EPA-600/2-77-H3
August 1977
Environmental Protection Technology Series
ASSESSMENT OF TECHNIQUES FOR
DETOXIFICATION OF
SELECTED HAZARDOUS MATERIALS
Municipal Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-77-143
August 1977
ASSESSMENT OF TECHNIQUES FOR DETOXIFICATION
OF SELECTED HAZARDOUS MATERIALS
by
i Benard J. Brown
Milton K. Christensen
Bernie E. Hackley, Jr.
Ronald L. Kassel
Gerald J. Kolaja
James H. Manthei
Charles E. Williamson
Chemical Laboratory, Edgewood Arsenal
Aberdeen Proving Ground, Maryland 21010
EPA-IAG-D4-0429
EPA-IAG-D5-0429
EPA-IAG-D6-0429
Project Officer
Charles Rogers
Solid and Hazardous Waste Research Division
Municipal Environmental Research Laboratory
Cincinnati, Ohio 45268
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
This report has been reviewed by the Municipal Environmental Research
Laboratory, U.S. Environmental Protection Agency, and approved for publica-
tion. Approval does not signify that the contents necessarily reflect the
views and policies of the U.S. Environmental Protection Agency, nor does
mention of trade names or commercial products constitute endorsement of
recommendation for use.
11
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FOREWORD
The Environmental Protection Agency was created because of increasing
public and government concern about the dangers of pollution to the health
and welfare of the American people. Noxious air, foul water, and spoiled
land are tragic testimony to the deterioration of our natural environment.
The complexity of that environment and the interplay between its components
require a concentrated and integrated attack on the problem.
Research and development is that necessary first step in problem solu-
tion and it involves defining the problem, measuring its impact, and
searching for solutions. The Municipal Environmental Research Laboratory
develops new and improved technology and systems for the prevention, treat-
ment, and management of wastewater and solid and hazardous waste pollutant
discharges from municipal and community sources, for the preservation and
treatment of public drinking water supplies, and to minimize the adverse
economic, social, health, and aesthetic effects of pollution. This publica-
tion is one of the products of that research; a most vital communications
link between the researcher and the user community.
This report discusses some of the processes used to detoxify pesticides
and gives test results for products produced by these processes.
Francis T. Mayo, Director
Municipal Environmental Research
Laboratory
iii
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PREFACE
The Environmental Protection Agency has identified a series of hazardous
and toxic materials which were manufactured on a large scale during the past
few years and now have been found to be harmful. These are characterized by
the polychlorinated hydrocarbon insecticides, polychlorinated biphenyls
(PCB's) and benzidine. In addition to these materials the EPA has listed
35 chemical pesticides that, because of their widespread distribution,
present difficult disposal problems. The first group of materials, which
includes four of the pesticides, is no longer to be used and is scheduled
for detoxification. Proper disposal of all of these hazardous materials
pose problems that are very serious from a health hazard viewpoint and can
be very difficult to solve. Municipal waste disposal plants are generally
not capable of treating such products, and their release into streams or im-
properly designed land disposal sites has led to widespread and highly
undesirable environmental contamination.
Studies of decontamination methods have been too limited to provide a
valid basis for the selection of a suitable detoxification procedure.
Studies that have been made have rarely included an adequate assessment of
the toxicity of the products obtained. No matter how free of toxicity, the
materials produced should be biodegradable and not accumulate in the food
chain. In general, the presence of chlorine atoms in chemical compounds
contributes to resistance to biodegradation and poor water solubility coupled
with high oil solubility. This often leads to accumulation in the food chain
and deposition in the body fats.
One stipulation of this agreement was that products produced by Edge-
wood Arsenal and other EPA Contractors would be subjected to toxicological
evaluation. Edgewood Arsenal has been engaged in the study of methods for
the detoxification of toxic materials for many years. Continuing studies of
this type are a fundamental part of Edgewood Arsenal's basic mission program.
This report describes some of the techniques for detoxification and gives
results of toxicological studies conducted on compounds produced by these
techniques.
iv
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ABSTRACT
A review and evaluation of available processes for detoxification of the
first group of hazardous materials was conducted during Phase I of the inter-
agency agreement (1974 calendar year). The processes used for specific
hazardous materials were identified. One process found during this litera-
ture survey described the reaction of PCB's with amines giving a variety of
products that were supposed to have useful properties. Two of these products
that were available were obtained and evaluated toxicologically. Both proved
to be highly toxic.
Products produced by catalytic decomposition at Worcester Polytechnic
Institute were to be studied for toxicity; however, some samples were not
large enough for adequate testing and some were insoluble. In many cases the
products were not adequately identified as to composition and concentration.
For these reasons, though some of the products may have been reduced in
toxicity, accurate toxicological evaluation could not be accomplished.
Using their expertise in detoxification methods, personnel from the
Chemical Laboratory at Edgewood Arsenal have developed a process by which a
number of the chlorinated hydrocarbon pesticides have been converted into
water soluble compounds. Acute toxicological studies indicated that these
products may be less toxic than the pesticides from which they were made.
As they are considerably more water soluble than the parent insecticide it
was hoped that they would not accumulate in wildlife or man. This should
be beneficial for purposes of health and the environment. Unfortunately
bioaccumulation studies have not been performed to prove this point. In the
preliminary stuides biodegradation did not occur.
Incinerator residue samples, produced by Midwest Research Institute,
were insoluble in all commonly used solvents so intravenous mammalian
evaluations could not be run. Some of the residues were pulverized and put
into fish tanks and screened for 96-hr toxicity to bluegills. All but one
of the samples were nontoxic at concentrations up to 1000 mg/1. The one
exception was considered practically nontoxic with a 96-hr TL50 of 320 mg/1.
This report was submitted in fulfillment of Interagency Agreements EPA-
IAG-D4-0429, EPA-IAG-D5-0429 and EPA-IAG-D6-0429 by the Toxicology Division,
Chemical Laboratory, Edgewood Arsenal, Aberdeen Proving Ground, Maryland,
under sponsorship of the U.S. Environmental Protection Agency. The report
covers the period from March 1974 to September 1976.
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CONTENTS
Foreword
Preface
Abstract
Figures
Tables
Acknowledgement
1. Introduction 1
2. Conclusions and Recommendations 2
3. Literature Search 3
4. Amine Reactions 4
Chemistry 4
Toxicity « 5
5. Catalytic Processing 8
Chemistry 8
Toxicity 8
6. Sulf onatlon 11
Chemistry 11
Toxicity 18
7. Incinerator Residues 25
Appendixes
A. Description of acute toxicity studies 27
B. Estimate of operating costs of sulfonation process 31
Glossary 33
vii
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FIGURES
Number Page
1 Postulated mechanism for electrochemical oxidation
of DDE to DBA 12
2 Some parent compounds and sulfonated products of
DDT and ODD 14
3 Sulfonation of three chlorinated hydrocarbon insecticides .... 16
4 Sulfonation of Aldrin 16
5 Attempted sulfonation of Endrin 17
6 Dehydrohalogenation of Chlordane 17
viii
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TABLES
Number Page
1 Toxicity Studies, Millmaster-Onyx Patent 6
2 96-Hr TL50 Static Bioassay-Bluegill 7
3 lexicological Studies of Compounds Produced by Worcester
Polytechnic Institute 9
4 Sulfonation of DDT, DDE and ODD 13
5 96-Hr Toxicity Screening-Sulfonates 18
6 IV Mouse LD50 (mg/kg) Sulfonates 19
7 Midwest Research Institute Incineration Residues 25
ix
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ACKNOWLEDGMENTS
During the period of time devoted to this program we were fortunate to
have valuable contributions by: J. Cooper, R. Biskup, 0. Owens and other
members of Toxicology and Chemical Research Divisions of Edgewood Arsenal.
