ARSENICAL PESTICIDES, KAN, AND THE EWMONMENT
ENVIRONMENTAL PROTECTION AGENCfi
1972
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ARSENICAL PESTICIDES, MAN, AND THE ENVIRONMENT
/ CONTENTS
Page No.
• Introduction - ..'.. 1
Summary and Conclusions * ../•..' 5
Chapter I. Pesticide Uses of Arsenic as . . . . . . ./ .
Related to Alternate Pesticides and Impact , .... ....
Summary 10
Table 1 through Table 8. Arsenical Pesticide; tfces with no
Registered Alternates ..... 11
Lead Arsenate Insecticide Uses and Conclusions ..... 15
Calcium Arsenate Insecticide Uses and Conclusions .... 30
Basic Copper Arsenate Insecticide Uses and Conclusions . . 40
Ammonium Arsenite Insecticide Uses and Conclusions. ... 44
Arsenic Acid Insecticide Uses and Conclusions ..... . 44
Arsenic Pentoxide Insecticide Uses and Conclusions . ^ 45
Arsenic Trioxide Insecticide Uses and Conclusions .... 45
Sodium Pyroarsenate Insecticide Uses and Conclusions ... 46
Wolman Salts Insecticides Uses and Conclusions 47
Cacodylic Acid Insecticide Uses and Conclusions .... 48
Sodium Arsenite and Potassium Arsenite Insecticiite Uses and
Conclusions . . . 49
Sodium Arsenate Insecticides Uses and Conclusions .... 50
Paris Green Insecticide Uses and Conclusions ... . . . 51
Cacodylic Acid Herbicide - Citrus and Conclusions .... 52
Ornamental Tree and Shrub Herbicides and Conclusions ... 52
Lawn and Ornamental Turf Herbicides and Conclusions ... 53
Herbicides for Non-Crop, Industrial Sites, Right33-of-Ways,
Driveways and Sidewalks and Conclusions . 54
Herbicides for Hardwood Tree Control and Conclusions ... 55
Semi-Soil Sterilant Herbicides and Conclusions ..... 56
Cotton Herbicide Uses and Conclusions 56
Cotton Desiccant and Defoliant Uses and Conclusims . . . 57
Grapefruit.Regulator Use and Conclusions 58
Rodenticide Uses and Conclusions 59
Agricultural Food Crop Fungicide Uses and Conclusions . . 59
Industrial Wood Preservative Uses and Conclusions .... 60
Chapter 'II. Chemistry and Methodology-Arsenic 66
Chapter III. Fate and Implications for Arsenic in the Ecosystem. 76
Chapter IV. Significance of Arsenical Pesticides in the
Environment 94
Chapter V. Residues in Crops and Food Items . ..«..' . . 105
Chapter VI. The Toxicology of Arsenic . . . 127
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Prepared- for the Office of ^es'.xcides Programs, Environmental
Protection Agency by:
* '
Special Pesticide Review Group
O. Garth Fitzhugh, Ph.D., Chairman
William F. Durham, Ph.D. , Vice-Chairir.an
Lamar B» Dale, Jr., Ph.D., Secretary
Homer E. Fairchild, Ph.D., Editor-
Cipriano Cueto, Ph.D.
Joseph G. Curnmings .
Thomas E. DeVaney
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INTRODUCTION
a metalloid which has useiuily served maikind beginning at
least as early as AGO B.C. Hippocrates is reported to have recommended'
a paste of the sulfide for the treatment of ulcers ((Buchanan, 1962).
Arsenic was also one of the most common homicidal agents of the Middle
Ages. It was so successful for this use that arsennc was soon suggested
for the- eradication of four-legged and six-legged pests. Roark (1935)
noted that arsenical baits were recommended for ant control as early as
1669. Frost (1967) records the development of PariB green (copper ^
acetoarsenite) in 1867 as the first pesticide to be used against the
Colorado potato beetle.
Fowlerfs solution or 'ague drops' (1% potassium arsniite) and other
inorganic arsenical preparations have been used for the treatment of
anorexia, neuralgia, rheumatism, arthritis, tubercuUosis, and skin
diseases. Fowler's solution is still used in the taeatment of myelogenous
leukemia. However, in most of these disorders, arssiic has fallen into
'disrepute or has been replaced by specific therapy (Bailee, et al., 1960).
Following Erlich's .discovery of the chemotherapeutir action of arsenicals
against trypanosomes in 1905, more than 8000 organic arsenicals were .in
use as chemotherapeutic agents by 1937. These agertts, including . .
arsphenamine, neoarsephenamine, and mapharsen were One most important
therapeutic weapons against syphilis and trypanosomoasis until the
introduction of the antibiotics about 1940. On the other hand, because
of the great toxicity of some arsenicals to man, arsenic has been considered
as synonymous with poison.
Arsenic is a ubiquitous element present in all soiDs, in amounts varying
from less than 10 to 500 ppm. It is found in metal ores, chiefly in
Canada, Saxony, and Sweden, combined with other mirearals such as realgar
(^283), orpiment (AS2S2), and arsenolite ^3203). Arsenic is not usually
mined separately, but is recovered as a byproduct frmra the treatment of
copper, lead, zinc, and gold ores. When ores or concentrates containing
these metals are smelted, the arsenic which does nctt melt at atmospheric
pressure, but suTblimes at 218°C, is liberated from.tflie flue dusfc and
separated by filters or electrostatic precipitators as an oxide, chiefly
as the trioxide (Brownine, 1969).
Arsenic has been detected and measured in practical!^ every area of man's
environment; in the earth's crust, the biosphere, snLil, water vegetation,
marine forms and food and cosmetics. Man in his tedinological advances,
has added to his exposure through different industries, such as mining,
and smelting of industrial ores, farming and vineyari activities where
arsenical pesticides are used, the herbicidal use of arsenic, in the
formulation of pesticides, and in medicated animal .'food production.
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Although there is r,o evidence that there is biornagnification of arsenic
in the food chain, marinr \\£Q is capable of bioconcentration of arsenir..
McHride p.nd Wolfe h?ve demonstrated thac microorganisms in ssdiraents that
contain arsenic convert arsenic into the highly toxic dimethylarsine
'. (Anony.TiOu.s, 1971). Therefore, a pollution hazard exists fc.r aquatic a.nd
' terrestrial environments that have large amounts of arsenic introduced
.where anaerobic organisms are growing.
< /
-i*;; Beginning around 1900, the inorganic arsenicals were very extensively
«• used as pesticides until they were, to a great extent, replaced as
insecticides by the chlorinated hydrocarbons and organic phosphorous
compounds following World War II. In fact, the amount of one arsenical
insecticide, lead arsenate, used in the Wenatchee, Washington area in
1937 amount to slightly more than the total use of that compound in the
United States in 1967 (Neal, jet _al., 1941; USDA, 1970).
The U.S. Department of Interior Minerals Yearbook for 1969 reported that
arsenic was used principally for its toxic qualities in insecticides and
herbicides. Lead arsenate, calcium arsenate, sodium arsenate, sodium
arsenite, and arsenic-containing organic compounds were used in formulating
pesticides. In 1968 the world production, excluding the United States, of
arsenic trioxide was 66,000 tons, an increase from the production of 55,000
tons in 1962. Over 4 million pounds of lead arsenate and about 2 million
pounds of calcium arsenate were produced in the United States in 1969.
Because of the limitations placed on the use of DDT and other organochlorine
~ insecticides, there has been some recent increase in the use of arsenicals
as insecticides.
Approximately one million gallons of arsenic acid at 1.5 quarts/acre are
used annually in the cotton producing areas of Texas and Southwestern
Oklahoma. This calculates to 2.5 to 3.0 million acres treated annually.
In Texas,, approximately 73% of the crop .is., machine stripped, 25% spindle
picked, and 2% hand harvested.
It has recently been reported that arsenic build-up in soils after years
of pesticidal use reached 1.8 to 830 ppm while untreated areas ranged
from 0.5 to 14 ppm in areas tested in North America. In orchard areas of
the United States where arsenic-containing pesticides have been in use for
decades, the arsenic has accumulated in the soil to the point where the
soil is toxic, shortening the life of trees and making it difficult for
the profitable use of orchard lands for the forage crops that normally
follow orchards in rotation (Mrak, 1969).
There have been reports of chronic arsenic intoxication from North Carolina
(Keyman, et^ juL., 1956) and from Texas (Micks, jet al_., 1956) in farmworkers
using calcium and lead arsenates. Earner, £t _al., 1949) reported lead
intoxication in a significant number of workers employed in apple orchards
in Washington. There is considerable confusion in the literature concerning
the role of arsenicals in the production of cancer. The earliest published
claim of arsenic cancer was made by Paris in 1820 in which he reported
occa's'itm'ai cases of cancer of the scrotum in copper smelters (Buchanan, 1962),
• .
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Other investigators have sit.-;e reported an increased incidence ot cancer
bot-h of the skin and Internd.L organs, in persons exposed to excessive
levels .-.£ arsenic. Attempt to demonstrate cancer in experimental animal-j
exposed uO arsenic generally have not met with success. ' 0
t
/Because of the increasing incidence of cases of arsenic poisoning, arsenic
: insecticides, were outlawed in Germany in 1942.
:The Canadian Department of Agriculture has recently cpmpleted a reevaluation
of arsenical pesticides as related to effectiveness, safety, and need. Their
memorandum of November 30, 1971, indicates a reduction of approved arsenical
pesticide uses in Canada by 1973. The following is a brief summary of the
expected arsenical pesticide registrations or eliminations from use which
will be followed by Canada for 1973:
(1) Ammonium methyl arsonate is eligible for registration to control
crabgrass, chickweed, and witch grass im lawns.
(2) Disodium methyl arsonate is eligible for registration to control
crabgrass in lawns.
(3) Monosodium acid methane arsonate is eligible for registration
as a precommercial thinning agent for yenmg conifer stands.
(A) Calcium arsenate is eligible for registration to control insects
on blueberries and for control of Poa anaua on golf courses.
(5) Lead arsenate is eligible for registration for control of apple
.maggot (apples), tent caterpillars (apple and pears), plum
ciirculio (plums) and earthworms (bowling greens and golf greens).
(6) Sodium arsenite will not be eligible for registration as a
herbicide.
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ARSENIC
BIBLIOGRAPHY
INTRODUCTION
'> '•
Ahnonymous. "Trace metals: unknown, unseen pollution threat." Chemical
:'; and Eng. News; pp 29, 30, 33. July 19 (1971).
^.Browning, E. Toxicity of Industrial Metals. Second Edition, 39-60,
• ' Appleton-Century-Croft, New York (1969).
Buchanan, W. D. Toxicity of Arsenic Compounds. Elseyier Publishing
Company, New York (1962).
Farner, L. M., et. al. "The hazards associated with the use of lead
arsenate in apple orchards." J_. Ind. Hyg. Toxicol. .31^(3): 162-8 (1949).
Frost, D. V. "Arsenicals in biology-retrospect and prospect." Fed.
Proc. 26 (1):194-208 (1967).
Heyman, A., Pfeiffer, J. B., Willett, R. W,, and Taylor, H. M. "Peripheral
neuropathy caused by arsenical intoxication," New Eng. .J. Med. 254:401-
409 (1956).
Micks, D. W., Neal, J., and Nau, C. A. "Arsenic as an occupational hazard
for farmers." Tex. State J. Med_ 52,: 746-748 (1956).
,*
Mrak, E. M. Report of the Secretary's Commission on Pesticides and Their
Relationship to Environmental Health, U.S. Department of Health, Education,
and Welfare (1969).
Neal, P. A., Dreesen, W. C., Edwards, T.I., Reinhart, W. H., Webster, S. H.,
Castberg, H. J., and Fairhall, L. T. ."A. study of the effect of lead
arsenate exposure on orchardists and consumers of sprayed fruit." Public
Health Bulletin No. 27. PHS (1941).
Roark, R. C. "Household insecticides." Soap and Sanitary Chemicals 11;
101 (1935).
United States Department of the Interior, Minerals Yearbook 1-2: 1175-1176
(1969).
Valee, B. L., Ulmer, D. D., and Wacker, W. E. C., ''Arsenic toxicology and
biochemistry." AMA Arch. Indust. Hlth. 21(2);132-151 (1960).
Farner, L. M., et. al. "The hazards associated with the use of lead arsenate
in apple orchards." J. Ind. Hyg. Toxicol. 31(3): 162-8 (1949).
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SUMMARY AND CONCLUSIONS
Arsenic is ubiquitous and occurs naturally in the environment. The
arsenic levels currently found in the environment may or may not be an
original deposition. Certain of these levels may be the result of
industrialization and agricultural uses. The burning of fossil fuel
and the smelting of ores release arsenic into the atmosphere from where
it may be carried back to earth by rain. The pesticidal usage of
arsenic in large dosage rates has produced local damage to soils resulting
in the inability of the soil to sustain plant life (soil sterilization).
Certain:forms of marine life contain high levels of arsenic and it appears
that these forms are capable of bioconcentration of arsenic. However,
biomagnification in the food chain does not seem to occur. Arsenic is
apparently stored in the tissues in a pentavalent-organically bound form
which, according to some experts, is unavailable (to man. Pentavalent
arsenic, both organic and inorganic, is less toxic than the trivalent
forms of arsenic. In the terrestrial environment the arsenites will
accumulate in mammalian and avian tissues. It may be concluded that
trivalent arsenic presents a hazard to the environment.
