hour, adequate air cleaning (including blowdown treatment
and solids handling) should cost a minimum of 25% of the incinerator
costs.  If unusually restrictive air cleaning is required because of acid
mists, toxic aerosols, etc. , this cost may increase.
Burial

       The most widely used disposal method for wastes from pesticide
manufacture is burial. Almost all plants visited used burial for the ulti-
mate disposal of some portion of their waste.  According to Meaning and
Keane (1971)  burial by landfill,  including proper compaction and cover
can be accomplished for approximately $1.50 per ton for large scale
                                 148

-------
  100.0
o>
c
*o
   10.0
CO
o
o
(0
o
CL
CO

o
1.0
                 INCINERATION>>IOmg/l COD

                 DOES NOT INCLUDE ASH DISPOSAL
           OPERATING 8  CAPITAL  COSTS  BASED

           ON  20 YEAR  AMORTIZATION
    0.1
                  ,1
      10
                  Kf
10*
                    WASTE  FLOW  (golxlO/day)



              Figure 34.  Capital Cost Relationship - Incineration.


              Source: EPA Report, 1970.

-------
operations (50,000 tons per year) or near $5.00 per ton for small fills
(10,000 tons per year). This includes labor costs, equipment costs,  and
miscellaneous expenses such as road maintenance, landscaping and
surveying.  The data are summarized in Figure 35.  There is no allow-
ance for costs of land, site preparations, or haul in this figure. These
data were obtained from studies of municipal waste disposal and should
be generally applicable to landfilled pesticide manufacturing wastes.

       Since pesticide wastes  require special care in handling and
hauling to reduce the  possibility of the  escape of toxic compounds, the
cost of haul to the fill site may be significant.  The wide variations in
equipment requirement, labor costs, haul distances, topography and
road conditions  make  it impossible to estimate the cost of haul. This
information  must be obtained for each specific set of circumstances.

       Likewise,  the cost of pit disposal, without interim cover or
compaction, is highly variable  and cannot be estimated for the "normal"
case.  In  general this type of burial is much cheaper in the short term,
but has a  higher probability of  causing future problems than the landfill
method.
Ocean Disposal

       In coastal areas ocean dumping is often a relatively low cost waste
disposal method.  However, new regulatory practices will undoubtedly
make this method more costly, if not impossible.  Table 25 contains esti-
mates of the present cost of ocean disposal for various types of waste
including industrial wastes.  The figures indicate that bulk industrial
wastes cost an average of $1.70  per ton in 1968 while containerized
wastes averaged $24.00 per ton.  Based on data from this report, the
average cost for bulk industrial waste is approximately $2.00 per ton.
If the waste flow is large enough to require a 5000 ton barge on a regular
schedule, the costs  per ton may be reduced to $0.50 per ton.  Excessive
haul distances ( > 100  miles) and on-shore storage requirements increase
the cost  of this type of disposal.  The wide range in costs for contain-
erized industrial wastes (Table 25) reflects the difference between long-
term contractual operations and the causal disposal of small amounts  of
toxic and hazardous  wastes by a  single  producer (Witt,  1971).  For
example, the disposal  of one lot  of 500  barrels containing 115 tons of
liquid waste requires the one time use of a barge and tug.  Depending
on the geographical area and the  location of the disposal site, the approx-
imate cost would be  over $2000,  or $17  per ton.
                                 150

-------
          Total cost per ton cover
           material  purchased  
           at  $l.50/cu.yd.
              Total cost  per ton
              cover material on site
              Cover material purchased
              at $l.50/cu.yd. 
            ^Landfill equipment
            X^ ,x _ .x V* jf - -.-*-** * I
                         andfi
    Cover materia
on site
  0       300     600     900     1200

  Solid Wastes, ton/wk. (six-day operation)


Figure 35.  The Cost of Solid Waste Disposal in Sanitary Landfills

Source:  Heaney, _et ai_. , 1970.
                    151

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                        Pacific Coast
                                                Table 25
                                  Estimated Marine-Disposal Cost for 1968
                                       Atlantic Coast         Gulf Coast
                                                        Total
     Type of Waste
                           Esti-
                 Annual    mated
                 Tonnage   Cost,$
                  Esti-
      Annual      mated
      Tonnage     Cost,$
                                  Esti-
                      Annual      mated
                      Tonnage     Cost.$
            Esti-
Annual      mated
Tonnage      Cost,$
vn
ro
Dredging spoils

Industrial
wastes
containerized
Refuse b
      c
Sludge
Miscellaneous
Construction &
demolition debris
Explosives

Total wastes
                     7,320,000  3,175,000


                       981,000   991,000
                           300     16,000

                        26,000   392,000
                           200
3,000
                     8,327,500  4,577,OOC
15,808,000a 8,608,000


 3,011,000   5,406,000
    2,200      17,000


 4,477,000  4,433,000



   574,000    430,000

    15,200    235,000

23,887,400 19,129,000
                            15,300,000 3,800,000


                               690,000 1,592,000
                                 6,000    171,000
                            15,986,000 5,563,000
38,428,000  15,583,000


 4,682,000   7,989,000
     8,500     204,000

    26,000     392,000
 4,477,000   4,433,000

       200       3,000


   574,000     430,000

    15,200     235,000

48,210,090  29,269,000
       Includes 200,000 tons of fly ash.
       At San Diego,  4,700 tons of vessel garbage at $280,000 dumped in 1968 (discontinued in Nov. 1968).
       Tonnage on wet basis.  Assuming average 4.5% dry solids, this amounts to about 200,000 tons/yr. of dry
       solids being barged to sea.
       Radioactive wastes omitted because sea-disposal operations were terminated in 1967.