We wish to express our sincere gratitude to the Project Officers, B.P.
McNamara, Chief, Toxicology Division, Edgewood Arsenal:and Charles Rogers,
Solid and Hazardous Waste Research Division, EPA, for their advice and
interest.
x
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SECTION 1
INTRODUCTION
Edgewood Arsenal has been engaged in the study of methods for the detox-
ification of toxic materials for many years. Continuing studies of this
type are a fundamental part of Edgewood Arsenal's basic mission program. In
1974, based on this experience, Edgewood Arsenal and the Environmental Pro-
tection Agency entered into an interagency agreement to study methods for
detoxification of a group of hazardous and toxic materials identified by EPA
as Aldrin, Dieldrin, Endrin, DDD, DDE, DDT, Toxaphene and the PCB's and
benzidine.
Studies of methods for deactivation of these compounds had involved
only the aspects of chemical transformation, ignoring the question of
toxicity of the resultant product. It was necessary, therefore, to review
and evaluate existing chemical processess, characterize the resultant
products, and assess their toxicity. These products will hopefully be non-
toxic, and either have useful properties or be biodegradable.
For the second year effort the Toxicology Division was asked, in
addition to the original group of hazardous materials, to assess techniques
for detoxification and disposal of small amounts (5 gal, or 50 Ib) of 35
common pesticides.
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SECTION 2
CONCLUSIONS AND RECOMMENDATIONS
This report discusses some of the processes investigated as methods of
eliminating hazardous and persistant materials from the environment. Two of
the processes, sulfonation and incineration, show some promise and should be
subjected to addtional investigation. There are other processes, not yet
studied, that may solve the problem. These should be studied.
Efforts should continue to seek new and more effective detoxification
processes.
Assessments should be made for the toxicity of the products obtained
and the safety of the processes used. Reaction products showing a low level
of toxicity, water solubility or biodegradability should be studied further.
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SECTION 3
LITERATURE SEARCH
A literature search was conducted in two phases. One, a machine search,
made use of the computerized information retrieval facilities of NERC,
Cincinnati. It emphasized the retrieval of existing information concerning
the reaction of the subject compounds. The other phase was manual search of
pertinent literature and included older literature published prior to that
compiled in the computerized system. Also included was the chemistry of
related compounds that might provide leads for new approaches to detoxifica-
tion of the subject compounds. The search was completed in December 1974.
A comprehensive report was prepared and submitted to EPA at that time.*
* A. Rednor and G. M. Steinberg, Assessment of Techniques for Detoxification
of Selected Hazardous Materials, A literature search, Dec 1974.
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SECTION 4
AMINE REACTIONS
CHEMISTRY
While searching the literature a patent was found for a process that
seemed to offer promise.* The patent, held by the Millmaster-Onyx Corp.,
New York, N.Y., described reactions of PCB's with amines to give a variety
of substituted amino-polychlorobiphenyls which were supposed to have some
useful properties.
The Millmaster-Onyx Corporation was contacted to obtain information
about the processes and samples for toxicological testing. The PCB
reactions were no longer being considered, but two available samples were
sent to us. They were analyzed for composition and purity then dissolved in
suitable solvents so they could be used for animal toxicity studies. The
glass-like solid AM 959 (from Aroclor 1260) was dissolved in water producing
solution with pH of 6.4. The viscous AM 1078 (from Aroclor 1248) was dis-
olved in PEG-200 producing a solution with a pH of 8.5.
To determine whether the Millmaster-Onyx process reduced the toxicity of
the PCB's,testing of the parent compounds was necessary. Aroclor is the
trade name of PCB's manufactured in the U.S.solely by the Monsanto Chemical
Company. An Aroclor is a complex mixture of isomers of PCB's. The various
Aroclors are differentiated by a four-digit number, with the last two digits
indicating the percentage of chlorine in the mixture. Aroclor 1242, for
example, is a mixture containing 42% chlorine; Aroclor 1254 contains 54%
chlorine. The Aroclors used in the Millmaster-Onyx reaction (1248 and 1260)
are no longer being made. From the Monsanto Chemical Company samples of
Aroclor 1242 and 1254 were obtained. These were used as comparative samples
to judge the toxicity of the original Aroclors. It must be realized that
the Aroclor 1242 and 1254 cannot be accepted as an absolute standard for
comparison to Aroclor 1248 and 1260. It is hoped that they might provide a
rough estimate for the toxicity of the originals.
* J.J. Merianos, E.G. Shay, B. Mead and A.N. Petrocci, U.S., E.663, May 16,
1972. "N-(Halogenated Biphenyl)-Diethylenetriamines".
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TOXICOLOGY
Comparative toxicity evaluations of Aroclor 1242, Aroclor 1254,
diethylenetriamine and the two PCB reaction products AM 959 (from Aroclor
1260) and AM 1078 (from Aroclor 1248) were conducted. Intravenous LDSO's
were determined in mice, oral toxicity was estimated in rats, and skin and
eye irritation evaluations following FDA procedures were performed in
rabbits.* Results, as summarized in Table 1, show the PCB reaction products
AM 959 and 1078 are 15 to 25 times more toxic to the mouse than the Aroclors
to which they were compared. These reaction products are also more toxic
(5 - 7 X) than diethylenetriamine in the mouse. Results in rats, though
limited by small samples sized for testing, also show that the reaction
products are more toxic than the Aroclors but about equally toxic to
diethylenetriamine. Results of the irritation evaluations show the reaction
products to be more irritating to the eye and equally irritating to rabbit
skin as compared to the Aroclors. Diethylenetriamine was a severe irritant
to both eyes and skin and by FDA standards would be classified as a primary
irritant. These findings regarding irritation are not unexpected as it is
known the amines, in general, are often culprits in this regard.
In addition to above mammalian toxicity evaluations, a 96-hr static
bioassay in Bluegill Sunfish was performed using solutions of AM 959 and AM
1057. Concentration levels between 1.0 and 100 ppm of each product were
used. All fish died within a few minutes at the 100 ppm level and at 4.8
ppm all fish died within 24 hours. The 96-hr TL50 for AM 1057 was found to
be about 2 ppm and for AM 959 about 1.0 ppm. Results are shown in Table 2.