Because of its phytotoxicity, the greatest threat of the unrestricted use
of pentavalent arsenical pesticides is soil sterilization. This has
occurred in the past when high use rates were employed in orchards and
may occur again if heavy uses of arsenicals are resumed.
The^Secretary's Commission on Pesticides and Theii Relationship to
Environmental Health recommended the use of arsenic be restricted to
specific essential uses. The Special Pesticide Review Group;'agrees
with.-this recommendation and concludes, that a total ban need not be
placed on the arsenical pesticides. Rather, that uses be retained
where a definite .need could be established; that (the usage rates in
-these retained .uses be reduced to the optimal effective rates; and
:that unnecessary uses and uses requiring excessively high dosage rates
..be abandoned.
.The Group has solicited the aid of members of the Department of
Agriculture in ascertaining which uses of arsenical pesticides are
:necessary in the production of food or fiber or im the preservation
of the beauty of the landscape.
The Special Pesticide Review Group has placed an (estimate on the
social .and economic impact caused by cancellation of certain uses of
the arsenical pesticides. The Group did not evaluate the full range
of economic and social consequences of cancellation. The conclusions
and proposals given below are based upon the assumption that all
registered uses of pesticides under consideration are economically and
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socially desirable. The Group has suggested that registration be
continued if effective alternates are not reasonably available and use
patterns indicate a relatively low hazard to mar. or hi..; environment.
Cancellation is suggested for those uses with the greatest hazards or
for those uses with lesser hazards if an acceptable alternate control
method exists to accomplish the same results. # .
.The arsenical pesticide uses with no acceptable registered alternates
were found to be limited to few crops or specific use sites. However,
there were needs currently considered essential for the arsenicals as
insecticides, herbicides, desiccant and defoliant, plant regulator,
fungicides and rodenticides. The general conclusions and proposals
for continued use or cancellation of the arsenical pesticides are:
1. Lead arsenate insecticide uses on apples, apricots,
cherries, peaches, pears, plums, prunes, nectarines,
quinces and grapes should be retained subject to review
by the Pesticide Regulation Division and phase out prior
to the 1975-use season if satisfactory alternates exist.
2. All calcium arsenate insecticide uses except the following
should be cancelled: dusts on selected fruits and vege-
tables; sprays for the fruitfly on blueberries; and baits
- on the soil to control armyworms, cutworms, slugs, snails,
and sowbugs attacking fruit, vegetables, and ornamentals.
3. The currently registered insecticide uses for basic copper
arsenate on vegetable crops should be cancelled.
A. Since there is no satisfactory substitute for arsenic in
the preservative mixture for insecticidal or fungicidal action,
. " registrations for ammonium arsenite, arsenic acid, arsenic
pentoxide, arsenic trioxide, sodium pyroarsenate sodium
arsenate, and Wolman salts should be retained for wood
preservation.
5. The use of cacodylic acid for insect trapping in the forest
should be restricted to U.S. Forest Service use only.
6. Sodium arsenite is too toxic for patterns of use involving
storage in the home environment. The registered uses for
control of subterranean termites and. ants by the homeowner
should be cancelled.
7. Sodium arsenite and potassium arsenite are essential in cattle
dips at the Mexico-United States border to protect against
introduction of the Texas fever tick. This application is
restricted to use by the United States Department of Agriculture
for quarantine purposes. The registered use should be retained
until a satisfactory alternate tickicide is developed with a
simple and efficient vat-side test.
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8. The registered u.ue of sodium arsenate should be retained
for termires, v^od destroying insects, ami ant baits.
(J. The registered uses of Paris greeu shouM be regained for
control of mosquito larvae, drywood termiites and in anti-
fouling paints to control insects and ctflner pests.
10. The registered use of cacodylic acid for weed control in
citrus should be retained. /
/
11. The registered uses of cacodylic acid,. DSMA. and MSMA around
ornamental trees and shrubs should be retained.
12. The following actions are suggested for -registered arsenical
herbicides on lawns and ornamental turf: arsenic acid should be
cancelled; calcium arsenate should be limited to Poa annua
control and restricted to optimal effective rates on golf
courses and related recreational turf; the use of cacodylic acid
should be retained; lead arsenate should be cancelled; DSMA, MSMA,
and AMA should be retained in use; and sadium arsenite and
arsenic trioxide should be cancelled.
13. The actions on herbicide uses of arsenic acid, cacodylic acid,
DSMA and MSMA for non-crop, industrial sites, rights-of-way,
driveways and sidewalks should be the sane as in Item 12,
above, for the respective pesticide.
14. The registered uses of cacodylic acid anfl MSMA for hardwood
tree control should be retained.
15. The presently registered uses for sodium"are arsenite and arsenic
trioxide as semi-soil sterilants should !be cancelled.
16. The currently registered uses of MSMA anfl DSMA alone or in
combinations for cotton should be retained.
17. The registered use of arsenic acid as a
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20. The registered fungicidal use of ^odiiin arsenite for
control of black measles, crown gall amd dead avm on grapes
should be retained.
21. The registered rses of basic copper araenate for the control
of early and late blight on tomatoes sHuould be retained
subject to review by the Pesticides Regulation Division of
the status of satisfactory alternates prior to the 1975-use
season.
22. Pressure treatment uses registered for the following arsenical
fungicide wood preservatives ahould be retained: arsenic acid,
sodium arsenate, arsenic pentoxide, soMum pyroarsenate; and
disodium arsenate.
23. Injection treatment fungicidal uses registered for arsenic
trioxide and sodium arsenate as wood pieservatives should be
retained.
24. Diffusion treatment fungicide uses registered for sodium
arsenate as wood preservatives should IDS retained.
25. Brush, mop or swab treatment fungicide uses registered for
ammonium arsenite, arsenic pentoxide, aid sodium arsenate as
wood preservatives should be retained.
26. The registered uses of 10, 10' -oxybisjftenoxarsine for control
of fungi attacking cotton fabric and vimyl films should be
retained.
27. Following is a table giving the arsenical pesticide cancella-
tions suggested in Chapter I_ according tto crop or site of
application: • -
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Pesticide
Cropor S ite of Application Suggested to be Cancelled
Lead Arsenate
(insecticide)
Calcium Arsenate
(Insecticide Sprays)
Basic Copper Arsenate
(Insecticide)
Sbdium Arsenite
(Insecticide)
Airs enic Acid
(herbicide)
Lftad Arsenate
(Herbicide)
Sodium Arsenite
(Herbicide) *
Arsenic Trioxide
(Herbicide)
Arsenic trioxide
(Rodenticide)
Sodium Arsenate
(Fungicide)
Asparagus (foliar application), tomatoes (foliar application), tobacco
(foliar application), ornamentals (foliar application) and lawns and
ornamental turf (soil and surface applications)*
Broccoli (foliar application), Brussels sprouts (foliar application),
cabbage (foliar application), cauliflower (foliar application), celery
(foliar application), cucumbers (foliar application), melons (foliar
application), peppers (foliar application), squash (foliar application),
tomatoes (foliar application), poultry houses (droppings under cages or
wire floors for fly control) and lawns and ornamental turf (soil and
surface applications).
Brussel sprouts (foliar application), cabbage (foliar application),
cauliflower (foliar application), kohlrabi (foliar application), and
tomatoes (foliar application).
Household and commercial (soil and bait applications).
/
Lawns and ornamental turf (soil application and non-crop industrial sites,
rights-of-ways, driveways, and sidewalks (soil application).
Lawns and ornamental turf (soil application).
Semi-soil sterilant (soil application), ornamental turf- (soil application),
Ornamental turf (soil application), semi-soil sterilant.
Rodents (baits - homeowner use).
Wood preservative (diffusion treatments)
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CHAFIER I
V^sjricide Uses of Arsenic as Related to Alternate Pesticides and Impact
Pesticidal compounds of arsenic have been used extensively for many year® .
in. the United. States. One of the significant early uses of arsenic was
in production of lead arsenate for control of the gypsy moth. Relatively
large amounts of arsenical insecticides were used until the introduction
of .DDT. More recently, during the past ten years, arsenical desiccants and
herbicides have been of increasing importance to the production of cotton
in large areas of the United States. Rodents and plants diseases are also
controlled with arsenical pesticides. Details on production and trends of
use are given in Chapters II and IV.
I. A. Summary
This chapter presents the arsenical pesticide uses currently registered
along with the registered alternate pesticides (substitutes) and the
conclusions or impact of any proposed action. Following is an outline of
the material presented:
•
1. Registered uses of arsenical pesticides for which there are
no alternate registrations (tables 1 through 8);
2. Registered arsenical insecticide uses with registered
alternates and suggestions for action (see I.I. 1. through
I.E. 13.);
3.. Registered arsenical herbicide uses with registered alternates
and suggestions for action (see I.E. 14. thromgh I.E. 20.);
4. Registered arsenical desiccant and defoliant mses with
registered alternates and suggestions for action (see I.E. 21..);
5. Registered arsenical regulator use with suggestions for action
(see I.E. 22.);
6. Registered arsenical rodenticides with alternates and suggestions
for action (see I.C.); and,
7. Registered arsenical fungicides with alternates and suggestions
for action (see I.D.).
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Table 1. Lead Arsenate Insecticide Uses Witth No Registered" Alternates
i • —'''
,.' Crop Pest Use Rate
; Apples Applethorn Skeletonizer
(Foliar)
Apricots
(Foliar)
Cherries
(Foliar)
Peaches
(Foliar)
Pears
(Foliar)
Plums
(Foliar)
Prunes
(Foliar)
Quince
(Foliar)
Grapes
(Foliar)
Case Bearers
Syneta Bettle
Syneta Beetle
Apple Maggot
Syneta Beetle
Red-Humped Caterpillar
Apple Maggot
Cankerworm
Syneta Beetle
Case Bearers
Syneta Leaf Beetle
Red-Humped Caterpillar
Round-Headed Apple Tree Borer
Pear Leafworm
Apple Maggot
Cankerworm
Cankerworms
Tent Caterpillar
Red-Humped Caterpillar
Syneta Beetle
California Oak Moth
Achnemon Sphinx Moth
Grape Rootworm
2 lbs/100 gal,
2-3 lbs/100 gal.
3 lbs/100 gal.
5-6 lbs/100 gal,
2-3 lbs/100 gal.
5-6 lbs/100 gal,
3-4 lbs/100 gal,
t-i/2 - 2 lbs/100 gal.
1-1/2 - 2 lbs/100 gal.
5-6 lbs/100 gal.
2-3 lbs/100 gal.
3 lbs/100 gal.
3-4 lbs/100 gal.
3 lbs/100 gal.
2 lbs/100 gal.
1-1/2 -
1-1/2 -
2 lbs/100 gal.
2 lbs/100 gal.
2-4 lbs/100 gal.
2-3 lbs/100 gal.
3-4 lbs/100 gal.
5 lbs/100 gal.
3-4 lbs/100 gal.
3-4 lbs/100 gal.
3-4 lbs/100 gal.
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Table 2. Calcium Arsenate Insecticide Uses Islith No Uegisterecl Alternates
. J Crop or Site Pest Use Rate
;'
«•'.- Cabbage
(Foliar) Colorado Potato Beetle 4 Ibs/acre
Celery
(Foliar) Colorado Potato Beetle 1-1-3/4 Ibs/acre
Baits used as-soil treatments are used against armyworms, cutworms,
slugs, snails and sowbugs. Used only in accordance with appropriate
clearance and limitations on crops as specified.
Table 3. Cacodylic Acid Insecticide Uses With No .Registered Alternates
Crop £r Site Pest Use Rate
Forest application Insect trapping - 1 ml/inch of
(U.S. Forest Service Englemen Spruce Beetle the surface
only) Mountain Pine Beetle
Douglas Fir Beetle
Round-headed Pine Beetle
Arizona Five-Spined Beetle
Pine Engraver Beetle
California Five-Spined Beetle
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Table ';. Sodium Arsenite and- Totassiura Arsenite Insecticide
Use With No /.pproved Alternate
Crop or Site Pests Use Rate
Livestock Quarantine - Ticks • 0.25% solution
as a dip
Cattle Dip
Table 5. Lead Arsenate Plant Regulator Use Mth No Registered Alternates
Crop Action Use Rate
Grapefruit Plant Regulator to 1.7-5.4 Ifes/acre
Reduce Acidity
Table 6. Sodium Arsenite Fungicide Use With ^fo Registered Alternates
Crop Disease Use Rate
Grapes Black measles 3-9 Ibs/acre
crown gall
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Special Uses of Arsenic Compounds as Wood
Preservatives With No Registered Alternates
Uses
Pressure treatments
Compounds*
Arsenic acid; arsenic pentoxide
dihydrate; sodium arsenate;
sodium hyroarsenate; arsenic
pentoxide; disodium arsenate
Injection treatments
Arsenic trioxide and sodium
arsenate
Diffusion treatments
Sodium arsenate
Brush, Mop or Swob
treatments
Ammonium arsenite; arsenic
pentoxide; and sodium
arsenite
Special Remarks
Used in varying concentra-
tions with other chemicals.
