TOXAPHENE STATUS REPORT
November 1971
ENVIRONMENTAL PROTECTION AGENCY
Washington, D.C.
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TOXAPHENE STATUS REPORT
Special Report
to the
Hazardous Materials Advisory Committee
Environmental Protection Agency
Consultant Group on Toxaphene
Gordon E. Guyer, Convener
Perry L. Adkisson
Kenneth DuBois
Calvin Menzie
H. Page Nicholson
Gunter Zweig
Industry Liaison
Charles L. Dunn
November 1971
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HAZARDOUS MATERIALS ADVISORY COMMITTEE
Dr. Erail M. Mrak Chairman
Chancellor Emeritus
University of California at Davis
Dr. William J. Darby Cochairman
President, Nutrition Foundation
and Chairman, Department of
Biochemistry
Vanderbilt University
Mr. Errett Deck
Chairman, Legislative Committee
Association of American Pesticide
Control Officials
Washington State Department of
Agriculture
Dr. Norton Nelson
Director, Institute of
Environmental Medicine
New York University Medical
Center
Dr. Leon Golberg
Scientific Director, Research Professor
of Pathology
Institute of Experimental Pathology
and Toxicology
Albany Medical College
Dr. Ruth Patrick
Chairman, Department of
Limnology
Academy of Natural Sciences,
Philadelphia
Dr. Frank Go1ley
Executive Director and Professor of
Zoology, Institute of Ecology
University of Georgia at Athens
Dr. William R. Rothenberger
Agricultural Production
Specialist
Frankfort, Indiana
Dr. Gordon E. Guyer
Chairman, Department of Entomology
Michigan State University
Dr. Paul E. Johnson
Executive Secretary, Food and
Nutrition Board
National Academy of Sciences
Dr. Earl Swanson
Professor of Agricultural
Economi cs
University of Illinois
Dr. Wilson K. Talley
Assistant Vice President
University of California,
Berkeley
Mr. William Murphy
President, Campbell Soup Company,
Camden
Dr. W. Leonard Weyl
Chief of Surgery
Northern Virginia Doctors
Hospital
McLean, Virginia
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Regular Consultants
Dr. Dale R. Lindsay
Associate Director of Medical and
Allied Health Education
Duke University
Dr. Caro Luhrs
Medical Advisor to the Secretary
U. S. Department of Agriculture
Mr. James G. Terrill, Jr.
Manager, Special Projects
Environmental Systems Department
Westinghouse Electric Company,
Pittsburgh
Staff
Dr. William S. Murray
Staff Director
Mr. W. Wade Talbot
Executive Officer
Mrs. Alva J. Ware
Clerk-Typist
Mrs. Dorothy I. Richards
Administrative Assistant
Miss Carolyn L. Osborne
Cl erk-Stenographer
Miss Ruby D. Armstrong
Secretary
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CONSULTANTS ON TOXAPHENE
List of Contributors
Convener and Member of the Hazardous Materials
Advisory Committee
Gordon E. Guyer, Ph.D.
Professor and Chairman of the Department of Entomology
Michigan State University
Consultants to the Hazardous Materials
Advisory Committee
Perry L. Adkisson, Ph.D.
Professor and Head of the Department of Entomology
Texas A & M University
Kenneth DuBois, Ph.D.
Professor of the Department of Pharmacology
University of Chicago
Calvin Menzie
Chief Toxicologist of the Office of
Environmental Quality
Bureau of Sports Fisheries and Wildlife
Department of the Interior
H. Page Nicholson
Chief of the Agricultural and Industrial Water
Pollution Control Research Program
Southeast Water Laboratory
Environmental Protection Agency
Gunter Zweig, Ph.D.
Director of the Life Sciences Division
Syracuse University Research Corporation
Syracuse, New York
- x -
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Industry Liaison with the
Hazardous Materials Advisory Committee
Charles L. Dunn
Manager of Ecological Research
Hercules Incorporated
- ii -
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TABLE OF CONTENTS
Page No.
INTRODUCTION 1
Use Patterns ------------------- 1
U.S. Department of Agriculture Pesticide
Use Census ------v------------ .1
Use Outside the U.S.A. 5
Future Trends 7
CHEMISTRY AND COMPOSITION 10
Chemical Structure and Production of Toxaphene ~ ~ 10
Uniformity of Toxaphene Production -------- n
Composition of Toxaphene ------------- 12
Partition Chromatography ------------- 14
Fractional Crystallization ------------ 14
Craig Liquid-Liquid Separation ---------- 15
METHODS OF ANALYSIS 19
Assay Procedures (Formulation Analysis) ----- 19
Total Chlorine Method 19
Infrared Spectrophotometer ---------- 19
Spectrophotometric Method --------- 20
Assays for Cattle Dips ---------- 20
Residue Analyses for Toxaphene --------- 21
Clean-up Procedures ------------ 22
Total Chlorine Method ~ __-- 24
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TABLE OF CONTENTS (Cont'd.)
Page No.
Active-Metal Reaction Methods 24
Spectrophotometric Method ____________ 26
Paper Chromatography ______________ 26
Thin Layer Chromatography ------______ 26
Gas Chromatography _______________ 27
(a) Review of method ___ 27
(b) Recommended procedures ________ 29
Discussion of Analytical Methods and Reporting Data - - 30
Conclusions on Analytical Techniques and Evaluation
of Residue Data , 32
FATE AND IMPLICATION IN THE ENVIRONMENT 44
Effect on Fish and Wildlife 44
Toxicity and Pharmacological Actions ______ 44
Persistence of Toxaphene ____________ 44
Residues ____________________ 45
Summary and Comments ______________ 45
Fate and Movement of Toxaphene in Terrestrial and
Aquatic Systems -------__-_-------- 59
Persistence in Soil 59
Occurrence and Movement in Watercourses ----- 63
Biological Accumulation ------------- 69
Summary ————————————————————— 73
— iv —
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TABLE OF CONTENTS (Cont'd.)
Page No.
Toxaphene Residues in Atmospheric Samples ------ 89
The Effect of Toxaphene on Beneficial Arthropods
Populations ----_-----____-_--_-_ 93
Effect of Toxaphene on Insect Pollinators - - - 93
a Summary -------------------- 95
Effect of Toxaphene on Insect Predators and
Parasites - a Summary _____________ 99
RESIDUES IN FOOD CROPS AND FOODS ------------- 104
Tolerances for Toxaphene Residues ---------- 104
Residues in Food -_-_-----__---_--- 105
Residues in Livestock ---------------- 107
Residues in Milk __________________ 1Q8
Residue Decline - Controlled Studies ________ 109
Possible Metabolities _--_--___---_--_ no
Metabolism in the Honey Bee -------------
TOXICOLOGY IN MAN AND ANIMALS , ------- -. ------ 120
Acute Toxicity and Pharmacological Actions _____ 120
Subacute Toxicity --- ------ ---- ----- 123
Chronic Toxicity - -- ----- - --- ------ 124
Reproduction, Tenatology and Mutagenesis -__--_ 124
Interactions ____________________ 125
Tissue Residues -_-_--_---__------- 126
Summary -_-------------_------- 127
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TABLE OF CONTENTS (Cont'd.)
o
Page No.
TOXAPHENE RESISTANCE 131
In Arthropods ____________________ 131
In Animals Other Than Insects, Mites and Ticks _ - - 150
- vi -
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INDEX OF TABLES
Page No,
Table Farm Use of Toxaphene — 1964 .and 1966
Crop Years 3
Table Regional Patterns of Toxaphene Farm Use —
1964/1966 4
Table Properties of Fractions from Fractional
Crystallization of Toxaphene 15
Table Craig Countercurrent Fractionation of Toxaphene . 17
Table Summary of Reported Toxaphene Residues by GLC .. 34
Table Toxaphene Residues 48
Table Toxaphene Residues In Wild Bird Tissues 50
Table Toxaphene Applied to Crops vs. Recovered
from Soil 75
Table Toxaphene by Seasons in Flint Creek, Alabama
Water 76
Table Toxaphene Concentration in California Surface
Waters 77
Table Toxaphene in Agricultural Drains in California . 78
Table Toxaphene in California San Joaquin Valley Tile
Drain Effluents 79
Table Toxaphene in California Central Valley Surface
Agricultural Waste Water Drains 79
Table Toxaphene in California Central Valley Surface
Waters 80
Table Toxaphene in California Bay and Oceans Waters .. 80
Table Toxaphene in California Sediments 81
Table Insecticides Residue in Alabama Soil Samples
Collected from 33 Cotton Fields 82
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INDEX OF TABLES (Cont'd.)
Page No.
Table Comparison of Insecticide Recovery from
Sediment and Water, Hartselle, Alabama Water
Treatment Plant 82
Table Toxaphene in Wisconsin Lakes, 1965 83
Table Insecticides in the Fat of Cattle after Multiple
Spray Treatments 84
Table Insecticide Residues Stored in the Fat of Cattle
Fed Known Amounts in their Diet 85
Table Toxaphene Residues in Atmospheric Samples 89
Table
Table Domestic Foods Surveillance by FDA — 1964 to
1967 114
Table Summary of Toxaphene Residues in Oil Seeds, Oils,
and By-Products (1964-1966) 115
Table Chlorinated Pesticide Residues in Meat and
Poultry 1969-1971 116
Table Toxaphene Residues Resulting From Supervised
Trials 117
Table Evaporation Rates — DDT vs. Toxaphene 118
Table Comparison of Toxicity of Toxaphene with
Hypothetical Metabolites 119
Table Acute Oral and Dermal 1050 Values for Toxaphene
and Other Chlorinated Hydrocarbons to Rats 121
Table Acute Toxicity of Toxaphene 122
Table Tabulation of Pests Reported to be Resistant to
Toxaphene, BBC, Organochlorine Insecticides and
Cyclodiene Derivatives 136
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INDEX OF FIGURES
Page No.
FIGURE
'Typical Gas Chromatogram with Toxaphene
36
FIGURE Toxaphene Analysis by Gas-Liquid
Chromatography and Microcoulometry
37
FIGURE Electron Capture Detector Responses To:
A-7 Nanograms Toxaphene, B-2.8 Nanograms DDT,
C-7 Nanograms; Toxaphene + 3.5 Nanograms DDT ,
38
FIGURE Gas Chromatogram for 30 ng. of Toxaphene
Before Alkali Treatment and After Alkali
Treatment
39
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INTRODUCTION
USE PATTERNS
The amount of polychloroterpene insecticide used in the United
States during the past 25 years totals about 940 million pounds,
averaging 38 million pounds annually. These figures, based on manu-
facturer production and sales information, are compared below with more
detailed knowledge developed in government studies of farm use of
pesticides.
USDA Pesticide Use Census
The Economic Research Service of USDA conducted the first
national census of pesticide use in 1965. Data from that study
were released in AES Report No. 131, January, 1968. A follow-up
study was conducted in 1967, and reported (AES Report No. 179) in
April, 1970. In each survey, approximately 10,000 farmers were
interviewed in depth to obtain the details of their use of pesti-
cides. Data concerning toxaphene have been abstracted from these
reports and are tabulated below. Because the crop designations are
not identical in the 2 studies, certain details may not be directly
compared, but the major uses and amounts used are clearly set forth.
The data indicate that crop uses for toxaphene (and toxaphene-
strobane in 1964) were in the range of 34 - 3 million pounds
+
annually (Table 1). Livestock use was 4.2 - 0.5 million pounds.
Combined usage was in the range of 38 - 4 million pounds annually.
These figures are only for farm use, and do not include amounts
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used for any government programs. Such usage would add only modest
amounts to the total, however, and the totals do agree reasonably
well with figures cited above, which are projected from production
and estimated consumption based on sales to formulators. In this
regard, it should be recognized that the major producer, Hercules
Incorporated, does not market any toxaphene formulations, but
sells to formulators who blend, distribute and sell finished formu-
lations . Toxaphene is sold by Hercules Incorporated as technical
toxaphene (100%), a 90% solution in xylene, and as a 40% dust base.
The 90% solution is preferred by many formulators because it
eliminates the inconvenience and expense of handling, melting, and
dissolving the waxy solid. The solution is commonly bulk-shipped
in rail and truck tank cars.
Certain regional discrepancies have been noted in the USDA
data (Table 2). In the Pacific states, for example, the volume of
toxaphene used is apparently understated. Major uses in the Pacific
states are on cotton, vegetables, and alfalfa seed. California
state data for 1970 (from that state's first year of dealer sales
reporting) show a total of 2.7 million pounds of toxaphene used on
0.75 million acres. Thus, the USDA data may understate toxaphene
usage for that region, but the total usage figures are believed to
be reasonably accurate.
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TABLE 1
Farm Use of Toxaphene — 1964 and 1966 Crop Years
Crop Use
Corn
Cotton
Soybeans
Tobacco
Other field crops
Vegetables
Total on Crops
Millions of Pounds in Indicated Years
1966 1964
0.004
27.3
1.0
0.2
1.6
0.8
30.9
Total on Crops
0.1
26.9
1.3
0.3
4.3
1.2
34.2
2.7 (Strobane)
36.9
Livestock Use
Cattle
Swine
Poultry
Sheep
Other
Total on Livestock
3.3
0.3
.02
.05
0.01
3.7
4.3
0.3
0.00
0.1
4.7
Total Crop + Livestock
34.6
41.6
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Table 2
Regional Patterns of
Toxaphene Farm Use — 1964/1966
Region
Northeast
Lake States
Corn Belt
Northern Plains
Appalachia
Southeast
Delta States
Southern Plains
Mountain
Pacific
Millions of Pounds
Millions of Acres
Treated (a)(b)
1966
0.004
0.1
0.4
0.01
2.5
13.7
7.2
5.0
1.4
0.6
1964
.003
.05
1.3
.001
4.2
11.5
10.3
5.1
1.0
0.8
1966
.002
.01
0.3
.01
0.5
1.6
1.2
1.3
0.2
0.2
1964
.02
.05
0.9
.002
1.1
1.8
2.2
1.4
0.2
0.2
Total
30.9
34.2
5.4
8.0
All Insecticide Use — 1964/1966
All organochlorine
All organophosphorus
All carbamate
All insecticides
82.8
is 36.6
12.4
138.0
89.8
30.5
15.4
143.0
35.0
26.0
5.0
67.0
41.0
24.0
5.0
71.0
(a) Acres treated do not distinguish between an acre treated only once in
the crop year or an acre treated many times.
(b) The same acre treated with 3 different insecticides is counted once for
each pesticide — e.g., one acre treated with tox-DDT-methyl parathion
would be tabulated as 2 organochlorine and one organophosphorus acres.
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Use Outside U.S.A.
Use of toxaphene outside the United States is principally
on cotton and livestock, with a variety of smaller uses on
vegetables, small grain, peanuts, soybeans, bananas, and pineapple.
Toxaphene manufacturing plants are located in0Nicaragua and
Mexico with local ownership predominating in Mexico. Russia is
believed to have toxaphene production facilities, but little is
known about the amount and nature of the material produced.
Other chlorinated terpene materials are encountered on the world
market. One of these, called "Melipax," is made in East Germany.
Other so-called chlorinated camphenes have been encountered in
Asia. In general, these other "chlorinated terpene" products
have been found to be of poor or highly variable quality, and in
bioassay tests often require doses several times that of toxaphene
to achieve equal insect kill.
While the overseas market for toxaphene is appreciably less
than that in the United States, it is also complicated by factors
other than safety and effectiveness of the product. Currency and
import restrictions, devaluations, trade policy agreements and
other complications can make pesticide marketing overseas more
difficult than in the United States; and product sales can vary
significantly from year to year. Informed opinion concerning the
likely impact on the international market of United States
restrictions on domestic use of toxaphene is that further United
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States restrictions would eliminate much of the use of toxaphene
overseas.
Crop Use Outside U.S.A.
Geographic Area
Central America
South America
Africa
Europe
Asia
Oceania
Principal Crop Use
cotton
cotton, small grains, soybean,
bananas
cotton, vegetables
cotton, rapeseed, vegetables
cotton, peanuts, vegetables,
rice
cotton
Livestock Use Outside U.S.A.
Africa
East, Central and South Africa, including Uganda, Kenya,
Tanzania, Rhodesia, Angola, Nigeria and South Africa
South America
Brazil
Peru
Ecuador
Columbia
Venezuela
Central America
Mexico
Costa Rica
El Salvador
Panama
North America
Canada
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None of the countries listed, except Canada, has formally established
residue tolerances in meat, although many have noted the 7 ppm tolerance
in the United States and are aware of the 28-day preslaughter interval.
FUTURE TRENDS
Farm practices reflect changes in political and economic pressures.
Federal farm programs, such as recent changes in acreage allotments and
projected yields for cotton, will undoubtedly cause re-examination of
insect control practices. Optimum farm operation may not emphasize
maximum yields, and both crop choice and production practices will be
re-evaluated for their net return to the producer. This could lead
to a reduction in the amounts of pesticides and other economic inputs
used for the production of certain crops.
There is a continuing need for insect control in crop and live-
stock production, but only a limited number of new pesticides are in
view. Older materials, such as toxaphene, as long as they are environ-
mentally acceptable, will continue to be used where they are still.
effective. It should be recognized, however, that toxaphene has
probably reached its maturity and while a rather stable volume is used,
no great expansion in its use can reasonably be foreseen.
The use of toxaphene on cotton (Table 1) far exceeds that on any
other agricultural commodity. Thus, any changes in future cotton insect
pest control strategies may greatly affect the amounts of toxaphene
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8
used in the United States. Toxaphene is rarely used alone for the con-
trol of the insect pests of cotton. Historically, the greatest use of
toxaphene on cotton has been in mixtures with DDT. The toxaphene-DDT
mixture was synergistic to the chlorinated hydrocarbon insecticide-
resistant strains of boll weevils, thrips and cotton fleahoppers which
developed during the 1950's.
The combination of toxaphene with DDT provided a pesticide that was
0
many times more toxic to the above pests than either component when used
alone. The toxaphene-DDT mixture, marketed in a formulation containing
two parts of toxaphene to one of DDT, provided very effective and eco-
nomical control of the three above pests as well as the bollworm and
tobacco budworm. The mixture also was very safe for applicators and
farm workers to handle. Because of these reasons, toxaphene-DDT has
been, and probably continues to be, one of the most widely used pesti-
cides on cotton.
If the use of DDT on cotton should be prohibited, this action
undoubtedly would have an effect on amounts of toxaphene used on the
crop. In states where DDT has been banned (Arizona and California),
or where the toxaphene-DDT mixture has lost its utility because of the
continued development of insecticide-resistant insect pests (Texas),
the DDT component of the mixture has been replaced with methyl parathion.
However, the toxaphene-methyl parathion mixture is not synergistic
against resistant insects, but simply additive. That is, each component
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provides toxicity to a given pest in direct proportion to the toxicity
of the component when used alone.
In toxaphene-methyl parathion mixtures, methyl parathion is by far
the most toxic component to insects. However, the addition of toxaphene
to methyl parathion provides certain advantages in that the resultant
o
pesticide is measurably more toxic to pest species than either insecti-
cide alone. The toxaphene-methyl parathion mixture also is more persis-
tent than methyl parathion; thus, the mixture may be applied with less
frequency than methyl parathion alone. In comparison to toxaphene-DDT,
the toxaphene-methyl parathion mixture poses a much greater acute hazard
to applicators and farm workers. This mixture also is much more toxic
to certain beneficial species of insect parasites and predators than
toxaphene-DDT. The amounts of toxaphene applied in mixtures with methyl
parathion oftentimes is less than in the traditional toxaphene-DDT
mixtures.
Future trends 'for the use of toxaphene on other crops and livestock
is not expected to change greatly. Toxaphene presently has considerable
utility in the production of small grains, pasture and hay crops, soy-
beans, vegetables and livestock. It also has some use for the control
of certain insect pests of corn, grain sorghum and other feed and food
crops. Toxaphene has a particular advantage (as will be discussed in
detail later in this report) in that it may be used on seed alfalfa,
clover and certain vegetable crops without causing great damage to bee-
pollinators.
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10
CHEMISTRY AND COMPOSITION
Chemical structure and production of toxaphene. Toxaphene is
defined as chlorinated camphene (67-69% chlorine) and has the empirical
formula CinH.._Clg with a molecular weight of 414.
The commercial production of toxaphene (U. S. Patents 2,565,471
and 2,657,164, Hercules) consists of the reaction between camphene and
chlorine activated by ultraviolet irradiation and certain catalysts to
yield the final product of chlorinated camphene with a chlorine content
of 67-69%. The final product is a relatively stable material with a
mild terpene odor and is a mixture of related compounds and isomers.
Physical Properties
Physical form; Amber, waxy solid.
Melting point; 70°-90°C.
Solubility: High solubility in most organic solvents, but greater in
aromatic solvents; water solubility is about 0.5 ppm.
Vapor pressure; 0.2-0.4mm/25°; 3-4mm/90°C.
Product Specifications
Total organic chlorine, % by weight 67.0-69.0
Acidity, % by weight as HC1 0.05% max.
Drop softening point, °C 70 min.
Infrared absorptivity at 7.2u 0.0177 max.
Specific gravity at 100°C/15.6°C 1.600 minimum
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11
Typical Properties (Not Specifications)
Specific gravity at 100°C/15.6°C 1.63 (average)
Specific gravity change per °C 0.0012
Pounds per gallon at 75°C 13.8
Viscosity, centipoises at 110°C 89
120°C 57
130°C 39.1
Specific heat, cal/g/°C at 41°C 0.258
95°C 0.260
Uniformity of toxaphene production. Toxaphene produced by
Hercules is regularly bioassayed and subjected to chemical and physical
tests lot-by-lot during the manufacturing process. The housefly is
a convenient test organism, although bioassay with other insects such
as plum curculio and Southern armyworm is also recommended to agencies
seeking standards of identity appropriate for specifying, purchasing
or evaluating toxaphene insecticides.
Recently, a series of nine samples from retained toxaphene produc-
tion manufactured by Hercules in the interval 1949-1970 was bioassayed
against female houseflies by the topical method. The laboratory toxa-
phene standard sample was used for comparison. Infrared absorption
spectra and electron capture gas chromatograms were also prepared. Re-
sults show that the toxaphene regularly produced by Hercules during
the past 23 years is quite uniform in its properties.
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12
Composition of toxaphene. A large number of chlorinated compounds
are present in toxaphene. A typical gas chromatogram suggests that 30
or 40 principal constituents may exist. The chlorine content in the
commercial product is limited to 67-69% since insecticidal activity
peaks sharply in that band.
Control of camphene feedstock quality and process variables is
important in achieving a material of uniform properties. Listed
previously are product specifications established by Hercules for
toxaphene produced by that manufacturer. The specification item of
infrared absorptivity at 7.2u helps distinguish toxaphene from other
chlorinated terpene products such as Strobane.
Toxaphene is prepared by the chlorination of the bicyclic terpene
camphene to contain 67-69% chlorine. The empirical formula for this
material is CL-H^Cl,,. Chlorination-grade camphene is prepared by the
isomerization of a-pinene, a product derived from the Southern pine
tree. Some tricyclene may accompany the camphene, but less than 5%
other terpenes are present.
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13
camplicnc
Structures of some of these perpenes are as follows:
(II) tricyclcne
(in)
o-pjncnc
(IV) cyclofenclicr.e
-fcuthcne
(VI) 0-fenchcnc
(VII) 7-fencliene .
(VIII)
bornvlcnc
dipctilene
C18
(X) toxaphene
(.XI) toxaphene according to Messing (3)
The structure X is commonly used to depict the structure of toxaphene.
The only published chemical structure that is more detailed than X is
that suggested by Messing (3), who proposed structure XI, though
•apparently with qualifications (1, 2).
Due to the complexity of the chemical reactions in the synthesis
of toxaphene,a large number of components is present in the product.
Separation of these components by a variety of means has been attempted.
A description of ^oBit >A these results J'.]]ov/s.
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14
Partition chromatography. A system of heptane on carbon and 90%
aqueous methanol was most useful in separating toxaphene components.
However, sharply defined peaks were not obtained. Melting points ranged
from 15°C to as high as 210°C, but none were sharp. Only slight differ-
ences in infrared absorption spectra were observed. Insecticidal
activity of v.arious fractions did not differ widely.
Fractional crystallization. A typical fractional crystallization
system applied to toxaphene utilized isopropanol solvent and carried
through 5 levels, combining mother liquors and crops to obtain addi-
tional fractionation. Five crops (3 crystalline and 2 non-crystalline)
were obtained. Melting points varied widely, but insecticidal activity
as measured by fly bioassay did not differ much. A summary of the
results is shown in Table 1.
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15
TABLE 1
Properties of Fractions from
Fractional Crystallization of Toxaphene
ZKill (Flies — Bell Jar)
Sample
Toxaphene
22
24
26
28
30
Melting Range
'
234-239°C
208-210°C
184-187°C
Noncrys t al 1 ine
semi solid
Viscous liquid
0.1% Cone.
AV. S. D.(b)
56(9) (a) 11.3
70(9) (a) 54
80(9) (a) 8.8
78(9) (a) 9.3
44(9) (a) 8.1
40 (9) (a) 8>3
0.05% Cone.
AV. S.
33 (8) (a)
39(8) (a)
40(8)(a)
40(8) (a)
29(8)00
22(8) (a)
D.(b)
16.1
8.1
11.8
11.4
13.4
7.5
(a) Numbers in parentheses are numbers of determinations.
(b)S.D. = standard deviation of test results.