* See Appendix A
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TABLE 1. TOXICITY STUDIES - MILLMASTER-ONYX PATENT
Compound
I.V. Mouse Oral, Rat
24-hr LD50 mg/kg 1 gm/kg
Irritancy, Rabbit
Eye (0.1 ml/eye)
Skin
Aroclor 1242 1242
(neat)
Aroclor 1254 975
(neat)
Diethylenetriamine 373
(neat)
AM 959* 48.7
(from Aroclor 1260)
AM 1078** 66.9
(from Aroclor 1248)
1/10
0/10
3/10, 343 min,
over night, >24
<48 hr
4/10 >24< 48 hr(2)
>48 <72 hr (2)
3/10
overnight (2)
48 hr (1)
0/6, Negative test
non-irritant
1/6, Negative test
non-irritant
6/6, Positive test
irritant compound
6/6, Positive test
irritant compound
6/6, Positive test
irritant compound
P.I.I.=2.16***
non-irritant
P.I.I.=0.69
non-irritant
P.I.I.=6.50
irritant compound
P.1.1.=0.79 (neat)
P.1.1.=2.25
P.1.1=2.13 (neat)
P.1.1.=2.46
non-irritant
* concentration =65.8 mg/ml in water for I.V. mouse study
1.038 gm/ml in water for other studies
** concentration = 295.1 mg/ml in PEG 200 for I.V. mouse study
0.9995 gm/ml in PEG 200 for other studies
*** P.I.I = Primary Irritation Index, ^5 = primary irritant
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TABLE 2. 96-hr TL STATIC BIOASSAY - BLUEGILL
Compound Cone . ppm
AM - 959 0
1.0
2.4
4.8
7.5
10.0
AM - 1057 0
1.0
2.4
4.8
7.5
10.0
1 2
0/6 0/6
0/6
0.6
1/6
6/6
6/6
0/6 0/6
0/6
0/6
0/6
4/6 6/6
6/6
5
0/6
0/6
2/6
6/6
-
-
-
-
-
3/6
-
_
Deaths in hours
7 8
0/6 0/6
0/6
4/6
-
_
-
-
-
_
4/6
-
- -
24
0/6
0/6
6/6
-
-
-
-
-
1/6
6/6
-
—
32 48 96
0/6 0/6 0/6
2/6 3/6 3/6
6/6
6/6
6/6
6/6
0/6
0/6
3/6 5/6 5/6
6/6
6/6
6/6
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SECTION 5
CATALYTIC PROCESSING
CHEMISTRY
As part of the interagency agreement between EPA and Edgewood Arsenal
(EA), compounds from other sources were to be submitted to EA for toxicolog-
ical characterization. Dr. Wilmer Kranich of Worcester Polytechnic
Institute, studying catalytic decomposition of chlorinated hydrocarbons, was
a principal source of compounds for evaluation.
TOXICOLOGY
Some difficulty was encountered in evaluating these compounds primarily
because the samples were too small and/or insoluble for toxicity testing.
In spite of these diffIculities attemptes were made to evaluate their
toxicity. To date, a total of 24 compounds submitted by Dr. Kranich have
been evaluated in the mouse. Five are products from Aroclor, eleven are
products from DDT, two are products from Toxaphene, and six are products from
Dieldrin. Results of these tests are given in Table 3.
These results are very difficult to interpret as solutions received
were not characterized by composition or concentration. As a consequence,
results could only be expressed in volume of material injected per kilogram
of body weight. Other materials were received as solids and could therefore
be weighed,and the weight of material per kilogram of body weight is used.
There is no way to make a direct comparison between the two expressions until
something is known about the solutions tested (specific gravity, concentra-
tion) that would allow translation of volume units to weight units.
For the Aroclor compounds, except for compound WPI-2, it would appear
that the products from Dr. Kranichfs catalytic processing are about as
toxic as the reference Aroclor tested. One, WPI-1, is almost half as toxic
(0.65 ml/kg) and one, WPI-13, twice as toxic (0.22 ml/kg).
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TABLE 3. TOXICOLOGYICAL STUDIES OF COMPOUNDS PRODUCED
BY WORCESTER POLYTECHNIC INSTITUTE
Sample
Number
Starting
Material
14-day
mouse, iv LD50 (95% CL)
Reference
WPI - 1
WPI - 3
WPI - 2
WPI - 12*
WPI - 13
Aroclor 0.37 (0.30-0.45) ml/kg
" 0.65(0.63-0.68) ml/kg
0.48(0.40-0.59) ml/kg
" 114.9 (104.7-126.2) ml/kg
" 0.37(0.34-0.41) ml/kg
^ 0.22(0^20-0.25) ml/kg
Reference
WPI - 4
WPI - 5
WPI - 6
WPI - 7
WPI - 8
WPI - 9
WPI - 10
WPI - 11
WPI - 22
WPI - 23
WPI - 24
DDT 76.
not
194.
1.
1.
0.
199.
" 162.
351.
0.
o.
0.
8(68.1-86.7) mg/kg
tested-bottle broken
4(155.5-243.0) mg/kg
0(0.95-1.05) ml/kg
41(1.29-1.54) ml/kg
071(0.064-0.079) ml/kg
(164-242) mg/kg
(144-182) mg/kg
(320-384) mg/kg
40 (0.37-0.43) ml/kg
79(0.73-0.86) ml/kg
56(0.56-0.56) mg/kg
Reference
WPI - 14
WPI - 15
Toxaphene 20.5(19.6-21.4) mg/kg
0.39(0.33-0.45) ml/kg
11 0.14(0.12-0.16) ml/kg
Reference
WPI - 16
WPI - 17
WPI - 18
WPI - 19
WPI - 20
WPI - 21
Dieldrin
ii
n
n
ii
n
10.5(9.3-11.8) mg/kg
0.29(0.26-11.8) ml/kg
0.35(0.31-0.40) ml/kg
0.11(0.10-0.14) ml/kg
0.40(0.37-0.43) ml/kg
* Supernatant fluid
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For DDT residues (expressed in mg/kg) compared with the reference
compound, it appears the residues WPI-5, 9, 10 and 11 are approximately
2 to 4.5 times less toxic than reference DDT. No other comparisions are
possible at this time. No comparisions are possible for the Toxaphene
compounds.
For the Dieldrin compounds the reference compound can only be compared
with WPI-21. In this case WPI-21 is about 13 time less toxic than Dieldrin.
A comparison with Dieldrin cannot be made for the other products, WPI-16
variation being a factor of 4, etc.
10
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SECTION 6
SULFONATION
CHEMISTRY
Background
Since compounds were not being received from outside sources, in June
1974 EPA suggested that Edgewood Arsenal might try chemical processess for
detoxification of the chlorinated hydrocarbons. Edgewood Arsenal personnel
have, since September 1974, been working on this problem.