Paintable and safer to
handle than cresote or
pentachlorophenol. Arsenic
containing preservatives
give up to 80 years life
to treated wood. Loss of
use considered a national
disaster.
Used in varying concentra-
tions with other chemicals.
No substitutes. Arsenic
containing preservatives
give up to 80 years life
to treated wood. Loss of
use considered a national
disaster.
Used with other chemicals.
No substitutes. Method of
application seldom used.
Effective but too time
consuming. Impact of with-
drawing this method of
application would be slight.
Used in combination with
other chemicals. No
substitutes. Effective
and necessary use. Impact
of withdrawal of use would
be great.
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I. B. Sumnary of Registered Arsenical insecticide and Herbicide Uses
and Substitutes
I. B. 1. Lead Arsenate Insecticide 'Uses
'..'-'
.',':'. ' . Fruit Crops
Crop or Site
of Application
Apples
Foliage
Application
Insect Pest
Codling moth
Maximum or Usual
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
2-3 Ib. per 100
gals.
Lead Arsenate
Limitations
30 days
Hemove excess
residues at
time of harvest.
Do not graze
livestock on
treated areas
.Plum Curculio 2-3 Ib. per 100 T
gals.
Registered
Alternates
Carbaryl
Diazinon
EPN
Ethion
Gardona
Guthion
Imidan
Malathion
Methoxychlor
Methyl
-Parathion
Parathion
Trithion
BHC
Carbaryl
EPN
Gardona
Guthion
Imidan
Lindane'
Malathion
Methoxychlor
Methyl
Parathion
Parathion
- 15 -
-------
Lead Arsenate Insecticide Uses
Crop or Site
of Application
Apples
Foliage
Application
Insect Pest
Red-Banded
Leafroller
Fruit; Crops (continued)
Maximum or Usual
Dosage Kate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
2-3 Ib. per 100
gals.
Lead Aisenate
Limitations
Registered
Alternates
BHC
Carbaryl
Gardona
Guthion
Imidan
Malathion
Methyl
Parathion
Parathion
Green 2-3 Ib. per 100
Fruitworm gals.
Tent: 2-3 Ib. per 100
Caterpillar _ gals.
Carbaryl
Guthion
BHC
Carbaryl
Lindane
Malathion
Apples
Foliage '
Application
Apple Maggot 2-3 Ib. per 100.
gals.
Cankerworm 2-3 Ib. per 100
gals.
Applethorn ' 2 Ib. per 100
Skeletonizer i gals.
Bagworm
3-4- Ib. per 100
gals.
Carbaryl
Diazinon
Gardona
Guthion
Imidan
Methoxychlor
Methoxychlor
None
Carbaryl
Malathion
Parathion
- 16 -
-------
Crop or Site
of Application
Apricots
Foliage
Application
L°.ad Arsenate Insecticide Uses
Fruit Crops (continued)
Insect Pest
Maximum or Usual
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
Round Headed 3 Ib. per 100
Applfe Treeborer gals.
Lead Aisenate
Limitations
Fall Webworm
Red Humped
Caterpillar
Eyespotted
Bud Moth
2 Ib. per 100
gals.
3-4 Ib. per 100
gals.
3 Ib. per 100
gals.
Case Bearers 2-3 Ib. per 100
gals.
Syneta.Beetle 3 Ib. per 100 gals.
Registered
Alternates
Parathion
Guthion
Malathion
Parathion
Guthion
Parathion
None
None
-. - 30 day*
~~ Remove excess
residues at time
of harwest. Do not
graze ttreated forage
to Irvssstock.
Syneta Beetle 5-6 Ib. per 100
gals.
Peach
Twigborer
3-4 Ib. per 100
gals.
None
Chlordane
Diazinon
Endosulfan
Guthion
Imidari
- 17 -
-------
Crop or Site
of Application
Lead Arscnate Insecticide r.ses
Fruit Crop? (continued)
r
Insect Pest Maximum or Usual Lead .Aisenate
Dosage Rate Limitations
(Lbs. of Actual /
Insecticide Per
100 Gallons or
. . . Per Acre)
Registered
Alternates
Leafroller
3-4 Ib. per 100
gals.
Cherries
Foliage
Application
Plum Curculio 3-4 Ib. per 100 30 days
.gals. Remove residues
at time of harvest,
Do not graze
treatefl forage
by livestock.
Cherry Fruit 2 Ib. per 100 gals.
2-3 Ib. per 100 -
gals.
2-3 Ib. per 100
gals.
3-4 Ib. per 100
gals.
2-3 Ib. per 100
gals.
Pear Slug 2-3 Ib. per 100
gals.
Codling Moth
Apple Maggot
Cankerworm
Red-Banded
Leafroller
Chlordane
Guthion
Imidan
Carbaryl
EPN
Guthion
Lindane
Methoxychlor
Parathion
Carbaryl
Diazinon
Guthion
Malathion
Methoxychlor
Parathion
Rotenone
Carbaryl
None
Parathion
Carbaryl
EPN
Parathion
- 18 -
-------
Crop or Site
of Application
Lead Aisenate Insecticide Uses
' Fruit Crop (continued)
Insect Pest
Black Cherry
Fruit Fly
Rose Chafer
Maximum or Usual
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
2-3 Ib. per 100
gals.
2 Ib. per 100
gals.
Syneta Beetle 5-6 Ib. per 100
gals.
Tent
Caterpillar
Red Humped
Caterpillar
Cherry Slug
3-4 Ib. per 100
gals.
3-4 Ib. per 100
gals.
3-4 Ib. per 100
gals.
Lead Arsenate
Limitations
Registered
Alternates
Diazinon
Parathion
Methoxychlor
Nqne
Carbaryl
Methoxychlor
None
Malathion
Methoxychlor
Parathion
Nectarines
Foliage
Application
Peach Twig 3-4 Ib. per 100
Borer gals.
30 days. Remove
excess residues
at time of harvest.
Do not graze live-
stock on treated
areas.
Carbaryl
Diazinon
Imidan
Peaches
Foliage
..Application
Leafroller 3-4 Ib. per 100
gals.
Plum Curculio 1.5-2 Ib. per
100 gals.
30 days. Remove
excess residues
at time of harvest.
Do not graze live-
stock on treated
areas*
Carbaryl
Imidan
EPN
Guthion
Imidan
Lindane
Methoxychlor
Methyl
Parathion
Parathion
'Toxaphene
- 19 -
-------
Lead Arsenate Insecticide Uses
Fruit Crops (continued)
Crop or Site
of Application,
Pears
Foliage
Application
Insect Pest
Peach
Twig .Borer
Maximum or Usual
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
3-4 Ib. per 100
gals.
Lead Arsenate
Limitations
Red-Banded 3-4 Ibs. per 100
Leafroller gals.
Cherry
Fruitfly
2 Ib. per 100 gals.
Registered
Alternates
Codling Moth 1.5-2 Ib. per 100
gals.
Apple Maggot 1.5-2 Ib. per 100
gals.
Cankerworm 1.5-2 Ib. per 100
gals. ;
Syneta Beetle 5-6 Ib, per 100
gals.
Codling Moth 2-3 Ib. per 100 30 days. Remove
gals. excess residues at
• time cf harvest.
Do not graze live-
stock OID treated
areas.
Carbaryl
Diazinon
Guthion
Imidan
Rotenone
Carbaryl
Guthion
Parathion
Methoxychlor
Carbaryl
Chloroph-
enamidine
None
None
None
Carbaryl
Delnav
Diazinon
Ethion
Guthion
Imidan
Malathion
Methoxychlor
Parathion
Trithion
- 20 -
-------
Crop or Site
of Application^
Lead Arsenate Insecticide Uses
- Fruit Crops (continued)
Insect Pest
Maximum or Usual
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
Plum Curculio 2-3 Ib. per 100 gals.
Lead Jtesenate
Limitations
Red Banded 2-3 Ib. per 100
Leafroller gals.
Fruit Tree 4 Ib. per 100 gal.
Leafroller
Apple Maggot 2-3 Ib. per 100 gals,
Tent 2-3 Ib. per 100
Caterpillar gals.
Green
Fruitworin
Case Bearers
Syneta Leaf
Beetle
2-3 Ib.' per 100
gals.
2-3 Ib. per -100
gals.
3 Ib. per 100 gals,
Registered
Alternates
BHC
Carbaryl
Guthion
Imidan
Lindane
Malathion
Methoxychlor
Parathion
Carbaryl
Guthion
Imidan
Malathion
Parathion
Guthion
Parathion
Carbaryl
Diazinon
Guthion
Methoxychlor
BHC
Carbaryl
Lindane
Carbaryl
Guthion
None
None
-------
't-ead Ai senate insecticide Usa-s
Fruit Crops (continued)
Crop or Site
of Application
Insect Pest
Plums -"
Foliage
Application
Lead .irsenate
Limitations
Red-Humped
Caterpillar
Round Headed
Apple Tree
Borer
Pear
Leafworm
Pear Slug
Plum Curculio
Cherry Fruit
Fly
Apple Maggot
Codling Moth
Cankerworm
Maximum or Usual
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
3-4 Ib. per 100
gals.
3 Ib. per 100
gals.
2 Ib. per 100
gals.
4 Ib. per 100 gals.
1.0-2 Ib. per 100 30 dajs. Remove
gals, excess residues
at tine of harvest.
.Do no± graze live-
stock on treated
. - areas..
2 Ib. per 100
gals.
1.5-2 Ib. per 100
gals.
1.5-2 Ib. per 100
gals.
1.5-2 Ib. per 100
gals.
Registered
Alternates.
None
None
None
Parathion
Carbaryl
Lindane
Methoxychlor
Methyl
Parathion
Parathion
Toxaphene
Carbaryl
Methoxychlor
None
Carbaryl
None
- 22 -
-------
Crop or Site
of Application
Plums
Foliage
Application
Prunes
Foliage.
Application
Lead Arscnate Insecticide U'scs
Fruit Crops (continued)
Insect Pest
Red-Banded
Leafroller
Peach Twig
Borer
Eye-spotted
Bud Moth
Maximum or Usual
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
1.5-2 Ib. per 100
gals.
3-4 Ib. per 100
gals.
3 Ib. per 100
gals.
Lead Arsenate
Limitations
Registered
Alternates
Plum Curculio 2 Ib. per 100 gals.
Carbaryl
Guthion
Carbaryl
Diazinon
Guthion
Carbaryl
Guthion
Methoxychlor
Parathion
30 days. Remove Carbaryl
excess residues Guthion
at time of harvest. Imidan
Do not graze live- Lindane
".stock on treated Methoxychlor
areas. Parathion
Peach Twig
Borer
3-4 Ib. per 100
gals.
Carbaryl
Diazinon
Guthion
Imidan
Leaf Rollers
3-4 Ib. per 100
gals.
Carbaryl
Guthion
Imidan
Eye-Spotted
Bud Moth
Cherry Fruit
Fly
3 Ib. per 100
gals.
2 Ib. per 100
gals.
Carbaryl
Guthion
Parathion
Carbaryl
Methoxychlor
- 23 -
-------
Crop or Site
of Application
Quince
Foliage
Application
Lead Arsenate Insecticide Uses
Fruit Crops (continued
r
Insect Pest Maximum or Usual Lead Arsenate
Dosage Rate Limitations
(Lbs. of Actual ^
Insecticide Per
100 Gallons or
Per Acre)
Registered
Alternates
Cankerworas
2-4 Ib. per 100
gals.
Syneta Beetle 5-6 Ib. per 100
gals.
Codling Moth 2-3 Ib. per 100 30 days. Remove
gals. excess residues at
time of harvest.
Do not graze live-
stock on treated
areas.
Plum Curculio 2-3 Ib. per 100
gals.
Cankerworm
Red-Banded
Leafroller
Tent
Caterpillar
Apple Maggot
Fruitworms
Red-Humped
Caterpillar
2-3 Ib. per 100
gals.
2-3 Ib. per 100
gals.
2-3 Ib. per 100
gals.
2-3 Ib.-per 100
gals.
2-3 Ib. per 100
gals.
3-4 Ib. per 100
gals.
None
Carbaryl
Delnav
Guthion
Malathion
Methoxychlor
Trithion
Guthion
Malathion
Methoxychlor
Parathion
Methoxychlor
Guthion
Guthion
Methoxychlor
Guthion
None
- 24 -
-------
Crop or Site
of Application
Grapes
Foliage
Application
Lead Arsenate Insecticide Uses
' Fruit Crops (continued)
Insect Pest
Maximum or Usual
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
Syneta Beetle 5 Ib. per 100
gals.
Lead Arsenate
Limitations
Registered
Alternates
California
Oak Moth
Achnemon
Sphinx Moth
Grape
Rootworm
Grape
Leaffolder
Grape
Leafroller
3-4 Ib. per 100
gals.
3-4 Ib. per 100 Do not apply after
gals. edible parts start
to form.
3-4 Ib. per 100
gals.
3-4 Ib. per 100
• gals.