     Source:  (Witt, 1971).

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                          CHAPTER  XIII

                       ACKNOWLEDGMENTS
       The author expresses his appreciation to a number of people,
industries, and agencies who assisted in the preparation of this report.
Many pesticide manufacturers cooperated fully and openly discussed
pesticide waste treatment practices and problems. Several state agencies
provided useful information.

       Mr. Rolando Flores, Mr. Larry Roberts, and Mr. Steve Naeve
assisted greatly in preparing this report and their contributions are
acknowledged. Dr. Davis Ford of Engineering Science, Inc. conducted
an extremely  beneficial review of the  report, and Mr. Thomas Sargent
and Dr. Robert Swank of the Office of Research and Monitoring  of the
Environmental Protection Agency conducted a detailed review of the
draft report.  Their suggestions and comments were most helpful.

       Finally, appreciation is expressed for the cooperation and
financial support of the Water Quality Office of the Environmental
Protection Agency.
                                 153

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                         CHAPTER K

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-------
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                                 156

-------
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29. Buescher, C. A.,  J. H. Dougherty, and R.  T. Skrinde, "Chemical
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32. Coffey, D. L. Adsorption of Herbicides by Activated Carbon and
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34. Coley, Gene and  C. H.  Stutz,  "Treatment of Parathion Wastes
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-------
36. Crosby, D.  G.,  "Experimental Approaches to Pesticide Photo-
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37. Dallaire, Eugene E., "Ocean Dumping: What and Where, If At All?"
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38. Eisenhauer, Hugh R., "Oxidation of Phenolic Wastes, Part I:
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39. Eye, David, "Aqueous Transport  of Dieldrin Residue in Soils,"
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40. Faust, S. D. and I. H. Suffet, "Recovery, Separation and Identifi-
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42. Fleck, E. E.,  "Chemistry of Insecticides," Pesticides and their
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45. Ford, Davis L. and W.  W.  Eckenfelder, Confidential Report, 1967.

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47. Greek, B. F. and  F. E. Rosenberg, "Design and Construction of a
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                                  158

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51. Ketchum and Ford, "Rate of Dispersion in the Wake  of a Barge at
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                                  160

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                                  161

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                                  162

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                         CHAPTER  X

                        APPENDICES

                                                          Page No.

A.  Common and Chemical Name, Oral
    Toxicity,  Solubility, and Soil Persistence
    of Some (Representative) Important
    Pesticides	      158

B.  Injection Well Act,  State of Texas, Article
    762b, V.T.C.S. as  Amended by 61st
    Legislature, Regular Session, 1969	      165

C.  Proposed Regulations, State of California,
    Subchapter 15, Waste Disposal to Land   	      169

D.  Statement by Governor William T. Cahill
    of New  Jersey on Sludge Barging to Sea,
    February 15,  1970	      177
                                163

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APPENDIX A
       I.  Common and chemical name, oral toxicity, solubility, and soil persistence of some
           (representative) important pesticides.
Common Name Chemical Name
Chlorinated
Aldrin

BHC
Chlordane
DDD
DDT
Hydrocarbon Insecticides
1,2,3,4,10, 1 0-hexachloro-l , 4 , 4a , 5 , 8
8a , hexahydro-l,4-endro-exo-5 ,8-
dimethanonaphthalene
benzenehexachloride
octachloro-4 , 7-methanotetrahydroindane
1 , l-dichloro-2 , 2-bis (p-chlorophenyl)
ethane
1,1, l-trichloro-2 , 2-bis (p-chlorophenyl)
Oral Toxicity
LD (mg/kg)
55

500-6000
570
2500-3400
113
Solubility
inH20
27 ppb

insol.
insol.
insol.
insol.
Persistence
in soil **
3

3
3
3
3
Dieldrin
ethane

1,2,3,4,10, lO-hexachloro-6,7-epoxy-l,
4,4a,5,6,7,8,8a-octahydro-l, 4-endo-
exo-5,8-dimethanonaphthalene
60
** 1 = 1 to 3 months; 2 = 3 to 12 months; 3 = more than 12 months
Source: Working Group on Pesticides,  1970.
185 ppb

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      APPENDIX A  I.  (Continued)
Common Name
                                 Chemical Name
                                                     Oral Toxicity
                                                           (mg/kg)
Solubility    Persistence
              in Soil
in HO
ON
vn
Endosulf an    6,7,8,9,10,10-Hexachloro-l ,5,53,6,
              9, 9a-hexahydro-6,9-methano-2 , 4,
              3-Benzodioxathiepin-3-oxide

Endrin        1,2,3,4,10,10-hexachloro-6, 7-epoxy-
              l,4,4a,5,6,7,8, 8a-octahydro-l, 4-
              endo-endo-5,8-dimethanonaphthalene

Heptachlor    1,4,5,6,7,8,8a-haptachloro- 3a, 4, 7a-
              methanoindene

Lindane       1,2,3,4,5,6-hexachlorocyclohexane

Methoxychlor  2,2-bis (p-methoxypheyl)-1,1,1-
              trichloroethane

Strobane      terpene polychlorinates

Toxaphene     chlorinated camphene

Organophosphorous Insecticides

Carbonphen-   S- (p-chlorophenylthio) methyl
 othion       O,O-dicthyl phosphorodithioate
                                                               110
                                                            7.3 - 43.4
                                                            130 - 135
insol.
insol.
56 ppb
90
6000
220
90
insol.
insol.
insol.
insol.
                                                                32.2
2 ppm

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       APPENDIX A I.  (Continued)
                                                             Oral Toxicity
       Common Name
                           Chemical Name
                                                            Solubility    Persistence
                                                             in H2O       in soil
ON
ON
       Demeton
Diazinon