The first attempts were to convert DDT to water soluble compounds. The
hope was that this would prevent accumulation in the food chain.
DDA has been found to be a metabolite of DDT in several animal species
and is excreted in the urine various species including man. It is, therefore,
not expected to accumulate in the food chain.
DBA is obtained by the basic hydrolysis of either DDT or its elimination
product l,l-dichloro-2,2-bis(p-chlorophenyl)ethylene (DDE) via alcoholic
potassium hydroxide or in ethylene glycol containing barium hydroxide. The
metabolism and fate of DBA is unknown to us.
DDT is notable for its lipophilicity and reluctance to enter the aqueous
phase. In order to cause reaction between DDT and nucleophilic reagents, a
suitable reaction medium is necessary. To accomplish this non-aqueous sol-
vents, bi-phasic aqueous-organic solvent mixtures and aqueous solutions con-
taining detergents or phase-transfer catalysts were considered.
As a class, nucleophilic reactions are base catalyzed. In the presence
of even mild base, DDT eliminates HC1 to produce DDE. For this reason,
DDE is usually a product of the nucleophilic reaction of DDT and is resistant
to further nucleophilic attack.
The conversion of DDT to DDA by phase-transfer catalysis was attempted
in a mixture of DDT, toluene, sodium hydroxide, water and tetrabutyl-
ammonium iodide by heating to 88°C for 6 hours. The DDT was completely con-
verted to this dehydrochlorination product DDE. No DDA was detected.
11
-------
DDA was successfully prepared from DDT by the action of potassium
hydroxide in diethylene glycol at 130°C for 6 hours. The yield, however,
was not quantitative and the product was fairly toxic (84 mg/kg, iv mouse).
The recently reported electrochemical oxidation of DDE to DBA is of
considerable interest. A postulated mechanism is outlined in Figure 1.
-HC1
1
Figure 1. Postulated mechanism for electrochemical oxidation of DDE to DBA.
Several attempted conversions of DDT to DBA using basic potassium permanga-
nate with phase-transfer conditions according to the following scheme results
in the conversion of DDT to DDE with little or no oxidation taking place.
OH~
DDT ^ DDE———?^ 7 DBA
-HOI __ <;-
Mn04
The attempted reaction of DDT with sodium thiosulfate by phase-transfer
catalysis using benzene as the orgainic solvent and tetrabutylammonium iodide
as the catalyst yielded the quantitative return of DDT.
The fusion of molten sodium hydroxide and DDT yielded a product that
was not water soluble (probable DDE). The fusion of molten sodium thiosul-
fate with DDT produced essentially the same results except two phases were
visible in the melt. The product was apparently unreacted DDT.
The attempted reaction of DDT with sodium thiosulfate in an aqueous-
detergent mixture also yielded only unreacted DDT. DDT was heated in an
aqueous solution of sodium thosulfate to which 25% (V:V) of Tween 40 ( a
nonionic detergent) had been added. Although the DDT appeared to dissolve
12
-------
at 60° to 70°C, no reaction occured and DDT was recovered quantitatively.
In attempts to prepare sulfate derivatives of DDT and DDE, several
experiments were performed. DDT was added to an aqueous solution of sulfuric
acid and cetyltrimethylammonium bromide. Heating to the boiling point did
not cause the DDT to dissolve. In other experiments, DDE was heated with
concentrated sulfuric acid at 80°C, at 160°C and in a refluxing solution of
sulfuric acid in DMF. In none of these instances did reaction occur.
These reactions demonstrate properties of DDT that govern its behavior
in the environment. Although these attempts were intended to solublize
and degrade DDT, they clearly demonstrated, instead, that this insecticide
can exist under certain reaction conditions even more severe than those
encountered in the environment. Although DDT is reactive as an electrophile,
its solubility is such that it can only rarely contact nucleophilic reagents.
When this does occur, elimination of HC1 readily yields DDE which is more
resistant to further attack.
Sulfonation Reaction
DDT, DDE, ODD
A report of a water soluble sulfonation product of undetermined
structure was found in the patent literature. Investigations have been
conducted for sulfonation of DDT, DDE and ODD under a variety of conditions.
Results are summarized in Table 4.
TABLE 4. SULFONATION OF DDT, DDE AND ODD
Substrate
Purity
%SO,
Temperature*
* S.B., Steam Bath; R.T., Room Temperature
** U, Unsymmetrical; S, Symmetrical; UK, Unknown
*** Contains 20% o,p' DDT **** Contains 25% o,pf
ODD
Product**
DDT
DDT
DDT
DDT
DDT
DDE
DDE
DDE
DDD
ODD
DDD
99%
99%
99%
99%
Tech***
99%
99%
99%
Tech****
Tech****
Tech****
30
30
20
20
20
30
20
20
30
20
30
S.B
150°
S.B.
R.T.
S.B.
S.B.
S.B.
S.B.
130°
R.T.
S.B.
U
U
S
S
S&UK
S
S
s&u
UK
S&UK
U&UK
13
-------
When DDT is treated with fuming sulfuric acid containing 20 percent free SO,,,
overnight at room temperature or for 5 hours on a steam bath, 2,2-bis(3-sulfo-
4-chlorophenyl)-l,l-trichloroethane (I) is formed. (Fig. 2) Upon treatment
with base during workup, hydrogen chloride is eliminated as with DDT to form
2,2-bis(3-sulfo-4-chlorophenyl)-l,l-dichloroethylene disodium salt (II).
When DDT is treated with fuming sulfuric acid containing 30 percent free SO
on the steam bath or at 150°, product isolated is 2-<3,5-disulfo-4-chloro-
phyenyl)2-(4-chlorophenyl)-l,l-dichloroethylene disodium salt (III).
II
SO' Na
Cl
Cl
VII
VIII
Figure 2. Some parent compounds and sulfonated products of DDT and ODD
In our ODD sulfonation experiments, technical grade ODD was used. It is a
mixture of approximately 75 percent p,p' DDD (IV) and 25 percent o,p' ODD
(V), and yields a mixture of products upon sulfonation. The p,p' DDD appears
to be sulfonated similarly to DDT in that treatment at room temperature with
20 percent S0« oleur.i*leads to the symmetrically substituted productCvi^ and
sulfonation with 30 percent S0_ oleum leads to the unsymmetrically substitut-
ed product (VII), In both cases, the o,p' isomer (V) gave rise to a product or
products whose structure(s) could not be determined by Nuclear-Magnetic
reasonance (NMR) while in mixture VI on VII. Sulfonation with 30 percent S0_
oleum at 130° gave a more complex mixture. Its NMR spectrum was too complex
to interpret.
* A heavy oily strongly corrosive solution of sulfur trioxide in anhydrous
sulfuric acid.
14
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When technical DDT containing 20 percent of o,p' isomer(VIII)was
sulfonated with 20 percent S0_ oleum on a steam bath, a mixture of the
symmetrically substituted product,(III} and other unknown product or products
were found.