Craig liquid-liquid separation. A 100-stage Craig liquid-liquid
extractor was used with solvent pairs that included isooctane-acetonitrile
isooctane-methyl cellosolve and isooctane-dimethyl formamide. The lack
of sharp peaks indicated isolation of individual components was not
obtained, but the broad spread of the resolved sample and the uneven
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16
contour of the Craig profile do indicate some separation. The biologi-
0
cal data for the indicated fractions are tabulated below. The system
isooctane-acetonitrile -concentrated about 10% of the sample in the most
polar phase, and the material was relatively nontoxic to flies.
Fractions separated in the system isooctane-methyl cellosolve were
tested individually. The results show material of lower toxicity to
be at both ends of the most polar-least polar spectrum. The fractions
between the extremes seem to approximate the toxicity of the middle
fractions of the isooctane-acetonitrile system.
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17
TABLE 2
Craig Countercurrent Fractionatlon of Toxaphene
Fraction No.
X9675-23-A
-B
-C
-D
-E
% of
Original
Sample
11.4
33.8
37.8
9.9
7.2
Toxaphene Standard
X9675-31-A
-B
-C
-D
-E
Tubes 5, 10,
Tube 45
Tube 85
Tube 125
Tube 185
Toxaphene Standard
% Fly Kill
at Indicated Concentration
Topical Application
0.6 mg
3
41
100
75
35
91
15 7
31
100
79
0
91
0.5 mg
0
22
100
54
3
81
0
22
97
63
3
57
0.4 mg
0
0
79
19
n
28
0
16
57
28
0
29
Solvent System
Isooctane-
Acetonitrile
Isooctane-Methyl
Cello solve
-------
18
REFERENCES
1. Donev, L. and Nikolov, N. I. (1965). Some Structural Changes During
Exhaustive Chlorination of Camphene and Bornylchloride. Zh. Prikl.
Khim. (USSR) 38, 2603. C. A. 64:3605h (1966).
2. V. Messing (1956). Khim Svedsta Zhaschitii Rasteni, 3, 70. This
journal is not listed in Chem. Abstracts or Current Contents.
No C. A. listing for V. Messing.
3. Nokolov, N. I. and L. D. Donev (1965). Relationships Between Content
of Bound Chlorine and Some Properties of Chlorinated Terpenes. Zh.
Prikl. Khim. 38. (3) 612, 617. C. A. 62:16302d (1965).
-------
19
METHODS OF ANALYSIS
Assay procedures (formulation analysis). The procedures for
toxaphene assays were described in two recently published books (17, 34),
and are based on the following technologies:
(1) Total chlorine method (metallic sodium reduction).
(2) Total chlorine method (sodium biphenyl reduction).
(3) Infrared spectrophotometry.
(4) Colorimetric spectrophotometry (diphenylamine-zinc chloride),
Total chlorine methods. In practice, an isopropyl alcohol solution
of the toxaphene sample is treated with metallic sodium; or a benzene
solution of the sample is reduced with sodium biphenyl reagent. The
liberated chloride is then titrated by the nitrobenzene modification of
the Volhard procedure. An alternate organic chlorine method for
toxaphene-sulfur dusts involves the liberation of chloride by the Parr
peroxide bomb method and the determination of chloride as above.
Infrared spectrophotometry. Toxaphene formulated as a dust, wettable
powder or emulsifiable concentrate may be assayed by Clark's (9) infra-
red method, which may also be used to measure toxaphene and DDT simul-
taneously. Concentrations of each component are read from calibration
curves prepared from CC1/-solutions of known toxaphene/DDT content, by
reading maximum and minimum absorbancies at 7.8y and 6.0y, respectively
for toxaphene and 9.ly and 5.8y for DDT.
I/ Contributed in part by F. J. Carlin, Hercules Res. Center
-------
20
Spectrophotometric method. Spectrophotometric methods may be used
to assay toxaphene formulations. The procedure of Graupner and Dunn
(20), which involves the development of a greenish-blue color by the
fusion of toxaphene with diphenylamine in the presence of zinc chloride,
has been applied to assay and residue analysis.
Two other methods were evaluated by Hercules. The colorimetric
procedure developed by Nikolov and Donev (32) using alkali and pyridine
to develop a reddish-brown color appears to be unsatisfactory because
of poor precision and accuracy. However, a procedure developed by
Hornstein (21) using thiourea and KOH to give a yellow color seems to
be satisfactory for toxaphene assay.
Assays for cattle dips. Total chlorine and infrared spectrophoto-
metric procedures were applied to the analysis of toxaphene in cattle
dips. Infrared procedures are more specific for toxaphene.
F. P. Czech (13) developed a rapid infrared method for toxaphene
in animal dips and sprays, which was based on the method by Clark (9).
The USDA also published a "Testing Procedure for Emulsifiable Concen-
trates of Toxaphene," which presented a compilation of total chlorine
and infrared procedures (41) applied to livestock dip analyses. In a
series of publications, Czech presented a rapid vatside test for toxaphene
and many chlorinated hydrocarbon insecticides (14, 16). The preferred
method (16) involved "salting-out" the insecticide, extracting it into
an organic solvent, removal of chlorine with sodium biphenyl reagent and
-------
21
coulometric titration of the chloride liberated. Using an automatic
coulometric titrator improved the precision of the analysis.
Both the total-chloride and colorimetric spectrophotometric methods
have been utilized for the analyses of toxaphene residues in agricultural
crops and foods. However, these methods suffer from non-specificity
(total chloride) and lack of sensitivity (total chloride and colori-
metric) . Infrared spectrophotometry has never achieved the required
sensitivity to become practicable for residue determinations.
Residue analyses for toxaphene. Until 1960, no analytical residue
methods for pesticides involved gas chromatographic techniques (11).
Thus, any pesticide residue data reported in the literature, at least
until 1960 , but more probably until 1963, were obtained by conventional
residue methods, e.g. spectrophotometry. This assumption must also be
made for toxaphene. The two methods of choice for residue analyses
of toxaphene until about 1963 were: total chlorine determination and
colorimetric spectrophotometric method.
As stated before, the total chloride method suffers from non-
specificity and the spectrophotometric from low sensitivity; both
methods require rigorous cleanup due to possible interferences from
plant or animal extractives.
Since about 1963, reported toxaphene residues in crops, foods,
tissues and other natural samples were probably obtained by gas chroma-
tography. Due to the heterogenous composition of toxaphene and
related chlorinated camphene products, these reports must be carefully
scrutinized. The inherent difficulty for toxaphene analysis is also
-------
22
shared by other chlorinated pesticides like Strobane and chlordane
and will be discussed in greater detail below.
In 1966, Archer and Crosby (1) described a pre-treatment of samples
suspected to contain toxaphene. This resulted in a gas-chromatographic
elution pattern more suitable for qualitative and quantitative deter-
mination of toxaphene residues than the multi-peak pattern of untreated
samples.
The treatment consisted of a partial dehydrohalogenation of
toxaphene by KOH in ethanol resulting in three major peaks emerging
sooner than DDE, the dehydrochlorinated product of DDT . This method
was modified by Hercules chemists and forms the basis of the recommended
method of toxaphene residue determinations.
Other ancillary techniques for residue determinations of toxaphene
are paper- and thin-layer chromatography, but these suffer from the
same diffuse patterns or multi-spots as the earlier gas chromatographic
technique.
Clean-up procedures. Two techniques are widely used to clean up
extracts for toxaphene residue analysis (35). Absorption chromatography
on Florisil permits removal of plant pigments and some waxes; also,
separation of toxaphene from a few chlorinated hydrocarbon insecticides
and most thiophosphate materials is accomplished by elution of toxaphene
with 6% (v/v) diethyl ether in hexane. Fats and oils are separated from
toxaphene by contact with concentrated sulfuric-fuming sulfuric acid
mixtures. 'A 1:1 mixture of the sulfuric acids is ground with Celite 545
-------
23
and packed into a chronatographic column. A hexane solution of the
fatty material is applied to the top of the column. Toxaphene is
eluted with hexane, while the sulfonated fats and oils are retained on
the column.
After nitration of extracts, DDT was removed as an interference
in toxaphene residue analysis (18). Also treatment with concentrated
sulfuric-fuming nitric acid mixtures did not alter the analytical
characteristics of toxaphene (23).
Two procedures for eliminating polychlorinated biphenyl (PCS)
interferences from chlorinated hydrocarbon insecticide residues were
evaluated. In a procedure by Reynolds (35), PCB's, along with
heptachlor, aldrin and DDE are eluted from Florisil with 200 ml of
hexane, but lindane, heptachlor epoxide, dieldrin, DDD and p,p-DDT
required 250 ml of 20% ethyl ether in hexane for complete elution.
The procedure by Armour and Burke (2) involved elution of PCB's
from a silicic acid/Celite 545 column with 250 ml of hexane, while DDT
and its analogs were eluted with 200 ml of a mixture of 1% acetonitrile
+ 19% hexane + 80% methylene chloride. Both procedures were applicable
to toxaphene; however, Reynolds' procedure is preferred. Armour and
Burke's procedure requires prior cleanup on a Florisil column, but
Reynolds' procedure is cleanup and separation on a single column.
Measurement of toxaphene residues may be accomplished by spectro-
photometric methods, total organic chlorine determinations, or
chromatography.
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24
Total Chlorine Methods
Schoniger Combustion
A procedure for the determination of toxaphene residues in animal
fat and butterfat involves combustion of the sample followed by
amperometric titration of the liberated chloride with silver nitrate
(22). Sensitivity of the method was 5 mg of toxaphene. Another
combustion procedure applicable to toxaphene was published by Lisk (28).
ii
The procedure involves combustion of the sample in a Schoniger flask
and spectrophotometric determination of chloride by displacement of
thiocyanate in the presence of ferric ion.
Zweig, at al (44) combined the Schoniger combustion method, following
fuming sulfuric acid treatment and amperometric titration of the liber-
ated Cl~ions to achieve an overall sensitivity of 0.02 ppm toxaphene in
whole milk. However, the "total organic chlorine" method is recommended
for samples of a known history, e.g. milk from cows fed known quantities
of toxaphene.
Active-Metal-Reaction Methods
. Sodium reduction techniques are widely used for residue analysis
of chlorinated hydrocarbons such as toxaphene. Phillips and DeBenedictis
(33) modified the sodium-isopropanol reduction method as applied to the
determination of chlorinated pesticides.
Liggett (27) and Chapman (8) used sodium biphenyl to determine
organic chlorine. Menville j^t ^. (29) and Koblitsky et^ _al. (25),
-------
25
utilized sodium dispersions for the decomposition of organic chlorine.
The latter method deals specifically with the detection of chlorinated
pesticides in animal fat.
The techniques preferred by Hercules for the determination of total
organic chlorine consist of a sodium-liquid ammonia decomposition method
followed by an amperometric titration using coulometrically generated
silver ions. The decomposition method is based on the work of Beckman
.eit_al. (3).
For quantitative measurement of the chloride resulting from any of
the above-mentioned techniques the automatic chloride titrator is
preferred, based on an instrument described by Cotlove (10) and sold
commercially by American Instruments Company, Silver Springs, Maryland,
or Buechler Instruments, Inc., 514 West 147th Street, New York 31, New
York.
This instrument has a silver coulometer to generate the reagent
and an amperometric end-point detecting system that automatically stop
the titration after the end point is reached. The time needed to complete
a titration is recorded on a built-in electric timer. This time is
easily related to chloride content of the sample.
Lisk (28) prefers the spectrophotometric determination of chloride
based on the displacement of thiocyanate from mercuric thiocyanate -in
the presence of ferric ion. The technique is suggested as an alternate
detection procedure for laboratories not equipped with the Cotlove
titrator.
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26
Spectrophotometric Method
The Spectrophotometric procedure (20, 17) is a moderately sensitive
method for qualitative and quantitative analysis. The greatest short-
coming of the method is the need for exhaustive cleanup because small
amounts of plant waxes develop colors and interfere with the detection
of toxaphene. The method may be used as a confirmatory technique,
however.
Klein and Link (24), in their studies on toxaphene residues on
kale compared residue data obtained by the diphenylamine method with
gas chromatography data. Agreement was good at residue levels about
10 ppm. Blank color formation was significantly reduced after treatment
of the crop extracts with a concentrated sulfuric-fuming nitric acid
mixture.
Paper Chromatography
Paper chromatography is used to detect and estimate chlorinated
organic pesticide residues (30). The limit of detection is about 0.2
micrograms of toxaphene, but chromatograms result in streaks (38).
Thin-Layer Chromatography
Thin-layer chromatography (TLC) resembles paper chromatography as
a technique, but provides the added advantages of greater speed, and
frequently, higher sensitivities.
The preferred TLC procedure is similar to that of Schechter (37)
and Moats (31). The TLC system employs layers of aluminum oxide and
the chromogenic agent, silver nitrate, added to the .absorbent when the
-------
27
TLC plates are prepared. The plates are spotted and developed in the
normal manner using hexane as the mobile phase. After solvent devel-
opment , the plates are exposed to UV light to reveal toxaphene at the
0.5 microgram level.
Gas Chromatography
Review of Methods
It became apparent from the first work on gas chromatography that
chlordane, Strobane and toxaphene resulted in at least seven peaks (12,
19) (See Fig. 1). Witt (43) tried to reduce these multi-peaks into
a single peak using a 1 1/4-ft-long column instead of the conventional
6-ft length. Using microcoulometry, 0.5 yg of toxaphene could be de-
tected at a retention time of less than 2 min (see Fig. 2).
This method was used to determine toxaphene levels in water,
aquatic plants and fish from lakes treated with toxaphene (40). Apparent
levels of toxaphene in untreated control samples ranged from an average
of 0.38 ppb in water to 0.55 ppm in fish. However, using a short gas
chromatography column decreases the resolution of toxaphene isomers
and related compounds as well as other commonly occurring pesticides.
Thus, absolute identification of single peaks is almost impossible.
To improve the method of identifying toxaphene residues by gas
chromatography, Bevenue and Beckman (3) fingerprinted toxaphene by three
major characteristic peaks on a 5% QF-1/Chromosorb-W column, eluting
after DDT, thus differentiating between DDT and toxaphene. The detecti-
bility of toxaphene with an electron-capture detection is claimed to be
-------
28
2 ng under ideal conditions but more usually 5-7 ng. To stress the
limitation of this method, these authors state,
".... the pesticide residue chemist has been placing
increased reliance on gas chromatographic data for the identifi-
cation of a pesticide residue. In the examination of a sample
for toxaphene residue, such data are not reliable, either
qualitatively or quantitatively. In particular, when state or
other regulatory agencies may wish to examine a shipment of
produce suspected of excess toxaphene residue, the use of gas
chromatography data alone for the basis for legal actions is an
invitation for criticism and rebuttal.
"We believe the same thesis could be applied to the compounds
chlordane and Strobane. Until it can be shown by some new, and
presently unknown, technique that toxaphene can be unequivocally
identified, the gas chromatographic procedure for the determina-
. tion of toxaphene, alone or in combination with other pesticides,
is at best highly questionable. Further investigation into the
'3-peak1 phenomena at the latter part of the gas chromatographic
curve may possibly produce a definitive fingerprint." (See Fig. 3)
Gaul (19) has recommended the planimetry of the last four peaks as
a quantitative measurement of toxaphene in the presence of DDT. If
Kelthane is present, superimposing a toxaphene standard at about the
same concentration as the unknown sample will correct the situation.
-------
29
The last four peaks of a toxaphene chromatogram are not always
observed, and samples containing toxaphene should be treated with con-
centrated sulfuric acid - fuming nitric acid (18). The acid treatment
does not appreciably alter toxaphene and chlorinated camphene, but it
effectively removes residues of DDT, aldrin, heptachlor, Kelthane,
Perthane, Tedion, Telodrin and Trithion (23).
Archer and Crosby (1) measure chromatogram quantities of toxaphene
in milk, fat, blood and alfalfa hay with a simple alkali treatment
for cleanup, partial dehydrohalogenation, and electron capture gas
chromatography on a column of 5% DC-710 silicone oil and 5% silicone oil
and 5% SE-30 at 200 C. They used a single modified toxaphene peak
eluting at 3.50 min for quantitative analysis and qualitative identifi-
cation. This peak has a shorter retention time than the modified peaks
of the DDT group (DDE and related compounds) commonly present in
samples (see Fig. 4),
2/
Recommended Procedure
The recommended method for the residue analysis of toxaphene involves
a sulfuric acid-Celite 545 column cleanup followed by dehydrohalogenation
and gas chromatography, which is a modification of the work of Archer
and Crosby. The sulfuric acid column removes fats and oils, and the
dehydrohalogenation gives a characteristic, reproducible pattern for
dehydrohalogenated toxaphene.
21 Carlin, F. J. Jr., Hercules Inc. (1970)
-------
30
' The sample to be analyzed is dissolved in a small amount of
n-hexane and passed through a H?SO.-Celite column with 100 ml of re-
distilled n-hexane. The hexane is evaporated and the sample treated
with ethanolic 25% KOH at 75-80° for 15 min. The reaction mixture is
diluted with water and extracted with 0.5 ml n-hexane. Aliquots of the
hexane layer are gas-chromatographed.
Gas chromatography is performed on a 9-ft. x 1/8 in. column, 1:1
mixture 5% SE-30, 5% DC-710 silicone oil on (100/120) Gas Chrom Q;
column temperature 200-210 ; electron capture detector. Column condition-
ing for 2 days at 250° is highly recommended. The area of major peak of
dehydrohalogenated toxaphene eluting at about 4.5 min or the entire
trace is measured by triangulation and used for quantitative analysis.
If additional cleanup of sample is needed, this can be done by
Florisil chromatography, toxaphene eluting with the "6% ethyl ether in
petroleum ether" fraction.
Thirty nanograms of toxaphene produced 80% of full-scale deflection
with .a 1 mv-recorder (1).
Recommended gas chromatographic conditions for unmodified toxaphene
are the following: 5 ft. x 1/8 in. - glass column packed with 3.8%
UCW-98 on Diataport S (80/100 mesh); column temperature 150°C; carrier
gas (N ) flow - 45 ml/min.
Discussion of Analytical Methods and Reported Data
The analysis of toxaphene by gas chromatography shows that due to
the heterogeneity of the compound, a definite identification of toxaphene
-------
31
by distinct peaks or fingerprints is unsatisfactory. Chemical modifica-
tions by acid-treatment and/or dehydrohalogenation result in a distinct
improvement of the elution pattern. Samples with a known spray history
can be analyzed by most of the analytical methods described above
o
including total chlorine, spectrophotometric and gas-liquid chromatog-
raphy.
However, environmental samples of soil, water, air, fish and
wildlife and human specimens, which have been analyzed for chlorinated
pesticides by gas-liquid chromatography without prior chemical treatment
cannot be unequivocally analyzed for toxaphene residues.
For example, Burke and Giuffrida (7) report the retention times,
relative to aldrin, of the major peaks of toxaphene on 10% DC200 at
200° and a carrier gas flow of 120 ml/min, to be:
2.34; 3.06; 3.61; 4.51 (Aldrin = 1.00)
Under the same conditions DDD has a relative retention time of 2.33
and p,p'-DDT, 3.03. Gaul (19) illustrates that methoxychlor has the
same retention time as one of the major peaks of toxaphene (No value
is given, but it is possibly the 4.51 min peak quoted by Burke and
Giuffrida, 7).
An attempt, therefore, was made to evaluate reports of the presence
or absence of toxaphene residues in natural samples of unknown spray
history in order to make a judgment of the validity of the reported
findings. Some of these reports are summarized in Table 1.
-------
32
Table 1 does not give detailed summary of toxaphene residues found
in crops, tissues or food, but rather illustrates the gas chromatog-
raphic technique used and the apparent success to analyze for toxaphene
with a high degree of certainty. Of the 10 examples chosen on the
basis of "toxaphene" in the title and published during the past 10
years, only one author, Archer (1) uses the chemical pre-treatment
method. All other reports on toxaphene residues cited in Table 1 rely
on the multipeak phenomenon of toxaphene and some authors (examples 3,
5, 8, 9, Table 1) actually state their inability to identify toxaphene
due to the complexity of the GLC elution pattern.
Conclusions on Analytical Techniques
and Evaluation of Residue Data
1. Any samples for the analyses of toxaphene should use from hereon
the recommended method involving acid clean-up and partial
dehydrochlorination prior to GLC.
2. Past reports on the monitoring of toxaphene should be scrutinized
for statements of sensitivity of method and any special pre-
treatment of samples prior to analysis. In future work on toxaphene,
explicit statements concerning lower limits of detection based on
fortified samples must be included.
3. While the modified GLC method for toxaphene is superior to
previously reported general GLC, it is subject to additional
improvement for specificity and sensitivity. Research along these
lines is encouraged.
-------
33
4. It would be highly useful to re-examine where possible, retained
samples, as for example environmental samples, by the improved
GLC clean-^up procedure for toxaphene and to verify previously
• reported results.
5. Decline and feeding studies with a known treatment history must
be considered to be reliable by whatever recognized analytical
techniques were employed, including total-chlorine, spectrophoto-
metric or "GLC-no treatment" methods.
-------
34
TABLE 1
Summary of Reported Toxaphene
Residues by GLC
Sample
Ladino clover seeds
1 Ib/A DDT; 2 Ibs/A toxaphene;
May 25, 1965
1.5 Ib/A DDT; 3 Ibs/A toxaphene;
1.5 Ib/A Aramite; July 5, 1965
Analyzed in May 1966
Ladino clover seeds (unknown
history)
Ladino clover seeds (unknown
history)
Kale, 2 Ibs/A toxaphene
Days after application: 0
3
7
14
' 21
28
Toxaphene
residue
(ppm)
65.7
16.0
6.3
155.0
44.3
16.9
1.4
0.3
0
Method of
analysis
GLC - dehydro-
chlorination
do. :
do.
GLC-EC
(no treatment)
(Area of 3
major peaks)
Lit.
Reference
(1)
do.
do.
(24)
3- 101 commercial animal feeds
containing 87 dairy feeds
or supplement;
15 samples were positive
Oysters, 133 samples
6 positive samples
Milk
6- Drinking water
7. Air samples
0.06-0.53(a)
med. 0.08
(b)
None detected
(c)
2520 ng/m
(c)
GLC-EC
(no treatment) (30)
GLC-EC (6)
(no treatment)
GLC-EC
(no treatment)
GLC-EC (36)
(no treatment)
GLC-MC (39)
-------
TABLE 1 (Cont'd)
35
Sample
Toxaphene
residue
(ppm)
Method of
analysis
Lit.
Reference
8. Apples, broccoli, cabbage,
grapes, lettuce, tea,
carrots, potatoes, cabbage
9. Fish tissue
10. Cows fed 15 mg/kg of toxaphene
for two weeks
I
Whole milk
butter
cheddar cheese
dry whole milk
-(d)
(e)
25.3 (av.)
27.9
28.1
24.9
GLC-EC
(no treatment)
a. GLC-EC
b. Clean-up, TLC
IR
GLC-EC
(no treatment;
measure 3
major peaks)
(5)
(26)
(a) Authors state that presence of toxaphene is somewhat uncertain and the
presence of toxaphene must be inferred from the general shape of the
chromatogram; the larger values are probably more reliable.
(b) Authors state that toxaphene and Strobane could not be calculated.
(c) Less than 2.5 ppb.
(d) • Authors state that chlordane and toxaphene could not be detected because
of their multi-component nature.
(e) Authors state that the infrared spectrum of toxaphene was not clear for
positive identification at a level of 50 yg or 2.5 ppm.
MC =.microcoulometry
EC = electron capture
-------
36
FIG. 1 Typical gas chromatogram of toxaphene (10%
DC-200 on Anakrom ABS (90/100; Tritium electron capture
detector; Column temp. 200°C; 125 ml/min nitrogen
carrier gas) (19).
-------
37
Millivolts
6
5
A- .
1 0 2
Retention Time in M.mutei
A
A - 1.C2
Intcfrslion
cf A; el
Millivolts
5
4
3
?
1
0
A
4.i (iiicrciumv Tcuphfnc
0 1 4 6 8 10 12 14 16 18 20 22 24 K K 30 32 34
Retention Tin* in Minulrc
B
Area in
Square Inches
2.0
0.$
1.0
Merogumj Touphrne
C
1.5
2.0
FIG. 2 Toxaphene analysis by gas-liquid chromatography
and microcpulmometry (43).
A, 1 1/2-foot column; B, 6-foot column; C, standard
curve of toxaphene.
-------
38
FIG. 3 Electron capture detector responses to: A-7 ng
toxaphene, B-2.8 ng DDT, C-7 ng, toxaphene + 3.5 ng DDT (3)
COLUMN:
4' x 1/4" with 5% QF - 1 on Chromosorb - W.
-------
39
O
16 14
12 , 10 8 6
Mlnutos
FIG.' 4 Gas chromatogram from 30 ng. of toxaphene (A)
before alkali treatment and after alkali treatment (B).
GLC conditions: 9' x 1/8" S.S. column mixed packing: 5%
DC 710 and 5% SE-30 on chromosorb W (HMDS-treated) 12" section
packed with CaC (20/30). Col. temp. 200° Nitrogen gas flow:
40-60 ml/min (1).
-------
40
REFERENCES
1. Archer, T. C. , and Crosby, D. G. (1966). Gas chromatographic
measurement of toxaphene in milk, fat, blood and alfalfa hay.
Bull. Exp. Cont. and Toxic. 1: 70.
2. Armour, A., and Burke, A. (1970). Method for separating poly-
chlorinated biphenyls from DDT and its analogs. J. of A.O.A.C.,
53, (4): 761-768.
3. Beckman, H. F., Ibert, E. R., Adams, B. B., and Skoolin, D. 0.
(1958). Determination of total chlorine in pesticide by reduction
with a liquid anhydrous ammonia-sodium mixture. J. Agri. and
Food Chem. 6: 104.
4. Bevenue, A., and Beckman, H. F. (1966). The examination of
toxaphene by gas chromatography. Bull. Environ. Contain. Toxicol.