Dichlorvos

Dimethoate


Ethion


EPN


Malathion
       Methyl-
       parathion
O- |_2-(ethylthio) ethyl J phosphoro-
thioate (thiono isomer) I and O/ O-
diethyl-S-  [2-(ethylthio) ethyl]
phosphorothioate (thiolisomer) II

O ,O-diethyl O-(2-isopropyl-6-methyl-
4-pyrimidinyl) phosphorothioate

2,2-dichlorovinyl dimethyl phosphate

0, 0-dimethyl S-(N-methylcarbamoyl-
methyl) phosphorodithioate

O,O ,O' ,O'-tetra ethyl S ,S'-methylene
biophosphorodithioate

O-ethyl-O-p-nitrophenyl phenyl-
phosphorothioate

O,O-dimethyl phosphorodithiate
of diethyl mercaptosuccinate

O,O-dimethyl O-p-nitrophenyl
phosphorothioate
                                                      2.5-12
76 - 108


56 - 90

185-245


  208


14 - 42


 2800


  9.4
                    60 ppm
40 ppm          2


1000 ppm

7000 ppm


insol.


insol.


145 ppm         1


50 ppm          1

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APPENDIX A I.  (Continued)
Common Name
Mevinphos
Parathion
Ph orate
Ronnel
Chemical Name
2-carbomethoxy-l-methylvinyl dimethyl
phosphate, isomer
O,O-diethyl O-p-nitrophenyl
phosphorothioate
O ,O-diethyl S-(ethylthio)- methyl
ph os phorod ith ioate
O , O-dimethyl-O-(2 , 4 , 5-trichloro-
Oral Toxicity
LD5Q (mg/kg)
6-7
6-15
1.6 - 3.7
1.75
Solubility
in H2O

24 ppm
85 ppm
40 ppm
Persistence
in soil
1
1
1
1
              phenyl) phosphorothioate

Methyl Carbamate Insecticides

Carbaryl      N-methyl-1-naphthylcarbamate
Mobam

Zectran


Mesurol
4-benzothienyl-N-methylcarbamate

4-dimethylamino-3,5-xylyl
methylcarbamate

4-(methylthio) -3,5-xylylmethyl-
carbamate
540

234

 15


130
                                                            < 0.1%

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       APPENDIX A  I (Continued)
       Common Name
                           Chemical Name
Oral Toxicity
      (mg/kg)
Solubility    Persistence
 in H2O       in soil
ON
CO
       Baygon
       Temik
       Isolan
              2-iso-propoxy-phenol-N-
              methylvarbamate

              2-methyl-2-(methylthio)
              propionaldehyde O- (methylcarbamoyl)
              oxime

              l-isopropyl-3-methyl-5-pyrazoly-
              dimethyl carbamate
   100
   0.93
    11
Phenoxyalkanoic Acid Herbicides                          mg/kq

2,4,D        2, 4-dichlorophenoxyacetic acid           300 - 1000

2,4,5-T       2,4,5-trichlorophenoxyacetic acid        100-300

MCPA        2-methyl-4-chlorophenoxyacetic acid        700

s-Triazine Herbicides

Simazine      2-chloro-4,6-bis (ethylamino)-.s-triazine  >5000

Atrazine       2-chloro-4-ethylamino-6-isopropyl-       1750 - 3080
              amino-s-triazine
ppm
620
251
825
5
33

1
2
1
2
3

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        APPENDIX A  I.  (Continued)
cr\
vo
Common Name Chemical Name
Prometryne 2-methylthio-4 , 6-bis (isopropylamino)-
Substituted Urea Herbicides
Monuron 3- (p-chlorophenyl) -1 , 1-dimethylurea
Diuron 3- (3 , 4-dichlorophenyl) -1 , 1-dimethylurea
Linuron 3- (3 , 4-dichlorophenyl) -1-methoxy-l-
methylurea
Phenylcarbamate Herbicides
CIPC isopropyl-N-3-chlorophenylcarbamate
IPC isopropyl-N-phenylcarbamate
Thiolcarbamate Herbicides
Oral Toxicity
LD5Q (mg/kg)
3750
3600
440
1500
5000 - 7500
5000
Solubility Persistence
in H2O in soil
48 1
230 2
42 3
75 2
88 1
250 1
       EPTC          S-ethyl N,  n-dipropylthiolcarbamate         1630 (rat)          375

                                                                 3160 (mice)



       Pebulate       S-propyl butylethylthiocarbamate            1120                92

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APPENDIX  A I.  (Continued)
Common
Name Chemical Name
Oral Toxicity
Solubility
in H2O
Persistence
in soil
Chlorinated Aliphatic Acids
Dalapon
TCA
2 , 2-dichloropropionate
trichloroacetate
8000
5000
90%
54%
1
1
Amine Herbicides

Trifluralin     a , a a -trifluoro-2 , 6-dinitro-N,
               N-dipropyl-p-toluidine
                                                          >10,000
<1

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                          APPENDIX B

                     INJECTION WELL ACT
                       STATE OF TEXAS

                    Article 7621b, V.T.C.S.
                 as amended by 61st Legislature,
                     Regular Session,  1969


Section 1. SHORT TITLE. This Act may be cited as the Injection Well Act.