The sulfonation of pure, DDE, both with 20 and ,30 percent fuming sulfuric
acid, on a steam bath, led to the symmetrical product. However, a recent
run has produced a mixture of 76 percent of the symmetrical isomer and 24
percent of the unsymmetrical isomer. This result is not yet understood.
Polychlorinated Biphenyls (PCB's)
The polychlorinated biphenyls(rCB's) are mixtures of biphenyls which
have been chlorinated to varying degrees. Theorethically 210 different
chlorination products can exist. In the U. S., the Monsanto Co. produces
these mixtures under the trade name Aroclor. We have undertaken the sul-
fonation of Aroclor 1242 and 1254 (products containing 42% and 54% chlorine
by weight, respectively). Both Aroclor 1242 and Aroclor 1254 when heated
at 95° with fuming sulfuric acid for 5 hours yield highly water soluble
ammonium sulfonates along with sulfur containing a material which is
insoluble in acid, base,water,and a wide variety of organic solvents. It is
probably a sulfonation product of highly chlorinated PCB's. Because of the
higher toxicity of the water soluble products (417 rag/kg and 247 mg/kg, i.v.
mouse, for PCB 1242 and 1254 sulfonates respectively) further investigations
of these products has not been continued.
Other Chlorinated Hydrocarbon Insecticides (See Figure 3 below)
Diuron (la) and Linuron (Ib) are readily converted to 3-(4,5-dichloro-
2-hydroxysulfonylphenyl)-ll-dimethylurea (Ila) and 3-(4,5-dichloro-2-hydroxy-
sulfonylphenyl)-l-methoxyl-l-methylurea (lib), respectively. Diuron sulfon-
ate was isolated as the free acid and Linuron sulfonate as the ammonium salt.
Chloraben (3-amino-2,5-dichlorobenzoic acid) III, was treated for 5
hours at 95° with 30 percent oleum. The reaction was worked up to yield
the water soluble ammonium salt of the sulfonation product. The NMR spectrum
shows a singlet in the aromatic region but the site of sulfonation could
not be determined by this technique.
15
-------
a; R = CH3
b: R = OCH
R
CO.H
III
Figure 3. Sulfonation of three chlorinated hydrocarbon insecticides.
Aldrin, when heated at 100° with 30 percent fuming sulfuric acid, yields
what NMR and mass spectrometry suggest to be the hydroxy sulfonate I. The
primary product of the sulfonated reaction is probably the sultone, II, which
yields the hydroxy sulfonate upon hydrolysis. (See Figure 4 below)
SO,
H
\
-C-0
-c-so2
H
H20
H
I
-C-OH
I
-C-SO.H
I 3
H
II
Figure 4. Sulfonation of Aldrin
16
-------
When Endrin was treated with fuming sulfuric, an exothermic reaction
ensued. The product from this reaction is ket^ endrin, a metabolite of
Endrin known to form under acidic conditions. (See Figure 5 below)
H.SO,
0
Endrin
Figure 5. Attempted sulfonation of Endrin
Chlordane was recovered almost quantitatively after treatment with 30
percent oleum on a steam bath for 5 hours. Treatment with alcoholic
potassium hydroxide led to the formation of the diene. (See Figure 6 below)
Cl
KOH
Cl
Chlordane
Figure 6. Dehydrohalogenation of Chlorodane
Attempted sulfonation of the diene resulted in the formation of a material
of unknown composition which contained no sulfur.
Workup of the reaction mixture of heptachlor and 30 percent fuming
sulfuric acid with ammonium hydroxide led to the recovery of ammonium
chloride but no sulfonation product.
Toxaphene on treatment with 30 percent oleum did not yield a sulfonated
product.
2,4-Dichlorophenoxyacetic acid (2,4-D) reacted exothermally with
charring when treated with 30 percent fuming sulfuric acid and no clean
product was isolated.
17
-------
An estimate of the approximate per pound cost for detoxification of
small and large amounts of pesticide using the sulfonation process is
enclosed as appendix B.
TOXICOLOGY
Acute
Acute 96-hr toxicity screening tests were conducted using DDE and DDE
disulfate sodium salts against bluegills. Six concentrations were used for
each compound: 100, 10, 1, 0.1 and 0.001 mg/1 for DDE. For the DDE
disulfate the lowest concentration was changed to 0.005 mg/1. The DDE was
dissolved in acetone. Control tanks were used with acetone equal to the in
the DDE solution. Four fish were exposed at each concentration. Table 5
gives the results of this study. The sulfonate produced no mortalities
while the unconverted DDE was toxic to fish at concentration for 1 mg/1 and
up. Table 6 shows the I.V. mouse LDSO's for reference samples and some of
the sulfonated compounds
TABLE 5. 96 Hr TOXICITY SCREENING SULFONATE
Compound
Species
Toxicity
DDE disulfate sodium salt
DDE (in acetone)
Acetone Control
Bluegills No mortality at concentra-
tion from 0.005 to 100 mg/1
Bluegills * 50% mortality at concentra-
tions of 10 and 100 mg/1
100% mortality at concen-
tration of 1 mg/1
Bluegills No mortality at concentra-
tions equal to those used
with the DDE
* Lower mortality at higher concentrations possible caused by DDE comming
out of solution in water.
18
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TABLE 6. I.V. MOUSE LD50 (rag/kg) SULFONATES
Compound
Aldrin (Ref . Sample)
Aldrin (Sulf onate)
Aldrin (Sulfate Na Salt)
Aroclor 1242 (Ref. Sample)
Aroclor 1242 (Ammonium Sulfonate)
Aroclor 1254 (Ref. Sample)
Aroclor 2154 (Ammonium Sulfonate)
Chlordane (Ref. Sample)
Chlordane (from Base)
DDT (Ref. Sample)
DDE (Disulfonate Sodium Salt)
ODD (Disulfate Sodium Salt)
LD50
24 hr
15.65
147
800.8
925
417
1214
288.8
159.6
171.5
80.7
648.2
1118.5
LD50
14 day
14.31
same
702.1
813
same
608
246.6
127.5
167.6
76.8
same
same
Eggshell Study
The effect of decreasing eggshell thickness and weight due to DDT or DDE
ingestion has been shown to occur both naturally and in controlled laboratory
experiments. Morphologic alterations in the eggshell gland were seen in
mallard ducks (Anas platyrhynchos) fed 75 ppm DDT for 6 weeks prior to egg
production in experiments conducted in this laboratory. DDE has been shown
to cause inhibition of Ca ATPase in in-vitro experiments. Ca ATPase is an
enzyme responsible for transport of eggshell calcium. A study was under-
taken to determine the effects of DDT, DDE and their sulfonated derivatives
on eggshell production. To be examined were (1) eggshell measurements in-
cluding weight, length, width, thickness, and the ratio of weight/length x
width; (2) light and electron microscopy of eggshell gland, liver and kidney
and (3) Ca ATPase activity.