1: 1.
5. Boyle, H. W. , Burttschell, R. H., and Rosen, A. R. (1966).
Infrared identification of chlorinated insecticides in tissues
of poisoned fish. Chem. Ser., 207-218 pp.
6. Bugg Jr., J. C., Higgins, J. E., Robertson Jr., E. A. (1967).
Residues in fish, wildlife, and estuaries. Pesticides Monitoring
Journal 1 (3): 9.
7. Burke, J., and Giuffrida, L. (1964). Investigation of EC gas
chromatography for the analysis of multiple chlorinated pesticide
residues in vegetables. J. Assoc. Offie. Anal. Chem. 47: 326.
8. Chapman, F. W., and Sherwood, R. M. (1957). Spectrophotometric
determination of chloride, bromide and iodide. Analytical
Chemistry, 29: 172.
9. Clark, W. H. (1962). Infrared analysis of insecticides to determine
toxaphene alone or in the presence of dichlorodiphenyltrichloroethane
(DDT). J. Agr. Food Chem. 10: 214.
10. Cotlove, E., Trantham, H. V., and Bowman, R. L. (1958). An instru-
ment and method for automatic, rapid, accurate, and sensitive
titration of chloride in biologic samples. J. of Laboratory and
Clinical Medicine 51: 461.
11. Coulson, D. M., Cavanagh, L. A., and Stuart, J. (1959). Gas
chromatography of pesticides. J. Agri. and Food Chem. 7: 250.
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41
References (cont'd.)
12. Coulson, D. M. (1962). Gas chromatography of pesticides. Adv.
Pest Control Res. (ed. by R. L. Metcalf) Interscience, 153-190 pp.
13. Czech, F. P. (1964). Rapid infrared method for toxaphene in
animal dips and sprays. J. Assoc. Offie. Agr. Chem. 47: 591.
14. Czech, F. P. (1965). Rapid quantitative vatside check test for
chlorinated hydrocarbons in aqueous emulsions: toxaphene and
lindane. J. Assoc. Offie. Agr. Chem. 48: 334.
15. Czech, F. P. (1965). Rapid quantitative vatside check test for
chlorinated hydrocarbons in aqueous emulsions: methoxychlor,
DDT, dieldrin, and chlordane. J. Assoc. Offie. Agr. Chem. 48:
1121.
16. Czech, F. P. (1968). Rapid analysis of malogenated organic
insecticides in aqueous animal dips, using sodium biphenyl.
J. Assoc. Offic. Agr. Chem. 51: 568.
17. Dunn, C. L. (1964). Toxaphene in analytical methods for pesticides,
plant growth regulators and food additives, Vol. II (G. Zweig,
ed.) 523-543 pp. Academic Press.
18. Erro, F., Bevenue, F. , and Beckman, H. F. (1967). A method for
the determination of toxaphene in the presence of DDT. Bull.
Environ. Contain. Toxicol. 2: 372.
19. Gaul, J. A. (1966). Quantitative calculation of gas chromato-
graphic peaks in pesticide residue analyses. J. Assoc. Offic.
Anal. Chem. 49: 389.
20. Graupner, A. J., and Dunn, C. L. (1966). Determination of
toxaphene by a spectrophotometric diphenylamine procedure. J. Agr.
Food Chem. 8: 286.
21. Hornstein, I. (1957). Colorimetric determination of toxaphene.
J. Agr. Food Chem. 5: 446.
22. Hudy, J. A., and Dunn, C. L. (1957). Determination of organic
chlorides and residues from chlorinated pesticides by combustion
analysis. J. Agr. Food Chem. 5: 351.
-------
42
References (cont'd)
23. Kawano, H., Bevenue, A., Beckman, H. F., and Erro, F. (1969).
Studies on the effect of sulfuric - fuming nitric acid treatment
on the analytical characteristics of toxaphene. J. Assoc. Offie.
Anal. Chem. 52: 167.
24. Klein, A. K., and Link, J. D. (1967). Field weathering of toxaphene
and chlordane. J. Assoc. Offie. Anal. Chem. 50: 586.
25. Koblitsky, L. , Adams, H. R., and Schechter, M. S. (1962). A
screening method for the determination of organically bound chlorine
from certain insecticides in fat. J. Agri. and Food Chem. 10:
2-3.
26. Li, C. F., Bradley Jr., R. L., and Schultz, L. H. (1970). Fate of
organo chlorine pesticides during processing of milk into dairy
products. J. Assoc. Offie. Anal. Chem. 53: 127.
27. Liggett, L. M. (1964). Determination of organic halogen with
sodium biphenyl reagent. Analytical Chemistry, 26: 74'8.
28. Lisk, D. J. (1960). Rapid combustion and determination of residues
of chlorinated pesticides using a modified schoniger method. J.
Agri. and Food Chem. 8: 119.
29. Menville, R. L. and Parker, W. W. (1959). Determination of organic
halides with dispersed sodium. Analytical Chemistry, 31: 1901.
30. Mills, P. A. (1959). Detection and semiquantitative estimation
of chlorinated organic pesticide residues in foods by paper
chromatography. J. Assoc. Official Agr. Chem. 42: 734.
31. Moats, W. A. (1966). Analysis of dairy products for chlorinated
insecticide residues by thin layer chromatography. J. Assoc.
Offie. Agr. Chem. 49: 795.
32. Nikolov, N. I., and Donev, L. D. (1963). A photometric method
for the determination of polychloroterpenes. Zh. Analit. Khim. 18,
532; CA 59, 4494.
33. Phillips, W. F., and DeBenedictis, M. E. (1959). Sodium reduction
technique for microdetermination of chlorine in organic insecti-
cides. J. Agr. and Food Chem. 2: 1226.
34. Raw, G. R. (1970). CIPAC Handbook, Vol. I - Analysis of technical
and formulated pesticides, publ. by Collaborative International
Pesticides Analytical Council Ltd. 132-170 pp.
-------
43
References (cont'd.)
35. Reynolds, L. M. (1969). Polychlorobiphenyls (PCB's) and their
interference with pesticide residue analysis. Bull. Environ. Contain.
Toxicol. 4: 128.
36. Schaffer, M. L., Peeler, J. T., Gardner, W. S., and Campbell,
J. E. (1969). Pesticides in drinking water - waters from the
Mississippi and Missouri Rivers. Environ. Sci. and Tech. 3: 1261.
37. Schechter, M. S. Comments on pesticide residue situation. J. of
A.O.A.C., 46, (6): 1063-9.
38. Sherma, J., and Zweig, G. (1971). Paper Chromatography. Vol. II
of Paper Chromatography and Electrophoresis. Academic Press p. 359.
39. Stanley, C. W., Barney II, J. E., Helton, M. R. and Yobs, A. R.
(1971). Measurement of atmospheric levels of pesticides. Envir.
Sci. and Tech. 5: 431.
40. Terriere, L. C., Kiigemagi, U., Gerlach, A. R., and Borovicka,
R. L. (1966). The persistence of toxaphene in lake water and its
uptake by aquatic plants and animals. J. Agr. Food Chem. 14: 66.
41. U. S. Department of Agriculture, Agr. Research Service Publ.
TSC-0264 (June 1964).
42. U. S. Department of Health, Education and Welfare, Food And Drug
Administration, Pesticide Analytical Manual, Volume 1, Second
Ed., 1968.
43. Witt, J. M., Bagatella, G. F., and Percious, J. K. (1962).
Chromatography of toxaphene using a shortened column. SRI
Pesticide Res. Bull. 2: 4.
44. Zweig, G., Pye, E. L., Sitlani, R., and Peoples, S. A. (1963).
Residues in milk from dairy cows fed low levels of toxaphene in
their daily ration. J. Agr. Food Chem. 11: 70.
-------
44
FATE AND IMPLICATION IN THE ENVIRONMENT
EFFECTS ON FISH AND WILDLIFE
Toxieity and Pharmacological Actions
Acutely toxic doses of toxaphene administered to birds produced
symptoms similar to those observed with other chlorinated hydrocarbon
insecticides. The symptoms consisted of ataxia, goose-stepping
ataxia, circling, low or high carriage, ptosis of eyelid, tremors,
phonation, tenesmus, hyperthermia, wing-beat convulsions or opisthotonos.
In some species of birds, symptoms were observed within 20 min;
however, mortality usually took 2 to 14 days (22).
Acute toxicity of toxaphene was measured in several species of
mammals, amphibia, birds, fish and invertebrates (21). In general,
toxaphene exhibited a higher acute toxicity to fish and wildlife than
DDT (Table 1).
Some feeding studies on quail and pheasant indicated an adverse
effect on reproduction. Additional studies were conducted at the
Patuxent Wildlife Research Center, Laurel, Maryland. However,
tabulated results are not available.
Persistence of Toxaphene
The length of time that a pesticide will persist varies and
depends on diverse factors such as temperature, rainfall, absorption,
pH, microbiological populations and exposure to UV. Although toxaphene
-------
45
apparently dissipates rapidly from crops in a few days, in soil this
may vary from several months to more than 10 years; and variations up
to 9 years were seen in lakes and ponds (10, 11, 12, 17, 21).
Residues
Analyses for toxaphene,are limited, probably due to lengthy and
time-consuming procedures involved. In fish monitoring studies con-
ducted by the Bureau of Sport Fisheries and Wildlife (8), toxaphene
was found at low levels (0.01-1.25 ppm) in fish taken in Maine, New
Jersey, Pennsylvania, South Carolina, Louisiana, Arkansas, Arizona
and Utah.
In soil monitoring studies conducted by the U.S.D.A. (20), toxaphene
was also observed in some samples. However, analyses for toxaphene
were conducted only on a small number of the collected samples. Tox-
aphene analyses in birds, eggs, fish and reptiles are summarized in
Table 2.
Analyses of catfish from fish farmers were conducted by the Bureau
of Sport Fisheries and Wildlife at the Fish Pesticide Research Laboratory,
Columbia, Missouri. Toxaphene residues in catfish fillet ranged from
0.3 ppm to 8.0 ppm; in mature channel catfish fat, 6-60 ppm (Av. 30);
and in ovaries, N.D. to 3 ppm (Av. 1.8) (7).
Summary and Comments
After some initial testing, the Bureau of Sport Fisheries and
Wildlife concluded that toxaphene should not be used as a pisciscide.
It is toxic to fish and wildlife and may persist for extended periods,
-------
sometimes preventing the re-stocking of waters for several years. In
waters treated with toxaphene, aquatic plants, benthic invertebrates
and fish accumulate toxaphene. Fish may accumulate in their tissues
several parts per million of toxaphene as long as a year after the
treated waters are no longer toxic.
Monitoring studies indicate that toxaphene may be adsorbed to soil
particles and carried into rivers. The mortality of fish-eating birds
at the Tule Lake and Lower Klamath Refuges was associated with residues
of toxaphene and other chlorinated hydrocarbons. Some birds were
found dead after toxaphene was used in some Nebraska lakes and in
Montana to control grasshoppers.
Research indicates that toxaphene "half-life" in soil may vary
from 3-10 years; and in water, up to 6 years. The data also indicate
that toxaphene can undergo bio-magnification, although to a lesser de-
gree than most hydrocarbon pesticides.
Analysis of fish and wildlife tissues for toxaphene residues is
most difficult and time consuming. Few laboratories can or are will-
ing to undertake the task of analyzing large numbers of samples for
toxaphene. This probably accounts for the fact that quantitative data
for toxaphene is meager. Data for monitoring studies is sometimes con-
flicting and inadequate.
Improved sensitive analytical procedures, capable of screening
many compounds, are needed for analysis of fish and wildlife tissues.
Information is also needed in respect to the effects of toxaphene on
-------
47
the reproduction of birds. These should be available soon at the
Patuxent Wildlife Research Center.
Beyond the fact that toxaphene toxicity dissipates in the environ-
ment, and that lakes and ponds become habitable for fish after
toxaphene treatment, we have no significant information concerning the
metabolism or degradation of toxaphene in the environment — neither
physiological nor chemical data. The void created by this situation
must be filled.
-------
48
TABLE- 1
Toxaphene Residues
Organism
Toxaphene
Common Name
Bullhead, black
Carp
Minnow, fathead
Goldfish
Sunfish
Bass, largemouth
Perch, yellow
Catfish, channel
Minnow, sheepshead
Spot
Bluegill
Trout, rainbow
Killifish, longnose
Mullet, striped
Salmon, coho
Salmon, chinook
Trout, brown
Scientific Name
48 hr LC (a) (ppm)
Ictalurus melas
Cyprinus carpio
Pimephales promelas
Carassius auratus
Lepomis cyanellus
Micropterus salmoides
Perca flarescens
Ictalurus punctatus
Cyprenodon Variegatus
Leiostomus xanthurus
Lepomis Macrochirus
Salmo Gairdneri
Fundulus similis
Mugil cephalus
Oncorhynchus kisutch
Oncorhynchus tshawytscha
Salmo trutta
0.005
0.0053
0.019
0.014
0.018
0.0051
0.018
0.0172
0.007
0.0032
0.014
0.014
0.028 (24 hr)
0.0032
0.012
0.008 (96 hr)
0.0084
Toad, Woodhouse's
Frog, n rthern chorus
Bufo woodhousi
Pseudacris triseriata
0.29
0.7
Oyster, eastern
Shrimp, brown
Shrimp, pink
Shrimp, glass
Shrimp, grass
Shrimp, Korean
Daphnia
Flea, water
Scud
Scud
Stoneflies
Stoneflies
Stoneflies
Damselflies
Crassostrea virginica
Peneus aztecus
Peneus duorarum
Palemonetes kadiakensis
Palemonetes pugio
Palemonetes macrodactylus
Daphnia pulex
Daphnia serrulatus
Gammarus fasciatus
Gammarus lacustris
Pteronareys californica
(Newport)
Clossonia sabulosa (Banks)
Pteronarcella Bodia (Hagen)
Ischmura verticalis
0.02 (96 hr)
0.0027
0.0042
0.006
0.0052
0.037
0.015
0.01
0.022
0.07
0.007
0.0032
0.0056
0.086
(a) These values may vary with temperature, pH, water hardness or the
pesticide formulation itself.
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49
TABLE 1 (CONT.)
Sex
Age
LD50(mg/Kg)*
Mallard ducklings
Mallards
Pheasants
Bobwhite quail
Sharp-tailed grouse
Fulvous tree ducks
Lesser sandhill cranes
Domestic goats
Mule deer
„
9.
9
0*
0"
0"
o
&
cf
7 days + 1
3-5 mo.
3 mo.
3 mo.
1-4 yr.
3-6 mo.
—
>5 yr.
16—17 mo.
30.8 (23.3-40.6)
70.7 (37.6-133)
40.0
85.4 (59.2-123)
10-20
99.0 (37.2-264)
100-316
>160
139-240
*95% conf. lim.
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TABLE 2
TOXAPHENE RESIDUES IN WILD BIRD TISSUES
Species
Tissues Analyzed(a) No. of Analyses
Range or Average of
Residues found in
ppm
Reference
Grebe, Western Fat
Aechmophorus occidentalis WB
1960 Carcass
1960 Fat
Gull, Ring-Billed
Larus delawarensis
Fat
5 analyses
8 analyses
6 analyses
2 analyses
1 analysis
0.0-39.0 Av. 12.66
0.0-0.8 Av. 0.02
Av.0.3
Av.31.5
4.8
16
16
14
14
16
Heron, Black-Crowned Night
Nycticorax nycticorax WB?
WB
1961 Carcass
WB found dead
Heron, Great Blue
Ardea herodias
Killdeer
Charadrius vociferus
Kingbird, Western
Tyrannus verticalis
Lark, Horned
Eremophila alpestris
Meadowlark, Western
Sturnella neglecta
WB
WB
Carcass
WB
WB found dead
WB young
WB sacrificed
WB found dead
WB found dead
WB
WB young
No. not given Up to 5.0
3 analyses 0.0-15.0 Av. 5.0
1 analysis 15.0
1/1 . 64.0
1/1
1/1
1/1
2/2
1/1
1/1
4/4
3/3
3/3
2/2
3/3
10.0
10.0
10.0
6.0
9.6
4.0
0.41-0.96 Av. 0.7
Tr., 2.5. 3.3
Tr.,Tr., 0.6
13.0
3.0
15
16
14
14
2
16
14
14
9
14
9
9
9
14
14
Ul
o
(a) WB-whole body; L-liver; K-kidney; H-heart; BM-breast muscle
-------
Species
TABLE 2 (CONT.)
TOXAPHENE RESIDUES IN WILD BIRD TISSUES
Tissues Analyzed (a) No. of Analyses
Range or Average
of Residues found
in ppm
Reference
Blackbird, Brewer's
Euphagus cyanocephalus
Coot, American
Fulica americana
Cormorant, Double-Crested
Phalacrocorax auritus
Cowbird, Brown-Headed
Molothrus ater
Dove, Mourning
Zenaidura macroura
Duck, Mallard
Anas...platyrhnchose
Duck Shoveler
Spatula clypeata
Egret , Common
Casmerodius albus
Grebe, Eared
Podiceps caspicus
WB found dead
WB found dead
WB
Carcass found dead
WB found dead
WB found dead
WB found dead
WB found dead
WB
Carcass
WB
WB
1/1
1/1
2/2
1/1
1/1
1/1
1/1
1/1
1/1
3 analyses
4 analyses
5 samples
5.0
17.0
2.2-9.5 Ave. 5.8
9.5
0.98
Tr.
10.0
12.0
17.0
Av. 9.2
0.0-17.0 Av. 6.92
0.0-4.0 Av. 1.9
14
14
16
14
9
9
14
14
2
14
16
16
(a) WB Whole body; L-liver; K-kidney; H-heart; BM-breast muscle
-------
TABLE 2 (CONT.)
TOXAPHENE RESIDUES IN WILD BIRD TISSUES
Range or Average
of Residues found
Species
Pelican, White
Pelecanus ervthrorhynchos
1960
1960
1960
1961
Phalarope, Wilson's
Steganopus tricolor
Sandpiper
Sp. not given
Shrike, Loggerhead
Lanius ludovicianus
Teal, Blue-Winged
,_Anas discors
Wren, House
JTroglodytes aedon
Tissues Analyzed (a)
L ^--1 bird
K )
L 2--1 bird
K )
1/2 bird (
L 1 bird -
K (
H,L,K,BM
L
K
Carcass
L
K
H,L,K,BM
WB found dead
WB found dead
WB sacrificed
WB
WB
No. of Analyses
1/1
1/1
1/1
49 analyses
3 analyses
3 analyses
1 analysis
3 analyses
3 analyses
12 analyses
4/4
1/1
1/1
3/3
2/2
in ppm
8.0
13.0
9.0
14.0
4.0
7.0
0.0-82.0 Av. 3.6
7.0-9.0 Av. 8.0
4.0-14.0 Av. 10.33
4.0
8.0
10.3
7.6
41.0
10.0
Tr.
7.0
41.0 -
Reference
2
2
2
2
2
2
2
16
16
16
13
13
13
13
13
14
14
9
14
14
(a) WB-wliole body; L-liver; K-kidney; H-heart; BM-breast muscle
-------
TABLE 2 (CONT.)
TOXAPHENE RESIDUES IN WILD BIRD TISSUES
Species
Tissues Analyzed
No. of Analyses
Range or Average
of Residues found
in
ppm
Blackbird, Red-Winged
Agelaius phoeniceus
Fat, B, K, L, H 1
Gizzard, m )
Not given
Tr. in all tissues
Reference
Pelican, White
Pelecanus erythrorhynchos
Lark, Horned
Eremophila alpestris
Shrike
Lanius ludovicianus
H,L,K,M
WB?
WB?
WB?
Not given
4 shot
7 found dead
1 shot
82.0
0.7
Tr. 9.6
0.7
• 22
22
22
22
Ln
U>
-------
TABLE 2 (CONT.)
TOXAPHENE RESIDUES IN WILD BIRD TISSUES
Species
Cormorant, Double-Crested
Phalacrocorax auritus
Duck, Gadwall
Anas strepera
Gull, Ring-Billed
Larus delawarensis
Pelican, White
Pelecanus erythrorhynchos
Tern, Forster's
Eggs Analyzed
Yolk
Yolk
Yolk
Egg
Yolk
No. of Analyses
2 analyses
5 analyses
1 analysis
22 analyses
1 analysis
Range or Average of
Residue found in
ppm
10.0
Av. 0.04
0.2
0.0-6.7 A. 0.39
15.5
Reference
16
16
16
16
16
Sterna forsteri
-------
TABLE 2 (CONT.)
TOXAPHENE RESIDUES IN FISH AND REPTILES
Range or Average of
Residues found in
Species
Bass, Largemouth
Micropterus salmoides
Bluegill
Lepomis macrochirus
Bullhead, Black
Ictalurus melas
Bullhead, Brown
Ictalurus nebulosus
Carp
Cyprinus carpio
Catfish, Channel
Ictalurus pjanctatus
Crappie, Black
Pomoxis nigromaculatus
Chub, Tui
Siphateles bicolor
Fish
Sp. not given
Pumpkinseed
Lepomis gibbosus
Tissues Analyzed
Flesh
Viscera
WB?
WB
Flesh
Flesh
Viscera
WB?
Fat
WB
WB
WB
WB
No. of Analyses'
13 analyses
8 analyses
22 analyses
89 analyses
3 analyses
1 analysis
2 analyses
27 analyses
8 analyses
3 analyses
29 analyses
Not given
1 analysis
ppm
0.0-0.3 Av. 0.05
0.2-2.0 Av. 1.13
0.0-2.06AV. 0.48
0.37-15-2
0.0-0.19 Av. 0.6
0.1
0.0-0.1 Av. 0.05
0.0-6.6 Av. 2.23
0.4
0.0-0.1 Av. 0.03
0.0-8.0 Av. 1.09
Tr.8.0
0.04
Reference
16
4
12
16
16
16
4
16
16
16
14
16
Ol
Ul
Fish
30 analyses
0.1-10.9 (8 samples)
19
-------
TABLE 2 (CONT.)
TOXAPHENE RESIDUES IN FISH AND REPITLES
Species
Tissues Analyzed
No. of Analyses
Range or Average of
Residues found in
ppm
Spot
Leiostomus xanthrus
Trout, Brown
.Salmo trutta
Juvenile (No mor-
tality but thickened
gill lamallae at 0.1
and 0.01 ppb)
Juvenile (50% mor-
tality within 6 days at
0.5 ppb)
Trout, Rainbow
Salmo gairdneri
(1962)
(1963)
(1964)
Turtle, Softshell
Trionyx spinifer
Tissue extract
Whole Body
Tissue extract
Tissue extract
Tissue extract
Whole body
Flesh
Viscera
5+ analyses
37 analyses
6 or more analyses
6 or more analyses
6 or more analyses
5/5
19 analyses
1 analysis
Reference
Salmon, Atlantic (1962
Salmo salar (1963)
(1964)
Shad, Gizzard
Dorsoma cepedianum
Tissue extract
Tissue extract
Tissue extract
Whole body?
2 analyses
2 analyses
2 analyses
17 analyses
2.6-2.9 Av. 2.75
1.11-5.5 Av. -3.24
1.5-2.1 Av. 1.8
0.0-4.75 Av. 1.49
21
21
21
4
8.3-24.8 Av. 12.46
0.43-5.4
1.2-12.0 Av. 5.7
2.75-13.7 Av. 7.72
3.2-3.8 Av. 3.5
0.13,0.28,0.43,0.98,1.3
0.0-2.57 Av. 0.22
1.0
1
21
1
21
21
21
5
16
16
Ul
-------
57
REFERENCES
1. Butler, P. A. (1964). Commercial fishery investigations—chronic
exposure of fish to pesticides. In "Pesticide-Wildlife Studies,
1963." p.9. U. S. Fish and Wildlife Service Circ. 199.
2. DeWitt, J. R., Crabtree, D. G., Finley, R. B., and George, J. L.
(1962). Effects of pesticides on fish and wildlife: A review
of investigations during 1960. U. S. Fish and Wildlife Service
Circ. 143.
3. El Sayed, E. I., Graves, J. B., and Bonner, F. L. (1967). Chlorin-
ated hydrocarbon insecticide residues in selected insects and
birds found in association with cotton fields. J. Agr. Food Chem.
15, 1014-1017.
4. Epps, E. A., Bonner, F. L., Newsom, L. D., Carlton, R., and
Smitherman, R. O. (1967). Preliminary report on a pesticide moni-
toring study in Louisiana. Bull. Environ. Contarn. & Toxicol. 2,
333-339.
5. Genelly, R. E., and Rudd, R. L. CL958). Effects of DDT, toxaphene,
and dieldrin on pheasant reproduction. AUK 73, 529-539.
6. Grant, B. F. (1970). Pesticide influence in channel catfish
culture. Presented at 32nd Midwest Fish and Wildlife Conference,
Winnipeg, Manitoba, Dec. 6-9.
7. Henderson, C., Johnson, W. L., and Inglis, A. (1969). Organo-
chlorine insecticide residues in fish. Pest. Monitor. J.,
3(3) 145-171.
8. Hillen, R. H. (1967). Special report—pesticide surveillance
program—range caterpillar control project. Coifax and Union Cos.,
New Mexico, Bur. Spt. Fish. Wildlife, Div. Wildlife Services,
Fort Collins, Colorado, 31 pp.
9. Johnson, W. C. (1966). Toxaphene treatment of Big Bear Lake,
California. Calif. Fish and Game, 52(3) 173-179.
10. Johnson, W. D., Lee, G. F., and Spyridakis, D. (1966). Persistence
of toxaphene in treated lakes. Air and Water Pollut. Int. J., 10,
555-560.
-------
58
References (cont'd.)