Section 2. DEFINITIONS.  As used in this Act, unless the context requires
          a different definition:
               (a) "board"  means the Texas Water Quality Board;
               (b) "commission"  means the Texas Railroad Commission;
               (c) "Person" means individual, corporation, organization,
government or governmental subdivision or agency, business trust,
partnership, associatiation,  or any other legal entity;
               (d) "Pollution" means the alteration of the physical,
chemical, or biological quality of,  or the contamination of, water that
renders the water harmful,  detrimental,  or injurious to humans,  animal
life, vegetation or property,  or to public health,  safety, or welfare, or
impairs the usefulness or the public enjoyment of the water for any lawful
or reasonable purpose;
               (e) "Industrial and municipal waste" is any liquid, gaseous,
solid or other waste substance or a combination thereof resulting from any
process of industry, manufacturing, trade, or business or from the develop-
ment or recovery of any natural resources, or resulting from the disposal
of sewage, or other wastes of cities, towns, villages, communities, water
districts and other municipal corporations, which may cause or  might
reasonably be expected to  cause pollution of fresh water;
               (f) "fresh waters" means waters whose bacteriological,
physical and chemical properties are such that they are suitable and
feasible for beneficial use for the purposes permitted by law;
               (g) "casing" means any material utilized to seal off strata
at and below the earth's surface;
               (h) "injection well"  means an artificial excavation or opening
into the ground, made by means of digging, boring, drilling, jetting, driving
or otherwise,  and made for the purpose  of injecting, transmitting, or dis-
posing of industrial and municipal waste  into a subsurface stratum; also a
well initially drilled for the purpose of producing oil and gas when used
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for the purpose of transmitting, injecting, or disposing of industrial and
municipal waste into a subsurface stratum; but "injection well" does not
include any surface pit, excavation or natural depression used to dispose
of industrial and municipal waste.
               (i) Notwithstanding any provisions of Subsection (e) of
this section, "waste arising out of or incidental to the drilling for or the
producing of oil or gas" includes, but is not limited to,  the following
items when they result from such drilling or producing activities;  salt
water, brine, sludge, drilling mud,  and  other liquid or semi-liquid
waste materials.

Section 3.   INDUSTRIAL AND MUNICPAL WASTES; APPLICATIONS TO  BOARD,
               (a) Before any person commences the drilling of an injection
well, or before any person converts  any  existing well  into an injection
well, for the purpose of disposing of industrial  and municipal waste, other
than waste arising out of or incidental to the drilling for or the producing
of oil or gas, a permit therefore shall be obtained from the board. The
board shall be available upon request without cost.  The board shall
require the furnishing of such information by an applicant as the board
may deem necessary to discharge properly the duties imposed by this Act.
An application for a permit to drill an injection well, or to convert any
existing  well to an injection well, shall be accompanied by a fee  of
$25. 00 which shall be collected by the board for the benefit of the state.
               (b) Upon receipt by the board  of  an application in proper
form and accompanied by the necessary fee for a permit to drill an injec-
tion well, or to convert an existing well to an injection well, the  board
shall cause an inspection to be made of the location of the proposed
injection well to determine local conditions and the probable, effect of
the injection well, and shall cause an evaluation to be made to determine
the requirements for the setting of casing, as provided in Section  5 of
this Act.
              (c) The board shall also send  copies of every application
received in proper form to the Texas Water Development Board, the Texas
State Department of Health, the Texas Water Well Drillers Board,  and to
such other  persons as the board may designate. The agencies and other
persons to  whom a copy of the application is sent may make recommenda-
tions to the board concerning any aspect of the application, and shall
have such reasonable time to do so as the  board may prescribe.
              (d) The board may hold a public hearing upon an application
if it is deemed necessary and in the public interest, but otherwise, a pub-
lic hearing is not required.  Notice of any public hearing and  its procedure
shall be  under such terms and conditions as the board  may prescribe.
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               (e) Any person applying to the board for a permit to inject
industrial and municipal waste, other than waste arising out of or inci-
dental to the drilling for or the  producing  of oil or gas, into a subsurface
stratum shall submit with the application  a letter from the commission
stating that the drilling of the injection well and the injection of  indus-
trial and municipal waste into the subsurface stratum will not endanger
or injure any oil or gas formation.

Section 4.  ISSUANCE OF PERMIT; CASING OF WELL;  RULES AND  REGULATIONS,
               If the board or commission, as the case may be, finds that
the installation of the injection well is  in the  public interest, will not
impair any existing rights, and that by requiring proper safeguards both
ground and surface fresh waters can be  protected adequately from pollu-
tion,  the board or commission,  as appropriate, may grant the application
in whole or in part and issue a  permit with such terms, provisions, condi-
tions  and requirements as are reasonably  necessary to protect fresh waters
from pollution by industrial and municipal waste.  Specifically, the board
or commission  shall require that the injection  well  shall  be so cased  as to
protect all fresh waters from pollution by the intrusion of industrial and
municipal waste.  The casing shall be set at such depth, with such mate-
rials, and in such manner as the  board or the commission may require.
The board or the commission, in establishing the depth to which casing
shall  be installed, shall consider known geological and hydrological
conditions and relationships, the foreseeable  future economic develop-
ment in the area, and the foreseeable future demand for the use of the
fresh  waters in the locality.  The board or commission may also require
the permittee to keep and furnish a complete and accurage record of the
depth, thickness and character of the different strata penetrated in the
drilling of the well.  In the event an existing well is  to be converted  to
an injection well, the board or  commission may require that the applicant
furnish an electric log or a drilling log of the existing well.  A copy of
every permit issued by the board  shall be furnished by the board to the
commission, the Texas Water Development Board, the Texas State
Department of Health, and the Texas Water Well Drillers Board.  A copy
of every permit issued by the commission shall be furnished by the com-
mission to the board, which shall in turn  forward copies  to the other
agencies named in the preceding  sentence.  The board and the commission
each  shall adopt rules, regulations and procedures  reasonably required
for the performance of the duties, powers and  functions prescribed for
each by this Act.  Copies of any  rules or  regulations  under this Act pro-
posed by the board or the commission shall, before their adoption, be
sent by each of these agencies to the other agency, and  also to the
                                   173

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Texas Water Development Board, the State Department of Health, the
Texas Water Well Drillers Board, and such other persons as the origi-
nating agency may designate. Any agency or person to whom the copies
of proposed rules and regulations are sent may submit  comments and
recommendations to the agency proposing the rules and regulations,  and
shall have such reasonable time to do so as the originating agency may
prescribe.