3 Ib. per 100
gals.-
None
None
None
None
Carbaryl
Diazinon
Guthion
Asparagus
Application
Tomatoes
Foliage
Application
Lead Arsenate Insecticide Uses
Vegetable Crops
Asparagus
Beetle
Tomato
Fruitworta
3 Ib. per acre
4-6 Ib. per acre
Do not apply
during cutting
season.
Remove excess
residues at
time of harvest,
Carbaryl
Malathion
Parathion
Rotenone
Calcium
Arsenate
Carbaryl
EPN
Methoxychlor
Me thorny1
Naled
-25 -
-------
Lead Arsenate Insecticide Uses
, Vegetable Crops (continued)
Crop or Site
of Application
Insect Pest
Hornworm
Maximum or Usual
Dosage Rate
(Lbs, of Actual
Insecticide Per
100 Gallons or
Per Acre)
3 Ib. per acre
Lead Arsenate
Limitations
Colorado 3 Ib. per acre
Potato Beetle
Flea Beetle 4 Ib. per acre
Grasshoppers 10 Ib. per acre
Registered
Alternates
Calcium
Arsenate
Copper
Arsenate
Carbaryl
Chlordane
Naled
Parathion
Rotenone
Calcium
Arsenate
Carbaryl
Di-Syston
Endosulfan
Methoxychlor
Parathion
Phosphamidon
Calcium
Arsenate
Copper
Arsenate
Carbaryl
Disyston
Endosulfan
Methyl
Parathion
Naled
Parathion
Rotenone
Carbaryl*
Parathion
*Bait Application
- 26 -
-------
Lead Arser>ate Insecticide Uses
. Vegetable Cro^s (continued)
Crop or Site
of Application
Insect Pest
Armyworms
Maximum or Usual
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
4-6 Ibs. per acre
Lead Arsenate
Limitations
Tobacco
Foliage
Application
Lead Arsenate Insecticide Uses
Field Crops
Hornworms 4-6 Ib. per acre
Registered
Alternates
Calcium
Arsenate
BHC
Carbaryl*
Chlordane*
Diazinon
Heptachlor
Lindane
Methyl
Parathion
Parathion
Toxaphene
Trichlorofon*
*Bait Application
Carbaryl
Guthion
Bacillus
Thuringiensis
Ornamentals
Foliage
'Application
California
Oak Moth
Bagworms
Lead Arsenate Insecticide Uses
Ornamentals
3-4 Ibs. per 100
gals.
3 Ibs. per 100
gals.
Bacillus
Thuringiensis
Calcium
Arsenate
Chlordane
Diazinon
Dylox
Malathion
Toxaphene
Trithion
-------
Crop or Site
of Application
Lead Arsenate In3ecti'.:ide Us:es
Oman entals (,'ontinued)
Insect Pest Maximum or Usual Lead Aisenate
Dosage Rate Limitations
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
Cankerworms
3 Ib. per 100
gals.
Pine Sawfly 3 Ib. per 100
gals.
Japanese
Beetle
Catalpa
Sphinx
Walnut
Caterpillar
Fall
Webworm
Eastern Tent
Caterpillar
3-6 Ib. per 100
gals.
3-6 Ib. per 100
gals.
4 Ib. per 100
gals.
4 Ib. per 100
gals."
4 Ib. per 100
gals.
Forest Tent 4 Ib. per 100
Caterpillar gals.
Gypsy Moth 4-6 Ib. per 100
gals.
Tussock Moth 4-6 Ib. per 100
gals.
Registered
Alternates
Calcium
Arsenate
Methoxychlor
Toxaphene
Malathion
Carbaryl
Chlordane
Methoxychlor
Toxaphene
Carbaryl
Toxaphene
Diazinon
Methoxychlor
Carbaryl
Diazinon
Dibrom
Malathion
Methoxychlor
Toxaphene
Carbaryl
Dylox
Gardona
Methoxychlor
Methoxychlor
-28 -
-------
Laac Arsenate Iu^cticide Cses
, Ornamentals (continued)
Crop or Site
of Application
Insect Pest
Elm Leaf
Beetle
Maximum or Usual
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
4 Ib. per 100
gals.
Lead Arsenate
Limitations
Codling Moth 2.0-3.0 Ib. per 100
gals.
Registered .
Alternates
Carbaryl
Methoxychlcr
Toxaphene
Guthion
Malathion
Methoxychlor
Lead Arsenate Insecticide Uses
Lawns and Ornamental Turf
Lawns and Ornamental
Turf
Soil and
Surface
.
Applications
Armyworms
Asiatic Garden Beetle
Cutworm
Earthworm
Japanese Beetle
Sod Webworm
White Grub
80
430
80
220
430
80
220
ID
8 -W
3 «)
•H C
U 0)
rH CO
«_ M
• -
X
X
X
X
X
X
>.,
u
s
nl
O
X
X
X
X
o
d
w
o
r-t
O
X
X
X
X
X
X
REG
c
o
c
N
CO
Q
X
X
X
REGISTERED ALTERNATES
M
O 0
C
CJ
(0
(U
CX
t-t co
Cu X
CD o
K H
X X
X
X
X
X
X
-------
I. B. .1. a. Conclus ions
Lead arsenate h^s been considered of: increasing importance during the
past several years for certain fruit insect contiol spray schedules.
Reasons given for considering the return tc lead arsenate as an insecticide
in integrated control programs have been:
1. Being a stomach poison, the lead arsenate does not kill beneficial
invertebrate parasites and predators in the orchards as do many
modern organic pesticides;
2. Need for use of a miticide is greatly reduced on fruit crops
treated with arsenical pesticides; and
3. If chlorinated hydrocarbon pesticides are severely restricted
or cancelled certain important fruit pests may not have a
satisfactory control agent.
All insecticidal uses of lead arsenate are recognized as presenting a hazard to
man and his environment. However, because of need in the integrated spray programs,
the registered uses of lead arsenate on selected fruit crops should be continued
subject to review and phase out prior to the 1975 use-season if satisfactory
alternates are developed. The following crop uses should be retained: apples,
apricots, cherries, nectarines, peaches, pears, plums, prunes, quinces and grapes.
All other uses of lead arsenate as an insecticide should be cancelled since
acceptable alternate pesticides are available.
I.B.2. Calcium Arsenate Insecticide Uses
Crop or Site
of Application
Insect Pest
Blueberries
Foliage
Application
Fruitfly
Berry Crops
Maximum or Usual
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or~
Per Acre)
2 Ibs. per 100
gals.
Calcium Arsenate
Limitations
Registered
Substitutes
14 days
(processed fruit)
30 days (fresh
fruit)
Carbaryl
Diazinon
Guthion
Malathion
Parathion
Rotenone
Broccoli
Foliage
Application
Vegetable Crops
Cabbage worms 3-4 Ibs. per acre
Do not apply
after edible
parts start
to form
Carbaryl
Chlordane
Endosulfan
Guthion
-------
Calcium Arsenate Insecticide Uses
Vegetable Crops (continued)
Crop or Site Insect Pest
of Application
Imported
Cabbage
Worm
Maximum or Usual
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
4 Ib. per acre
Calcium Arsenate
Limittations
Cabbage
Foliage
Application
Cabbage 3-4 Ib. per acre
Worm
Cabbage 4 Ib. per acre1
Looper
Registered
Alternates
Do not apply after
edible p.arts start
to form.
.Basic copper-
arsenate
Carbaryl
Chlordane
Diazinon
Endosulfan
Guthion
Lindane
Malathion
Methomyl
"Methyl
Parathion
Naled
Parathion
Perthane
Toxaphene
Rotenone
Carbaryl
Chlordane
Endosulfan
Guthion
Lindane
Malathion
Methoxychlor
Methyl
Parathion
Naled
Parathion
'Rotenone
Endosulfan
Guthion
Malathion
Methomyl
Methyl
Parathion
Naled
-31 -
-------
Calcium Arseaate Insecticide •*&&
Vegetable Crops (continued]!)
Crop or Site
of Application
Insect Pest
Maximum or Usual
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
Calcium Arsenate
Limitations
Cabbage
Looper
cont.
Imported
Cabbage
Worm
4 Ibs. per acre
Diamond
Back
Moth
4 Ibs. per acre
Fruitworm 4 Ibs. per acre
Tomato 4 Ibs. per acre
Hornworm
Registered
Alternates,
Parathion
Perthane
Rotenone
Basic copper
arsenate
Carbaryl
Endosulfan
Guthion
Malathion
.Methomyl
Methyl
Parathion
Naled
Parathion
Perthane
Rotenone
Basic copper
arsenate
Endosulfan
Guthion
Malathion
Methorayl
Methoxychlor
Naled ;
Parathion
Rotenone
Malathion
Methomyl
Malathion
- 32 -
-------
C'.lcium /U'seriatie. Insecticide Uses
Vegetable. Crops (continued)
Crop or Site
of Application
V
Insect Pest
Maximum or Usual
, Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
Flea Beetle 3-4 Ib. per acre
Calcium Arsenate
Limitations
Registered
Alternates
Carbaryl
Chlordane
Diazinon
. Di-Syston
Endosulfan
Methoxychlor
Methyl
Parathion
Parathion
Cauliflower
Foliage
Application
Colorado 4 Ibs. per acre
Potato Beetle
Cabbageworm 3-4 Ib. per acre
& Imported
Cabbageworm
Cabbage
Looper
3-4 Ib. per acre
None
Do not apply after Basic copper
edible parts start arsenate
to fora.
Carbaryl
Chlordane
Endosulfan
Guthion
Malathion
Methomyl
Methoxychlor
Methyl
Parathion
Parathion
Phosphamidon
Rotenone .
Toxaphene
Basic copper
arsenate
Chlordane
Endosulfan
Guthion
Malathion
Methomyl
Methyl
Parathion
- 33 -
-------
Calcium Arsenate Insecticide U.scs
Vegetable Crops (continued^
Crop or Site
of Application
Insect Pest
Cabbage
Looper .
cont.
Maximum or Usual
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
Calcium Ars'enate
Limitations
Registered
Parathion
Perthane
Rotenone
Celery -'
Fplia ge
Application
Flea
Beetles
3-4 Ib. per acre
Colorado
Potato
Beetle
Flea
Beetles
Leaf
Hoopers
Celery
Leaf
Tier
1-1.75 Ib. per acre
Do not apply after
bunch begins to
form or after
plants are half
'grown
Carbaryl
Chlordane
Endosulfan
Si-Syston
Methoxychlor
Methyl
Parathion
Parathion
Rotenone
None
1-1.75 Ib. per acre -
1-1.75 Ib. per acre
4.0-5.5 Ib. per acre
Meth.oxychlor
Methyl
Parathion
Methoxychlor
Methyl '
Parathion
Parathion
Methoxychlor
Parathion
Tarnished 4.0-5.5 Ib. per acre
Plant Bug
Methoxychlor
Parathion
-------
Crop or Site
of Application
Cucumbers
Foliage
Application
Calcium Arsenate T.nsect\cide 'Jsas
Vegetable Crops (continued)
Insect Pest
Striped
Cucumber
Beetle
Maximum or Usual
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
1-1.75 Ib. per acre
Calcium Arsenate
Limitations
Remove excess
residues at
harvest
Registered
Alternates
Carbaryl
Guthion
Malathion
Methoxychlor
Parathion
Rotenone
Squashvine
Borer
Methoxychlor
Parathion
Rotenone
Melons
Foliage
Application
Striped
Cucumber
Beetle
1-1.75 Ib. per acre
Squash Bug 4.0-5.5 Ib. per acre
Squash Vine 4.0-5.5 Ib. per acre
Borer
No time
limitation
Carbaryl
Guthion
Methoxychlor
Parathion
Rotenone
Car.baryl
Guthion
Methoxychlor
Parathion
Peppers
Foliage
Application
Imported 4 Ib. per acre
Cabbageworm,
Cabbage Looper,
Diamond back
Moth
Fruitvorm 4 Ib. per acre
Tomato
Hornworm
4 Ib. per acre
Remove excess
residues at
harvest
Methyl
Parathion
Carbaryl
Carbaryl
Endosulfan
- 35 -
-------
Crop or Site
of Application
Squash
Foliage
Application
Tomatoes
Foliage
Application
Calcium Arsenate Insecticide Mses
Vegetable Crop" (continued}
Insect Pest
Colorado
Potato
Beetle
Flea
Beetles
Imported
Cabbage
Worm
Cabbage
Looper
Maximum or Usual
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
4 Ib. per acre
4 Ib. per acre
Calcium Arsenate
Limitations
Striped 1-1.75 Ib. per acre Remove excess
Cucumber residues at
Beetles - . harvest:
4 Ib. per acre
4 Ib. per acre
Remove excess
residues at
harvest
Diamond 4 Ib. per acre
Back Moth
Registered
Alternates.