11. Keith, J. 0. (1966). The effect of pesticides on white pelicans.
4th Conf. Use of Agr. Chem. in Calif., Feb. 8, 1966, Davis,
Calif., 8pp.
12. (1966)a. Insecticide contaminations in wetland
habitats and their effects on fish-eating birds. Pesticides in
the environment and their effects on wildlife. J. Appl. Ecol. ,
3(Suppl.) 71-85.
13. Keith, J. 0., Mohn, M. H. and Ise, G. (1965). Pesticide contamina-
tions in wildlife refuges. U.S. Fish and Wildlife Service Circular
No. 226, 37-40 pp.
14. Keith, J. 0., and Hunt, E. G. (1966). Levels of insecticide
.residues in fish and wildlife in California. Trans. 31st N. Amer.
Wildlife and Nat. Res. Conf., 150-177
15. Klein, A. K., and Link, J. D. (1967). Field weathering of toxaphene
and chlordane. J.A.O.A.C., 50(3): 586-591.
16. Nicholson, H. P. (1967). Livers of fish from Tombigbee - Alabama
River Complex north of Mobile, Alabama (Oct. 1964). Science 158,
871-6.
17. Rucker, R. R. (1967). Ground water toxic to fish. Proc. N.W. Fish
Culture Conf., 87 p.
18. Terriere, L. C., Kiigemagi, G., , A. R., Borovicka, R. L.
The persistence of toxaphene in lake water and its uptake by aquatic
plants and animals. J. Ag. Food Chem., 14(1): 66-69.
19. Tucker, R. K., and Crabtree, D. G. (1970). Handbook of toxicity of
pesticides to wildlife. Bureau of Sport Fisheries and Wildlife
Resource Publication No. 84, 116-117.
20. U. S. Department of Agriculture, ARS (1966). Monitoring agricultural
pesticide residues. A Preliminary Report of Studies on Soil, Sediment
and Water in Mississippi River Delta. U.S.D.A., A.R.S. 13-81.
21. U. S. Department of Interior, Bureau of Sport Fisheries and Wildlife
Laboratories at Columbia, Missouri and Denver, Colorado; and the
laboratory at Gulf Breeze, Florida, formerly B.C.F. and now E.P.A.
22. U. S. Department of Interior (1967). Bureau of Sport Fisheries and
Wildlife. Publication 43.
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59
FATE AND MOVEMENT OF TOXAPHENE IN TERRESTRIAL AND AQUATIC SYSTEMS
.Persistence in soil0. The fate and movement of a pesticide in and
from the soil are influenced by the following broadly categorized factors:
(a) the pesticide characteristics; (b) edaphic considerations; (c)
climate; (d) topography; and (e) land use Cand management. Any of these
factors that tend to promote the pesticide's persistence will tend to
increase its potential for environmental dispersion.
Pesticide movement through or across soil is facilitated by the move-
ment of water. Overland flow is generally more important in pesticide
transport than passage through soil. Two processes are involved: (a)
pesticide movement while dissolved in water and (b) pesticide movement
while dissolved in water: Sodium humate, a natural organic compound
found in water, can increase the water solubility of DDT by a factor of
20 (32). Thus, the solution and movement of other organic pesticides
may be facilitated by a variety of dissolved or emulsified organic sub-
stances found in water. The water solubility of toxaphene is variously
reported as 0.4 mg/1 and 3 mg/1. (10)
Bailey and White (2) stated that the principal means of pesticide
transport within soils are: (a) diffusion in the airspaces of soil (b)
diffusion in soil water; (c) downward flowing water; and (d) upward moving
water.
Movement by diffusion through the soil and air spaces is important
with pesticides having high vapor pressure such as soil fumigants. This
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60
process plays a dominant role in the eventual loss of pesticides from the
soil by volatilization. Percolation is the principal means of movement
of relatively non-volatile pesticides; diffusion in soil water is impor-
tant in transport over very short distances. Upward movement may occur
in irrigated areas where high evapo transpiration ratios are prevalent.
Therefore, the total amount of rainfall or irrigation water received,
intensity (water flux), and frequency of received water all appear to
affect pesticide movement in soils. These also influence overland trans-
port and facilitate the entrance of pesticides into solution.
Most literature on toxaphene persistence in soil is disappointing
in quality and quantity, especially that predating the era of general
availability of gas-liquid chromatography. During this time, analytical
results were based on nonspecific methods. Some studies at grossly
exaggerated application rates or other abnormal conditions, are useful
for specific purposes, but may be misleading in calculating the half-
life of toxaphene. Abnormally high concentrations in the soil may over-
come the ability of soil microorganisms to detoxify the compound. There
is little information specifically related to toxaphene degradation by
soil microbiota.
Mulla (23) applied toxaphene at the rate of 17.2 Ib/acre to well
prepared irrigated soil in California to evaluate Hippelates control
methods. The toxaphene was disked into the soil. One month after
application, effective control was 77%. The percentage of control
remaining slightly over 2 years later varied from 13 to 19%. Shaw and
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61
Riviello (26), in laboratory and small scale field tests with toxaphene
applied topically to the soil at 50 Ib/acre, found that effectiveness in
killing Mexican fruit fly larvae declined to zero after 373 days. Thus
persistence on the soil surface may be much less than when incorporated
into the soil.
Bradley, et al., (6) working on small plots of Norfolk loamy sand and
Goldsboro sandy loam soil in North Carolina on which cotton grew, applied
toxaphene as foliar sprays of aqueous emulsion at approximately weekly
intervals from early June until September 1969. The accumulated applica-
tion was 23.9 Ib/acre. Respectively, 10 and 5% remained in the soil in
September of 1969; 4% was found the following March. Less than one per-
cent was accounted for in water and sediment runoff.
Stevens, et al. . (28) conducted studies nationwide at 51 locations
in 1965-1967 to determine pesticide levels in soils.. Samples were col-
lected from 17 areas in which pesticides are used regularly, 16 areas with
a record of at least one pesticide application and in 18 areas with no
history of pesticide use. The only evidence of pesticide build-up was in
some orchards that had been treated repeatedly with DDT over a number of
years.
The data in Table 1 show that residues of toxaphene from crop appli-
cations over periods ranging from 1-14 years are present at only small
t r.-u-t ions ot t lu* araoimt applied. In areas of regular pesticide use, 60%
ot the vegetable and/or cotton-growing fields sampled contained toxaphene/
Scrobano (0.66-9. J8 mg/kg). Only one orchard (3%) and 12% of small grain
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62
and root crop-growing areas were positive. None was found in limited use
and no use areas. In Montana toxaphene was applied at 1.5 Ib/acre in
diesel oil to range land and 44% could be accounted for in the soil after
one day; only 3% remained after 84 days (8).
Nash and Woolson (24) determined the vertical distribution of toxa-
phene in Congaree sandy loam soil of .Maryland that had received accumulated
applications of 65 or 130 Ib/acre during 1951-1953. Between 85 and 90%
of the toxaphene remaining 13 years after the last application was found
in the upper 23 cm, which corresponds to the cultivated zone. The
quantity in the surface 7.6 cm was less than the mean quantity between
7.6 cm and 23 cm depths.
Volatility and photodecomposition may play an important part in dis-
sipation of chlorinated insecticides in the surface layers. Thomas (30)
working in natural watersheds in Texas studied the potential for insecticide
vertical movement through soil to a depth of 5 ft. Very little toxaphene
occurred below a depth of 1 ft. About 20% of the toxaphene applied in the
preceding 10 years could be accounted for in the soil profile.
Formulation also apparently can influence the persistence of toxa-
phene. The United States Forest Service at Gulfport, Mississippi (27) is
continuing studies of insecticides in soil to prevent termite damage.
Toxaphene in No. 2 fuel oil applied to the soil surface at 1/2 pint/sq ft
(0.4 Ib toxaphene or 17,000 Ibs/acre) was 100% effective for 16 years and
90% effective for 22 years. Soil depth penetration was estimated at 6 in.
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63
However, when applied at the same rate as an emulsion (1/2 pt contain-
ing 0.4 Ib toxaphene), only 80% effectiveness remained at the end of
one year and 50% at 3 years.
The references indicate that toxaphene is a long-lived, but by no
means "immortal" insecticide. Residues in and on the soil may be de-
tected for several months to several years, but there is no evidence
that build-up has occurred in the soil in areas of regular usage. Major
losses occur from the soil surface by processes suggested but not well
documented. These include microbial decomposition, photodecomposition
and/or volatilization.
Incorporation of toxaphene into soil tends to prolong persistence.
This insecticide is not normally used to control soil insects, but
residues remaining on the soil from foliar applications may be turned
under by cultivation and plowing. Downward migration through the soil
does not normally occur to any significant degree. The formulation in
which toxaphene is applied may also influence persistence. Studies are
needed to clarify the fundamental mechanisms that control persistence
a
and loss of toxaphene from the soil.
Note on the Half-Life of Toxaphene in Sandy Clay Soil
A recent report (14) gives half-life figures on a number of chlori-
nated pesticides, including toxaphene, in Holtville sandy clay. The
application of toxaphene sprayed onto the soil surface and disked the
same day into the upper 6 in. of the soil was as follows:
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64
Year Ib/A active ingredient
toxaphene DDT
1953
1954
1955
1956
1957
19.6
20.0
20.8
20.8
22.4
19.5
20.0
20.8
23.2
20.0
By regression analysis, the half-lives of•toxaphene and DDT were 4
years.
Occurrence and movement in watercourses. The most intensive in-
vestigation in a single watershed of toxaphene occurrence in surface
water is reported by Nicholson, et al., (25) who studied a 400/sq mile
cotton producing watershed in Alabama for 6 1/2 years. Water samples of
2,000 to 10,000 gal were processed through activated carbon adsorption
units for recovery of insecticides. Analysis was by gas chromatography.
A peculiarity of the method was that water was extracted over
periods 1 to 2 weeks thus averaging peak occurrences. The extended
sampling period insured against missing toxaphene if its presence was
discontinuous. The values were not absolute because of possible incom-
plete extraction from water and recovery from carbon. However, at least
the indicated amounts were present. Efficiency may be about 50%. The
sampling devices were operated almost continuously for the entire study
period.
The cotton acreage varied annually from 12,700 to 16,500. Annual,
toxaphene usage and recovery data are given in Table 2. The authors
attribute the presence of toxaphene in Flint Creek primarily to surface
runoff.
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65
Significant findings of this study were: (a) low toxaphene con-
centrations (less than 1 Mg/1) were recovered from Flint Creek and were
associated with small cotton farm operations where ground equipment was
primarily used; (b) the source of toxaphene was the watershed as a
whole rather than a few favorably located fields; (c) occurrence in the
samples was year around with largest recoveries in the summer applica-
tion season; and (d) there were indications of a reduction in frequency
of occurrence and in concentration in river water beginning about 6 mos.
after the first of several seasons of much reduced toxaphene usage. The
letter suggests the period required under Alabama conditions for land
surface cleansing to begin.
Bradley, et al., (6) studies runoff from 180 sq. ft. instrumented
plots in North Carolina on which cotton was grown and treated with toxa-
phene and DDT singly and combined. Less than one percent of the toxa-
phene occurred in the water and sediment running off these plots. Where
DDT alone was used, 2.83% ran off, while 1.03% of DDT was found in run-
off from those plots also treated with toxaphene. The rate of toxaphene
application was about twice that of DDT.
These data do not imply that these percentages of toxaphene and DDT
in runoff would reach lakes and streams. A large proportion of the
transported insecticides were tied up on soil particles (96% of the DDT
and 75% of the toxaphene) and is expected to deposit in the first low spot
or settling area reached. Thus, the field location relative to a lake or
watercourse is important.
Nearly 20% of all pesticides used in the United States is applied
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66
in-California. Therefore, data from California have special significance.
Irrigation farming is widely practiced and a peculiarity, in some areas,
is the presence of underground tile drainage systems. :
Bailey and Hannum (3) reported on the analysis of more than 630
samples taken in California of surface waters, agricultural drainage,
sediments and aquatic organisms. Data for surface waters are given in
Table 3. Although toxaphene was recovered at 14 of 20 sampling stations,
concentration values were less than 1 pg/1. The concentrations found of
DDT/DDD, DDE, heptachlor epoxide, lindane, dieldrin and BHC each were
within the same range.
Somewhat more toxaphene was recovered in water from agricultural
drains (Table 4). Pesticide concentrations were highest in areas affected
by agricultural development and decrease in surface water in proportion
to inflow dilution and uptake by sediments and aquatic organisms. The
temporal distribution was related to agricultural drainage practices and
to runoff from heavy rainfall.
Johnson, et al., (18) studied pesticide concentrations in tile drain-
age and open drains in the San Joaquin Valley of California between 1963
and 1965. Toxaphene was detected in 13 of 66 analyses of tile drainage
effluent in concentrations varying from 0.13 pg/1 to 0.95 Mg/1 and
averaging 0.53 Mg/1. Water from surface drains that collected surface
and subsurface water was positive for toxaphene 60 out of 61 samples.
Concentrations varied from 0.10 ug/1 to 7.90 ug/1 and averaged 2.01 ug/1.
The predominant residues found in surface water were DDT/DDD and toxa-
phene. The average concentration of toxaphene was higher than any other
chlorinated hydrocarbon insecticide and it was found most frequently.
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67
The annual reports of the San Joaquin District of the California
Department of Water Resources (1963-1969) contain a wealth of data on
toxaphene occurrence in Central Valley tile drainage effluent (Table 5)
and in surface waste water drains (Table 6) from irrigated areas, in
other Central Valley surface waters (Table 7), and in bay and ocean water
(Table 8).
Twelve percent of 422 water samples from tile drainage systems con-
tained toxaphene in concentrations ranging from 0.2 pg/1 to 1.26 Mg/1.
Forty-eight percent of 447 agricultural surface water drains contained
concentrations ranging from 0.04 ug/1 to 7/yg/l. Due to the small de-
gree of vertical movement through the soil demonstrated elsewhere for
toxaphene, its recovery in underground tile drains in the concentrations
indicated needs explanation.
There is a strong possibility of direct access of surface water to
the drains under some conditions (5). Toxaphene was found in 12% of 712
other Central Valley surface waters in concentrations ranging from 0.02
Ug/1 to 0.93 pg/1, and in 4% bay and ocean water samples in concentra-
tions of 0.03 yg/1 to 0.60 yg/1.
Routine monitoring (7, 20, 22, 31) of waters of the United States
has not indicated the presence of toxaphene. One reason may be that the
amount required for detection in routine screening analyses is greater
than that of most pesticides reported. Lichtenberg (21) states that
the minimum toxaphene concentration required for recognition in his
monitoring of 1 liter water samples is 1 pg/1, although lesser amounts
may be determined in samples in which toxaphene presence is anticipated.
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68
Toxaphene may be transported by water in solution or dissolved in
organic constituents. It may also be absorbed on sediment that is
suspended or deposited permanently or temporarily. Sometimes it is
transported in or on the bodies of aquatic organisms.
The amount of toxaphene in sediment undoubtedly reflects the degree
0
of usage as well as watershed soil management practices. Baily and
Hannum (3) working in California reported toxaphene in sediment in much
higher concentrations than they found in water (Tables 3, 4 and 9).
Generally, sediments of smaller particle size had higher pesticide con-
centrations than did those of larger size.
Barthel, et al., (4) studied agricultural chemicals contained in
stream bed materials of the Lower Mississippi River. Toxaphene/Strobane
was found only in a 5-mile stretch in the vicinity of West Memphis,
Arkansas. The concentrations varied from 100 to 600 yg/kg and were
attributed to upstream agricultural usage.
Grzenda and Nicholson (9) studied cotton field soil, water, river
bottom sediments, bottom fauna and fish at Flint Creek, Alabama, to de-
termine the distribution of toxaphene, DDT and BHC among the biotic and
abiotic components of a stream system. Soils from 33 cotton fields
representing 206 acres were sampled. Data on insecticide residues in
soils are given in Table 10 (See Table 2 for data on insecticide residues
in water.)
No toxaphene was recovered from river bottom sediment, but DDT/DDE
was found in 23 of 58 samples at 8 to 6400 pg/kg, and 6 contained traces
of BHC. This was reflected in infrequent occurrence of toxaphene and BHC
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69
in bottom fauna, while DDT/DDE was found in all samples. All fish
samples, however, contained toxaphene, DDT/DDE and BHC.
Nicholson, et al., (25) showed the relative importance of sediment
versus solution in the transport of toxaphene, DDT and BHC in Flint Creek,
Alabama. Suspended sediment seemed less frequently involved in toxa-
phene and BHC transport than in DDT transport (Table 11). This suggests
a lesser affinity for solid substrates of toxaphene in low water concen-
trations than that possessed by DDT, which is notoriously hydrophobic.
Support for this contention comes from the fact that toxaphene was fre-
quently recovered in clarified and treated municipal drinking water while
DDT rarely was found.
Although toxaphene is not registered for use in fishery management,
some of the experiences with its use for that purpose cast light on the
fate of toxaphene in lake water. Various studies reported that toxaphene
persistence was influenced by the concentration applied, sunlight, tem-
perature, oxygen, alkalinity, hardness, turbidity, presence of bacteria,
and pH, but no quantitative relationships were found between these factors
and persistence. Previous conclusions were based on the time required
for detoxification and restocking. Johnson, et al. (17) used gas chro-
matography to study the mechanisms of detoxification. Their results are
given in Table 12.
This tudy shows that toxaphene may persist in a lake for several
years after application for fishery management even though detoxifica-
tion is rapid. All of the lakes were shallow and eutrophic. The authors
point out that detoxification is accomplished, in part, by sorption
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70
reactions rather than degradation, but indicate some evidence that toxa-
phene may be modified based on the shape of the gas chromatographic
"fingerprint."
Virtually no information seems to be available on the chemical break-
down products of toxaphene in soil and water.
Biological accumulation. Biological accumulation occurs by two pro-
cesses i.e., direct absorption through body surfaces exposed to the ex-
ternal environment, and through the food. When natural food is involved,
especially when increased concentrations of a contaminant occur through
ascending trophic levels of a food chain, this accumulation is called
"biological magnification."
Research shows that toxaphene is sufficiently stable to be available,
in areas of regular usage, for biological accumulation if other critical
requirements are satisfied; namely, that rates of uptake, metabolism and
excretion are favorable for accumulation. Information is available on
biological accumulation of toxaphene in warm blooded animals from feed-
ing studies using domestic animals. Toxaphene/Strobane storage in
animal fat will occur. The degree of concentration seems less than for
some other chlorinated hydrocarbon insecticides and persistence of the
toxaphene residues is of shorter duration (Tables 13 and 14).
Comparatively little information is available about bioaccumulation
of toxaphene/Strobane in aquatic organisms. Studies indicate the
presence of toxaphene residues in fish, but little information is given
relating exposure rate and frequency values, and none have determined
residue residence time after cessation of exposure.
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71
Johnson and Lew (16) determined chlorinated hydrocarbon insecticide
residues in fish of the Lower Colorado River system which drains on
irrigated agricultural area where insecticides are often used. The fol-
lowing residues of DDT and its congeners, DDE and TDE, and toxaphene were
reported in the fat and/or viscera of these fish.
Carp: DDT, etc., 2.0 - 185.0 mg/kg (87.0 ave.); toxaphene, 50.0 mg/kg
Channel Catfish: DDT, etc., 10.0 - 77.0 mg/kg (47.8 ave.); toxaphene,
8.2 - 11.4 mg/kg (9.8 ave.)
Sonoran Sucker: DDT, etc., 7.3 - 46.3 mg/kg (23.9 ave.); toxaphene,
2.8 - 172.9 mg/kg (32.5 ave.)
Gila Sucker: DDT, etc., 36.2 - 39.5 mg/kg (37.8 ave.); toxaphene,
25.2 - 49.9 mg/kg (34.9 ave.)
Henderson et^ al^., (12, 13) reported the results of the National
Monitoring Program analysis of organochlorine insecticide residues in
fish collected from 50 sampling stations located in the Great Lakes and
major river basins throughout the United States. Twelve toxaphene re-
coveries were reported from 590 composite samples taken in the fall of
1967 and spring of 1968. Concentrations ranged from 0.01 mg/kg to 1.25
mg/kg. Toxaphene was not reported in the 1969 survey. A check with the
two laboratories making the analyses indicated that toxaphene was sus-
pected in a number of samples but was not reported because of inherent
analytical difficulties (11). These difficulties seem in part responsi-
ble for the relative scarcity in the technical literature of data on
toxaphene in aquatic life.
Although the practice of applying toxaphene in lakes for fisheries
management has been discouraged, one study of that usage revealed infor-
mation on bioaccumulation in the hydrosphere under conditions of gross
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72
contamination. Terriere et^ al_., (29) applied toxaphene in Davis Lake,
Oregon at 88 yg/1 in 1961 and found in 1962 and 1963 that toxaphene was
present in water at average values of 2.1 ug/1 and 1.2 yg/1, respectively.
They reported a concentration factor of about 500 for aquatic plants,
1000 to 2000 for aquatic invertebrates, 10,000 to 20,000 for rainbow trout,
4,000 to 8,000 for Atlantic salmon and 1000 to 2000 for lake bottom mud.
This lake was successfully restocked one year after treatment.
Hughes (15) has made the most complete recent study of biological
accumulation in the aquatic environment in his study of toxaphene per-
sistence in Wisconsin lakes. When applied to the lakes in fisheries man-
agement, toxaphene in the lake water declined rapidly to less than detect-
able amount (1 yg/liter) within 9 to 12 months. However, aquatic fauna,
particularly fish stocked in the lakes following treatment, accumulated
as much as 18 pg of toxaphene residues per gram of body weight. In gen-
eral, prey fish accumulated higher concentrations of toxaphene than did
predators. Bluegills stocked in Fox Lake about eight months following
the last of 3 treatments accumulated 9.4 yg/g in 176 days and then toxa-
phene residues began declining until, after 787 days, 0.8 ug/g remained.
Two months after fish were stocked, plankton contained 34 Mg/g. Hughes
believes that toxaphene was accumulated through both the food chain and
directly from water.
More information is needed to evaluate the nature and significance
of biological accumulation and food chain involvement, especially in
aquatic life. Controlled studies will more adequately reveal the re-
lationship of exposure to build-up in the tissues, and also indicate
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73
rates of metabolism and excretion once exposure is discontinued. Im-
proved analytical techniques' and the availability of 36Cl-labeled toxa-
phene should make rapid a quisition of needed data possible.
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74 '
SUMMARY
Toxaphene is a long-lived insecticide. Residues in soil may be de-
tected for several months to several years, but no build-up has occurred
in the soil in areas of regular usage. Microbial decomposition, photo-
decomposition and/or volatilization may account for major losses from
the soil surface but this is not well documented. Downward migration
through the soil does not normally occur to a large degree. Studies are
needed to clarify the fundamental mechanisms controlling the persistence
and loss of toxaphene from the soil, and to identify break-down products.
Toxaphene can be transported from the soil surface to watercourses,
"dissolved" in runoff water and adsorbed on mineral and organic sediment.
Concentrations reported from stream and lake water are usually less than
1 ug/1; values for bottom sediments may be several thousand times
greater. There is no evidence at this time of wide-spread occurrence of
toxaphene in the nation's waters comparable to the distribution of DDT
and dieldrin. However, chemists are beset by analytical limitations with
toxaphene not experienced with DDT and dieldrin.
Little information is available about bioaccumulation of toxaphene/
Strobane in aquatic life and of food chain involvement. Toxaphene is
sufficiently persistent in the physical environment to be available, in
areas of regular usage, for biological accumulation if other critical re-
quirements are satisfied; namely, that rates of uptake, metabolism and
excretion are favorable for accumulation.
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75
A study in a lake where toxaphene was applied for fisheries manage-
ment suggests that biological accumulation and transfer through the food
chain to higher trophic levels can occur under such conditions. However,
direct application to water resulting in sustained gross exposure of
aquatic organisms is not recommended. Toxaphene residues have been found
in fish, but little data are available relating frequency and rate of
exposure to residue concentrations, and none have determined rate of
metabolism and/or excretion during exposure or after cessation of exposure
These studies are needed.
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TABLE 1
76
Toxaphene Applied to Crops vs Recovered from Soil (a)
LOCATION
LB APPLIED/ACRE
RESIDUE IN mg/kg
Lower Rio Grand Valley
Field 1
Field 2
Field 3
Field 4
Field 5
Dade County, Fla.
Field 1
Field 2
Field 3
Field 4
Field 5
Eastern So. Carolina
Field 1
Field 2
Field 3
1956-64
16.2
1958-64
47
1958-64
34(+1.7 Strobane)
1955-64
29.25
1956-64
39.16
1958-64
8
1962-64
2.2
1962-64
31.59
1952-64
3
1956-64
15
1957-64
47
1965 1966
3 • 2
1965 1966
7 1.25
1965 1966
9 1.
1965
4
1965 1966
4 2
1965
4
1965
9
1965
19.90
1966
3
1965 1966
9 18
Oct 1966
2.90
Oct 1966
1.98
Oct 1966
1.77
Oct 1966
2.01
Oct 1966
2.43
Mar 1968
1.21
Mar 1968
2.64
Mar 1965
0.66
Mar 1968
4.14
Mar 1968
7.00
Aug 1966
2.99
Aug 1966
5.64
Aug 1966
0.99
Field 4
1956-64
38
j Aug 1966
i 2.04
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Table 2
Toxaphene by Seasons in Flint Creek, Alabama Water (yg/1) (a) (b)
Thousand Lb . Technical
Agricultural Toxaphene Applied in
Year Study Area
1959-60
1960-61
1961-62
1962-63
1963-64
1964-65
1965
56.5
37.9
64.6
72.0
7.5
8.0
8.5
Summer Fall Winter Spring
Max. Min. Average
0.28
0.41
0.11
0.15
0.08
•0.11
0.08
0.04
0.01
0.04
0.05
0.04
0.00
0.00
0.11
0.21
0.07
0.10
0.16
0.05
0.01
Average Average Average
0.08
0.06
0.03
0.07
0.03
0.01
0.00
0.05
0.02
0.05
0.05
0.01
0.00
—
0.05
Positive
No Sample
0.07
0.01
0.00
—
» Source (25)
'b) Values are not corrected for the efficiency of the sampling and extraction methods.