Section 5. WILLING COPY OF PERMIT.   Any person receiving a permit
to inject industrial and municipal waste, shall, before injection opera-
tions are begun, file a copy of the permit with the health authorities of
the county, city and town where the well is located.

Section 6. ENFORCEMENT.  Any person who fails to comply with the
provisions of this Act, or with any rule  or regulations promulgated by
the board or the commission under this Act, or with any term, condi-
tion or provision in his permit issued pursuant to  this Act, shall be
subject to a civil penalty in any sum not exceeding One Thousand
Dollars ($1,000.00) for each day of non-compliance and for each act of
non-compliance, as the court may deem proper. The action may be
brought by the board or the commission,  as appropriate, in any court
of competent jurisdiction in the county where the  offending activity is
occurring or where the defendant resides.  Full authority is also given
the board or commission, as  appropriate, to enforce by jurisdiction in
the county where the offending activity is occurring, any and all reason-
able rules and regulations promulgated by it which do not conflict with
any law, and all of the terms, conditions and provisions of permits
issued by the board or commission pursuant to the provisions of this
Act.  At the request of the board or the commission, the attorney general
shall institute and conduct a suit in the name of the State of Texas for
injunctive relief or to recover the civil penalty, or for both the injunctive
relief and civil penalty, authorized in this section.  Any party to a suit
may appeal from a final judgment as in other civil cases.  The obtaining
of a permit under the provisions  of this Act by a person shall not act to
relieve that person from liability under any statutory law or the Common
Law.
                                    174

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                          APPENDIX C

                   PROPOSED REGULATIONS
                    STATE OF CALIFORNIA

                        Subchapter 15
                   Waste Disposal to Land
                          Article I
                      General Provisions
Section 2500 DEFINITION OF TERMS,   (a) "Disposal site" means any
place used for the disposal of solid or liquid wastes.  It does not include
sewage treatment ponds or locations of waste disposal from pipes or
ditches into waters of the state.
               (b)  "Disposal Area" is the actual area of the site which
has received or is receiving wastes.
               (c)  "Percolate" is fluid resulting from the percolation or
draining of a liquid through a waste substance.
               (d)  "Usable" ground or surface water includes potentially
usable water.
               (e)  "Hydraulic continuity" is a condition existing when
fluid occupying an interstice of a saturated material is able to move,
under a head differential imposed by gravity, to adjoining interstices
and/or surface  channels  containing fluid.
               (f)  "Capillary fringe"  is the partly saturated zone immediately
above the water table in  which water  is held  by  capillary forces.

Section 2501.  DISPOSAL AT CLASSIFIED SITES.  Disposal of either solid
or liquid wastes at disposal sites shall be only  at those sites which have
been classified by the appropriate regional water quality control board in
the establishment of waste discharge  requirements in conformity with this
subchapter unless requirements are waived by the regional board pursuant
to Section 2530 (c).
                            Article 2
               Classification of Waste Disposal Sites

Section 2510. CLASS I DISPOSAL SITES.  Class I disposal sites are
those at which protection is provided for the quality of ground and
                                    175

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 surface waters from all wastes as determined by the following criteria:
               (a)  The disposal area is underlain by non-waterbearing
 geological formations or by unusable groundwater which is isolated from
 other usable waters.
               (b)  Geological conditions must be naturally capable of
 preventing both vertical and lateral continuity between liquids and gases
 from waste in the site and usable groundwaters,  or have been modified
 to achieve such capability in a manner acceptable to the regional board.
               (c)  Underlying geological formations which contain rock
 fractures or fissures of questionable permeability must be  sealed to pro-
 vide a competent barrier to the movement of liquids or gases from the
 disposal site.
               (d)  Surface drainage from tributary areas outside the site
 must be precluded from entering areas of the site which have received or
 are receiving wastes until the site is closed in accordance with require-
 ments  of the regional board.
               (e)  Subsurface flow into the disposal area and percolate
 resulting from internal drainage shall be contained within the site unless
 other disposition is made in accordance with requirements of the regional
 board.
               (f)  Class I sites made suitable for use  by man-made
 physical barriers shall not be located where improper operation or main-
 tenance of man-made physical containment structures will impair usable
 ground or surface water quality or create a hazard to public health.
               (g)  Class I sites shall not be  located over zones of active
 faulting or where other forms of geological change would reduce the cap-
 ability of natural or man-made features to prevent continuity with usable
 groundwaters.
               (h)  Class I sites for unlimited use must not be subject to
washout or inundation by floods.
               (i)  Sites which comply with a,b,c,e,f, and g but would
 be subject to inundation by a flood of greater than 100 year frequency may
 be classified by the regional board as  a limited Class I Disposal Site
 subject to waste discharge requirements which would include limits on
 (1) the type and quantity of material entering the site,  (2) the concentra-
tion of material  in the waste deposited  on the site, (3)  the amount  of
residue present  or remaining on the site after evaporation of the liquid.