Young adult mallard ducks obtained from a local supplier were randomly
assigned to cages, 5 females and 1 male per cage, and maintained on
commercial poultry laying mash. After a 2 month acclimatization period
egg production was induced by regulating the photoperiod. When peak egg
production was reached feeding continued with either 10 or 50 ppm of DDT,
DDE, DOT-SO, or DDE-SO added to the same poultry laying mash. Four groups
were fed the normal diet. Eggs were collected daily from each group for 30
days. The contents were removed from the eggs and the hollow shells were
19
-------
air dried and stored until measurements were made. A total of 434 eggs were
measured for (1) weight (grams), (2) overall length and width (cm), and
(3) shell thickness (mm). Four measurements were made around the girth of
each egg.
One hen from each group was sacrificed after 1 week of feeding the
compounds. The remaining hens were sacrificed after 30 days. Sections of
eggshells gland, liver and kedney were fixed in 4% formaldehyde, 1%
glutaraldehyde and 200 millimols PO, buffer for evaluation by light and
electron microscopy. Additional sections of eggshell gland were collected
and processed to obtain a microsomal fraction for Ca ATPase determination.
Sections of fat, brain and eggshell gland were taken from each group to be
analyzed for pesticides by gas chromatography. Statistical analysis of all
data was done by Least-Squares and Maximum Likelihood General Purpose
Program.*
In all statistical analyses performed, no differences were seen between
dose levels of the compound fed and the 10 and 50 ppm groups are considered
together. Figure 1 shows the results of eggshell thickness measurements over
the 30 day experimental period. There were no statistical differences in
mean thickness of control eggs between the days measured; the mean value was
.401 mm. As expected, the thickness of the eggs from ducks fed DDE was
significantly reduced (p.01) at day 1 and remained thinner for the entire
30 day period. The eggs from the ducks fed DDT remained as thick as control
eggs until day 14 but were significantly thinner (p. 01) for the remainder
of the experimental period. The DDT-SO, and DDE-SO ducks produced eggs
which were identical in thickness measurements and were grouped together.
The sulfonated groups laid eggs which were the same thickness as controls
except on day 18. Where there was significant difference (p. 01). The
thickness returned to control levels at day 27 and remainder of the experi-
ment.
Figure 2 shows the R-values** obtained for eggshells from ducks fed DDT,
DDE, sulfonated derivatives and control diets. The purpose of the R-values
is to correct for eggshell weight in relation to size. A significant reduc
tion is shown in the R-values for eggshells from DDT and DDE fed ducks when
compared to controls. There was no significant difference between the R-val-
ues obtained from the sulfonated and control eggshells. The DDT-SO, and DDE-
SO, values did not vary significantly and were considered as one group. The
graph in figure 2 shows a sharp decline at day 18 because heat drying was
used instead of air drying from this day until the end of the experiment.
Since all groups were treated in the same manner, the relationship between
the groups remained constant. The weights of the eggshells followed the same
pattern as thickness measurements. Significant differences were seen in
length and width measurements of eggshells from the DDE-SO, and DDT fed ducks.
*I wish to acknowledge the assistance in computer programming and statis-
tical analysis of the cfataby Mr. Elden Leighton and Dr. Jerry F, Hardisty.
** R = Weight
Length X Width
20
-------
H
O
.410-
.400-
.390-
.380.
.370-
.360-
.350-
.340-
.330-
.320-
\
10
—T
15
~T
20
T
25
~T
30
DAYS
Figure 1. Mean Eggshell Thickness From Ducks Fed DDT, DDE, Sulfonates and Control Diets
-------
N)
.270"
.260*
.250-
.240-
.230-
.220-
.210-
.200-
.190-
.180--
Control
R-Value = weiSht
T
10
15
I
20
I
25
30
DAYS
Figure 2. Mean R-Values for Eggshells From Ducks Fed DDT, DDE, Sulfonates and Control Diets
-------
These differences were corrected for by using R-values.
The tissues collected for electron microscopy are being processed and
results will be available soon. All samples collected for Ca ATPase analysis
are being stored at -60°C. In vitro analysis of DDT, DDE and sulfonated
compounds will be performed.
The results of this experiment show to that while DDT and DDE fed at
levels of 10 and 50 ppm cause significant alterations in eggshell measure-
ments such as thickness, weight, and R-values, their sulfonated derivatives
do not share these characteristics. Thickness measurements show that while
the sulfonated compounds cause a reduction of thickness at day 18 this
decreased thickness is not as severe as that caused by DDT or DDE and is
transitory effect.
The R-values show that DDT and DDE are potent agents in causing a
reduction of the weight to size of eggshells but the sulfonated compounds
cause no change. The final portion of this study, the electron microscopic
study of eggshell gland, liver and kidney and the Ca+ ATPase measurements
should be of additional value in determining whether these sulfonated
derivatives share some of the toxic properties of the parent compounds.
BIODEGRADATION STUDIES
One of the hoped for goals of any pesticide conversion product is that
it be biodegradable.
Several experiments have been carried out to determine if some of the
water soluble sulfonates described above are biodegradable. In our first
experiment, sodium salts of unsymmetrical disulfonic acid, (derived from DDT).
symmetrical disulfonic acid (derived from DDE), and an undefined mixture
of sulfonation products derived from ODD, all at a concentration of 98 mg/1,
were incubated at room temperature in a basal mineral medium which was
inoculated with 5 volume percent of raw sewage from the Sod Run Sewage
Treatment Plant of Harford County, Md. Substarate concentrations were
determined spectrophotometrically on a periodic basis. After seven weeks no
change was observed.
Since soil contaiminated with DDT might contain microorganisms capable
of utilizing sulfonated DDT derivatives as a source of carbon, additional
experiments were performed. Such a soil was obtained from the manufacturing
area of Pine Bluff Arsenal throught the courtesy of Robert Donald, Ecological
Research Office, Biomedical Laboratory. The sulfonates derived from DDT and
DDE (150 mg/1) were incubated in the medium of which two weight percent of
23
-------
soil was added. The samples were shaken continuously on a rotary shaker.
Aliquots were periodically taken, centrifuged, and the level of the pesticide
remaining in the supernatent was determined. After eight weeks, no change
was observed.
Recent investigations have indicated, however, that mixed bacterial
cultures can mineralize some chlorinated aromatic compound which do not
sustain microbial growth, if they are supplied with another source of carbon
and energy, the so called "co-substrate enrichment technique." In our
experiments using this method, we chose as substrates, the symmetrical and
unsymmetrical sulfonates of DDT, the sulfonates of diuron,linuron, and as
positive controls, 2,4-D and p-chlorobenzoic acid, both of which are known
to undergo microbial degradation. The chlorinated substrates were added
to the medium at a concentration of 25 mg/1. Each compound under study was
incubated both with glucose as a co-substrate (500 mg/1) and without glucose.