-------
Table 3
Toxaphene Concentration in California Surface Waters (yg/1) (a) (b)
78
Sampling Station
Max.
Min.
Average
Feather River at Nicolaus Bridge
American River at Sacramento
Sacramento River at Walnut Grove
Mokelumne River at Highway 99
Little Connection Slough at Atherton Road
Middle River at Victoria Canal
Delta Mendoto Canal at Head
San Joaquin River at Antioch
Suisan Bay at Martinez
Nap a River at Duttons Landing
San Pablo Bay at Pt. San Pablo
San Francisco Bay at Berkeley Pier
San Fran'cisco Bay at Treasure Island
So. San Francisco Bay at San Mateo Br.
Golden Gate Br. at Fort Point
San Joaquin River at Vernalis
San Joaquin River at Fremont Ford
Salton Sea near North Shore
Alamo River
All American Canal at Alamo River
_.
—
0.40
—
—
—
0.12
0.32
0.09
—
—
0.23
—
—
—
0.93
0.46
0.40
0.65
0.08
—
0.03
—
—
—
0.03
0.05
0.05
—
—
0.03
—
—
—
0.02
0.04
0.05
0.30
0.04
—
0.10
0.04
0.16
—
0.08
0.15
0.06
—
0.08
0.13
—
0.26
—
0.26
0.13
0.14
0.47
0.06
(a) Source (3)
(b) Sample size 5 liters; analytical method, microcoulometric gas chromatography;
sensitivity of method, 0.02 to 0.05 ug/1.
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Table 4
Toxaphene in Agricultural Drains in California (ug/1) (a)
79
Sampling Station
Max.
Min.
Average
Reclamation District
No. 108 Drain
Colusa Basin
Drain
Staten Island
Drain
Roberts Island Drain at Whiskey Slough
Panoche
Drain
Salt
Slough
5.50
0.44
0.10
0.04
0.23
1.47
0.17
(a) Adapted from Daily and Hannum (3).
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80
Table 5
Toxaphene in California San Joaquin Valley Tile Drain Effluents (ug/1) (a)
Concentration
Number Times
Year Samples Detected
Sept. 1963-Dec. 1964
1965
1966
1967
1968
1969
16
50
105
121
79
51
6
7
17
4
10
7
Max. Min. Average (b)
0.70
0.95
0.88
0.32
0.50
1.26
0.20
0.13
0.21
0.02
0.02
0.09
0.43
0.61
0.37
0.15
0.26
0.44
Totals
422
51
12 %
1.26
0.02
(a) Source (1)
(b) Average of positive samples. !
Table 6
Toxaphene in California Central Valley Surface Agricultural Waste Water Drains(ug/1)(a)
Concentration
Number Times
Year Samples Detected
Sept. 1963-Dec. 1964
1965
1966
1967
1968
1969
73
115
89
95
56
19
40
67
56
15
27
11
Max. Min. Average (b)
5.50
8.16
7.60
71.00
15.00
31.50 •
0.04
0.23
0.115
0.06
0.11
0.216
1.02
2.08
1.42
10.13
2.47
4.80
Totals
447
216
48 %
71.00
0.04
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81
Table 7
Toxaphene in California Central Valley Surface Waters (ug/1) (a)
Concentration
Number Times
Year Samples Detected
Sept. 1963-Dec. 1964
1965
1966
1967
1968
232
158
203
61
58
73
12
2
0
1
Max. Min. Average (b)
0.90
0.93
0.31
—
—
0.02
0.29
0.08
—
—
0.11
0.50
0.20
—
0.10
Totals 712 88
12 %
(a) Source (1).
(b) Average of positive samples.
Table 8
Toxaphene in California Bay and Ocean Waters (ug/1) (a)
Concentration
Number Times
Year Samples Detected
Sept . 1963-Dec . 1964
1965
1966
1967
1968
32
49
51
47
21
7
1
0
0
0
Max. Min. Average (b)
0.26
—
—
—
—
0.03
—
—
—
—
0.12
0.60
—
—
—
Totals 200 8
4 %
(a) Source (1).
(b) Average of positive samples.
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82
Table 9
Toxaphene in California Sediments (ug/1) (a)(b)
Source
Max.
Min.
Average
Streams
Feather River at Nicolaus Br.
Sacramento River at Walnut Grove
Little Connection Slough at Altherton Road
Middle River at Victoria Canal
San Joaquin River at Antioch
San Joaquin River at Vernalis
Bays
Sunset Bay at Martinez
San Pablo Bay at Pt. San Pablo
So. San Francisco Bay at San Mateo Br.
Agricultural Drains
Reclamation District #108 Drain
Colusa Basin Drain
Staten Island Drain
Roberts Island Drain at Whiskey Slough
130
110
88
57
170
140
110
99
210
110
380
(a) Source (3)
(b) The method of reporting concentration is unique and not relatable to ug/g
of sediment in the usual manner. Concentrations are reported as parts of
pesticide per parts of wet sediment. A representative location of the sample
was dried and a moisture content determination was made. The pesticide con-
centrations were then adjusted to parts per parts of dry sediments from the
relationship Cs=100C-CwSm in which Cs=dry weight pesticide concentration in
Sd
overlying water sample; Sm=percent soil moisture in sample; and Sd=percent
dry material in sample.
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Table 10
83
Insecticide Residue in Alabama Soil Samples Collected from 33 Cotton Fields (a)
(ug/kg)
Mean Cone. Mean Cone.
Compound Percent Positive All Samples Positive Samp. Range
Toxaphene
DDT
BHC
58
85
49
410
250
20
710
300
50
160-1600
20-530
10-380
(a) Source (9)
Table 11
Comparison of Insecticide Recovery from Sediment and Water,
Hartselle, Alabama Water Treatment Plant (a)
Sample Source
No. Sample
Percent Positive for
DDT
DDEToxaphene
BHC
Sediment from treatment
plant settling basis
Suspended sediment extracted
from raw water by filtra-
tion prior to carbon
filtration (b)
Carbon adsorption samples
collected from water after
removal by above filtra-
tion
45
77
77
71
69
13
64
62
12
18
10
31
22
17
74
(a) Source (25)
(b) A Cuno Micro-Klean filter that removed sedimentary particles larger
than 25 microns was used. Smaller particles pass through to the carbon
adsorption units.
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Table 12
Toxaphene in Wisconsin Lakes, 1965 (a)
(parts per billion)
Lake
Year of
Treatment
Treatment
Rate
Water (b)
Suspended
Matter
Aquatic
Plants
Sediment
Little Green
Emily
Kusel
Marl
Big Twin
Wilson
Round
Corns tock
(Surface)
6.5 meters
1956
1959
1960
1960
1963
1964
May 1965
1964 & 1965
June, 1965 (c)
100
100
100
100
100 & 50
2.5-3.5
5 Epilimnion only
5 + 5
100
1
4
3
3
2
4
2
. 20
4
40
20
200
9
20
80
200
100
500
—
400
70
80
40
50
80
50
20
200
400
1000
800
500
600
1000
(a) Source (17)
(b) Remaining in water after filtration through Whatman GF/A glass filters,
(c) Cornstock Lake was treated 14 days prior to sampling.
00
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35
Table 13
Insecticides in the Fat of Cattle after Multiple Spray Treatments (a)
Insecticide
DDT, 0.5%
Dieldrin,
0.5%
Heptachler,
0.5%
Strobane,
2%
Toxaphene ,
0.5%
Spray
Interval
(weeks )
3
3
2
2
2
After indicated sprayings (b) mg/kg
1st 2nd 3rd 4th 5th 6th
18
7
11
0
31
10
14
0
16
14
1
33
24
20
7
18
10
35
19
29
6
After last spraying
mg/kg
12
wks
8
11
wks
17
8
wks
16
6
wks
9
4
wks
4
24
wks
5
28
wks
6
16
wks
2
10
wks
4
6
wks
4
36
wks
2
14
wks
3
(a) Source (19).
(b) Fat samples were taken at the end of the intervals between spraying.
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86
Table 14
Insecticide Residues Stored in the Fat of Cattle Fed
Known Amounts in Their Diet (a)
Insecticide
Aldrin
BHC
Chlordane
DDT
Toxaphene
mg/kg
in Feed
25
100
25
25
100
mg/kg
Weeks after feeding
4 8 12 16
50
159
12
22
26
78
223
18
34
34
230
42
33
250
40
38
mg/kg
Weeks after feeding ceased
4 8 16 20 24
51
84
14
19
14
36
5
3
17
11
20
0
6
(a) Source (19).
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87
REFERENCES
1. Anonymous. Annual summaries of water-borne chlorinated hydrocarbon
pesticide program, 1963-1969. San Joaquin District Dept. of Water
Resources, Calif.
2. Bailey, G. W. and White, J. L. (1970). Factors influencing the ad-
sorption, desorption, and movement of pesticides in soil. Residue
Reviews. 32, 29-92.
3. Bailey, T. E. and Hannum, J. R. (1967). Distribution of pesticides
in California. J. Sanitary Engineering Div., Proc. Amer. Soc.
Civil Engineers, SA 5: 27-43.
4. Barthel, W. F. , Parsons, D. A., McDowell, L. L., and Grissinger,
E. H. (1966). Surface hydrology and pesticides. In Pesticides and
their effects on soils and water. ASA Spec Publ #8. Soils Sci.
Soc. America, Madison, Wis. 128-144 pp.
5. Beck, Louis A., Senior Sanitary Engineer, Calif. Dept. of Water
Resources, Sacramento. Personal Communication (1971).
6. Bradley, J. F., Jr., Sheets, T. J., and Jackson, M. D. DDT and
toxaphene movement in surface water from cotton plots. N. C. State
Univ. Agr. Exp. Sta. To be published.
7. Brown, E. and Nishioka, Y. A. (1967). Pesticides in selected
western streams - A contribution to the national program. Pest.
Monit. Jour. 1(2): 38-46.
8. (Ent. Res. Div., ARS, USDA) (1959). Residues in fatty acid, brain
and milk of cattle from insecticides supplied for grasshopper con-
trol on range land. J. Ent. Soc. Am. 52(6): 1206-1210.
9. Grzenda, A. R. and Nicholson, H. P. (1965). The distribution and
magnitude of insecticide residues among various components of a
stream system. Proc. 14th Southern Water Resources and Pollution
Control Conf., Univ. of North Carolina, Chapel Hill, 165-174 pp.
10. Gunther, F. A., Westlake, W. E., and Jaglan, P. S. (1968). Re-
ported solubilities of 738 pesticide chemicals in water. Residue
Reviews. 20, 1-145.
11. Henderson, C., Chief of Environmental Improvement Branch Div.
Fisheries Services Branch Bur. Sports Fisheries and Wildlife, Dept.
of the Interior, Washington, D. C. Personal communication, July 15,
1971.
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88
12. Henderson, C., Johnson, W. L., and Inglis, A. (1969). Organochlorine
insecticide residues in fish (National Pesticide Monitoring Program).
Pest. Monit. Jour. 3(3): 145-171.
13. Henderson, C., Johnson, W. L. and Inglis, A. (1969). Organochloride
insecticide residues in fish - fall 1969 National Pesticide Monitor-
ing Program. Pest. Monit. Jour. 5(1): 1-11.
14. Humanson, H. P., Gunther, F. A., Anderson, L. D. and Garber, M. J.
(1971). Installment application effects upon insecticide residue
content of a California soil. J. Agr. Food Chem. 19: 722.
15. Hughes, R. A. (1970). Studies on the persistence of toxaphene in
treated lakes. PhD thesis, University of Wisconsin (Water Chemistry).
16. Johnson, D. W. and Lew, S. (1970). Chlorinated hydrocarbon pesti-
cides in representative fishes of Southern Arizona. Pest. Monit.
Jour. 4(2): 57-61.
17. Johnson, W. D., Lee, G. F., and Spyridakis, D. (1966). Persistence
of toxaphene in treated lakes. Univ. of Wise. Eng. Exp. Sta. Reprint
#914. Air and Water Pollut. Int. J. Pergamon Press, 10: 555-560.
18. Johnson, W. R. , Ittihadieh, F. T., and Craig, K. R. (1967). In-
secticides in the tile drainage effluent. Water Resources Research
3(2): 525-537.
19. Knipling, E. F. and Westlake, W. E. (1966). Insecticide use in live-
stock production. Residue Reviews 13: 1-32.
20. Lichtenberg, J. J., Eichelberger, J. W., Dressman, R. C., and Long-
bottom, J. E. (1970). Pesticides in surface waters of the United
States - A 5-year summary, 1964-68. Pest. Monit. Jour. 4(2): 71-86.
21. Lichtenberg, J. J., Analytical Quality Control Laboratory, EPA,
Cincinnati, Ohio. Personal communication (1971).
22. Manigold, D. B. and Schulze, J. A. (1969). Pesticides in Selected
western streams - A progress report. Pest. Monit. Jour. 3(2):
124-135.
23. Mulla, M. S. (1961). Control of Hippelates gnats with soil treat-
ment using organochlorine insecticides. J. EC. Ent. 54(4): 637-641.
24. Nash, R. G. and Woolson, Q. E. (1968). Distribution of chlorinated
insecticides in cultivated soils. Soil Sci. Soc. Amer. Proc- 32,
525-527.
25. Nicholson, H. P., Grzenda, A. R. and Teasley, J. I. (1966). Water
pollution by insecticides: a six and one-half year study of a water-
shed. Proc. Symposium on Agricultural Waste Waters. Rept. #10 of
Water Resources Center, Univ. of Calif., Davis. 132-141 pp.
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89
26. Shaw, J. G. and Rlviello, M. S. (1961). Exploratory studies with
soil toxicants to control the Mexican fruit fly. J. EC. Ent.
54(4): 666-668.
27. Smith, V. K. Forest Service, USDA, Gulfport, Miss.0 Personal com-
munication July 1, 1971.
28. Stevens, L. J., Collier, C. W., and Woodham, D. W. (1970). Moni-
toring pesticides in soils from areas of regular, limited, and no
pesticide use. Pest. Monit. Jour. 4(3): 145-164.
29. Terriere, L. C., Kiigemagi, U., Gerlach, A. R., and Borovicka,
R. L. (1966). The persistence of toxaphene in lake water and its
uptake by aquatic plants and animals. Agr. and Food Chem. 14(1):
66-69. °
30. Thomas, G. W. (1970). Movement of insecticides in soil and water.
Entry 5.1472, Water Resources Research Catalogue, Vol. 6, 1-653 pp.
31. Weaver, L., Gunnerson, C. G., Breidenbach, A. W., and Lichtenberg,
J. J. (1965). Chlorinated hydrocarbon pesticides in major U. S.
river basins. Public Health Reports 80(6): 481-493.
32. Wershaw, R. L., Burcar, P. J., and Goldberg, M. C., (1969). Inter-
action of pesticides with natural organic material. Environmental
Science and Technology. 3: 271-273.
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90
TOXAPHENE RESIDUES IN ATMOSPHERIC SAMPLES
Data of toxaphene residues in atmospheric samples are very limited
(1,3). Nine locations for pesticide monitoring were established at
Baltimore, Md. , Buffalo, N. Y., Dothan, Ala., Fresno, Calif., Iowa City,
Iowa, Orlando, Fla., Riverside, Calif., Salt Lake City, Utah, and Stone-
ville, Miss. The identification of toxaphene was carried out by gas-liquid
chromatography using two different column packings. Toxaphene identi-
fication was verified by three characteristic elution peaks on the
chromatograph, one peak emerging just before p,p'-DDT and the other two
after DDT (2). Further verification of the presence of toxaphene in the
air samples was obtained from the person collecting the samples in Stone-
ville. He reported that toxaphene, DDT, and methyl parathion had been
recently used at the Stoneville location (2).
Of the nine locations monitored, three showed significant toxaphene
residues as follows (1):
Location
Dothan
Orlando
Stoneville
Total Number
of Samples
90
99
99
Positive
Samples
11
9
57
Range
(ng/m3)
27.3-79.0
20.0-2520.0
16. -1110.
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91
Syracuse University Research Corporation under contract with NAPCA
(now Research and Monitoring, EPA) has monitored pesticides in the atmos-
phere at six locations in New York State, one at Winter Haven, Fla., and
one at Lubbock, Tex. for the past 6 mo. No toxaphene residues were present,
although DDT, aldrin and endrin residues were found in some of the
stations (4).
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92
REFERENCES
1. Stanley, C. W. Study to determine the atmospheric contamination by
pesticides. Final Report, PHS Contract PH 21-2006; Midwest Reserach
Institute Project No. 3068-C. October, 1968.-
2. Stanley, C. W. Letter to A. R. Yobs, EPA, Chambley, Ge., dated
July 6, 1971.
3. Stanley, C. W., Barney II, J. E., Helton, M. R., and Yobs, A. R.
1971). Measurement of atmospheric levels of pesticides. Envir.
Sci. and Techn. 5: 431.
4. Syracuse University Research Corporation. Progress Report to EPA,
Contract No. CPA 70-145.
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93
THE EFFECT OF TOXAPHENE ON BENEFICIAL
ARTHROPOD POPULATIONS
The information presented on this general subject has been sepa-
rated into effects of toxaphene on pollinators and insect parasites and
predators. Some excellent reviews have been published on the effect of
pesticides on nontarget organisms (1, 25, 34, 39).
Effect of toxaphene on insect pollinators. The honey bee has been
used in many toxicity tests because it is the most beneficial pollinating
insect. The honey bee is the major agent in the pollination of most of
fruit, vegetable, seed and pasture crops. The work conducted on the
effect of arsenicals on honey bees, before the introduction of toxaphene,
is not discussed in this review. Since the development of organochlorines,
researchers have used laboratory and field observations to determine the
effect of synthetic organic insecticides on pollinators. This work has
been centered in Washington, California, Arizona, Texas and to some ex-
tent in other states and countries. In Texas tests were conducted to
determine the effect of organochlorines on honey bees (49, 50, 51, 52,
53, 54). Toxaphene applied as a dust (20% toxaphene - 40% sulphur) was
practically nontoxic producing only 5% mortality. Toxaphene sprays had
little toxicity to bees when applied to cotton inside large cages while
toxaphen - DDT, dusts of toxaphene, DDT. gamma BHC-DDT and chlordane
killed from 8.2 to 10.4% of the bbes after eight applications.
In tests to determine the toxicity of organic insecticidal sprays
to bees, the decreasing order of toxicity was gamma BHC>chlordane>DDT>
toxaphene.
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94
In another series of tests toxaphene dusts were slightly more toxic to bees
than sprays. To summarize, the decreasing order of toxicity to bees of
several insecticides was calcium arsenate>parathlon>dieldrin>aldrin>BHC>chlor-
dane>DDT>toxaphene. Toxaphene applied to vetch before it bloomed heavily
showed promise for control of lygus bugs and pea aphids with minimum damage
to pollinating insects.
Commercial applications of toxaphene to control injurious insects in
alfalfa can be made without serious loss of bees (5, 7, 24, 25, 26, 27, 30).
Toxaphene is low to moderate in toxicity and is not hazardous if applied when
bees are not foraging. Roberts and Barnes (40) grouped pesticides according
to their toxicity to bees as: (1) highly toxic, (2) moderately toxic and
(3) relatively nontoxic. Toxaphene and Strobane were grouped as relatively
nontoxic. In a USDA leaflet (450), toxaphene was listed as relatively non-
hazardous to bees.
Todd and McGregar (43) classified the agricultural chemicals
according to toxicity to bees and indicated that toxaphene was least
dangerous to bees. Toxaphene, methoxychlor and sulphur were classi-
fied as materials which could be used with safety. Hocking (23) in-
dicated that the danger of toxaphene to honey bees was very low. Todd
et al (44) indicated that toxaphene was much less lethal to bees than
parathion, chlordane or DDT and caused no damage to the colonies.
In laboratory tests conducted in New Zealand, the ascending order of
toxicity to honey bees was toxaphene>Strobane>thiodan>diazinon (36, 37).
Toxaphene and Strobane were sprayed on white clover fields early in the
morning without causing bee mortality. In Canada, toxaphene was also applied
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95
to red clover without causing abnormal mortality to pollinating insects
(32).
Johansen (26) indicated that toxaphene was hazardous to the alfalfa
leaf cutter, but not to alkali bees. Menke (33) concluded that 15% toxa-
phene dust applied to blossoming alfalfa had little effect on the activity
of the alkali bee.
Effect of toxaphene on insect predators and parasites. Since
arthropod species tend to come to an equilibrium or "balance," removing
one or more species by frequent pesticide applications may upset the
balance in arthropod populations at any given time. The resurgence of
.pest populations after insecticide treatment is explained by (1) the re-
duction of natural enemies by the pesticide along with the pest, (2)
favorable influences of pesticides on the phytophagus arthropods and (3)
removal of competitive species (39).
The effect of toxaphene on beneficial insects has been studied by
many entomologists. Soon after toxaphene became available for cotton in-
sect control, Parcencia and Ewing (38) found that in experiments where
no sulphur was added to toxaphene an increase in red spider mite popula-
tions was evident. Spider mite infestations were also present in cotton
fields next to pastures where toxaphene was used to control grasshoppers
(16). Where sulphur was added to the toxaphene no spider mite increases
were seen. Apparently toxaphene destroyed the parasites or predators
of the red spider mites, creating an environment conductive to mite
increases.
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96
an environment conducive to mite increases.
A single application of toxaphene for cotton fleahopper control reduced
populations of beneficial insects; but, the populations increased in the
following - 3 weeks if no further applications of toxaphene were made (17, 18).
After the second to fourth application of toxaphene—sulphur dust made in a
regular boll weevil control program, the beneficial arthropod populations
(lady beetles, flower bugs, lacewings, Geocoris, assassin bugs and spiders)
were practically eliminated.
In laboratory tests, toxaphene at the rate of 2.5 Ibs per acre killed
from 84 to 85% of the spotted ladybeetle, Ceratomegilla fuscilabris and
Scymnus sp., but only about 50% of the convergent ladybeetle, Hippodamia
convergens, population (12). Results of field observations indicate that
toxaphene showed a moderate to high effect on all predators in the cotton
fields.
Burke (10, lla) reported that toxaphene was less toxic to adults of
Cpllops balteatus, larvae of Hippodamis convergens and adult Orius insidiosus
than dieldrin or endrin. Toxaphene, dieldrin and endrin were of about the
same toxicity to larvae of Chrysopa oculata when applied by the dipping
technique. Toxaphene and dieldrin exhibited a low level of toxicity to the
several insects included in these studies.
Almand (2) reported the results of observations made on three cotton
fields following insecticidal treatments. Carbofuran and toxaphene treated
fields contained the greatest number of predaceous insects. Attallah and
Newsome (6) reported that toxaphene decreased longevity and prevented ovi—
position of Coleomegilla maculata.
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97
Newsom and Smith (35) reported that toxaphene-sulphur (20%-40%) reduced
the population of beneficial species. Severe bollworm infestations developed
on a large cotton acreage which received 3 to 5 applications of either a 20%
toxaphene dust or benzene hexachloride-DDT mixture for boll weevil control.
Injurious bollworm infestations developed from comparatively small numbers of
eggs in fields treated with chlorinated hydrocarbon insecticides.
Bartlett (8) tested 61 pesticides against 5 hymenopterous parasites and
6 coccinellids. Toxaphene was highly toxic to all species of hymenopterous
parasites and showed low to medium toxicity to the coccinellids.
c
Van Den Bosch et al (46) tested the toxicity of widely used insecticides
on beneficial insects in cotton and alfalfa fields of California. Insects of
the following genera were included in the study: Orius, Geocoris, Nabis,
Chrysopa, and Hippodamia. All insecticides studied were toxic to the bene-
ficial insects to some degree but seemed to fall into three distinct groups:
1. highly toxic-parathion and toxaphene DDT combinations; 2. moderately
toxic - toxaphene, endrin, and DDT; 3. slightly toxic - demeton. Considerable
specificity was evident in the toxicities of the various insecticides.
Chrysopa larvae and Orius sp. were relatively tolerant to the wide variety of
insecticides tested.
Toxaphene - DDT spray mixtures applied at the rate of 1.3 Ibs DDT and
2.6 Ibs toxaphene were extremely toxic to Hippodamia convergens, and aphid
parasite, (Trioxys utilies), Geocoris spp. Orius spp., Nabis ferus and Sinea
diadima (42). DDT applied at the rate of 1.3 Ibs per acre was nearly as toxic
to the beneficial insects as the toxaphene DDT mixture.
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98
Toxaphene applied at the rate of 2.7 Ibs per acre was not as toxic as
DDT and was far less toxic than the toxaphene-DDT mixture. Parathion applied
at the rate of 3.6 oz per acre was comparable to toxaphene - DDT and had
generally drastic effects on the beneficial species.
Harries and Valcarce (21) found that 5% toxaphene killed 32% of the
Collops vittatus 12% of the Hippodamia convergens and 36% of the Colesmegilla
maculata; while 5% Strobane killed 10%, 18% and 12%, respectively. These
chlorinated hydrocarbons were not as toxic to these beneficial insects as the
organophosphorus compounds.