Carbaryl
Methoxychlor
Toxaphene
Carbaryl
Endosulfan
Methoxychlor
Methyl
Parathion
Parathion
Toxaphene
Carbaryl
Methoxychlor
Parathion
Rotenone
Methyl
Parathion
Methomyl
Methyl
Parathion
Tomato 1-1.75 Ib. per acre
Fruitworm
Lead Arsenate
Carbaryl
EPN
Methomyl
Methoxychlor
Naled
- 36 -
-------
C.'iiciura Arsenate Insecticide Uses i
Vegetable Crops (continued)
Crop or .Site
of Application
Insect Pest
Hornworm
Maximum or Usual
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
3 Ib. per acre
Calcium Arsenate
Limitations
Budworm
Colorado
Potato
Beetle
3.5-7 Ib. per acre
1-1.75 Ib. per acre
Flea Beetle 3 Ib. per acre
Leafhoppers 1-1.75 Ib. per acre
Registered
Alternates •
Lead Arsenate
Copper Arsenate
Carbaryl
Chlordane
Naled
Parathion
Rotenone
Lead Arsenate
Carbaryl
Di-Syston
Endosulfan
'Methoxychlor
Parathion
Phosphamidon
Lead Arsenate
Copper Arsenate
Carbaryl
Di-Syston
Endosulfan
Methyl
Parathion
Naled
Parathion
Rotenone
Carbaryl
Di-Syston
Methyl
Parathion
Parathion
- 37 -
-------
Calcium Arsenate iasacticide Uses
•o ••
*
Poultry Houses
Crop or Site Insect Pest Maximum or Usual Calcium Arsenate Registered
of Application Dosage Rate Limitations Alternates
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
Poultry Houses Housefly and 1.7 Ib. per 100 Apply to surface Kepone
for application Soldier fly sq. ft. of poultry of droppings under Dicapthon
to droppings larvae droppings . birds in cages or Zython
under birds in -.on wire floor for
cages or on control of fly
wire floors . larvae.
Calcium Arsenate Insecticide Uses
Special Applications—Baits
Calcium Arsenate baits limited to soil treatments are acceptable for use against
armyworms, cutworms, slugs, snails and sowbugs. This 'type application may be used
only in accordance with appropriate "Summary clearance and limitations on crops
so specified,
Calcium Arsenate Insecticide Uses
Lawns and Ornamental Turf
of Application .
-------
Calciun Arsenate Insecticiui Uses
Lawns and Orn-irnental Turf (continued)
Crop or Site
of Application
«
Lawns and ^ g c °
Ornamental Turf £? -3 § "5 < J:
(0 (-1 i-( CO CL
,Q O N 4J TJ CO
Soil and Surface £ £ « g- « g
Applications o o o sa ^ H
Japanese Beetles 430 X X X X
Sod Webworms" 430 X X X X X
White Grubs" 430 XXX
^Incidental claims - Use of 430 Ibs. per acre primarily registered for crabgrass
control.
I.E. 2. a. Conclusions
Calcium arsenate dusts and baits ^have been used extensively for pest control
in many crops and ornamentals. Dust applications of the calcium arsenate
are effective when used at rates up to 10 pounds of actual per acre in
confo.rmity with registrations and tolerances. The bait treatments are used
as soil applications for armyworms, cutworms, slugs, snails and sowbugs.
Baits of calcium arsenate are registered on a number of crops at rates of
JL5 pounds of actual per acre. The baits are effective when used in conformity
with current registrations and tolerance clearances. Reasons given for retention
of calcium arsenate for vegetable and selected fruit control programs have been:
1. Calcium arsenate does not seriously affect beneficial invertebrate
parasites and predators in vegetable crops as do many modern organic pesticides; and
2. Need to use a miticide is greatly reduced on vegetables treated with
calcium arsenate.
The currently registered uses of calcium arsenate for dusts on vegetables,
baits, and for fruitfly on blueberries will be continued. The following uses
should be retained:
Type of Application Crops or Uses
Dusts • Blueberries, Broccoli, Brussels Sprouts, Cabbage,
Cauliflower, Celery, Cucumbers, Melons, Peppers,
Squash, Tomatoes..
•
Baits on Soil General Use.
Sprays Blueberries
All other uses of calcium arsenate as an insectici.deoc3EC.uld be cancelled since
these uses present a hazard to man and his environment and acceptable alternate
pesticides are available., * •
- 39 -
-------
I. B. 3. Basic Copper Arscnate Insecticide Uses
Vegetable Crops
Crop or Site
of Application
Insect Pest
Brussels Sprouts Cabbage
•Foliage^ Looper
Applications
Maximum or Usual
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
8 Ibs. per acre
Basic Copper
Ar senate
Limitations
Do not apply after
edible parts start
to
Imported 8 Ibs. per acre
Cabbageworm
'Cabbage
Foliage
Application
Imported 8 Ibs.
Cabbageworm
per acre
Do not apply after
edible parts start
to form.
Registered'
Alternates
Calcium
Arsenate
Chlordane
Endosulfan
Guthion
Malathion
Me thorny1
Methyl
Parathion
.Naled
Parathion
Perthane
Rotenone
Calcium
Arsenate
Carbaryl
Chlordane
Diazinon
Endosulfan
Guthion
Lindane
Malathion
Methomyl
Methyl
Parathion
Naled
Parathion
Perthane
Rotenone
Toxaphene
Calcium
Arsenate
Carbaryl
Endosulfan
Guthion
-------
Crop or Site
of Application
Basic Copper Arscnate Insecticide Uses
'Vegetable Crops (continued)
Insect Pest
Maximum or Usual
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
Basic Copper
Arsenate
Limitations
Imported
Cabbageworm
cont.
Diamond 8 Ibs. per acre
Back Moth
Cauliflower
Foliage
Application
Cabbage 8 Ibs. per acre
Worm
Do nott apply after
curd starts to
form.
Registered
Alternates-
Malathion
Methorny1
Methyl
Parathion
Naled
Parathion
Perthane
Rotenone
Calcium
Arsenate
Endosulfan
Guthion
Malathion
Methorny1
Methoxychlor
Naled
Parathion
Rotenone
Calcium
Arsenate
Carbaryl
Chlordane
Endosulfan
Guthion
Malathion
Methomyl
Methoxychlor
Methyl
Parathion
Parathion
Perthane
Phosphamidon
Rotenone
Toxaphene
- 41 -
-------
Crop or Site
of Application
Basic Copper Arsenure Insecticide Uses
r-
Vegetable Crops (continued)
Insect Pest. Maximum or Usual Basic Copper
Arsenate
Limitations
Dosage Rate Arsenate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
Imported 8 Ibs. per acre
Cabbageworm
Cabbage
Looper
8 Ib. per acre
Registered
Alternates
Calcium
Arsenate
Carbaryl
Chlordane
Diazinon
Endosulfan
Guthion
Malathion
Methomyl
Methoxychlor
Methyl
Parathion
Parathion
Perthane
Phosphamidon
Rotenone
Toxaphene
Calcium
Arsenate
Chlordane
Endosulfan
Guthion
Malathion
Methomyl
Methyl
Parathion
Parathion
Perthane
Rotenone
- 42 -
-------
Basic Copper Arsenate Insecticide Uses
*
Vegetable Crops (continued)
Crop or Site
of Application
Insect Pest
Kohlrabi
Foliage
Application
Cabb'age
Looper
Maximum or Usual
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
8 Ibs. per acre
Basic Copper
Arsenate
Limitations
Do not apply after
edible parts start
to form.
Imported 8 Ibs. per acre
Cabbageworm
Tomatoes
Foliage
Application
Flea
Beetles
15 Ibs. per acre
No time limit.
•Hornworms 15 Ibs. per acre
Registered
Alternates
Chlordane
Carbaryl
Lindane
Methyl
Parathion
Naled
Parathion
Rotenone
Chlordane
Carbaryl
Lindane
Methyl
Parathion
Parathion
Lead
Arsenate
Calcium
Arsenate
Carbaryl
Di-Syston
Endosulfan
Methyl
Parathion
Naled
Parathion
Rotenone
Lead Arsenate
Calcium Arsenate
Carbaryl
Chlordane
Naled
Parathion
Rotenone
-------
I. B,3 . a. Cone3 uj.; ons
The registered uses for bas-.c copper arssnate as an tn=ecticiuB should
=nd >!it
I.E. 4. Ammonium Arsenite Insecticide Uses
V Wood Preservative
Crop or Site
of Application Insect Pest
Wood
Preservative
Wqod
Destroying
Insects
Maximum or Usual
Formulation
Ingredient
*
7.77,
Registered
Alternates
Creosote
Pentachlorophenol
*Pressurized with other ingredients
I.E.4.a. Conclusions
The registered use for ammonium arsenite as a wood preservative (insecticide
and fungicide) should be retained. For more details, see I.E.9.a. and I.D-,
Industrial Wood Preservatives.
I.E. 5. Arsenic Acid Insecticide Uses
Wood Preservative
Crop or Site
of Application
.Wood
Preserva tive
Insect Pest
Wood
Destroying
Insects
Maximum or Usual
Formulation
Ingredient
42.0%*
Registered
Alternates
Creosote
Pentachlorophenol
*Pressurized with other ingredients
- 44 -
-------
I. B. 5 . a . Cone lusion.s
The registered use of arsenic a.viid for <:ood destroying insects should
be retained. For more details see I.E.9.a. and I.D., Industrial
Wood Preservatives.
I.E. 6. Arsenic Pentoxide Insecticide Uses
Wood^Preservative
Crop or Site Insect Pest Maximum or Usual Registered
of Application Formulation Alternates
Ingredient
Wood Wood 4.08-34.07.* Creosote
Preservative Destroying Pentachlorophenol
Insects
*Pressurized with other ingredients
I.E.6.a. Conclusions
The registered use of arsenic pentoxide for wood destroying insects
should be retained. For more details see I.B.9.a. -and I.D.,
Industrial Wood Preservatives.
'.. I.E.7. Arsenic Trioxide Insecticide Uses
Wood Preservative
Crop or Site insect Pest Maximum or Usual Registered
of Application Formulation Alternates
Ingredient
Wood Wood 37.0%* Creosote
Preservative Destroying Pentachlorophenol
Insects
-45 -
-------
Arsenic Trioxiue Insecticide Uses
Wood Preservative (continued])
Crop or Site
of Application
Insect Pest
Maximum or Usual
Formulation
Ingredient
Registered
Alternates
Antifouling
Paint
Insect and
Invertebrate
Pests
1.5%*
Metallic
copper compounds
Tri-N-Butyltin
Flouride
Tri-N-Butyltin
Oxide
Tri-N-Butyltin
Resinate
*Pressurized with other ingredients
I.E.7.a. Conclusions
The combination of arsenic trioxide or Paris green with copper compounds in
anti-fouling paints enhances the anti-fouling activity vafaich cannot be achieved
with copper compounds alone. The organic tin compounds are also toxic and
on a cost basis less effective than the arsenicals. Th;e quantities used
and the dispersal achieved in a body of water can have mo general effect on
the ecosystem and the arsenic content of sea water. The registered uses of
arsenic trioxide as a wood preservative and in antifouliing paint should be re-
tained. For more details, see I.E.9.a. and I.D. Industrial Wood Preservatives.
I.E.8. Sodium Pyroarsenate Insecticide Uses
Wood Preservative
Crop or Site
of Application
Wood
Preservative
Insect Pest
Wood
Destroying
Insects
Maximum or Usual
Formulation
Ingredient
6.2%*
Registered
Alternates
Creosote
Pentachlorophenol
*Pressurized with other ingredients.
- 46 -
-------
I.B.8.a. Conclusions .
The'registered use of sodium pyroarsenate for wood destroying insects should
be retained. For more details, see I.E.9.a.
y.'
I.E.9. Wolman Salts Insecticide Uses
Wood Preservative
Crop or Site Insect Pest Maximum or Usual Registered
of Application Formulation Alternates
Ingredient
:Wood Wood . 6.2-26.9%* Creosote
Preservative Destroying Pentachlorophenol
Insects
*Pressurized with other ingredients.
I.E.'9.a. Conclusions
•* ••• • .,— —•. i .I -..-
Arsenic is a standard ingredient in water soluble preservatives which are
used to pressure impregnate wood products. In pressurized treatments
the chemicals are contained in an enclosed system which is recycled and
do not contaminate the environment. Two common mixtures contain salts of
copper, chromium and arsenic. Another is a fluoro-chrome-arsenic-
phenol mixture. The purpose of treating the wood with these preservatives
is to protect it against decay and insect attack.
Arsenic exhibits both fungicidal and insecticidal properties. It is an
important ingredient of the preservative mixture. Arsenic plays an important
role in the fixation of the chemicals in wood. The chemicals undergo reactions
with the wood and are converted to insoluble compounds. The arsenic is fixed
to the wood and does not leach out.
There is no satisfactory substitute for arsenic in the preservative mixture.
For these uses, we should retain the registrations for arsenic acid, ammonium
arsenite, arsenic pentoxide, arsenic trioxide, sodium pyioarsenate, sodium
arsenate, and Wolman salts. ,
- 47 -
-------
Crop or Site
of Application
i
1: _'
Forest
Application
By U.S. Forest
Service only
I. B. 10. Cacodylxc Acid Insecticide Uses
Forest Application
Insect Pest
Insect
Trapping
Engleman
Maximum or Usual
Dosage Rate
Limitations
Registered
Alternates
1 ML per inch
None
Spruce Beetle of tree surface
Mountain Pine
Beetle
Douglas Fir
Beetle
. Round Headed
Pine Beetle
Arizona Five-
Spined Beetle
Pine Engraver
Beetle
California Five-
Spined Beetle
I. B. 10. a. Conclusions
The registration of cacodylic acid for forest application (trapping insects)
should be retained for the U.S. Forest Service.