The cultures were inoculated with 2.7 volume percent of sewage from the Sod
Run Plant and incubated at ambient temperature on a rotary shaker. Levels of
substrates were determined as above. After 24 hours, all systems to which
co-substrate had been added had become quite turbid indicating bacterial
growth. After 20 days incubation, 47 percent of the original 2,4-D absor-
bance at 283 mm remained in the culture*no co-substrate, and no absorbance
was observed in the culture with co-substrate.
Both p-chlorobenzoic acid cultures has about 45 percent of their origi-
nal absorbance at 267 mm. No change was observed in the other systems.
24
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SECTION 7
INCINERATOR RESIDUES
Twenty-four incinerator residue, samples, produced by Midwest Research
Institute (Table 7), were submitted by EPA for toxicological testing. These
samples were insoluble in all commonly used solvents so i.v. mammalian
evaluations could not be run. Since standard methods could not be used, 11
of the residues were pulverized, placed in fish tanks and screened for 96-hr
toxicity to bluegills. Most of the material settled out after 24-48 hours
with the highest concentration (1000 mg/1) remaining quite turbid after 96
hours. Of all samples only Captan run #148 horizontal stack residue
produced mortality below 1000 mg/1. The 96 hr TL50 for this sample was
320 mg/1. All other samples appeared to be non-toxic at concentration up to
1000 mg/1.
TABLE 7. MIDWEST RESEARCH INSTITUTE SAMPLES
Test No.
Pesticide
Residue Sample(s)
After
After
After
After
After
After
44* DDT Dust
45 DDT Dust
61* Aldrin Granules
64 Aldrin Granules
86 Picloram Pellets
87 Picloram Pellets
104* Malathion Dust
105 Malathion Dust
122 Toxaphene Dust
124* Toxaphene Dust
146 Captan Dust
148** Captan Dust
149 Zineb Dust
150 Zineb Dust
170 Mirex Bait
172 Mirex Bait
148** Captan Dusts Tests
159 Zineb Dust Tests
159 Zineb Dust Tests
126 Toxaphene Dust Tests
50 DDT Dust Tests
126 Toxaphene Dust Tests
Primary and Secondary Chambers
Primary and Secondary Chambers
Primary and Secondary Chambers
Primary and Secondary Chambers
Primary Chamber (Ground)
Primary Chamber
Primary and Secondary Chambers
Primary and Secondary Chambers
Primary and Secondary Chambers
Primary and Secondary Chambers
Primary and Secondary Chambers
Primary and Secondary Chambers
Primary and Secondary Chambers
Primary and Secondary Chambers
Primary Chamber
Primary Chamber
Horizontal Stack Residue
Scrubber 1 Residue
Vertical Stack Residue
Scrubber 1 Residue
Scrubber 1 Residue
Horizontal Stack Residue
25
-------
Table 7. continued
Test No. Pesticide Residue Sample(s)
After 106 Malathion Dust Tests Horizontal Stack Residue
After 50* DDT Dust Tests Horizontal Stack Residue
*Single sample tested - these samples were tested for toxicity in fish.
**2 samples tested - these samples were tested for toxicity in fish.
26
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APPENDIX A
DESCRIPTION OF ACUTE TOXICITY STUDIES
ACUTE LD50 DETERMINATION IN THE MOUSE
Male mice from the Edgewood Arsenal colony are used in these tests. All
animals are acclimated to the test environment at least 24 hours before
test. Ten animals are tested per dose level and a minimum of 4 logrithmical-
ly spaced dose levels are used in an effort to produce 0% mortality, 100%
mortality and two partial mortality fractions. All injections are made into
the lateral tail vein. LDSO's with 95% confidence limits are calculated for
24 hours results as well as for 14 day observation results. Where possible
doses are expressed in mg/kg values. When solutions of unknown characteri-
zation is tested doses are expressed in ml/kg.
ORAL TOXICITY TESTS
Rats from the Edgewood Arsenal colony are used in these tests. Except
for the species and route of administration (stomach tube), tests are conducted
in a manner similar to that described for mice. Where insufficient sample
amounts are available to perform a complete test a selected dose or two of
material are given to the animals and the result out toxicity response com-
pared.
SKIN IRRITATION (CFR, TITLE 21, PARA 191.11)
Primary irritation to the skin is measured by a patch-test technique
on the abraded and intact skin of albino rabbits whose backs were clipped
free of hair 24 hours prior to compound application. Six animals are used
for each material tested. The test compound, as a liquid (0.5 ml) or a
solide (0.5 gm) is applied under a gauze patch to the abraded and intact
skin of each animal. Immediately after compound application the animals
trunk is wrapped withimpermeable plastic to retard evaporation. After 24
hours of exposure the plastic and gauze are removed from each animal and the
resulting reactions to the skin are evaluated and scored according to the FDA
27
-------
procedure. See Table A-l. Readings are again made 72 hours after initia-
tion of exposure.
TABLE A-l. FDA SCORING TABLE FOR SKIN IRRITATION
Skin Reaction Value
Erythema and Eschar Formation
No erythema 0
Very slight erythema 1
Well defined erythema 2
Mod to severe erythema 3
Severe erythema/eschar 4
Edema Formation
No edema 0
Very slight edema 1
Slight edema 2
Moderate edema 3
Severe edema 4
To establish the primary irritation index score (PII), readings
obtained for skin reactions against abraded and jutact skin are added
together for both the 24-hour readings for both eyrthema/eschar formation
and for edema formation. Thus, a total of four values for erythema/eschar
and four values for edema are obtained. The total of the eight values are
added together and divided by four to give the primary irritation index score
for the compound. When the PII score equals or exceeds a value of 5, the
compound is rated as a primary skin irritant. No ratings are provided for
this test by the FDA for values fo less than 5 though it is clear that com-
pounds having a PII score between 3 and 4.9 are significant skin irritants
but would not, by definition, be classified as a primary skin irritant.
28
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EYE IRRITATION TEST (CFR, TITLE 21, PARA, 191.12)
Six albino rabbits are used to evaluate eye irritancy potential of
each test material. Both eyes of test animals are examined prior to testing
using flucrescein and UV light to assure that only animals without eye
damage or irritation are used for testing. All animals are maintained in
facilities free of sawdust, wood chips, or other type bedding material that
may produce eye irritation.
Each test animal is given 0.1 ml of liquid compound or 100 mg of solid
compound into one eye, The other eye serves as a comparative control. The
test substance is placed into a cup formed by gently pulling the lower lid
out. After instillation of the test compound the eye lids are held together
for approximately five seconds to insure thorough distribution. Test com-
pounds are not washed out of the eye until 24-hours after instillation at
which time they are flushed thoroughly with copious quantities of distilled
water.
Eyes are examined, graded, and recorded for ocular reaction at 24, 48
and 72 hours after compound instillation. After recording the observations
at 24 hours, all eyes are further examined after instillation of fluorescein
dye using ultraviolet light.