Lingren et al (31) reported that toxaphene-DDT and azodrin were highly
toxic to spiders. The mean numbers of all predators were significantly
greater in plots treated with trichlorofon than in those treated with Azodrin,
Bidrin®and toxaphene-DDT.
Toxaphene was not as toxic to Hippodamia convergens, Qrius^ insidiosus and
Scymnus spp. as Strobane - DDT, carbaryl, trichlorfon or dicrotophos applied
for cotton fleahopper control (48). Toxaphene was more toxic to spiders
than Strobane-DDT mixture. About 2 weeks after the second application was
made, the beneficial insect population resurged to effective predatory levels.
Wille (55) reported a large increase of Heliothis virescens occurred
following treatments of DDT, BHC or toxaphene. Apparently these materials
killed the beneficial insects without eliminating the pest.
Click and Lattimore (19) found that toxaphene BHC and chlordane reduced
the beneficial insects in cotton. Toxaphene was less destructive of pre-
dators than either BHC or chlordane and the addition of DDT to the chlorinated
hydrocarbons increased the toxicity to predators.
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99
Fenton (15) studied the effect of several insecticides applied to
alfalfa on beneficial insect populations. Toxaphene generally reduced
the beneficial insects less than parathion, endrin or demeton.
Toxaphene is only slightly toxic to bees and can be safely used
in bee pastures to control injurious insects, particularly if the mate-
rial is applied when the bees are not foraging.
SUMMARY
Toxaphene is highly toxic to predators and parasites of some
species and low in toxicity to others. Apparently one application of
toxaphene will reduce certain beneficial insects, but they usually re-
surge to normal levels within a few weeks. Regularly scheduled toxa-
phene treatments applied at intervals of 5 to 7 days generally will
eliminate beneficial insect populations in crops.
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100
REFERENCES
1. Akesson, N. B., and Yates W. E. (1964). Problems relating to appli-
cation of agricultural chemicals and resulting drift residues. Ann.
Rev. Ent. 9285-318.
2. Almand, L. K. (1970). The effects of insecticide applications on
predaceous insect and spider populations in cotton fields and a
comparison of sampling methods. M.S. Thesis. Texas A & M Univ.
3. Anderson, L. D., and Atkins, Jr. E. L., (1958). Effects of pesti-
cides on bees. Calif. Agri. 12(11): 3-4. '
4. Anderson, L. D., and Atkins, Jr. E. L., (1958). Toxicity of pesti-
cides to honeybees in laboratory and field tests in souther Cali-
fornia, 1955-1956. Econ. Ent. 51(1): 103-8.
5. Anderson, L. D., and Tuft, T. 0. (1952). Toxicity of several new
insecticides to honeybees. J. Econ. Ent. 45(3): 466-69.
6. Attallah, Yousef H. and Newsome, L. D., (1966). Ecological and
nutritional studies on Colemegilla macalata DeGeer (Coleoptera:
Coccinellidae) III. The effect of DDT, toxaphene and endrin on the
reproductive and survival potential. J. Econ. Ent. 59(5): 1181-87.
7. Atkins, E. L., Jr., and Anderson, L. D., (1954). Toxicity of pesti-
cides dusts to honeybees. J. Econ. Ent. 47(6): 969-972.
8. Bartlett, B. R. (1963). The contact toxicity of some pesticide resi-
dues to hymenopterous parasites and cocinellid predators. J. Econ.
Ent. 56 (5): 694-98.
9. Bartlett, B. R. (1964). Toxicity of some pesticides to eggs, larvae
and adults of the Green lacewing, Chrysopa carnea. J. Econ. Ent.
57(3): 366-69.
10. Burke, H. R. (1959). Insecticidal studies on several predaceous in-
sects associated with cotton. Ph.D., Thesis, Texas A&M Univ.
11. (1959a). Toxicity of several insecticides to two species of bene-
ficial insects on cotton. J. Econ. Ent. 52(4): 616-18.
12. Campbell, W. V. and Hutchins, E., (1952). Toxicity of insecticides
to some predaceous insects on cotton. J. Econ. Ent. 45(5):829-33.
13. Daniels, N. E. (1955). Insects affecting alfalfa seed production.
J. Econ. Ent. 48(3): 339-340.
-------
101
14. Eckert, J. E. (1949). Determining toxicity of Agricultural Chemi-
cals to honeybees. J. Econ. Ent. 42(3): 261-265.
15. Fenton, F. A. (1959). The effect of several insecticides on the
total arthropodopopulation in alfalfa. J. Econ. Ent. 52(3): 428-32.
16. Gaines, J. C. and Dean, H. A., (1949). Insecticide tests for boll
weevil control during 1948. J. Econ. Ent. 42(5): 795-798.
17. Gaines, R. C., (1954). Effect on beneficial insects of several
insecticides applied for cotton insect control during 1954. J.
Econ. Ent. 47(3): 543-44.
18. Gaines, R. C. (1955). Effect of beneficial insects of three in-
secticide mixtures applied for cotton insect control during 1954.
J. Econ. Ent. 48(4): 477-78.
19. Click, P. A. and Lattimore, W. B., Jr. (1954). The relation of
insecticides to insect populations in cotton fields. J. Econ. Ent.
47(4); 681-684.
20. Graves, J. B. and Mackensen, 0., (1965). Topical application and
insecticide resistance studies on the honeybee. J. Econ. Ent.
58(5): 990-93.
21. Harries, F. H. and Valcarce, A. C. (1955). Laboratory tests of
the effect of insecticides on some beneficial insects. J. Econ.
Ent. 48(5): 614.
22. Hetrick, L. A. and Moses, P. J., (1953). Value of insecticides
for protection of pine pulpwood. J. Econ. Ent. 46(1): 160-161.
23. Hocking, B. (1950). The Honeybees and agricultural chemicals. The
Bee World 31(7): 49-53.
24. Johansen, C. A., (1965). Bee poisoning, a hazard of applying agri-
cultural chemicals. Wash. Agr. Exp. Sta., Cir. 356 1-13.
25. Johansen, C. A., (1966). Digest of bee poisoning, its effects and
prevention. The Bee World 47(1): 9-25.
26. Johansen, A., (1969). The bee pisoning hazard from pesticides.
Wash. Agr. Exp. Sta. Bull. 709 1-14.
27. Jones, D. G. and Connell, J. U. (1954). Studies of the toxicity to
worker honeybees (Aphis mellifera L.) of certain chemicals used in
plan protection. Ann. Appl. Biol. 41(2): 271-279.
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102
28. King, D. R. and Rosberg D. W., (1956). Control of Tetranychus
hicoriae McG. on pecans. J. Econ. Ent. 49(3): 404-405.
29. La Croix, E. A. (1962). Use of some miticides in the control of
red spider mites on cotton. Emp. Cott. Gr. Rev. 39(3): 197-202.
30. Lieberman, F. V., Bohart, G. E., Knowlton, G. F. and Nye, W. P.,
(1954). Additional studies on the effect of field applications of
insecticides on honeybees. J. Econ. Ent. 47(2): 316-320.
31. Lingren, P. D., Ridgway, R. L., Cowan, C. B., Jr., Davis, J. W., and
Watkins, W. C., (1968). Biological control of the bollworm and
tobacco budworm by arthropod predators affected by insecticides.
: J. Econ. Ent. 61(6): 1521-25.
32. MacVicar, R. M., Braun, E., Gibson, D. R., and.Jamieson, C. A.
(1952). Studies in the Red Clover seed production. Sci. Agri.
32(2): 67-80.
33. Menke, H- F. (1954). Repellency of toxaphene dust and parathlon
spray to Nomia melanderi in blossoming alfalfa. J. Econ. Ent.
47(3): 539-540.
34. Newsom, L. D. (1967). Consequences of insecticide use on nontarget
organisms. Ann. Rev. Ent. 12:257-286.
35. Newsom, L. D. and Smith, C. E., (1949). Destruction of certain in-
sect predators by .applications of insecticides to control cotton
pests. J. Econ. Ent. 42(6): 904-908.
36. Palmer-Jones, T. (1958). Laboratory methods for measuring the
toxicity of pesticides to honeybees. New Zeal. Agri. Res. 1(3):
290-300.
37. Palmer-Jones, T., Foster, I. W. and Line, L. S., (1958). Effect of
honeybees of toxaphene and strobane applied to white clover pasture.
N. Zeal, Agr. Res. 1(5): 694-706.
38. Parencia, C. R. and Ewing, K. P. (1948). Control of cotton flea-
hopper by chlorinated camphene, DDT and sulphur. J. Econ. Ent.
41(5): 735-738.
39. Ripper, W. E. (1956). Effect of pesticides on balance of arthropod
populations. Ann. Rev. of Ent. 1:403-83.
40. Roberts, J. E. and Barnes, G. (1966). Suggestions for protecting
honeybees from pesticides. Agr. Ext. Serv., Univ. of Arkansas,
leaflet unnumbered.
41. Ruinard, J. (1958). Onderzoekingen omtrent levensivijze, economishe
betekenis en beslrijdengmogelijkhenden der Stengel boorders van Let
suikeriet op Java. Proefschr. Landbbuwhogesch. Wagenining.
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103
42. Stern, V. M., Van den Bosch, R. and Reynolds, H. T., 1959. Effects
of Dylox and other insecticides on entomophagous insects attacking
field crop pests in California. J. Econ. Ent. 53(1): 67-72.
43. Todd, F. E. and S. E. McGregor, (1952). Insecticides and bees.
Insects USDA Agriculture Yearbook pp. 131-135.
44. Todd, F. E., Lieberman, F. V., Nye, W. P., and Knowlton, G. F.
(1949). The effect of field applications of insecticides on honey-
bees. Agri. Chemicals (8) 27-29, 77.
45. USDA. (1967). Protecting honey bees from pesticides. 544 1-6.
46. Van den Bosch, R., Reynolds R. T. and Dietrick, E. J. (1956).
Toxicity of widely used insecticides to beneficial insects in Cali-
fornia cotton and alfalfa fields. J. Econ.! Ent. 49(3): 359-63.
47. Van den Laan, R. A. (1951). De mogelijkhenden van destryding det
rijsolboorders (possibilities of controlling rice-borers) Landborer
23(7-9) 295-356. Djakarta (From Review of Applied Entomology).
48. Walker, J. K., Jr., Shepard, and Sterling, W. L. (1970). Effect of
insecticide applications for the cotton fleahopper on beneficial in-
sects and spiders. Tex. Agr. Exp. Sta. Prog. Rept. 2755 1-11.
49. Weaver, N., (1949). Toxicity of certain organic insecticides to
honey bees. J. Econ. Ent. 42(6): 973-75.
50. Weaver, N..± (1950). Toxicity of organic insecticides to honey bees:
Stomach poison and field tests. J. Econ. Ent. 43(3): 333-37.
51. Weaver, N., (1951). Toxicity of organic insecticides to honey
bees: Contact spray and field tests. J. Econ. Ent. 44(3): 393-397.
52. Weaver, N., (1952). The toxicity of organic insecticides to honey
bees. J. Econ. Ent. 45(3): 537-538.
53. Weaver, N., (1953). Toxicity of insecticides to honey bees. Texas.
Agri. Exp. Sta. Prog. Rept. 1554 1-3.
54. Weaver, N., and Garner, C. F. (1955). Control of insects on hairy
vetch. J. Econ. Ent. 48(5): 625-626.
55. Wene, G. P., (1955). Effect of some organic insecticides on the
population levels of the serpentine leaf miner and its parasites.
J. Econ. Ent. 48(5): 596-597.
56. Wille, J. E., (1951). Biological control of certain cotton insects
and application of new organic insecticides in Peru. J. Econ. Ent.
44(1): 13-18.
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104
RESIDUES IN FOOD CROPS AND FOODS
Tolerances for Toxaphene Residues
The following tolerances for toxaphene residues in raw agricultural
crops have been established and were in effect as of September 1971 in
the United States, Canada, Germany and The Netherlands:
United States
2 ppm
Soybeans
3 ppm
Pineapples
Bananas (0.3 ppm in edible pulp)
5^ ppm
Grain (Barley, oats, rice, rye, sorghum grain, wheat,
cottonseed)
6 ppm
Crude Soybean Oil
7_ ppm
Fruits (stone, pome, citrus, cane and strawberries)
Nuts (Hazel, hickory, pecan, walnut)
Meat Fat (Beef, sheep, goat, swine, horse)
Vegetables (Beans, black-eyed peas, broccoli, brussels sprouts,
cabbage, cauliflower, carrots, celery, collards, corn, cowpeas,
eggplant, green beans, horseradish, kale, kohlrabi, lettuce,
lima beans, okra, onions, parsnips, peanuts, peas, peppers,
radishes, rutabagas, snap beans, spinach, tomatoes)
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105
Canada
3 ppm
Oats, rye, wheat, pineapples
5 ppm
Barley, grain sorghum, rice
7 ppm
Fruits (citrus, peas, strawberries)
Meat fat (cattle, goats, sheep, swine)
Vegetables (beans, black-eyed peas, broccoli, brussels sprouts,
cabbage, cauliflower, celery, eggplant, kohlrabi, lettuce,
okra, onions, peas, tomatoes)
Germany
0.4 ppm
Pears, strawberries, raspberries, cherries, plums
The Netherlands
0^.4 ppm
Fruit, vegetables (except potatoes)
Residues in Food
Toxaphene is registered for a variety of uses on food crops and
livestock. During 1965-1968, FDA market-basket surveys showed toxaphene
to be virtually absent from these samples. The frequency of occurrence
of toxaphene residues in these studies was less than that of the first
15 most commonly found pesticides. The market— basket samples represent
the total diet of a 16-19 year-old male , and are obtained from retail
stores in 5 regions at bi-monthly intervals. Food is prepared for
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106
consumption and analyzed for pesticide residues using gas-liquid
chromatography methods.
In the later period June 1968-April 1969, toxaphene was detected
in 13 of the 360 composite samples analyzed. Range of residues was
0.02 to 0.33 ppm in food categories, garden fruit, vegetables, and
meat fat. DDT was the most frequently found residue being detected in
176 samples in the range of 0.003 to 0.47 ppm.
FDA surveillance studies include an annual examination of about
25,000 samples. These samples are taken objectively to characterize
the pesticide residues of food shipped and consumed in the United
States. They are in addition to those that are analyzed in enforcement
programs designed to verify suspicions of excessive residues resulting
from pesticide misuse.
A summary of the surveillance program results for toxaphene in
the period 1964-67 is given below using the food categories established
by FDA (see Table 1). These data reflect the widespread usage of
toxaphene on vegetables and the retention of some of the residue in
the processed (canned, dried, or frozen) food. Toxaphene residues were
sixth most frequent in occurrence of all pesticides in processed foods,
but few, if any, were in excess of the 7 ppm tolerance.
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107
Toxaphene finds its most intensive agricultural use on cotton.
It is also used to a lesser extent on other oil seed crops such as
soybeans, peanuts and corn. Analysis of oil and other products derived
from these crops show toxaphene is found in about 30% of the cotton-
seed samples, 8% of the soybean samples and 2% of the peanut samples.
Above-tolerance residues have not been a problem either in the raw
agricultural commodities or in the processed oils and meals. Table 2
is a summary of toxaphene residues found during 1964-1966 in oily crops.
Residues in Livestock
Toxaphene residues can be accumulated in fat of animals from
ingestion and by dermal absorption. The storage level is much less
than that of most other chlorinated hydrocarbon pesticides, and an
equilibrium with the exposure level is rather quickly achieved. Elimi-
nation of toxaphene from the fat is quite rapid when the input is
reduced. Storage—feed ratios for various animal species are summarized
as follows:
(a.)
Storage-feedv ' Observation
Cattle
Sheep
Dog
Rat
ratio
0.5
0.3
0.3
0.4
ppm in fat
Tat--ir* — i-=
Period
16 weeks
16 weeks
2 years
2 years
/ \ o_ c j *. • ppm -in rat
(a) Storage-feed ratio = :—^—-
& ppm in feed
The rapid elimination of toxaphene residues from the fat of neat
animals allows it to be used for ectoparasite control on livestock
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108
within 28 days of slaughter. Where shorter pre-slaughter intervals
are required, other pesticides must be used.
USDA Meat and Poultry Inspection Programs have been established
to regularly examine tissues from meat animals and poultry slaughtered
in federally-inspected plants. Total number of animal tissue samples
analyzed in the 27-month period from January, 1969 through March, 1971
was 7,265. Of these, only 5 contained toxaphene residues. In the
same period, of 5,504 poultry samples analyzed, 2 contained toxaphene.
A tabulation of these data is given in Table 3. No residue levels
are given in this summary report. Only 1-2% of the samples found to
contain any pesticide residues were above the tolerance limit.
Residues in Milk
Consistent with the fat-storage properties of toxaphene in live-
stock, transmission of toxaphene residues to milk follows the same
pattern (8). Equilibrium with input is reached within about one week,
and the ratio of toxaphene concentration in the feed to that in the
milk is about 100:1. Excretion of toxaphene in milk declines quickly
when exposure ceases.
In feeding trials, milk free of toxaphene residues was produced
within 2 weeks after cessation of feeding at levels of 10 ppm. Fluid
milk or dairy products do not often contain toxaphene in FDA sur-
veillance programs. At a feeding level of 20 ppm in the daily diet
for 11 weeks, toxaphene-free milk was produced A weeks after toxaphene-
containing feed was discontinued.
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109
Residue Decline - Controlled Studies
Table 4 is taken from the FAO-WHO monograph on toxaphene residues
in food. It selectively.summarizes toxaphene residue data on repre-
sentative crops when normal agricultural practices are followed.
Half-lives of toxaphene residues on growing leafy crops are in
the range of 5-10 days; residues from emulsifiable formulations are
typically higher than those from wettable powders or dusts.
Studies of toxaphene residues on alfalfa and clover show that
.half-lives (corrected for crop growth dilution) are consistently in the
range of 9 to 13 days under widely varying climatic conditions. Studies
were conducted in Arizona, California and Delaware.
Mechanism of Residue Loss
Evaporation. Summarized in Table 5 are data comparing volatility
of toxaphene with that of DDT. These measurements as well as field
studies indicate that toxaphene is more volatile than DDT, and that
volatility can be a significant factor in the loss of toxaphene from
treated areas. Tests of toxaphene volatility from thin film on glass
plates show greater loss of early-eluting GC components. Examination
of field—weathered crop residues do not show evidence of such selective
loss, but are similar in composition to parent toxaphene.
Toxaphene was easily washed from smooth glass surfaces by heavy
rains, in contrast to deposits on crops, which are much more resistant
to wash-off by rain. Sunlight had little effect on the rate of loss
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110
of thin films of toxaphene from glass plates. Half-lives of 4 days
were found under conditions of indoor exposure at summer temperatures
ranging to 34°C. Indoor exposure during winter months (19-24°C)
revealed a half-life of 26 days. In an oven heated to 38 C, a half-
life of 3 days was observed. Addition of alfalfa plant wax caused an
appreciable decrease in the rate of loss at 38°C, the observed half-
life being 8 days.
Attempts to detect possible toxaphene metabolites. The complex
composition of toxaphene has made explicit metabolic fate studies in
crops and animals impossible. Early research workers have used non-
specific "total organic chloride" methods, lacking specificity, and
yet accounting for all of the chlorine-containing species, whether
parent compound or derived therefrom. Other methods for analyzing
possible toxaphene metabolites were also unsuccessful, including
paper-and thin-layer chromatography and gas-liquid chromatography.
There is no evidence for the existence of toxaphene conversion
products in weathered crop residues or in fat deposits from animals
exposed or fed with toxaphene. Carter ^jt
-------
Ill
Klein and Link (6) examined residues on toxaphene-sprayed kale
and found that over 99% of the original residue was lost during the
first two weeks. Gas chromatographic analysis of the residues indicated
a modest loss of early-eluting GLC components. However, the composition
of the residue even after 4 weeks was readily recognizable as toxaphene
from the GLC elution pattern.
Carlin (2) concluded that no toxaphene conversion products were
formed in alfalfa treated with toxaphene and allowed to weather. These
conclusions were based on "total chloride" methods, electron capture
GLC, and bioassays, the last showing no greater toxicity than authentic
toxaphene.
Possible metabolites of toxaphene. Attempts to introduce functional
groups into toxaphene by in vitro chemical reaction have been unsuccess-
ful, and the availability of model compounds as authentic reference
standards for various separation and detection systems has been limited.
Recently, samples of "keto-toxaphene" and "hydroxy-toxaphene" were
prepared by Buntin. (1) Camphor was chlorinated to a value correspond-
ing to the addition of 7 atoms of chlorine. The resulting "keto-
toxaphene," a viscous pale yellow liquid, was reduced with lithium
aluminum hydride to form "hydroxy-toxaphene." These compounds are less
toxic to flies and rats than toxaphene; gas chromatography shows they
elute with the early peaks of toxaphene.
Cleanup techniques applied to keto-toxaphene and hydroxy—toxaphene
show that the former survives fuming sulfuric acid, but that hydroxy-
-------
112
toxaphene does not. Dehydrohalogenation (as applied to toxaphene prior
to gas chrbmatography)'showed"-that'2 these 'compounds are retained^in the
alkaline'aqueous phase when^it is extracted with hexarie. nBoth-compounds
• are extracted" by hexane from-distilled1 wate"rr;-:- - .;,:-i^?,. ..•••;•:> ;'• .: i
'-' r Weathered toxaphene residues from alfalfa:were-exainined-for1 the -
o
possible presence of' keto-toxaphene or hydroxy-toxaphenei • No -evidence
for their presence was found (2).
Metabolism in the Honey Bee
A study of toxaphene residues in rape oil, honey, and bees was
conducted by Jumar and Sieber (5). They prepared a Cl-tagged toxaphene
• '.. "/ .'':.' :_; •• ;. •:.':•:•::'• -;^.,.;-". i .-, ...'".-'?.'.- : •:::.'. .-?;•:; ' .:. '.:. i?.-. :• : • •-': j.'.:.
and determined that residues were transmitted to rape oil in the range
of 0.3 to 1.5 ppm, depending on the method of application to the rape
plant. Honey made by bees exposed to the toxaphene-treated rape plants
contained less than 0.01 ppm toxaphene. The study on toxaphene in the
bee employed 82Br-toxaphene (one Cl atom replaced by 82Br). More than
95% of toxaphene absorbed by bees from feeding was stored briefly in the
body before release as a chlorine-containing water-soluble compound
which was not identified.
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113
REFERENCES
1. Buntin, G. A. (1970). Hercules Research Center, Wilmington,
Delaware. Unpublished Results.
2. Carlin, F. J. (1970). Hercules Research Center, Wilmington,
Delaware. Unpublished Results.
3. Carter, R. H., Nelson, R. H., and Gersdorff, W. A. (1950).
Organic-chlorine determinations as a measure of insecticide
residues in agricultural products. Advances in Chem. 1: 271-3.
4. Hercules Research Center, Wilmington, Delaware. Unpublished
Results.
5. Jumar, A. and Sieber, K. (1967). Residue studies in rapeseed
oil and honey with toxaphene - 36 Cl. Z. Lebens,- Unters,
Forsch. 133: 357-364.
6. Klein, A. K., and Link, J. D. (1967). Field weathering of
toxaphene and chlordane, J. Assoc. Off Anal. Chem. 50: 586-591.
7. Lloyd-Jones, C. P. (1971). Evaporation of DDT. Nature 229:
65-66.
8. Zweig, G., Pye, E. L., Sitlani, R., and Peoples, S. A. (1963).
Residues in milk from dairy cows fed low levels of toxaphene
in their daily ration. J. Agr. Food Chem. 11: 70.
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114
TABLE 1
DOMESTIC FOODS SURVEILLANCE BY FDA — 1964 to 1967
Toxaphene Residues
Food Category
Large Fruits
Small Fruits
Grains and Cereals for
human use
Leaf and Stem Vegetables
Vine and Ear Vegetables
Root Vegetables
Beans
Eggs
Nuts
Processed Foods
Grains (animal)
Fluid Milk (fat basis)
Dairy Products (fat basis)
Incidence
Percent
0.3
1.3
0.3
6.4
1.4
1.1
0.9
0.2
0.3
5.0
0.1
Average
ppm
T*
0.01
T
0.18
0.01
T
T
T
T
0.45
T
T* = < 0.005 ppm (trace)
-------
TABLE 2
Summary of Toxaphene Residues
In Oil Seeds, Oils, and By-Products (1964-66)
Toxaphene
Incidence Average
SOYBEANS
Crude Oil
Meal (cake)
Refined Oil
PEANUTS
Crude Oil
Meal (cake)
Refined Oil
COTTONSEED
Crude Oil
Meal (cale)
Refined Oil
CORN GRAIN
Crude Oil
Refined Oil
Percent
8.0
4.1
_*
4.3
1.7
2.8
_*
_*
30.4
1.3
1.1
12.2
_*
_*
_*
ppm
0.004
0.024
**T
0.006
0.008
0.023
0.010
0.003
0.140
* Signifies not detected
**T Signifies less than 0.001 ppm
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116
TABLE 3
Chlorinated Pesticide Residues
In Meat and Poultry 1969-1971
(Frequency of a specific residue in animal and poultry tissue)
Animal
Pesticide
Aldrin
BHC
Chlordane
Dieldrin
DDT + me tab.