Section 2511 CLASS II DISPOSAL SITES. Class II disposal sites are those
at which protection is provided to water quality from Group 2 and Group 3
wastes as determined by the following criteria:
               (a)  If the site has hydraulic continuity with usable ground
or surface water, there must be physical features to prevent degradation


                                    176

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of groundwater quality due to liquid or gases emanating from the waste.
The types of physical features and the extent of protection of groundwater
quality further divides Class II sites into two general categories.
                      (1)  A Class II-l site is isolated from vertical
               hydraulic continuity with usable groundwater by natural
               impervious geological formations  or artificial barriers,
               or it is underlain by non-waterbearing rocks, but it may
               have lateral hydraulic continuity with groundwater basins
               containing usable groundwater.
                      (2)  A Class II-2 site may have vertical hydraulic
               continuity with usable groundwater but it is either modi-
               fied by artificial barriers or has natural geological and
               hydraulic features, such as soil type and depth to ground-
               water, which prevent degradation of the  quality of usable
               groundwater underneath the site.
               (b)  Class II disposal sites located in flood plains shall be
protected by natural or artificial features so as to assure protection from
washout  andjlooding which could occur as a result of floods having a
predicted frequency of once in 100 years.
               (c)  Surface drainage from tributary areas shall be precluded
from contacting waste in the site.
               (d)  Gases emanating from waste in the site will be prevented
from degrading groundwater during the predictable life of the  site by physi-
cal features or rate of groundwater movement in hydraulic  continuity with
the site.
               (e)  Internal drainage of the site or subsurface flow into
the site and the depth at which water soluble materials  are placed shall
be controlled  during construction and operation of the site to minimize
percolate and assure that the waste material will be above the highest
anticipated elevation of the capillary fringe of the groundwater.  Such
control may include discharge from the  site subject to waste  discharge
requirements prescribed by the regional board.

Section 2512  CLASS III DISPOSAL SITES.  Class  III disposal sites are those
at which protection is provided for water quality from Group 3 wastes as
determined by the following criteria:
               (a)  Each site  is located and constructed to prevent erosion
or transport of deposited material.
               (b)  Operation or construction of the site shall not result
in degradation of surface water quality due to erosion of adjacent land
areas.
                                    177

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Section 2513  WASTE WELLS.  Wells suitable for the disposal of wastes
shall provide  protection to usable groundwater from wastes of Groups 1
or 2 in any form as determined by the following conditions:
               (a)  The receiving formation shall not be in hydraulic
continuity with any usable groundwater.
               (b)  The construction and injection procedure will be such
that no paths  of percolation are  developed which will permit the movement
of the waste to a usable aquifer or to the surface.
               (c)  Certification has been provided by the  California
Division of Oil and Gas that construction and operation of waste wells
under its jurisdiction will conform to regulations of the Division.
               (d)  Wells used for the disposal of wastewater and the
resultant recharge of groundwater, or for the disposal  of used irrigation
water, under requirements adopted by the regional board may be exempted
from provisions a,  b, and c.
               (e)  Construction and operation of sewer wells shall be in
conformance with applicable regulations for the protection of public health.
                          Article 3
           Classification of Wastes Discharged to Land

Section 2520 GROUP I WASTES.  Group I wastes consist of or contain
substances directly harmful or dangerous to the health and safety of man
or other living organisms during disposal operations or in the event of
mixing with usable water, or substances which may significantly impair
the quality of usable waters.  Examples include but are not limited to
the following:
               (a) Municipal Wastes
                  (1) Saline fluids from water or waste treatment and
                      reclamation processes .
                   (2) Community incinerator ashes .
               (b) Industrial  Wastes
                   (1)  Saline brine from food processing, oil well
                      production, water treatment, industrial processes
                      and geothermal plants.
                   (2) Toxic or hazardous  fluids from industrial processes
                      or resulting from spills, or blowdown.   These fluids
                      may include spent cleaning fluids, petroleum
                      fractions, chemicals,  acids, alkalies,  phenols,
                      and spent washing fluids.
                                   178

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                   (3)  Substances from which toxic, materials can leach
                       such as process ashes, chemical mixtures, and
                       mine tailings.
               (c) Agricultural Wastes
                   (1)  Agricultural chemicals such as herbicides,
                       insecticides,  fungicides, and chemical fertil-
                       izer and their containers to the extent they are
                       actually toxic or hazardous to human health or
                       water quality after mixing with water.
               (d) Other toxic wastes such as compounds of arsenic or
mercury, chemical warfare agents, etc.

Section 2521 GROUP 2  WASTES.  Group 2 wastes consist of or contain
decomposable organic material which does not include substances which
are toxic or significantly impair the quality of usable water. Group  2
wastes may be  deposited in either a Class II-1 or II-2 site unless spe-
cifically limited by the  regional board or the regulations of other appro-
priate authorities.  Examples include but  are not limited to the following:
               (a) Municipal and industrial wastes
                   (1)  Garbage consisting of putrescible wastes from
                       processing, preparation,  cooking, and serving
                       of food
                   (2)  Market wastes from handling, storage,  and
                       processing of produce
                   (3)  Construction and demolition materials containing
                       paper, cardboard, tin cans, wood, glass, bedding,
                       rubber products, roofing paper,  wallpaper, stumps,
                       and other materials
                   (4)  Rubbish and street refuse consisting of putrescible
                       and non-putrescible material such as sweepings,
                       dirt, leaves, catch basin dirt, litter, yard clippings,
                       glass, paper, wood and metals in various forms or
                       combinations.
                   (5)  Dead animals
                   (6)  Abandoned vehicles
                   (7)  Sewage treatment  residue including  solids from
                       screens and grit chambers and sludge
                   (8)  "Water treatment residue including solid organic
                       matter collected on  screens and in settling tanks
                   (9)  Ashes from household burning
                                    179

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                  (10) Infectious materials and hospital or laboratory
                       wastes authorized for disposal to land by official
                       agencies charged with control of plant, animal,
                       or human disease.
                  (11) Magnesium and other highly flammable or pyrophoric
                       materials
                  (12) Miscellaneous industrial wastes such as metals and
                       metal products, wood and paper materials,  oils,
                       chemicals and sludges which are not toxic or
                       hazardous within  the definition of Group 1 wastes.
               (b)  Agricultural wastes
                   (1) Stalks, vines, green drops, culls, stubble,  hulls,
                       lint and seed from field  and seed crops
                   (2) Vines, stalks, roots, green drops, and culls from
                       vegetable crops
                   (3) Stumps, prunings  and trimmings, culls, and green
                       drops from fruit and nut  crops
                   (4) Manures
                   (5) Dead animals or materials of animal origin.