- 48 -
-------
I.B.ll. Sodium Aisenite and Potassriin Arsenite Insecticide Ls'is
Soil, Household and Commercial -° '•
Crop or Site Insect Pest Maximum or Usual* Sodium Arsenite Registered
of Application Dosage Rate Limitations Alternates
Soil Subterranean 9% Solution Chlordane
Termites Heptachlor
Pentachloro
. phenol
Household and Ants . 2.0% . Kepone
Commercial
(Bait
Application)
*Formulation Ingredient
Sodium Arsenite and Potassium Arsenite Insecticide Uses
Livestock
USDA . Ticks 0.25% Solution None
Livestock
Quarantine
(Cattle Dip) - -
*Formulation Ingredient
'I.B.ll.a. Conclusions
Sodium arsenite is too toxic for patterns of use involving storage in the
home environment. The registered uses for control of subterranean termites
and ants by the homeowner should be cancelled.
The essential program of guarding the United States - Mexico border against
introduction of the Texas cattle fever tick is based on the u§e of sodium
arsenite and potassium arsenite in dip tanks. This use is restricted to the
United States Department of Agriculture. There is no safe and effective
alternate pesticide which has a simple and efficient vat-side test for
determining pesticide concentration. The risk of re-introduction of this tick
into the United States would be great without availability of the arsenical
dip or until ,an..ja4tern?.££ *fiic«kicide irs -developed... . c"
-------
'I. B. 12. Sodium Arsenate Tnsec'.^cide Uses
Soil, Structures, Woud Preservative, Household and Commarcial
'2
Crop or Site
of Application
Structural
Soil
Wood
Preservative
Household and
Commercial
(Bait
Application )
Insect Pest
Drywood
Termites
Subterranean
Termites
Termites and
Wood Destroying
Insects
Ants
Maximum or Usual'-*
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
43% Dust
2% Solution
14.0-43.5%*
0.7-3.0%
Registered
Alternates
Hydrogen Cyanide
Methyl Bromide
Sulfuryl Flouride
Chlordane
Heptachlor
Pentachlorophenol
Creosote
Pentachlorophenol
Kepone
*Pressurized with other ingredients.
**Formulation Ingredient • -
I.E.12.a. Conclusions
The package for the household bait should not exceed one fluid ounce containing
2.5 percent sodium arsenate or any combination of concemtration and package
size that contains no more than 0.75 gram of sodium arsenate. The use of sodium
arsenate should be retained for structural and soil applications by pest control
operators only to control drywood and subterranean termites. The use of sodium
arsenate as a wood preservative should be retained. For more details, see
I.E.9. and I.D., Industrial Wood Preservatives (fungicide).
- •- --50'-
-------
I. B. 13. Paris Grosn Insecticide Uses
Aquatic, Structures, and Antifoulimg. Paint
Crop or Site Insect Pest
of Application
Aquatic Areas
Mosquito
Larvae
Structures
Antlfouling
Paint
Maximum or Usual
Dosage Rate
(Lbs. of Actual
Insecticide Per
100 Gallons or
Per Acre)
0.6-15 Ibs. per acre
Lead Arsenate
Limitations
Dry Wood
Termites
(Insect and
Invertebrate
Pests)
Cribbles
Teredos
Shipworms
1007, Dust
16-26.5%
Registered
Alternates
Abate
BHC
Coal Tar
Neutral Oils
Cresylic Acid
Malathion
Methoxychlor
Hydrogen Cyanide
Methyl Bromide
Sulfuryl Fluoride
Metallic
Copper Compounds
Tri-N-Butyltin
Fluoride
Tri-N-Butylin
Oxide
Tri-N-Butyltin
Resinate
I.B.13.a. Conclusions
Paris green has been used in a large volume (957,144 pounds of 5% granules
Florida in 1970) in several Southeastern states during tthe past 15 years.
While several insecticides are available for use as a lanrvicide, oil is
the only known substance that can be used in place of Baris green without
risking loss of control due to resistance.' Oils, which may be substituted
in the spring, have to be abandoned when the vegetation prevents adequate
penetration. In addition to the resistance problem, thr synthetic organic
pesticides are generally more hazardous to fish and wiMlife than Paris green.
- 51 -
-------
Personnel of the West Florida Arthropod Research Laboratory have, conducted
r.v.earch on the disappearance of -?r°-T.?'c from soil auu water. Mr. C.B. Rathburn
ir an article entitled "The Arsenic Content in Soil Following Repeated
Applications of Grsnular Paris Green" (Mosquito News Ii3, 537-539, 1966;
states that from data obtained th^re appears to be no Evidence of an
accumulation of arsenic in soil following repeated (8) applications of * '
granular Paris green to the water surface as a larviciSe.
The registered uses of Paris green should be retained for control of mosquito
larvae, drywood termites and in antifouling paints to -control insect and invertebrate
pests.
For use in antifouling paint see I.E.7.a.
I.B.14. Herbicide—Citrus
Arsenical
Action
Cacodylic Weed Control
Acid
Usual Dosage Rate
(Lbs. of Actual
Per Acre)
2-5
Limitations
Nonbearimg citrus
only. Ba> not
exceed 3 applications
per year. Do not
harvest i&ruit from
treated {trees within
one year
Registered
Alternates
Bromacil
Dalapon
Dichlobenil
DNBP
Diphenamid
Diuron
Eptam
Paraquat
Monuron-TCA
I.E.14.a. Conclusions
The registered use of cacodylic acid for weed control 03311 citrus should be retained.
Cacodylic acid is essential for the control of'emerged Johnsongrass.
I.E.15.a. Herbicide-.-•Around Ornamental Trees and Shrubs
Arsenical Action
Cacodylic Weed Control
Acid
Usual Dosage Rate
(Lbs. of Actual
Per Acre)
10-20
'- D3MA
5-15
MS MA
2-5*
Arsenic
Limitatiffins
Do not graze..
Do not contaminate
water.
Do not contaminate
water.
Do not treat
newly sec-wed lawns,
Registered
Alternates
Atrazine
Benefin
Betasan
CDEC
Dae thai
Dichlobenil
I PC
No re a
Paraquat
Simagine
Silvex
- 52 -
-------
'I.E.15.a. Conclusions
The registeied uses of cacu-'lylic ar.id, DSMA and MS HA around ornamental trees
and- shrubs should be retained. o
These materials are essential for control of emerged jofcnsongrass
\ "
I.E."'16. Herbicides--Lawns and Ornamental Turf
Arsenical Action
Arsenic
.Acid
Weed Control
Calcium
Arsenate
(tricalcium
arsenate)
Cacodylic
Lead Arsenate
DSMA
Usual Dosage Rate Arsenic!
(Lbs. of Actual Limitations
Per Acre)
10-40
80-600
10-20
70-200
5-15
Do not water for
3 days after
treatment.
Do not apply to
newly seeded lawns.
Do noit allow
children or pets
on lasm before it
dries.
Do noit, graze.
Do noit contaminate
water.
Keep (children and
pets
-------
I.B.16=a. Conclusions
The following actions are suggested for the registered arsenical herbicides0 '
for lawns and ornamental turf:
1. Arsenic'acid is too toxic for this use and shcuild be cancelled;
2. Calcium arsenate use limited to Poa annua conteol and restricted
to optimal effective rates on golf courses ani related recreational
turf;
3. Cacodylic acid use should be retained, especially for control of
emerged johnsongrass;
4. Lead arsenate should be " cancelled to reduce tike amount of lead
introduced into the home environment.
5. DSMA, MSMA and AMA should be retained, especially for control
of emerged johnsongrass4
6. Arsenic trioxide and sodium arsenite are too :toxic for this use
and should be cancelled.
I.E.17. He.rbicides--Non-Crop, Industrial Sites, Rights-of-Way
Driveways and Sidewalks
Arsenical
Action
Arsenic Acid Weed Control
Cacodylic
Acid
DSMA
Usual Dosage Rate
(Lbs. of Actual
Per Acre)
10-40
2-5 lbs/100 gal,
H20
2-5 lbs/100 gal.
H20
Arsenic
Limitations
Spray to runoff.
Do wat graze
treated areas.
Do not contaminate
water..
Registered
Alternates
Amitrole
Ammonium
sulfamate
Atrazine
Bromacil
Dicamba
Diphenamid
Diuron
DNBP
Eptam
Fenac
Linuron
- 54 -
-------
Arsenical
MSMA
Ac-iion
Weed Control
Driveways arid Sidewalks (continued)
Usual Dosage Rate Arsenic
' (Lbs. of Actual Limitations
Per Acre)
2-5 lbs/100 gal.
H20
Registered
Alternates
Monuron
Paraquat
Petroleum oil
Simazine
Silvex
2,4-D
2,4,5-T
I. B. 17. a. Conclusions
The actions on arsenic acid, cacodylic acid, DSMA and MSMA should be the
same as given for I.E.16.a.
Arsenical
I. B. 18. Herbicides—Hardwood Tree Control
Action Usual Dosage Rate Arsenic
(Lbs. of Actual Limitations
Per Acre)
Cacodylic
Acid
MSMA
Tree
Injection
1 ml/cut
l-2ml/cut
Registered
Alternates
Dicamba
.2,4-D
2,4,5-T
Picloram
I.E.18.a. Conclusions
This method of application minimizes environmental contamination. The
registered uses of cacodylic acid and MSMA for hardwood .tree control
should be retained.
- 55 -
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I. B. 19. — Herbicides Serai-Soil S'fcerilant
Arsenical
Sodium
Arsenite
(Arsenic
Trioxide)
Sodium
Arsenite
(Arsenic
Trioxide)
Action
Weed Control
Usual Dosage Rate Arsenic
(Lbs. of Actual Limitations
Per Acre)
To 50 Ibs/A.
Bare ground
application and
must b:e enclosed,
50 or more Ibs/A. Must be covered
by pawement.
Registered
Alternates
Bromacil
Sodium
Borate-Chlorate
Combinations
Ammonium
Sulfamate
Same
I. B. 19.a. Conclusions
The registered uses for sodium arsenite and arsenic trioxide as a semi-soil
sterilants are too hazardous and ^should be cancelled. Safer alternates are
available and should be substituted.
Arsenical
MSMA
Action
Post
emergence
weed
control
I.E. 20. Herbicides—Cotton
Usual Dosage Rate
(Lbs. of Actual
Per Acre)
1-2
Lead-Arsenic
Limitations
Do not graze or
feed forage to
livestock. Do
not apply after
first bloom.
Registered
Alternates
Betasan
Daethai
Diuron
Eptam
Monuron
Norea
Treflan
DSMA
NOTE:
2-3
Large, favorable response requesting use after Fedeial Register Notice.
- 56 -
-------
T, F«. 20.a. Cone j.us ions
These materials arc. essential in canb\nat:ir>n or alone ivn post-emergence weed
control progiTPTns of cotton to minimize L.-'S? of crop due to emerged johnsongrass
and other hart! to control weeds. MS MA or DSMA are usefl on 4,000,000 acres *'* '
of cotton for control of weeds. It has been estimated that up to 12,000,000 pounds
of these materials are used annually on cotton in the United States.
Inability to use MS MA and DSMA in cotton would result -in losses of about
$60,000,000 per year. It would 'also require heavy use of other replacement
herbicides and hand labor.
Registered uses of DSMA and MS MA do not increase the coitent of arsenic
in cotton seed. Danger to workers in cotton production,, to wildlife and to
farm animals is minimal. There has been concern expressed by investigators
that the increasing use of these materials could lead .ta» residual amounts
of arsenic in the soil. More than 5 ppm available arsenic in the soil may
be hazardous to field crops.
The registered uses of MSMA and DSMA for weed control .ia cotton should be
retained.
I.E. 21. Desiccant and Defoliant—Cotton
Arsenical Action Usual Dosage Rate
(Lbs. of Actual
Per Acre)
Arsenic
Acid
Harvest aid
(desiccant and
defoliant)
2-4.4
Arsentic
Limitations
Apply 7-10 days
before harvest.
Registered
alternates
Sodium borate
Sodium chloraf
Ammonia
Ammonium nitrat
Neo-decanoic
acid
Def
Folex
NOTE: Large favorable response requesting use after Federal Register Notice.
-------
I.E. 21.a. Conclusions
Approximately 900,000 gallons of arsenic acid are used each year as a
pre'harvest desiccant of cotton. An effective desiccar.t is essential for ^
economical production of cotton on about 2,000,000 acres of land in
Texas and Oklahoma. In these two states, where the arsenic acid is needed,
the'cotton is harvested by mechanical strippers which are used on special
varieties of cotton after defoliation. No economically satisfactory
desiccant, other than arsenic acid, has been developed in the specific'
areas of Texas and Oklahoma. Inability to use the arsenic acid as a desiccant -
defoliant would cause an estimated loss of $163,000,000 in the two states.
The hazard of using arsenic acid as a desiccant on cotton has been recognized.
However, the United States Department of Agriculture is not aware of serious
injury to people exposed during the cotton production and processing procedures.
There has been concern expressed by investigators that increased use of arsenic
acid could lead to residual amounts of arsenic in the soil.
The registered use of arsenic acid as a desiccant and defoliant of cotton
should be retained.