Endrin
Heptachlor
Lindane
Methoxychlor
Toxaphene
Total with residue
Total Samples
Total over limits
1969
14
523
2
1,336
2,671
27
752
505
74
2
2,907
3,169
35
1970
66
610
2
1,549
2,835
104
1,006
425
39
3
3,238
3,528
55
3 mo. 1971
2
59
1
219
402
18
61
34
13 '
0
473
568
4
1969
6
294
0
1,639
2,187
87
313
197
28
2
2,181
2,199
10
Poultry
1970
51
517
0
2,270
2,850
111
877
242
27
0
2,951
2,999
33
3 mo. 1971
0
14
0
138
299
29
54
13
0
0
303
306
2
-------
TABLE 4
Toxaphene Residues Resulting From Supervised Trials
117
Vegetables
Lettuce
Kale
Cabbage
Spinach
Celery
Cauliflower
Broccoli
Tomatoes
Greenbeans
Lima Beans
Carrots
Potatoes
Field Peas
Oil Seeds
Cotton (seed)
Soybeans
Peanuts
(shelled)
Fruit
Oranges
Bananas
Pineapple
Cereal Grains
Wheat
Barley
Oats
Rice
Sorghum
Corn (maize)
Fat of Meat
Animals
Beef
Swine
Shelled Nuts
Almonds
Rate of
Application
(kg/ha)
5.5
5.0
1.9-12
5.0
1.1-1.6
3.8
10
1.3-2.5
7.5
3.9
25
0.95-2.5
2.5
3.9-5.0
3.8
25-50
5.7
3.8
2.8
1.9-3.8
1.9-3.8
1.9-3.8
1.9-3.8
2.5
2.5
0.5%
0.5%
4.0
No. of
Treat-
ments
1-1
4
2-6
4
9
1
1
8-9
1
1
2-4
6
,. 3
15
3
1
2
1
2
1
1
1
1
1
1
12
2
3
Pre-harvest*
Interval
(days)
10
36
9-38
30
13
8
8
5-7
7
14
21
4
6
60
7-70
1
81-96
14-21
7-28
7
7-28
28
12
28
28
136
Residue
at Harvest
(ppm)
5.8-7.9
3.3-7.2
0.8-6.6
16.7-18.8
1.8 stalks
6 . 5 leaves
1.1
3.4
2.0-4.3
1.3
0.3
0.9-3.3
0 detected
1.8
3.6-5.2
0.5
0 detected
0-10.9 skins
0-0.3 pulp
0.3-1.3
1.3-2.7
0.5-1.8
0.7-14.2
1.0-2.6
1.5-5,6
2.5-3.1
0.08 kernals
5.0
0-0.6
1.5
Comments
whole head
on outer leaves
washed
(processed com-
mercially & frozen
before analysis)
unwashed
shelled beans
soil applic. 1 yr.
lint bearing seed
soil treat.
whole fruit
whole fruit
unfinished grain
12 weekly sprays
2 sprays
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118
Table 5
Evaporation Rates — DDT(7) vs. Toxaphene(4)
\j
yg/cm2/hr Ibs/acre/year
Conditions DDT Toxaphene DDT Toxaphene
Room Temperature - no sunlight 2 x 10"3 5 x 10~3 1.6 3.9
Outdoors 3 x I0"k 6.4 x 10~3 0.2 5.0
Outdoors - 20°C, 10 mph wind 1 x 10"3 0.8
Framglass, summer 2.0
Framglass, winter 0.3
32-38°C, (oven) - toxaphene alone 11.9 x 10-3 9.3
32-38°C, (oven) - toxaphene + alfalfa wax 1.7 x 10~3 1.3
-------
Table 6
Comparison of Toxicity of Toxaphene
with Hypothetical Metabolites
119
Housefly Bioassay
Compound
LC
50!
(a) From earlier test
Toxicity Ratio
Toxaphene standard
Keto-toxaphene
Hydroxy-toxaphene
0.052
0.17
0.32
1
1/3
1/6
Rat Toxicity
Rat Toxicity
Compound
Toxaphene standard (a)
Ke to- toxaphene
Hydroxy-toxaphene
.LD_n, mg/kg
50'
120
425
>1,080
Toxicity Ratio
1
I/A
>l/9
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TOXICOLOGY IN MAN AND ANIMALS
Acute toxicity and pharmacological actions. Acutely toxic doses
of toxaphene produce effects that are typical of the chlorinated hydro-
carbon insecticides (1, 5, 12). Symptoms include salivation, spasms
of the leg and back muscles, nausea, vomiting, hyperexcitability, tremors,
chronic convulsions and tetanic contractions of all skeletal muscles.
Most of these effects are the results of diffuse stimulation of the
cerebrospinal axis. After lethal doses the convulsions continue until
death occurs. Respiration is arrested due to tetanic muscular contractions
and then increases in amplitude and rate as the muscles relax (17, 18).
Toxic symptoms begin within an hour and death occurs in 4 to 8
hours, but may be delayed as long as 24 hours after lethal doses. The
pathological changes in acute toxaphene poisoning consist of petechial
hemorrhages and congestion in the brain, lungs, spinal cord, heart and
intestine. Pulmonary edema and focal areas of degeneration in the brain
and spinal cord are also present.
The basic mechanism responsible for the toxicity of toxaphene is
unknown since no studies on this aspect of the toxicology of toxaphene
have been reported. However, due to the close similarity between the
pharmacological actions of toxaphene and DDT, it seems likely that
findings made on the action of DDT will be applicable to toxaphene. The
similarity between the pharmacological actions of toxaphene and DDT is
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substantiated by the fact that phenobarbital and other barbiturates
effectively treat acute poisoning by both compounds.
The pharmacological actions of toxaphene and its mammalian toxicity
have been known for almost 20 years. As a result, the references
commonly used as sources of information for diagnosis and emergency
treatment of pesticide poisoning (4, 10, 11, 20) contain essential
information needed to prevent and treat toxaphene poisoning.
The acute toxicity of toxaphene was measured in a number of species.
A comparison of the oral and dermal toxicity of several chlorinated
hydrocarbon insecticides in rats under standardized conditions was
published by Gaines (8). Table I contains data from that report. For
oral administration, the compounds were dissolved or suspended in peanut
oil and for dermal application xylene solutions were used.
TABLE 1
Acute Oral and Dermal LD,.- Values for Toxaphene and Other Chlorinated
Hydrocarbons to Rats (a)
Compound
Toxaphene
DDT
Chlordane
Aldrin
Dieldrin
Endrin
Oral LD3
Males
90
113
335
39
46
18
0 (mg/kg)
Females
80
118
430
60
46
8
Dermal LI
Males
1075
-
840
98
90
-
)5Q (mg/kg)
Females
780
2510
690
98
60
15
(a) Data from Caines (8)
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122
o
The data in Table 1 show that toxaphene resembles DDT in acute
oral toxicity to rats but is more toxic by single dose dermal applica-
tion than DDT. A number of factors influence the toxicity of toxaphene.
The route of administration, the solvent used for the tests, and the
species must be considered in evaluating the potential hazard. Informa-
tion on the influence of these factors on the toxicity of toxaphene was
obtained by compiling the acute toxicity data in the literature.
The data in Table 2 show the range of variation in toxicity of toxa-
phene given orally to several common species.
Table 2
Acute Toxicity of Toxaphene (a)
Species
Rat
Rat
Rat
Mouse
Dog
Dog
Guinea pig
Guinea pig
Cat
Rabbit
Rabbit
Cattle
Goat
Sheep
Rat
Rabbit
Rabbit
Route
oral
oral
oral
oral
oral
oral
oral
oral
oral
oral
oral
oral
oral
oral
dermal
dermal
dermal
LD50
(mg/kg)
90
60
120
112
49
>250
270
365
25-40
75-100
250-500
144
200
200
930
>4000
< 250
Vehicle
peanut oil
corn oil
kerosene
corn oil
corn oil
kerosene
corn oil
kerosene
peanut oil
peanut oil
kerosene
grain
xylene
xylene
xylene
dust
peanut oil
(a) Bulletin by Hercules Incorporated (12)
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123
Assuming man resembles the most sensitive experimental species, the
lethal dose for a 70 kg adult would be around 2 to 3.5g. The fatal dose
for man was estimated to be from 2 to 7g (1, 4, 10).
Acute toxaphene poisoning in humans is rare. When this material was
first used (17), four cases of poisoning by ingestion in children under
4 years of age were reported occurred. The same report contained a
description of severe toxaphene poisoning in adults following misuse of
the pesticide in agriculture. The quantity of toxaphene estimated to
have been ingested by three of the people ranged from 9.5 to 47 mg/kg.
Due-to the long period of use and experience with toxaphene and its
moderate toxicity, accidental poisoning by this insecticide is now
extremely uncommon. In contrast, accidental poisoning by possible
substitutes such as the organophosphorus insecticides are expected to
exceed those that resulted from toxaphene because of the higher toxicity
of the organophosphates.
Inhalation of toxaphene can cause irritation of the respiratory tract.
Warraki (22) has described acute bronchopneumonia with miliary shadows in
two men with an occupational history of heavy and prolonged exposure to
toxaphene sprays. The threshold limit value for atmospheric levels of
toxaphene has been established at 0.5 mg per cubic meter of air (7).
Subacute toxicity. The subacute toxicity of toxaphene was studied
by Ortega et al., (19) in small groups of rats fed 50 and 200 ppm in the
diet. These dietary levels produced no clinical signs of toxicity or
inhibition of food consumption or growth rate. Only the livers, spleens
and kidneys were examined histologically. There was no damage to the
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124
kidney or spleen but the livers of 3 of 12 rats that received 50 ppm
showed slight liver changes. Six of 12 rats fed 200 ppm showed distinct
liver changes.
A subacute toxicity study on dogs was done (16) in which two dogs
received 4 rag/kg (about 160 ppm) for 44 days and two other dogs received
the same dose for 106 days. There was occasional central nervous system
stimulation for a short time after administration. Degenerative changes
in the kidney tubules and liver parenchyma were seen.
Cattle and sheep were fed toxaphene at concentrations as high as
320 ppm in the diet for 134 and 151 days. At the highest level (320 ppm)
two steers showed central nervous system stimulation with tremors. There
was no hematological or pathological changes in the tissues.
Chronic toxicity. The chronic toxicity of toxaphene has been
studied in rats using the conventional 2-year feeding period at levels
of 25, 100 and 400 ppm in the diet (6). Only the liver showed signi-
ficant changes at the 100 and 400 ppm levels.
In dogs fed 40 ppm of toxaphene in the diet for 2 years there was
slight degeneration of the liver, and at 200 ppm moderate degeneration
of the liver occurred (21). There were no liver changes in groups of
2 dogs fed 5, 10 or 20 ppm of toxaphene for 2 years (2).
Reproduction, teratology and mutagenesis. A three-generation re-
production study was conducted on rats fed 25 and 100 ppm toxaphene (14).
This study was carried out using the currently accepted protocol with
respect to numbers of animals and the types of measurements that were made.
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125
There were no differences between control and toxaphene-treated rats in
reproductive performance, fertility, lactation, or the viability, size and
anatomical structure of progeny.
An earlier study was done on pheasants fed 100 and 300 ppm of
toxaphene (9). The 300 ppm level caused a decrease in egg laying and
hatchability and in the food intake and weight gain. Both dose levels
caused greater mortality in young pheasants during the first 2 weeks after
hatching than was observed in the controls.
No evidence of a carcinogenic action by toxaphene was obtained in
the chronic toxicity studies described above. A recent experiment (13)
was conducted to detect turmorigenicity of pesticides by oral administra-
tion of maximum tolerated doses to mice starting at 7 days of age and
continuing to 4 weeks of age. From 4 weeks of age until 18 months of
age, the chemicals were fed in the diet at levels near the maximum tolerated
dose. Toxaphene was not included in that study but the closely related
material, strobane, given at a daily dose of 4.64 mg/kg caused a higher
incidence of lymphomas than was seen in controls. No studies on the
possible mutagenic effects of toxaphene have been reported.
Interactions. Toxaphene can change the toxicity of drugs and other
chemicals detoxified by hepatic microsomal enzymes and alter steroid
metabolism because it induces synthesis of hepatic microsomal enzymes
(15). Dose-response relationships for enzyme induction by toxaphene
were measured by feeding various dietary levels to rats for 13 weeks.
The lowest dietary level of toxaphene that cause induction of one or more
of the three microsomal enzyme systems studied was 5 ppm.
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126
o
Maximum induction occurred within the first 3 weeks of the feeding
period at all levels of toxaphene that cause enzyme induction. After
this time the activity was maintained at a constant elevated level until
feeding of the pesticide was discontinued.
These results show that levels of 5 ppm and higher could alter the
metabolism rate of other chemicals. Similar enzyme induction was
obtained with DDT at a dietary level of 1 ppm. 'No similar quantitative
measurements of dose-response relationships for enzyme induction with
toxaphene were conducted on other species.
Except for interactions caused by enzyme induction, there have been
no studies showing any other type of interactions that could be caused
by toxaphene.
Tissue residues. Toxaphene accumulates in the fat of man and
animals. With any given rate of subacute intake, a certain storage level
is attained with no build up above this level, and when the intake of
toxaphene is stopped the residue rapidly decreased (3).
The storage level of toxaphene is lower and elimination is more
rapid .than with most other chlorinated hydrocarbons. In cattle and
sheep ,the storage level in fat is one-fourth to one-half of the level in
the feed. The storage level in fat of hogs is somewhat less than in
other .livestock probably because of the greater total fat content. No
residue studies were reported on human tissues. Future analysis of
autopsy material for pesticide levels should include toxaphene.
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Summary
The mammalian toxicity of toxaphene was measured in various
experimental animals. Since toxaphene was one of the earliest chlori-
nated hydrocarbons intoduced into widespread use, the toxicity studies
conducted over 20 years ago are summarized in most of the common refer-
ences on the toxicity, diagnosis and treatment of poisoning by pesticides.
A few cases of fatal accidental poisoning from ingestion of toxaphene
occurred during the early period of the practical use of toxaphene.
Evaluation of the acute toxicity of toxaphene and its pharmacological
actions is adequate as it resembles other chlorinated hydrocarbon insecti-
cides in many respects.
Measurements of the subacute and chronic toxicity of toxaphene in
experimental animals revealed that repeated high doses cause central
nervous system excitation and liver injury. The latter effect occurs at
lower doses fed to animals over a prolonged period. However, no liver
injury occurred when rats were fed 25 ppm of toxaphene or when dogs
were fed 20 ppm of toxaphene for two years.
The conventional three generation rat reproduction study showed no
adverse reproductive or congenital effects by toxaphene in this species
at dietary levels of 25 and 100 ppm. Egg production and hatchability
decreased in pheasants fed 300 ppm and at this level, as well as 100 ppm,
there was greater mortality of young pheasants during the first 2 weeks
after hatching.
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128
The conventional 2-year feeding studies in rats and dogs showed no
evidence that toxaphene is carcinogenic. However, a different type of
exposure in which young mice were treated from 7 days to 18 mo of age with
a maximum tolerated dose indicated that Strobane caused a higher incidence
of lymphomas than was seen in control mice. Toxaphene has not yet been
tested for mutagenicity.
The pattern of uptake and storage of toxaphene in animal tissues is
biochemically similar but quantitatively different from most other
chlorinated hydrocarbons. The level of uptake is lower and the rate of
elimination more rapid than with most other chlorinated hydrocarbons.
The metabolism of toxaphene, including the use of isotope-labeled
material, has received very little attention. Most investigators are
reluctant to study a substance that is a mixture of related compounds
rather than a single chemical agent.
Toxaphene causes induction of hepatic microsomal enzymes when
dietary levels of at least 5 ppm are fed to rats. There is no evidence
that toxaphene could change the toxicity of other chemicals through any
mechanism other than enzyme induction.
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REFERENCES
1. Amer. Med. Assoc. Committee on Pesticides, (1952). Pharmacological
properties of toxaphene, a chlorinated hydrocarbon insecticide.
J. A. M.A. 149: 1135-1137.
2. Calandra, J. C. (1965). Unpublished report of Industrial Bio-Test
Laboratories, Inc.
3. Claborn, H. V., Radeleff, R. D., and Bushland, R. C. (1960). Pesti-
cide residues in meat and milk. United States Department of Agri-
culture, ARS, 33-36.
4. Dreisbach, R. H. (1969) Handbook of Poisoning. Diagnosis and
Treatment, 6th Edition. Lange Medical Publications, Los Altos,
California. 91-93 pp.
5. FAO/WHO-(1968). Evaluations of some pesticide residues in food.
267-283 pp.
6. Fitzhugh, 0. G., and Nelson, A. A. (1951). Comparison of chronic
effects produced in rats by several chlorinated hydrocarbon in-
secticides. Fed. Proc. 10, 295.
7. Gafafer, W. M. (1964). Occupational Diseases, A Guide to Their
Recognition. U. S. Public Health Service, Division of Occupational
Health. 244 pp.
8. Gaines, T. B. (1960). The acute toxicity of pesticides to rats.
Toxicol. Appl. Pharm. 2, 88-99.
9. Genelly, R. E. and Rudd, R. L. (1958). Effects of DDT, toxaphene,
and dieldrin on pheasant reproduction. Auk. 73:529-539. Chem.
Abstr. 52: 1658c.
10. Gleason, M. W., Gosselin, R. E., Hodge, H. C., and Smith. R. P.
(1969). Clinical Toxicology of Commercial Products. 3rd Edition.
The Williams and Wilkins Co., Baltimore, p 222.
11. Hayes, W. J. (1963). Clinical Handbook on Economic Poisons. Emer-
gency Information for Treating Poisons, U, S. Dept. of Health, Edu-
cation and Welfare, Communicable Disease Center.
12. Hercules Inc. (1970). Toxaphene, use patters and environmental
aspects. Bull. 172 pp.
13. Innes, J. R. M., Ulland, B. M., Valerio, M. G., Petrucelli, L. ,
Fishbein, L., Hart, E. R., Pallotta, A. J., Bates, R. R., Falk,
H. L., Gart, J. J., Klein, M., Mitchell, I., and Peters, J. (1969).
Bioassay of pesticides and industrial chemicals for tumorigenicity
in mice; A preliminary note. J. Nat. Cancer Inst. 42(11): 1-1114.
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14. Kennedy, G., Frawley, J. P., and Calandra, J. C. Multi-generation
reproduction study in rats fed Delnav, Herban, and toxaphene.
Toxicol. App. Pharmacol. (Accepted for publication.)
15. Kinoshita, F. K., Frawley, J. P., and DuBois, K. P. (1966).
Quantitative measurement of induction of hepatic microsomal enzymes
by various dietary levels of DDT and toxaphene in rats. Toxicol.
Appl. Pharmacol. 9: 505-513.
16. Lackey, R. W. (1949). Observations on the acute and chronic toxicity
of toxaphene in the dog. J. Ind. Hyg. Toxicol. 31: 117-120.
17. McGee, L. C., Reed, H. L., and Fleming, J. P. (1952). Accidental
poisoning by toxaphene. J.A.M.A. 149: 1124-1126.
18. Negherbon, W. 0. (1959). Toxaphene. Handbook of Toxicology. Vol.
III. Insecticides, a compendium. 754-769 pp.
19. Ortega, P., Hayes, W. J., and Durham, W. F. (1951). Pathologic
changes in the liver or rats after feeding low levels of various
insecticides. A.M.A. Arch. Pathol. 64: 614-622.
20. von Oettingen, W. F. Poisoning. A Guide to clinical Diagnosis and
Treatment. 2nd Edition. W. B. Saunders Co. p. 577 (1958).
21. Treon, J. F., Cleveland, F., Poynter, B., Wagner, B., and Gahegan,
T. (1952). The physiologic effects of feeding experimental animals
on diets containing toxaphene in various concentrations over pro-
longed periods. Unpublished report of the Kettering Laboratory.
22. Warraki, S. (1963) Respiratory hazards of chlorinated camphene.
Arch. Environ. Health 7: 253-256.
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TOXAPHENE RESISTANCE
IN ARTHROPODS
Some insects have always been able to survive the most effective
insecticidal treatments that man has been able to devise. Insect re-
sistance to insecticides was first realized in 1908, when the San Jose
scale developed resistance to lime-sulphur in the State of Washington.
The term resistance is used here to describe an insect population which
consistently exhibits greater survival from repeated exposures to a
chemical insecticide than was noticed when the chemical was first used
(16). The World Health Organization Expert Committee on Insecticides
(7), proposed the following definition:
"Resistance to insecticides is the development of an ability
in a strain of insects to tolerate doses of toxicants which
would prove lethal to the majority of individuals in a normal
population of the same species. The term "behavioristic" re-
sistance describes the development of the ability to avoid a
dose which would prove lethal."
The "behavioristic resistance" concept is associated with the feed-
ing preferences or the avoidance of a chemical deposit. For example,
certain mosquitoes may move away from an insecticidal before absoring a
lethal dose or they may not remain on an insecticidally treated surface
long enough to be poisoned before being stimulated to fly away. Thus,
they have developed behavioral traits which prevent them from being
poisoned by certain chemicals.
There are two types of resistance to chlorinated hydrocarbon, in-
secticides: (1) to DDT and its analogues, and (2) to the cycLodiene
derivatives such as dieldrin, chlordane, toxaphene and gamma-BHC. In-
sects, made DDT-resistant with DDT selection pressure are cross-resistant
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to DDD, and resistant to methoxychlor and perthane, but not the cyclo-
diene derivatives, toxaphene or BHC. Insects made dieldrin-resistant
by dieldrin selection pressure are cross-resistant to the other cyclo-
diene derivatives and to BHC, but not to DDT and its relatives. Cyclo-
diene-resistant strains of insects are cross-resistant to gamma BHC,
and gamma BHC-resistant insects are cross-resistant to cyclodienes.
Cyclodiene-resistant strains are apparently always resistant to toxa-
phene (7, 8).
According to Brown (8), all cases of resistance to dieldrin and
other cyclodiene derivatives, and to BHC involves resistance to toxa-
phene also. Where the word toxaphene or dieldrin is listed under in-
secticide (Table 1), it is because this type of cyclodiene-BHC-resistance
was induced under toxaphene or dieldrin pressure.
Several authors (5, 6, 7, 8, 10, 19, 20, 23) have reviewed the
literature on insect resistance. The mechanism of resistance to cyclo-
diene derivatives such as dieldrin, endrin and heptachlor still is un-
known. The well-known cyclodiene-resistant strains of the boll weevil
do not absorb less dieldrin than nonresistant strains and apparently do
not detoxify this compound.
The nerves of cyclodiene-resistant flies refract high levels of
dieldrin, which means the composition of the ganglia may be crucial for
developing this kind of resistance. The excretory activity of the
Malpighian tubules is inhibited by dieldrin. Cyclodiene-resistant flies
continue to excrete dieldrin long after susceptible flies have ceased
activity, but this may be a consequence, not a cause.
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Some BHC-resistant flies absorb gamma BHC at a lower rate .than
normal resistant flies. However, the lower rate of absorption and higher
detoxification does not fully explain BHC-resistance. As with cyclo-
dienes, resistance apparently resides in the ganglia themselves.
Insecticide-resistant pests are a problem in both agricultural and
medical entomology. Melander (21) is generally credited with publishing
the first report of an insect developing resistance to an insecticide.
In field experiments conducted at several locations in the State of
Washington, Melander found that San Jose scale was resistant to lime-
sulphur at Clarkston. Flint also (12) reported the same findings in
Illinois. The examples of resistance to lime-sulphur, lead arsenate,
hydrogen cyanide, phenothiazine and tarter emetic are discussed in the
reviews.
In 1946, 2 years after the introduction of DDT, housefly resistance
to this compound was demonstrated in Italy and Sweden. In 1947, DDT re-
sistance in the housefly appeared in Egypt and New York and in 1948
was reported in many state in the United States. Resistance of the house-
fly to DDT led many scientists to study the physiology, mechanism and
genetics of resistance. Many of these studies included the other organo-
chlorines. Most scientists agree that cyclodiene-resistance is com-
pletely separate from DDT resistance. By 1962, the housefly was resistant
to the BHC-dieldrin group in the United States, Scandinavia, South
America, Africa, USSR, Japan, India, Caribbean and Romania.
It is estimated that DDT-resistance developed in the housefly two
years after the introduction of DDT, and cyclodiene-resistance usually
develops within one year after the substitution of BHC or dieldrin.
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134
Thirty-six species of Anopheles are resistant to dieldrin in various
countries of the world. Twelve species of Culicine mosquitoes are re-
sistant to the BHC-dieldrin group of insecticides (13).
DDT-resistance first appeared in the body louse during 1951 in Korea
(11). At this time, toxaphene gave complete kill of the DDT-resistant
lice, indicating they were not resistant to toxaphene. Later, BHC-
resistant strains appeared in Japan that were also resistant to toxa-
phene. Malathion is now used to control the BHC-resistant lice.
Seven species of ticks are resistant to the BHC-dieldrin group of
insecticides; (8, 34, 36) two of these species are found in the United
States.
The boll weevil developed resistance to the chlorinated hydrocarbon
insecticides, i.e., endrin, heptachlor, dieldrin and toxaphene (26, 27)
in 1955. Soon after the first report of chlorinated hydrocarbon-resistance
in the boll weevil in Louisiana, resistant weevils were reported in Texas
(31), in most of the other cotton growing states where weevils occur
(4, 17, 24), and in Mexico and Venezuela (8).
Cyclodiene resistance now has been reported in at least 18 species
of insects that attack cotton. This list includes: boll weevil (17, 27,
31); bollworm (2); tobacco budworm (1, 2); cabbage looper (4); cotton
leafworm (4); cotton fleahopper (24); Lygus sp. (3, 22); thrips spp. (25,
30); and salt-marsh caterpillar (29, 32). According to Brown (8) there
also has been a marked increase in the past five years in the number of
cyclodiene-resistant species of tobacco, rice and stored products insects.
Toxaphene-resistance in the Egyptian cotton leafworrn had al.most as
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135
drastic an effect on cotton production in Egypt as the development of in-
secticide resistance in the boll weevil in the U. S. BHC-resistance of
the sugar-cane borer in Trinidad and -the rice stem borer in Japan has
also caused similar crises in agricultural production.