Section 2523  DISPOSAL OF GROUP I WASTES IN CLASS II - I SITES.
               Regional board may allow  the disposal  of certain Group I
wastes in a Class II-l site when, in the  judgment of the board, such
disposal will not constitute a threat to water quality.  Such selected
disposal of specific Group I wastes  shall be subject to terms and condi-
tions considered appropriate by the regional board.
                             Article 4
                           Implementation

Section 2530 WASTE DISCHARGE REQUIREMENTS FOR WASTE DISPOSAL
              SITES.
               (a)  Operators of existing sites for which requirements have
not been prescribed, shall notify the appropriate regional board prior to
July 1, 1972 for the purpose of receiving  site classification and waste dis-
charge requirements consistent with the  provisions of this subchapter.
               (b)  Persons planning to establish new waste disposal
sites  or expand existing sites shall notify the appropriate regional board
for the purpose of receiving waste discharge requirements prior to the
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disposal of waste at the new or expanded site in accordance with Section
13260 et seq of the Water Code.
               (c)  The regional board may waive the approval and
classification of sites or the establishment of waste discharge require-
ments as provided by Section  13269 of the Water Code when an operation
is not hazardous to water quality because of the  type of waste and dis-
posal operation, or an operation is in compliance with ordinances or
regulations of other governmental agencies which adequately protect
water quality.  Such waivers shall be conditional and may be terminated
by the regional board at any time.
               (d)  The disposal of wastes in a site prior to the
installation and operability of physical structures and control measures
required for compliance with waste discharge requirements is prohibited.
               (e)  Actions of the operator which impair or threaten to
impair the  physical integrity of the site may result  in reclassification
of the site or abatement proceedings by the regional board.
               (f)  Operators  of Class I and Class II-l sites shall be
required to maintain records of the volume and type of Group I waste
received at the site and the manner and location  of disposal. Such records
shall be maintained in good legible condition for a  period of not less than
ten years on forms provided by the board and in accordance with  instruc-
tions which accompany the forms.  Records shall be subject to inspection
by representatives of the state or regional board  at any time during normal
business hours.
               (g)  Nothing in this  subchapter shall be construed to limit
the power of a regional board, city, county, or other jurisdiction to adopt
and enforce equal or higher standards for the protection of water quality in
connection with the disposal of waste  materials to  land, or to  adopt and
enforce  land use restrictions which govern the location and operation of
waste disposal sites.

Section  2531 COMPLETION OF FILL OPERATIONS.
               (a)  Prior to cessation of fill operations at a waste disposal
site, the operator shall submit a technical report to the appropriate regional
board describing the methods and controls to be used to assure protection
of the quality of surface and groundwaters of the area during final operations
and with any proposed subsequent use of the land.  This report shall be
prepared by or under the supervision of a registered and certified engineer-
ing geologist.
               (b) The methods used to close a site and maintain protection
of the quality of surface and groundwater shall comply with waste discharge
requirements established by the regional board.
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Section 2532 ABANDONMENT OF WASTE WELLS.
               (a)  Prior to abandonment of waste wells,  the operator
shall file a technical report with the appropriate regional  board describing
the methods and controls to be used for closing the well.
               (b)  Abandonment of waste wells, other than those within
the jurisdiction of the Division of Oil and Gas, shall be under the super-
vision of a registered engineering geologist, a registered petroleum
engineer, or the California Division of Oil and Gas.
               (c)  Abandonment of Wells within the jurisdiction of the
Division of Oil and Gas shall be under the supervision and direction of
the division.
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                        APPENDIX  D

    Statement by Governor William T.  Cahill of New Jersey
                   on Sludge Barging to Sea

                     February 15,  1970
       Earlier this week, it became necessary for me to proclaim a state
of emergency in New Jersey in order to prevent horrendous pollution of our
northeast rivers and bays.  Under my  statutory powers to protect the pub-
lic in an emergency, it was further necessary for this State to commendeer
three ocean-going barges and their crews to effect the disposal of sludge-
the material removed from sewage by treatment-from six of the State's
largest sewage treatment plants.  Still further, it was necessary for me to
seek, and obtain, through the offices of the President of the United States
the use  of U.S. Coast Guard tugs to propel these barges to sea for dump-
ing.  Our inability or failure to take any one  of these steps would  have
resulted  in the  release into our rivers and bays of 500 million gallons per
day of untreated sewage  and industrial wastes.  This amounts to about
one-half of the wastes treated in all of New Jersey's sewage plants and
its raw release is clearly intolerable.

       The immediate cause of this emergency was the labor strike of
tugboat  operators. It seems to me, nowever, that much larger issues are
involved than that of the strike.

       In the last fifty years the citizens of  New Jersey have invested
almost $1 billion in sewage collection and disposal systems for the con-
venience and water quality protection they would provide.  With the aid
of our 1969 clean water bond issue we are now launched on another $1
billion construction program for water pollution control.  For the operation
of a substantial part of these facilities precariously to depend on whether
or not there is a tugboat strike,  or a strike of barge operators or upon the
vagaries of weather affecting ocean-going travel,  or upon other such
undertainties is wrong and  unacceptable.  Such brinkmanship is incom-
patible with our ambitious efforts to eliminate the pollution of our
waterways.