I.E. 22. Regulator—Grapefruit
Arsenical
Lead
Arsenate
Action
Plant regulator -
Reduce acidity
Usual Dosage Rate
(Lbs. of Actual
Per Acre)
1.7-5.4
Arsenic
Limitations
Do not use on
other citrus.
Do not apply
within 3 days
of harvest
Registered
Alternates
None
I.E.22.a. Conclusions
Arsenic is needed as a regulator of grapefruit intended for harvest in Florida.
Lead arsenate has been registered for the use (reduce acidity) at rates of
1.7 to 5.4 pounds of actual per acre. It is not intended for use on other
citrus or within 3 days of harvest. Successful marketing of Florida grapefruit
would not be possible without arsenic to reduce natural acidity.
Lead arsenate has had a long history of successful use on Florida grapefruit.
In the central part of the state where approximately 75 percent of the Marsh
Seedless grapefruit, 60 percent of the Red and Pink grapefruit, and 85 percent
of the seedy grapefruit are produced, arsenic is used on 90 percent of the
acreage. It is estimated that this use represents a total of approximately
60,000 acres of Florida grapefruit.
- 58 -
-------
Residues from the use of leud arsenate as described above on mature washed
rx;'it are less than 0.5 ppm arsenic and seldom over 0,5 ppm lead on the whcle-
fr'iit basis. Arsenic residues in the edible portion T-*n£p. ,
i.cn To nii
yre me
iroia tan
i "i;"5 f" p •"
J i.It-. L, C- w .
- 59 -
-------
I.D.I.a. Conclusions
Sodium Arsenide* on Grapes;
This use is confined to western areas, principally in the San Jo^quin Valley
of California where it is the only fungicide which effectively controls th&;
diseases for which it is registered. On some farms it is necessary to apply
annually, on others it may be used once every two or three years. In
California 30,000 acres require treatment annually. Annual losses in
California without treatment have been estimated for 1.5 to 5.0 percent with
an average of 3.0 percent. Losses in individual vineyard range from 1.0 to
40.0 percent of the fruit. Infected fruit have no economic value. The
California crop is valued at $165,000,000 with an average loss without
treatment at $7,000,000. Note that the University of California is presently
engaged (with EPA) in a cooperative monitoring study.
The California Pesticide Use Report lists 534 applications of a total of
90,000 pounds of Sodium arsenite on grapes in 1970.
The registered uses of sodium arsenite as a dormant application for black
measles, dead arm and crown gall control on grapes should be retained.
Basic Copper Arsenate on Tomatoes:
The currently registered uses of basic copper arsenate for early and late
blight on tomatoes should be retained subject £o review and phase out prior to
the- 1975 use season if satisfactory alternates exist.
I.D. 2. Industrial Uses as Wood Preservatives
Pressure Treatments
Arsenical Pesticides
and other Compounds
14% arsenic acid, 34%
chromic acid and 97,
copper oxide
427, arsenic acid,
277o chromic acid and
157o copper oxide
357o arsenic acid,
36.57o. sodium arsenate,
and 28.1% sodium dichromate
30.57o arsenic
pentoxide dihydrate,
6.27, sodium hypoarsenate,
31.57, sodium dichromate and
26.87, copper sulfate
Special Comments
Used as 1 to 5%
aqueous solutions
Used as 1 to 57»
aqueous solutions
Used "only by importer
in his plant
Used as 1 to 57,
aqueous solutions
Registered
Substitutes'
None
-------
I.D.?., (cont'd)
Arsenical Pesticides
and other Compounds
»•
34% pentoxide,
26.5%'chromic acid, and
14.57, cupric oxide
26.9% arsenic pentoxide,
42.6% sodium dichromate,
and 25.5% copper sulfate
23.8% arsenic pentoxide,
33.35% chromic acid,
and 12.95% copper oxide
17% arsenic pentoxide,
23.75% chromic acid, and
9.25% cupric oxide
10% arsenic pentoxide,
53% potassium dichromate,
and 32% copper sulfate
2318% disodium arsenate,
34.2% sodium chrornate,
27.5% sodium fluoride,
and 9.5% technical sodium
pentachlorophenate
23.8% sodium arsenate,
35.6% sodium chromate,
23.8% sodium fluoride,
and 11.8% pentachlorophenol
6.0% sodium arsenate,
33.3% sodium fluoride,
32% sodium dichromate,
and 4..3% 2,4-dinitrophenol
Special
Used as 1 Lo 5 %
aqueous solution
Used as a 1 to 5%
aqueous solution
.Used as to 1 to 5%
aqueous solution
Used as a 1 to 5%
aqueous solution
Used as a 1" to 5%
aqueous solution
Used as 0.5 to
5% aqueous solution,*:
Used as 0.5 to 5%
aqueous solutions
Used as 1.5 to
.3% solution
None
None
None
None
None
None
None
None
*Creosote, pentachlorophenol and etc. are oil-borne proiucts which can be
substituted only in limited use for the above pressure' treatments.
- 61 -
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I.D.2. (cont'cl)
Arsenical Pesticides
and Other G impounds
2070 arsenic trioxide,
51% sodium fluoride and
21 .''5% 2,4-dinitrophenol
11.59% arsenic trioxide,
26.04% sodium fluoride,
16.23% 2,4-dinitrophenol,
and 5% pentachlorophenol
4.8% sodium arsenate and
: 10.9% sodium fluoride
Irejec tion Trea f.ments
Special Comments
Injected as an
aqueous paste
a ready-to-use
liquid for injection
Dilute 1 gallon of
concentrate with 1.5 gals.
of water and inject 1 gallon
of diluted solution/cubic
foot of wood or until refusal
Registered
Substitute'
Hone
**Creosote, pentachlorophenol and etc. are oil-borne products which can be
substituted only in limited use for the above injection treatments.
Diffusion Treatments
6% sodium arsenate,
33% sodium fluoride,
32% sodium dichromate,
and 4.3% dinitrophenol
Use on green mine timfoers.
Method of application
seldom used. Effective but
time consuming
None
7.7% ammonium arsenite and
4.3% metallic copper in a
copper-ammonium complex
4.08% arsenic pentoxide,
3.8% chromic acid, and
1.74% cupric oxide
25% sodium arsenate,
32.98% sodium fluoride,
32% sodium dichromate,
and 6.3% 2,4-dinitrophenol
Brush, Mop or Swab Treatments
Brush or spray to surfaces of
spray to surfaces of None
chemonite pressure treated
wood with new exposures due to
cutting, notching or dapping
A ready-to-use solution for None
brush, mop or pressure treating
of wood.
Apply solutions of 1.14 to lt.6 None
specific gravity to gr«'en timbers and
posts. Cover air tight and allow
to stand 30 days or lounger to allow
diffusion of ingrediecitts into timbers
-62 -
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I.D.2. (cont'd)
Arsenical Pesticides
and Other Compounds
5.04% sodium arsenate,
7% potassium aichromate,
6.86% sodium fluoride, and
1.23% 2,4-dinitrophenol
1.4% sodium arsenate,
2.1% sodium chromate,
1.4% sodium fluoride,
1.4% pyridine and
0.7% 2,4-dinitrophenol
I.D. 2.a. Conclusions
Special Comments
Apply Jo mine timbers
Apply to exposed surfaces
when cutting, dapping or
notching pressure-treated
wood.
Registered
Substitute
None
Pressure treatments for wood preservatives:
The arsenic containing wood preservatives are "permanent" and treated woods
have a useful life of up to 80 years in products such as poles, ties, bridge
members and other heavy members. Properly treated railroad ties are replaced
for mechanical failure before failure of the preservatives.
A total of 260.3 million cubic feet of wood products were treated by the
United States wood-preserving industry in 1970. It has been estimated that
291,449,000 board feet of lumber and timber, 7,680,000 square feet of plywood,
715,000 cubic feet of miscellaneous materials, 431,000 posts and 27,000 cross
ties were treated with arsenic compound products in 197®' in the United States.
Failure to maintain long service life would result in astronomical replacement
costs. In some areas failure to adequarely provide treated wood would require
a switch to other, more expensive and less desirable building materials, and in
the case of poles and ties, to relatively less safe substitutes. Certain types
of wood products intended for particular uses have substitute materials available,
particularly creosote. No substitute for the arsenic preservatives are available,
for other types of wood where color, paintability, presence of certain fungi or
other factors are involved. These data and comments are also applicable to
injection treatments. It is concluded that the pressure treatments of all the
arsenic compounds should be retained.
Injection treatments for wood preservatives:
For more details see the "Conclusions" for pressure treatments. The injection
treatments of the arsenic compounds should be retained.
Diffusion treatments for wood preservatives: •
Diffusion treatments are more effective than brush or spray applications of the
same type of products and less effective than pressure •treatments of the same
products. These treatments are needed especially in Alaska where simplicity
of equipment and a small capital in.ves£n;en;t -are -necessary, to maintain an
industry. The double diffusion treatments should be re-rained for industrial
application only. " '•
- 63 -
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Brush, M.op or swab treatments
wood p7:cservatives :
Products designed for application by brush, mop or swab are used as a •
follow-up after cutting, notching or dapping of pressure or injection
treated wood. They are applied "on the job" by the conrttruction contractor
personnel to insure maximum protection of the wood to he placed under
extreme exposure conditions. These treatments are a variable adjunct and
"insurance policy" for extended useful life of sills, foundation timbers,
bridges and other structures. The volume of such use is very small, less
than 1.0 percent of the total use of commercial wood preservatives, and it
does not represent a hazard to man and his environment.
The brush, mop and swab treatments should be retained.
I.D.3. Other Industrial Uses
Arsenical
Pesticide
Use
Special.
Commentts
10,10'-oxybisphenoxarsine Cotton fabric Apply Hy padding
coated with thermo- to retain 400 to
plastic system 1000 pgrn.
protects against
fungi
Registered
Substitutes
3,4'5-tribromo-
salicylanilide
10,10"-oxybisphenoxarsine
Vinyl films(shower
curtains, wall
coverings, and
similar items.
Use at 300-500
ppm-bjy weight.
Not to be used
on clodhing or
other material
for which pro-
longed contact
with .s&in is
recommmded
Bistributyltin
oxide; bistributyl
tin oxide in
combination with
dialkyl dimethyl
ammonium chloride,
salicylic acid and
isopropanol.
Captan; 2,4-
dichloro-6-(0-
chloroariilino) -S-
triazine; tributyl
tin linoleate;
phenylmercuric
hydroxide; 3,4',
5-tribromosalicyl-
anilide; zinc 2-
pyridimethiol
1-oxide
- 64 -
-------
i D.3.a. Conclusions
Textiles - cotton fabric coated with thermoplastic systems: „
r-
10,10'-oxybisphenoxarsina is more effective than the substitute chemical
and possibly less subject to leaching. Impact of withdrawal of this use for
arsenic would be severe, particularly on boat fabrics iin tropical and semi-
tropical locations. This is the principle use descrifed above.
The use of 10,10'oxybisphenoxarsine in textiles should Be retained.
Vinyl films (shower curtains, wall coverings and other similar items):
10,10'oxybisphenoxarsine is more effective and less sdfoj.ect to leaching than
the substitute compounds. It is estimated that this arraenical compound is
used in 90 percent of all flexible polyvinyl chloride Sims produced to
control all commercially important fungal organisms associated with surface
growth and vinyl degradation. Millions of pounds of vomyl film formulations
were treated with 10,10'-oxybisphenoxarsine in 1970. !BhLs represents tens
of millions of dollars in protected vinyl films and coatings.
Use of 10,10'oxybisphenoxarsine in vinyl films should fete retained.
- 65 -
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CHAPTER IT
CHEi-IISTRY AND METRO?;. OGY - ARSMIC
Arsenic is one of the elements for which a review cff its distribution
.and significance in the environment has been found assential. Such a
'•review' would hot be complete without a suimnarizatiox of pertinent facts
.for arsenic from the analytical viewpoint. <
II. A. General Chemistry — Arsenic (As) has the atonic number 33 and an
atomic weight of 74.92. In the periodic table of 'tiiB elements, arsenic
is midway between germanium and selenium in atomic mass. Arsenic, as a
member of Group V of the periodic table has physiodlemical properties
similar to phosphorus. Arsenates strongly resemble phosphates in
solubility and crystal form. Arsenic also forms triihalides analogous
to those of phosphorus. (Vallee, ejt _al_. , 1960).
The important compounds of arsenic are classified "into three groups:
,(a) Inorganic arsenicals: white arsenic (arsenic .ttrLoxide) , arsenate
salts,, and arsenite salts; (b) organic arsenicals: These compounds
include the mono and disodium salts of methanearsonoc acid, and cacodylic
(dimethylarsenic) acid; and (c) gaseous arsenic, that is, arsine, or
hydrogen arsenite.
-In the native state, arsenic usually exists as a suDfide ore — orpiment
(AS2S3) , realgar (As2S2) , or arsenopyrite (FeAsSf) . Arsenic sulfides
are usually found with metal sulfides, silver, lead,, copper, nickel,
antimony, and cobalt, as well as iron. Arsenic tr'iaxide (also called
arsen(i)ous acid, arsen(i)ous oxide, or white arsent'e) is a byproduct
of the smelting of copper and lead ores. Most arseiical pesticides are
prepared from arsenic trioxide, although lead arserate is not.