The test is considered positive if four or more animals in the test
group exhibited a positive reaction. If only one animal exhibits a reaction
the test is regarded as negative. If two or three animals exhibit a positive
reaction the test is repeated using another group of six animals. In the
second test if three or more animals exhibit a positive reaction the test is
positive. If one or two animals exhibit positive reaction the test is
repeated again. If none of the animals exhibit positive irritation the
test is negative. In the third test if one or more animals exhibit a
positive response the test is positive and if no positive responses are seen
the test is negative.
Grades for ocular lesions as defined by the FDA in OFR, Title 21, para.
191.12 are shown in Table A-2.
29
-------
TABLE A-2. GRADATION OF EYE EFFECTS
Grade
Cornea (C)
No ulceration or opacity 0
Scattered or diffuse areas of opacity (other than
slight dulling of normal luster), details of
iris clearly visible 1*
Easily discernible translucent areas, details of
iris slightly obscured 2
Nacreous areas, no details of iris visible, size
of pupil barely discernible 3
Iris (I)
Normal 0
Markedly deepend folds, congestion, swelling
moderate circumcorneal injection (any of these
or combination of any thereof), iris still re-
acting to light (sluggish reaction is positvie) 1*
No reaction to light, hemorrhage, gross destruc-
tion (any or all of these) 2
Conjunctival Redness (R) (refers to palpebral and
bulbar conjunctivae excluding cornea and iris)
Vessels normal 0
Some vessels definitely injected 1
Diffuse, crimson red, individual vessels not
easily discernible 2*
Diffuse beefy red 3
Chemosis (CH)
No swelling 0
Any swelling above normal (includes nictiating
membrane) 1
Obvious swelling with partial eversion of lids 2*
Swelling with lids about half closed 3
Swelling with lids more than half closed 4
* Indicates lowest grades considered positive under Section 191.12 of
the Federal Hazardous Substances Labeling Act Regulations.
30
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APPENDIX B
APPROXIMATE OPERATING COSTS OF PROPOSED PROCESS
We have applied commodity costs taken from current Chem. Marketing
Reporter and current labor costs in Chemical Process Technology Branch to
the process information you gave us on 25 Feb. From this, we arrived at
estimates for the process of chemical destruction of DDT (representative of
chlorinated aromatic hydrocarbons) in batch quantities of 50 and 2000 Ibs per
day.
The estimated costs are for rough labor and material only. Not included
are facility acquisition costs or the costs of any further disposition of
the reaction products.
PROCESS DATA USED
1. 30% fuming sulfuric per kilo DDT =1.5 liter
2. NaOH equivalent to all of acid used.
3. Digestion of DDT in acid for 5 hrs at 95°C.
4. Neutralization of reaction mass with aqueous NaOH.
COMMODITY DATA
1. Acid - $53.25/ton (less than carload lots) for 100% acid X 1.045
for 20% fuming (30% not listed).
2. NaOH - 76% beads $15.00/100 Ibs.
MATERIAL REQUIREMENTS AND COST PER POUND OF DDT
1. 2000 Ibs DDT equivalent to 910 Kg, equivalent to 13551- acid
1355 1- acid equivalent to 375 gals
375 gals at 1.9 sp. g. (approx) = 5940 say 6000 Ibs
6000 Ibs acid at 53.25 X 1.045 $/ton = $167 = $0.083/lbs DDT
31
-------
2. 30% fuming H SO *106.7% total H SO
1.067 X 6000 X 80/98 * 5226 Ibs NaOH (100%)
5226/0.76 = 6876 say 6900 Ibs 76% NaOH
6900 Ibs at $15.00/100 Ibs - $1035
$1035/2000 Ibs DDT = $0.52/lbs DDT
3. Total material requirements and costs:
Fuming sulfuric acid - 3 Ibs/lb DDT - $0.083/lb DDT
76% NaOH - 3.45 Ib/lb DDT- 0.52/lb DDT
$0.63/lb DDT
Round off to $0.75/lb DDT to account for steam, water and power.
ESTIMATED LABOR COSTS
50 Ibs DDT/day basis - 8 man hours
2000 Ibs DDT/day basis - 16 man hours
At prevailing Cml Proc Tech stabilized labor rate of $30.38/hr, labor costs
are:
50 Ibs/day rate - 243 say $250 = $5.00/lb DDT
2000 Ibs/day rate - say $500 = $0.25/lb DDT
LABOR AND MATERIAL COSTS SUMMARY
50 Ibs/day rate $0.75 H- $5.00 = $5.75/lb DDT
2000 Ibs/day rate $0.75 + $0.25 = $1.00/lb DDT
* The authors wish to thank Mr. Robert E. Cox of Chemical Process Technology
Branch, Chemical & Plants Div., Manufacturing Technology Dir of this estimate.
32
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GLOSSARY
DBA: 1,1-dichloro benzilic acid
DBA: l,l-dichloro-2,2-bis(p-chlorophenyl)acetic acid
DDD: 1,l-dichloro-2,2-bis(p-chlorophenyl)ethane
DDE: 1,l-dichloro-2,2-bis(p-chlorophenyl)ethylene
DDT: 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane
DDF: dimethylformamide
33
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing}
1. REPORT NO.
EPA-600/2-77-143
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
ASSESSMENT OF TECHNIQUES FOR DETOXIFICATION OF
SELECTED HAZARDOUS MATERIALS
5. REPORT DATE
August 1977 (Issuing Date)
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S) Benard J. Brown, Milton K. Christensen,
Bernie E. Hackley, Jr., Ronald L. Kassel, Gerald J.
Kolaja, James H. Manthei, Charles E. Williamson
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Chemical Laboratory, Edgewood Arsenal
Aberdeen Proving Ground, Maryland 21010
10. PROGRAM ELEMENT NO.
1DC618
11. CONTRACT/GRANT NO.
EPA-IAG-D4-0429
EPA-IAG-D5-0429
EPA-IAG-D6-0429
12. SPONSORING AGENCY NAME AND ADDRESS
Municipal Environmental Research Laboratory—Cin., OH
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA/600/14
15. SUPPLEMENTARY NOTES
Project Offier: Charles Rogers (513-684-7881)
16. ABSTRACT
A review and evaluation of available processes for detoxification of the
first group of hazardous materials was conducted during Phase 1 of the inter-
agency agreement (1974 calendar year). The processes used for specific hazardous
materials were identified. One process found during this literature survey
described the reaction of PCB's with amines to give a variety of products that
were supposed to have useful properties. Two of these products that were available
were obtained and evaluated toxicologically. Both proved to be higly toxic.
Products produced by catalytic decomposition were also evaluated for toxicity.
In many cases the products were not adequately identified chemically and accurate
toxicological evaluation could not be accomplished.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
COSATI Field/Group
Detoxification
Incinerators
Wastes
Pesticides
Disposal
Catalysts
Treatment
Pesticide Waste
Hazardous Waste
13B
6F
8. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (This Report)
UNCLASSIFIED
21. NO. OF PAGES
44
20. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (Rev. 4-77)
34 £ U.S. GOVERNMENT PRINTING OFFICE: 1977-757-056/61(96 Region No. 5-11 —
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