The resistance to aldrin, dieldrin and heptachlor in soil insects
has become widespread. Three species of wireworms are resistant to cyclo-
diene insecticides. Dieldrin resistance in the onion maggot, cabbage
maggot and carrot rust fly is now widespread and has increased in the
seed corn maggot and turnip maggot. Insecticide resistance also has been
developed by four species of Diabrotica root worms, the alfalfa weevil
and white fringed beetle.^''
Summary
Cyclodiene-resistant strains of insects are cross-resistant to gamma
BHC and gamma BHC-resistant insects are cross-resistant to the cyclodienes.
Cyclodiene-resistant strains are apparently always resistant to toxaphene.
Among the 149 insect species that have developed resistance to
toxaphene, BHC, organochlorine insecticides and cyclodiene derivatives,
65 are of agricultural importance and 84 of public health or veterinary
importance. The list of resistant agricultural pests include such im-
portant crop pests as the boll weevil, bollworm, tobacco budworm, cab-
bage looper, cotton fleahopper, rice steam borer and others; while the
list of resistant public health pests include 26 species of Anopheles
and 12 species of culicine mosquitoes as well as many ticks, flies, lice,
roaches, etc.
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136
Table 1.
Tabulation of Pests Reported to be Resistant to Toxaphene, BHC,
Organochlorine Insecticides and Cyclodiene Derivatives (a).
Pest
Insecticides
Location
Beet armyworm
Spodoptera exigua
Boll weevil
Anthonomus "grandis
Bollworm
Heliothis zea
Cabbage looper
Trichoplusia ni
Cotton leaf worm
Alabama argillacea
Spodoptera littoralis
Lygus hesperus
Salt marsh caterpillar
Estigmene acraea
Stink bug
Euschistus conspersus
Frankliniella occidentalis
Cotton
Organochlorine com-
pounds
Organochlorine com-
pounds
Toxaphene - DDT
Organochlorine com-
pounds
Endrin and Toxaphene
Organochlorine com-
pounds
Toxaphene
Toxaphene
Toxaphene, DDT
Endrin
Organochlorine com-
pounds
Organochlorine com-
pounds
Ariz., Ark., Calif.,
Miss.
Ala., Ark., Geo.,
La., Miss., N.C.,
Oklah., S.C., Tenn.
Tex., Mex., Venezuela
Texas
Ala., Ark., Calif.
La., Miss., Okla
Ariz.
Ark., La., Tex.,
Venezuela, Colombia
Egypt, India
Calif.
Ariz., Calif.
Calif.
Texas
Toxaphene
New Mexico
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137
Pest
Insecticides
Location
Thrips
tabaci
Anomis texana
Tobacco budworm
Heliothis virescens
Cotton fleahopper
Pseudatomoscelis serlatus
Cotton leaf perforator
Bucculatrix thurberiella
Cotton aphid
Aphis gossypii
Spiny bollworm
Earias insulana
Cotton stainer
Dysdercus peruvianus
Sugarcane Froghopper
Aeneolamia varia
Sugarcane borer
Diatraea saccharalia
Tomato hornworm
Protoparce sexta
Dark sided cutworm
Euxoa messoria
Sandhill cutworm
Euxoa detersa
Organochlorine com-
pounds
Toxaphene
Strobane plus DDT
Toxaphene plus DDT
Endrin
Chlorinated hydrocar-
bons
Chlorinated hydrocar-
bons
BHC
Endrin
BHC
Sugarcane
BHC
Endrin
Tobacco
Endrin
Dieldrin
Aldrin
Texas
Peru
Texas
Texas
La., Miss., Tex.,
S.E. USA
Calif.
S.E. USA
Israel, Spain
Peru
Trinidad
La.
S.C., N.C.
Ont.
Ont.
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138
Pest
Insecticides
Location
Potatoe tuber moth
Phthorimaea opercullella
Rice leaf beetle
Lema oryzae
Rice stem borer
Chilo suppressalis
Rice water weevil
Lissorhoptrus oryzophilus
Smaller brown plant hopper
Delphacodes striatella
Rice paddy bug
Leptocoris varicornis
Black rice bug
Scotinophora lurdia
Red flour beetle
Tribolium castaneum
Rice weevil
Sitophilus oryzal
Granary weevil
Sitophilus granarius
Maize weevil
Sitophilus zeamais
Black cutworm
Agrotis ypsilon
Singhara beetle
Galerucella birmancia
Chinch bug
Blissus pulchellus
Endrin
Rice
BHC
BHC
Aldrin
BHC
BHC, Endrin
BHC
Stored Products
BHC
BHC
BHC
BHC
Miscellaneous
Aldrin
BHC
BHC
Queensland
Japan
Japan, Taiwan
Ark., La., Miss.,
Tex.
Japan
Ceylon, Thailand
Taiwan
Kenya
England, Queensland
S. Africa
Kenya
Brazil, Taiwan
N. India
Panama
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139
Pest
Insecticides
Location
Coca capsid
Distantiella theobroma
Wooly apple aphid
Eriosoma lanigerum
Pear psylla
Psylla pyricola
Brown coca capsid
Sahlbergiella singularis
Citrus thrips
Scirtothrips citri
Banana tree weevil
Cosmopolites sordidus
Tuber flea beetle
Epitrix tuberis
Potato beetle
Leptinotarsa decomlineata
Strawberry aphid
Chaetosiphon fragaefolii
Serpentine leaf miner
Liriomyza archboldi
Southern potato wireworm
Conoderus fallii
Tobacco wireworm
Conoderus vespertinus
Sugarbeet wireworm
Limonius californicus
Western corn rootworm
Di.ibrolica virgifera
Northern corn rootworm
Diabrotica longicornis
BHC
BHC
Dieldrin
BHC
Dieldrin
Dieldrin
Dieldrin
BHC
Endosulfan
Aldrin
Soil Insects
Chlordane
Dieldrin
Aldrin
Aldrin
Aldrin
Ghana, Nigeria
Queensland
Washington
Nigeria
Calif.
Guinea, Ivory
Coast, Cameroun
B.C.
Europe
Wash.
Florida
S.C.
N.C.
Washington
Nebr., Kan., S.D.
Iowa, Mo., Minn.
S.D., Ohio, 111.,
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140
Pest
Insecticides
Location
Southern corn rootworm Aldrin
Diabrotica undecimpunctata
Banded cucumber beetle Aldrin
Diabrotica balteata
N.C., Va.
La., S. C.
Alfalfa weevil
Hypera postica
White fringed beetle
Graphognathus leucoloma
Onion maggot
Hylemya antiqua
Bean seed maggot
Hylemya liturata
Cabbage maggot
Hylemya brassicae
Seed corn maggot
Hylemya platura
Turnip maggot
Hylemya floralis
Barley fly
Hylemya arambougi
Spotted root maggot
Euxesta notata
Heptachlor
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Heptachlor
Dieldrin
Dieldrin
Utah, Mont., Wyo.,
Nev., Calif., Va., Md; ,
N.Y., Pa., Del., N.C.,
Ala.
Wis., Mich., Ont., Wash.,
Ore., B.C., 111., N.Y.,
Man. Que., Minn., Me.,
Ohio, France, Holland,
Japan
Ont., Conn., Que.,
Nfld.
Ill, Wis., Wash., B.C.,
Que., Nfld.
Ont., Eng., N.Y., N.S.,
Maine, Pa., Ohio,
.Belgium, Germany,
Sweden
B.C., Ont., Japan,
England
Saskatchewan,
Germany, Norway
Kenya
Ont.
Large blub fly
Merodon equestris
Aldrin
England
Carrot rust fly
Pslla rusae
Dieldrin
Ore, B.C., Ont., Wash.,
France, Holland
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141
Pest
Insecticides
Location
Public Health and Veterinary Importance
Body louse
Pediculus corporis
Lingonathus africanus and
Lingonathus stenopsis
Cattle sucking louse
Haematopinus eurysternos
Goat biting louse
Boophilus limbata and
Boophilus caprae
Oriental cockroach
Blatta orientalis
BHC, dieldrin
German cockroach
Blattella germanica
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
France, Japan,
West Africa, South Africa,
Iran, India, Korea,
Tanganyika, Sudan
South Africa
Alberta
Texas
Germany,
Czechoslovakia
Texas, S.E. U.S.A.
N.E. USA, Calif.,
Panama,
Cuba,
Puerto Rico,
Canada,
Trinidad,
Japan,
Poland,
England,
Germany
Denmark, Hawaii,
Australia, New Guinea
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142
Pest
Insecticides
Location
Periplanta brunnea
Bed bug
Cimex lectularius
BHC, dieldrin
BHC, dieldrin
Tropical bed bug
Cimex hemipterus
Human flea
Pulex irritans
Dog and cat flea
Ctenoeephalides canis
and/or Ctenoeephalides felis
Oriental rat flea
Xenopsylla cheopis
Xenopsylla astiu
Blue tick
Boophilus decoloratus
Cattle tick
Boophilus microplus
Lone star tick
Ambloyomma americanum
Brown dog tick
Rhipicephalus sangujneus
African red tick
Rhipicephalus evertsi
Brown ear tick
Rhipicephalus appendiculatus
American dog tick
Dermacentor variabilis
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
Florida
Italy, Israel,
Indonesia,"Zambia,
Rhodesia, Borneo,
S.olndia, S. Africa,
N. India, Egypt
West India, Tanganyika,
Kenya, Haute, Volta,
Dahomey, Zanzibar,
Malaya, Gambia,
Malagasy, S. India
Tanganyika,
Turkey, Egypt
USA, Hong Kong,
Hawaii, Japan
W. India, S.E. India
Thailand
S. India
Cape Province, Transvaal,
Northern Rhodesia
Queensland, Brazil,
N. India, Guadeloupe
Madagascar
Okla., Madagascar
N. Jersey, Panama,
Tex., Puerto Rico
S. Africa
S. Africa
Mass.
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143
Pest
Insecticides
Location
House fly
Musca domestica
Stable fly
Stomoxys calcitrans
Sheep blowfly
Phaenicia cuprina
Green bottle fly
Phaenicia sericata
African latrine
Chrysomyla putoria
Horn fly
Haematobia irritans
Little house fly
Fannia canicularis
Fannia femoralis
Midge
Chironmus zealandicus
Midge
Glyptotendipes paripes
Filter fly
Psychoda alternate
Biting midge
Cullcoides furens
Eye gnat
Hippelates collusor
Borborid fly
Leptocera hirtula
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
Calif., Sardinia,
USA, Scandinavia,
S. America, Africa,
USSR, Japan, India,
Caribbean, Romania
Norway, Florida,
Germany
Norway, Florida,
Germany, Australia
New Zealand,
S. Africa
Congo, Malagasy,
Zanzibar
Texas
Calif.
Calif.
New Zealand
Florida
England
Florida, Panama
Calif.
Malaya
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144
Pest
Insecticides
Location
Culex fatigans
(quinquesfasciatus)
BHC, dieldrin
Culex pipiens
Culex tarsalis
Culex tritaeniorhynchus
Aedes aegypti
Aedes sollicitans
Aedes taeniorhynchus
Aedes nigromaculis
Aedes melanimon
Aedes cantator
Psorophora confinnis
Psorophora discolor
Anopheles sacharovi
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
BHC, dieldrin
Dieldrin
Calif.,,Malaya, India,
E. Asia, S. America,
W. Africa, Panama,
Zanzibar, Congo, Tex.,
Mali, Madagascar,
Brazil, Tanganyika,
China, Togo, Ivory
Coas t, Queensland
Italy, Israel, .France,
Japan, Korea, Morocco
Calif., Ore.
Dahomey, Ryukyus,
Korea
Puerto Rico, Jamaica,
Haiti, Curacas,
Virgin Islands, Sur-
inam, Guyane, Cambodia,
S. Vietnam, Tex.,
Cameroun, Tahiti,
Thailand, Congo, Senegal,
Ivory Coast, Liberia,
Togo, Nigeria, Upper
Volta
Florida, Delaware
Florida, Georgia
California
California
New Brunswick
Mississippi
Mississippi]
Greece
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145
Pest
Insecticides
Location
Anopheles quadrimaculatus
Anopheles gambiae
Dieldrin
Dieldrin
Anopheles subpictus
Anopheles CPUS tani
Anopheles pulcherrimus
Anopheles albimanus
Anopheles pseudopunctipennis
Anopheles aquasalis
Anopheles culcifacies
Anopheles vagus
Anopheles barbirostris
Anopheles annularis
Anopheles sergenti
Anopheles fluviatilis
Anopheles splendidus
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Miss., Ga., Mex.,
Nigeria, Liberia,
Ivory Coast, Da-
homey, Upper Volta,
Cameroun, Sierra Leone,
Togo, Ghana, Mali,
Conga (Brazz), Sudan,
Mauritius, Madagascar
Java, Ceylon, N.
India, W. Pakistan
Arabia
Arabia
Salvador, Guatemala,
Nicargua, Honduras,
Jamaica, Ecuador,
Mexico, Br. Honduras,
Cuba, Dominican Rep.
Haiti, Colombia
Mexico, Nicaragua,
Peru, Venezuela,
Ecuador
Trinidad, Venezuela,
Brazil
W. India, Nepal
Java, Philippines
Java
Java
Jordan
Arabia
N. India
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146
Pest
Insecticides
Location
Anopheles Stephensi
Anopheles minimus flavirostris
Anopheles Pharoensis
Anopheles albitarsis
Anopheles labranchiae
Anopheles strodei
Anopheles triannulatus
Anopheles sundaicus
Anopheles aconitus
Anopheles neomaculipalpus
Anopheles crucians
Anopheles filipinae
Anopheles maculipennis
Anopheles rangeli
Anopheles maculipennis
messeae
Anopheles labranchiae
atroparvus
Anopheles philippinens is
Anopheles funestus
Anopheles nili
Anopheles rufipes
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Dieldrin
Iran, Iraq
Philippines, Java
Egypt, Sudan, Israel
Colombia, Venezuela
Morocco, Algeria
Venezuela
Venezuela, Colombia
Java, Sumatra, Sabah
Java, India
Trinidad, Colombia
Carolina, Dominican
Rep.
Philippines
Romania
Venezuela
Romania
Romania, Bulgaria
Sabah
Nigeria, Ghana, Kenya
Ghana
Mali
(a) Source (4).
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147
REFERENCES
1. Adkisson, P. L. (1967). Development of resistance by the tobacco
budworm to mixtures of toxaphene or strobane plus DDT. Econ. Ent.
69(3): 788-91.
2. Adkisson, P. L. and Nemec, S. J. (1966). Comparative effectiveness
of certain insecticides for killing bollworms and tobacco budworms.
Tex. Agri. Exp. Sta. Bull. No. 1048 1-4 pp.
3. Andres, L. A., Burton, V. E., Smith, Ray F. and Swift, J. E. (1955).
DDT tolerance by Lygus bugs on seed alfalfa. Econ. Ent. 48(5):
509-513.
4. Annual (24th) Conference Report on Cotton insect research and contro.
1971. USDA, Agri. Res. Serv. in cooperation with 13 cotton-growing
states.
5. Babers, F. H. (1949). Development of insect resistance to insecti-
cides. USDA Bur. Ent. Pit. Quar. E-776 1-31 pp.
6. Babers, F. H. and Pratt, J. (1951). Development of insect resistance
to insecticides II— a critical review of the literature up to 1951.
USDA, Bur. of Ent. Pit. Quar. E-818 1-45 pp.
7. Brown, A. W. (1958). Insecticide resistance in arthropods. World
Health Organization, Monograph Series No. 38: 1-240.
8. Brown, A. W. (1969). Insecticide resistant part 1: nature and
prevalence of resistance; part II: mechanisms of resistance; part
III: development and inheritance of resistance; part IV: counter-
measures for resistance, farm chemicals, 132(9): 50-51, 54-56, 58,
60, 62, 64, 66, 68, (10): 42-43, 46-47, (11): 52, 54-55, 58, 133
(2): 50-51, 54, 56, 84-85.
9. Bruce, W. N. and Decker, G. C. (1950)- House fly tolerance for in-
secticides. Soap and Sanitary Chemicals 26(3): 122-25; 145-147.
10. Crow, J. F. (1957). Genetics of insect resistance to chemicals.
Ann. Rev. Entomol. 2 227-246.
11. Eddy, G. W. (1952). Effectiveness of certain insecticides against
DDT-Resistance body lice in Korea. Econ. Ent. 45(6): 1043-1051.
12. Flint, W. P. (1923). Shall we change our recommendations for San
Jose scale control. Econ. Ent. 16 209-212.
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148
13. Gjullin, C. M. and Peters, R. F, (1952). Recent studies of
mosquito resistance to insecticides in California. Mosquito News
12(1): 1-7.
14. Graves, J. B., Glower, D. F. and Bradley, J. R., Jr. (1967). Re-
sistance of the tobacco budworm to several insecticides in Louisiana.
Econ. Ent. 60(3): 887-88.
15. Grayson, J. McD. (1953). Selection of the large milkweed bug
through seventeen generations for survival to sublethal concentra-
tions of DDT and toxaphene. Econ. Ent. 46(5): 888-890.
16. Grayson, J. M. and Cochran, D. G. (1955). On the nature of insect
resistance to insecticides. Vir. Jour. Sci. 6(3): 134-145.
17. Hamner, A. L. and Hutchins, E. (1957). Boll weevil resistant to
poison. Miss. Agr. Exp. Sta., Miss. Farm Research 20(1). 1 and 5.
18. Herrera, A. J. (1958). Resistencia de ciertas plagas del algodonero
a los insecticidas organicos en el Valle de Canete. Rev. Peruana
Ent. Agr. 1(1): 47-51. (From the English summary.)
19. Hoskins, W. M. and Gordon, H. T. (1956). Arthropod resistance .to
chemicals, Ann. Rev. Ent. 1: 89-122.
20. Knipling, E. F. (1954). On the insecticide resistance problem.
Agr. Chem. 9(6): 46-47, 155.
21. Melander, A. L. (1914). Can insects become resistant to sprays?
Econ. Ent. 7 167-173.
22. Menke, H. F. (1954). Indications of Lygus resistance to DDT in
Washington, J. Econ. Ent. 47(4): 704-705.
23. Metcalf, R. L. (1955). Physiological basis for insect resistance
to insecticides. Physiol. Reviews. 35(1): 197-232.
24. Parencia, C. R., Jr. and Cowan, C. B., Jr. (1960). Increased
tolerance of the boll weevil and cotton fleahopper to some chlori-
nated hydrocarbon insecticides in central Texas in 1958. Econ.
Ent. 53(1): 52-56.
25. Richardson, Ben H. and Wene G. P. (1956). Control of onion thrips
and its tolerance to Certain chlorinated hydrocarbons. J. Econ.
Ent. 49(3): 333-335.
26. Roussel, J. S. and Clower, D. F. (1055). Resistance to chlorinated
hydrocarbon insecticide in the boll weevil (Anthonomus grandis Boh.)
La. Agr. Exp. Sta. Cir. 41 1-9.
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149
27. Roussel, J. S. and Glower, D. F. (1957). Resistant to chlorinated
hydrocarbon insecticides in the boll weevil. J. Econ. Ent. 50(4):
463-468.
28. Smith, H. S. (1941). General discussion of segregation of resistant
races. J. Econ, Ent. 34(1): 1-3.
29. Stevenson, W. A., Sheets, W. and Kaufman W. (1957). The saltmarsh
caterpillar and its control in Arizona. J. Econ. Ent. 50(3):
278-280.
30. Tuttle, D. M. and Wene, G. P. (1959). Early season cotton thrips
control in Yuma,' Arizona area. J. Econ Ent. 52(1): 35-36.
31. Walker, J. K., Jr., Hightower, B. G. Hanna, R. L. and Martin, D. F.
(1956). Control of boll weevils resistant to chlorinated hydro-
carbons. Tex. Agr. Exp. Sta. Prog. Rept. No. 1902 1-4 pp. ,
32. Wene, G. P., Tuttle, D. M. and Sheets, L. W. (1960). Salt-marsh
caterpillar control on cotton in Arizona. J. Econ. Ent. 53(1):
78-80.
33. Wilson, H. G. and Graham, J. B. (1948). Susceptibility of DDT-
resistant houseflies to other insecticidal sprays. Sci. 107: 276-
277.
34. Wharton, R. H., Roulston (1970). Resistance of ticks to chemicals.
Ann. Rev. Ent. 15: 381-404.
35. Whitehead, G. B. (1958). Acaricide resistance in the blue tick,
Boophilus decoloratus (Koch.). Bull. Ent. Res. 49(4): 661-673.
36. Whitehead, G. B. and Baker, J. A. (1961). Acaridae resistance in
the red tick, Rhipicephalus evertsi Neuman. Bull. Ent. Res. 51(4):
755-765.
37. Wolfenbarger, D. O. (1958). Serpentine leaf miner: brief history
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Econ. Ent. 51(3): 357-359.
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150
TOXAPHENE RESISTANCE IN ANIMALS
OTHER THAN INSECTS, MITES AND TICKS
Since many pest species have developed resistance to the chlori-
nated hydrocarbon insecticides, it seems unlikely that nontarget species
have remained unaffected. That nontarget organisms have been affected
is shown by the occurrence of small numbers of resistant individuals in
susceptible populations of certain fish coupled with cross-resistance
and retention of resistance in several generations of fish reared in
the absence of insecticides. This suggests that a genetically based
development of insecticide-resistant strains of fish have evolved in
areas which have been subjected to intensive insecticidal treatment
(1 and 13).
Endrin resistance in mosquito fish was attributed to physiological
tolerance, when no evidence of excretion or detoxification was found
(10 and 11). In heavily contaminated environments supporting insecti-
cide resistant strains of marine organisms, top piscivores such as
/
largemouth bass maybe absent. This suggests that selection in the food
chain may occur through biological magnification. Presumably, the re-
sistant fish which survive accumulate and tolerate high levels of
residues. These individuals aggravate the problem, because the preda-
tors which feed on them may be killed by the insecticides in the bodies
of the resistant fish.
Insecticide contamination of runoff water apparently is a major
factor involved in the development of insecticide resistant fish popu-
lations (13). According to Ferguson et al (5 and 6), muds from natural
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151
waters in runoff from cotton fields may contain sorbed pesticides
greatly in excess of levels lethal to certain fish. Although lethal
quantities of these sorbed insecticides can be extracted with organic
solvents, they are not released in lethal amounts into standing water.
Resistance in fish. Resistance and cross-resistance has been re-
ported in populations of mosquito fish to DDT, endrin, aldrin, dieldrin,
toxaphene and heptachlor (1 and 2). Although fish may be cross-
resistant to an insecticide to which they have had no prior exposure,
the nature of cross-resistance seems to differ from that of insects.
Only low levels of DDT-resistance are known in fish; cross-resistance
to DDT is poorly developed or absent.
Resistance in invertebrates other than insects. Ferguson et al
(4, 5, 6) states that invertebrates known to contain resistant popula-
tions include a clam, Eupera singleyi; a snail, Physa gyrina; 6 species
of cyclopoid copepods and a freshwater shrimp, Paleomonetes kadiakensis.
Resistance in vertebrates. Among the vertebrates, pesticide-
resistance has been demonstrated in fishes, anuran amphibians and mammals.
Six species of fishes (golden shiner, black bullhead, yellow bullhead,
mosquito fish, bluegills, and green sunfish) from cotton-producing areas
in the Mississippi delta are known to be resistant when compared with
the same species for areas of minimal pesticide use. Most species re-
sist several pesticides, particularly the chlorinated hydrocarbons endrin,
toxaphene and Strobane (4, 8 and 15).
Northern and southern cricket frogs and Fowler's toads near cotton
fields show as much as 50-fold levels of resistance when tested against
several chlorinated hydrocarbon insecticides (10).
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152
In Virginia apple orchards endrin did not control wild pine mice
in certain areas. Webb and Horsfall (19) reported a 12-fold endrin re-
sistance in the pine mouse, Pitymys pinetorum.
Ferguson (10, 11) indicated that in general, levels of resistance
are highest for the most stable chlorinated hydrocarbons especially the
cyclodiene derivatives including toxaphene.
Summary
Invertebrates other than insects known to be resistant to chlori-
nated hydrocarbon insecticides include a clam, a snail, a freshwater
shrimp and 6 species of cyclopoid copepods.
Among the vertebrates, resistance has been demonstrated in fishes,
anuran amphibians and a mammal. Six species of fish are resistant to
insecticides in the cotton-producing areas in the Mississippi delta when
compared with the same species collected from areas of minimal pesticide
use.
Among the amphibians, northern and southern cricket frogs and
Fowler's toad from near cotton fields show as much as 50-fold levels of
resistance when tested against several chlorinated hydrocarbon insecti-
cides.
A wild population of pine-mice is resistant to endrin.
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153
SPECIES RESISTANT TO CHLORINATED HYDROCARBONS
Black bullhead
Ictalurus melas
Yellow bullhead
Ictalurus natalis
Golden shiner
Notemigonus crysoleucas
Mosquito fish
Gambusia affinis
Bluegills
Lepomis macrochirus
Green sunfish
Lepomis cyanellus
Cyclopoid copepods
Eucyclops agilis
Orthocyclops modestus
Macrocyclops albids
Cyclops vernalis
Cyclops bicuspidatus
Cyclops varicans
Pine mouse
Pitymys pinetorum
Clam
Eupera singleyi
Snail
Physa gyrina
Freshwater shrimp
Paleomonetes kadiakensis
Fowler's toad
Bufo woodhousei fowleri
Cricket frog
Acris cfepitans
Cricket frog
Acris gryllus
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154
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155
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mouse. Sci. 156: 1762.
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