       In addition, there is the question of the impact upon our marine
emvironment of the continued practice of dumping millions of tons  of
                                    183

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sewage sludge,  harbor dredgings and certain chemicals in disposal areas
less than twleve miles off the Sandy Hook beach.  A study of this impact
has been underway for more than a year by the Sandy Hook Marine Labo-
ratory on behalf of the U.S. Army Corps of Engineers.  An interim report
of the findings of this study was made available to us late yesterday.
I have discussed this issue and the significance of the report with offi-
cials of the State Health Department.

       The report offers  evidence that harbor dredgings  dumped at the sea
disposal site are finding their way to the New Jersey coastline.  Evidence
has not yet been adduced that sludge dumpings  reach our surf waters.  It
is clear that the disposal sites and their environs are devoid of marine
life.  I am also informed that the invasion of the red tide-a proliferation
of toxic microorganisms- which  afflicted our beaches two summers  ago may
have its genesis in the nutrient  materials at the dump site.

       While the report deals exclusively with  dumping off Sandy Hook,
similar questions can be raised about dump sites ten miles from the
entrance to Delaware Bay used by the cities of  Camden, Philadelphia,
Baltimore  and others.

       All things considered, it is my judgment that the ocean dumping of
harbor dredgings and sewage sludge a scant twelve miles from our coast
is a primitive, insensitive and unacceptable method of disposal.  I realize
that as is usually the case  in environment protection, there  is not a clear
choice between the right way and the wrong way.  There is a need to make
a choice among several somewhat unsatisfactory alternatives.  In my
opinion we should do the following:

       1.   Begin phasing out ocean dumping as a regular, accepted
            method of disposal of sewage sludge off our coast, and of
            toxic industrial materials off the continental shelf one
            hundred miles to sea.
       2.  For the next few years that it will inevitably take to provide
            on-land sludge disposal facilities require that all dumping of
            sewage sludge and harbor dredgings be one hundred miles at
            sea off the continental shelf.  This  can be accomplished by
           agreement or by Congressional enactment requiring that such
           deep sea dumping be a condition of all permits issued by the
           Army Corps of Engineers.
       3.  Incorporate in the design of all new sewage treatment plants
           facilities for sludge disposal other  than by dumping at sea.

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       4.  Seek through agreement or by Congressional enactment the
           requirement by the Army Corps of Engineers that a condition
           of ocean dumping permits will be a showing by the applicant
           that some steps  are being taken to provide  an on-shore
           treatment and disposal in the future.
       5.  Seek the agreement of New York State in this changed approach
           to sludge disposal in recognition of the fact that New York City
           and other communities  now dump more than twice as much sludge
           as does the State of New Jersey; and, as well, to seek the
           concurrence of the States of Pennsylvania and Maryland.
       I am informed that sludge disposal by landfill or by incineration
are not without their own problems-problems of potential land and air
pollution, as well as the high cost of facilities.  I am also informed that
many of the toxic industrial chemicals now disposed of by deep-sea dump-
ing are difficult and expensive to treat otherwise.  We  hope that in all
of these areas technology, upon demand, will give us innovative improve-
ments.  In any case, however, hard choices must be  made now if we are
to restore and protect the  quality of our physical environment.
                                     185

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i Accession Number

f. Subject Field & Croup
05D
SELECTED WATER RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
5 Organ'za"on Department of Civil Engineering
                University of Texas  at Austin
                Austin, Texas  J8712
    TK/e
           The Pesticides Manufacturing  Industry-Current Waste Treatment and Disposal
           Practices
 1 Q Avthorfs)
        Atkins, Patrick R.
                                1 JL  Project Designation
                                           EPA/OHM  Grant No.   1202 FYE  0$/72
                                    21  N
22
    Citation
23
    Descriptors (Starred First)
      ^Pesticides, Water Pollution,  *Wastewater Treatment, ^Industrial Wastes,
      Air Pollution, Solid Waste Disposal, Ocean Dumping, Landfill
 25
Identifiers (Starred First)
            ^Pesticide Chemistry, #Pesticide Production, ^Biological Wastewater
 Treatment, ^Physical-Chemical Wastewater Treatment, Economics, Air Pollution Control,
 Solid Wastes
27
    Abstract
          This  document reports on the "state of the art" of pesticide manufacturing
     waste treatment and disposal practices.  An indepth review of the literature,
     including  government information documents, technical reports,  the  technical journals,
     industrial publications and twenty plant interviews with plant  managers and
     operators  were used as the data base for this study.  The information is presented
     as  concisely and objectively as possible.  No attempts were made to prove or disprove
     statements made in the literature or statements made in the interviews.  The report
     contains chapters dealing with:  a) the present and rpojected pesticide demands in
     the United States, b) the chemistry of pesticides including production processes and
     waste generation, c) waste treatment possibilities discussed in the literature,
     d)  pesticide wnste treatment systems that have been or currently are  in full scale
     operation  and, e) the cost of pesticide waste treatment systems.   Conclusions and
     recommendations are presented.  Eighty-six references ara included in the report.
Abstractor
      Patrick R. Atkins
 WR;102 (REV. JULY 1909)
 WR5IC
                              Institution.
                                 'University of Texas at Austin
                                                  WATER RESOURCES SCIENTIFIC INFORMATION CENTER
                                                  U.S. DEPARTMENT OF THE INTERIOR
                                                  WASHINGTON, D. C. 20240

                                                                           * CPO: 19C9-359-339

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