To prepare lead arsenate, litharge (lead oxide) is tthe starting material.
Litharge plus acetic acid yields acetate, which rearts with sodium
arsenate to form lead arsenate. Lead arsenate has freen used as an
insecticide in the United States since 1892 (Mrak, 11969).
Briefly, other common arsenic pesticides are prepared as follows: (1)
Sodium arsenite is the reaction product of arsenic Urioxide plus sodium
hydroxide; (2) Oxidation of sodium arsenite by nitrfa'c acid or hydrogen
peroxide yields sodium arsenate; (3) DSMA is manufactured by methylation
of sodium arsanite with methylchloride; and, (4) MS3A is produced by
treatment of BSMA with hydrochloric acid. . . . .
-66-
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II. B. Analytical Methods - There are a nur.iher of official AOAC
methods for analyses of arsenic in pesticide formoiilations, foods,
drugs, animal feeds, and mineral waters. The methods are nonspecific & '•
with regard to parent pesticides (Anonymous, 1970a and Anonymous, 1971).
In addition to the officially adopted methods, me-dhods based on atomic
absorption and activation analysis have been applied. The extreme
sensitivity attainable by the latter method is somewhat nullified .by
the endogenous arsenic or background found in most soils, crops, marine
organisms, and animal tissues. Discussion of methods for the individual
substrates are given below.
II.B.I. Analysis of Formulations - The hydrazine sulfate distillation
procedure (AOAC Method 6.004) is said to be suitable for analysis of
Paris green, lead arsenate, calcium arsenate, zinc arsenite, and
Bordeaux mixtures. Nitrates do not interfere with success of the method.
If the formulation contains sulfides, sulfites, thiousulfates, and large
quantities of organic matter, the method of choice would be the iodimetric
titration (AOAC Method 6.007) following nitric-sulfuric acid digestion.
However, iron, copper, chromium, tin, antimony, arf manganese interfere
with the titration.
Inorganic arsenates and arsenites in formulations may be determined by
an ion exchange method (AOAC Method 6.009).
II. B. 2. Analysis of Food Crops - Residues of arsenic in food crops may
be determined by the official molybdenum blue method (AOAC 25.014) or
the official silver diethyldithiocarbamate method (AOAC 25.016). These
methods have to some extent supplanted the traditional Gutziet method
for measuring evolved arsine. The estimated sensitivities in food
products are about 0.1 ppm for the molybdenum blue method and 0.01 ppm
for the silver diethyldithiocarbamate method (expressed as As 0 ). Atomic
absorption procedures for analysis of arsenic in foods appears promising.
II.'B.S. Analysis of Biologicals - Residues of arsenic in biological
materials may be analyzed by the. AOAC silverdiethyldithiocarbamate
method, following digestion to remove organic material. Neutron activation
methods have also been used.
II.B. Analysis of Water - Water is generally analyzed by modifications
of the above methods. However, the usual procedure is the silver
diethyldithiocarbamate method.
-67-
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li. a. 5. - Analysis of Soils •• Several of the various analytical techniques
mentioned abo/a could probably bo adapted to soil.c. At !;!*e present time,
fhe methods of choice for arsenic in soils would 'te the official AOAC
uo.lorimc..ric procedures (AOAC 25.014 or AOAC 26.OM). Successful application
of these methods to soils were reported by Baker, «£ al^ (1969).
Application of an atomic absorption procedure to arsenic analyses of soils •
was reported by Stevens, _ej^ al (1970).
II. C. Arsenic in Soil -
II. C. 1. Buildup in Soil - Arsenic is one of the common constituents of
all native soil. Vinogradov (1959) found the average arsenic content of
soils from various countries to be above five partis per million (ppm).
Other investigators report varying concentrations of arsenic in untreated
soil in North America; Greaves (1913) found about 41- ppm; Olson et al.
(1940) report 7.1 to 18.4 ppm; Jones and Hatch (19*5) determined 2.7 to
6.1 ppm; and Bishop and Chisholm (1962) found 3.7 tto 7.9 ppm arsenic in
soil.
Another important use is arsenic acid applied as a dessicant to cotton.
Only one application per year is made, at a rate off about 2.3 pounds per
acre of arsenic equivalent. Pennwalt Corporation ((Gulver, 1971) reports
that after 5-10 years dessication use, the concentration in the upper
0.24 inches of soil is 4.6-8.1 ppm arsenic. This iis not much higher than
the report figures for untreated soil.
II. C. 2. Fate of Arsenic in Soil - Arsenic residues are relatively
stable when fixed in the soil. Fixation of arsenir. in soil is related
to soil textures and colloidal content. Heavy soiBs fix large amounts
of arsenic, rendering it unavailable to plants (Rosenfels and Crafts 1939).
Iron and Aluminum cations in the soil chemically citeorb (tightly bind),
and thus detoxify inorganic arsenate (Anonymous, 3ST69). Where the iron
and aluminum content of soil is low, arsenic moves downward through the
soil profile and becomes fixed as it encounters Iran and aluminum ions.
This causes arsenic distribution through a large sail cross section,
but removal from the soil by leaching is said to hr. insignificant
(Jacobs, et al., 1970).
Arsenites are fixed more rapidly in soil than are arsenates. The appearance
of sillica suggests an exchange of Si03 for HAs04 ((Wiklander and Frederickson,
1946). Keaton and Kardos (1940) as well as QuasteU. and Scholefield (1953)
independently concluded that the more toxic arsenides are oxidized to
arsenates on' contact with ferric oxide (also fouad by Schroeder and Balassa
1966). Von Endt _e_t jl. (1968), say that organic arsaenicals such as MSMA
degrade to inorganic arsenates in the soil. Thereafter, their behavior is
that of inorganic arsenates.
II. D. Uptake by Plants - Plants grown in virgin (untreated) soil commonly
contain 1.7 to 6.1 ppm arsenic (Olson, e_t_ _aJL,, J.9.43)) . Residues in plants
are related loosely to the amounts of arsenic in dire soil whether natural
or added, but are modified by variables including TO!ant spocies, geographic
regions, and soil type.
-06-
-------
Arsenic residues in vegetables have not occurred in si^nif ir.?nt amounts
even when grown in soils treated with up to 1000 pounds of lead arsenata
per acre. The. amount of arsenic uptake varied between plant species and
increased with the amount in the soil, but residues were generally low. # .
Residues in plants growing in soil treated with 1000 pounds of lead
arsenate per acre ranged from a trace to 0.8 ppm (MclLean, _et al^, , 1944).
Olsen, jsjt _al. (1940), concluded that there is no relation between the
arsenic content of soil and the arsenic content of plants.
When arsenic compounds are applied to soil, residues accumulate under
certain conditions. Unlike some organic pesticides wMch eventually are
degraded in soils the repeated application of arsenicals leads to build up
of the arsenic content of soils (Woolson et^ a^; unpublished). A soil
monitoring project of the USDA (Stevens, et_ al. , 197®) analyzed soil from
areas having various histories of arsenical use. The results may be
summarized:
Arsenic Content
Crop History No. of Samples ppm As
Cotton, vegetables 20
Orchards 30
Small grain and root crops 16
1.50 - 54.1
1.27 - 220.0
1.38 - 26.6
In the lower R.io Grande Valley of Texas, 75.0 Ibs/acie of arsenic in the
form of calcium arsenate was applied to a field during the period 1956 -
1965. Arsenic soil residues were 11.7 ppm in April 1965, and 10.22 ppm
in October 1966. In Bade County, Florida, 73.0 Ibs/sicre of arsenic in
the form of calcium arsenate was applied during the 1955 - 1966 period.
This led to 50.92 ppm arsenic in the soil when analysed in March 1968.
Soils in five orchards in Adams County, Pennsylvania^ were analyzed. The
results are:
Orchard No.
1
2
3
4
5
Period
1955-1965
it
Arsenic Applied
Ibs/acre
As Lead Arsenate
40
110
110
95
110
Elemental As
Content (ppm)
47-130
93-220
56-113
18-42
54-118
Woolson, et al. (unpublished) claim that these high (concentrations may
not be harmful for crops and livestock. If the soil contains iron and
aluminum, these elements combine with the arsenate ian to "fix" the
•,..a.&s.e/sdc .^as- insoluble .compounds.
-69-
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Additional studies rep^rL the concentration of arserdi£. in tt-^itcd soils as
138 ppm (Gile, 1336); 2-109 ppm (Greaves, '934); 53-Jb?. ppm (./ones and Hatch,
1945); and 10-124 ppm (Bishop and Clr'shoV.i, 1962). In should be noted tr.at
the foregoing figures are. for arsenic whoa large qualities (up to 3600
pounds of lead, arsenate) have been applied to the soil!. *'
Additional studies confirm that arsenic uptake from sail by plants depends
on the species, organ, soil type, and concentration ii soil (Jones and Hatch,
194'5; Taylorson, 1966; Stewart and Smith, 1922; Vanderaveye, et_ al., 1936;
and Von Endt, je£ al. , 1968).
II. E. Production - The use and production figures of arsenical pesticides
are described in detail under "Trends of Use" in Chapiter IV.
-70-
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CHAPTER 2
BIBLIOGRAPHY (Chemistry"/
r '"> ••
Anonymous. Chemical and Engineering News. Pesticide Residues:
No danger from arsenic. 49(37): 8 (September 6, 1971).
Anonymous. Official Methods of Analysis of the Association of
Official Analytical Chemists, llth Editrion. Box 540,
Benjamin Franklin Sta., Washington, D..S. 20044 (Methods
6.006, 6.007, 6.009 for formulations -and Methods 25.006,
.25.011, 25.014, 25.016 for food residues). (1970a).
Anonymous. Pesticide residues in food. Rejj-ort of the 1968
Joint FAO/WHO Meeting. FAO-UN Rome. EAO Agric. Studies
No. 78, WHO Tech. Report Series No. 4.17, (1969).
Anonymous. Pesticide residues in food. Reg.ort of the 1969
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Baker, R.S., Arle , H.F., Holstun, J.T., Jr.., and Miller, J.H.
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Bradicich, R. , Foster, N.E., Hons , F.E. Jefffus, Mt. , and Kenner,
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Buchanan, W.D. Toxicity of arsenic compounds. Elsevier Pub.
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--7-1-
-------
Chesters, G,; and Konrsd, J.G. Effects of pest-icicle usage on
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1 i
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-------
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* *
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-------
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-------
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' V •
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CHAPTttv Ixl
FATE AND IMPLICATIONS FOR ARSENIC IN T8E ECOSYSTEii
• 'One of the most crucial considerations in this review of arsenic is
• consideration of its fate and eventual effect upon all forms of life
which make up the environment. Following is a summary primarily of
fish and wildlife and other associated organisms- as influenced by
the presence of arsenic.
III. A. Toxicity to Fish and Wildlife - The chemical and biological
characteristics of arsenic compounds vary greatly. Therefore, in this
review, they must be seen as related but finally considered as indi-
vidual compounds. The toxicity of arsenicals decrease as the three
valence states (-3, +3, and +5) increase. Another important classi-
fication, as far as toxicity is concerned, is that of the organic
and inorganic arsenic compounds. Ars_enic refers t*o inorganic arsenicals
and arsenic and ars_inic denote organic arsenicals. The methyl-arsenic
bond in organic arsenical compound lowers the acute toxicity much below
that which is normally associated with inorganic compounds. See
Table 1 for relative comparison of acute toxicities for arsenic
compounds .
Following is a review of the available toxicity daita for the different
arsenicals to mammals, birds, fish and. other aquatic organisms.
III. A. 1. Sodium Arsenite
III. A. l.a. Mammals and Birds - The acute oral LD^Q for sodium arsenite
to rats is 10-50 mg/kg (House, et al., 1967), and ftoar the mouse, 51 mg/kg
Meliere, 1959). The acute oral toxicity for 3-4 momth old mallard hens
was 323 mg/kg accompanied with acute symptoms of ataxia, high carriage and
tetanic seizures (Tucker and Crabtree, 1970). Mallards tolerated 8 mg/day
for a period in which the total dose reached 973 mg/Ftg (USDI, 1963).
-76-
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TABLE 1. Relative Toxicity of Arsenical^.
Clabjifi-atiou Arsenical LbJQ(rat
• . 1 (mouse)
Inorganic ars:ne J
u
sodium arsenite 10
on 2 - •
calcium arsenate 20
2
lead arsenate . 100
arsenic acid 48-100
Organic DSMA 1000 3
3
cacodylic' acid 1350
MSMA 1800
4
triethanolamine 14,000
methanearsonate
methanearsonic acid 1400
1
The Merck Index of Chemicals and Drugs; Merck and Co., Inc. 1960.
2
MSMA-DMA Weed Control; Vineland Chemical Company.
3
FCH Farm Chemicals Handbook; The Meister Publishing Co.,
Willoughby, Ohio. 1970.
4
Frear, D.E.H., Pesticide Index; College Science Publishers, State
College, Pa. 1969.
5
Unpublished data. Ansul Chemical Company. 19'63.
-------
III. A. l.b. F ish a nd 0 th er Aqua tic Or g a n Is ms - Several investigators
have determined the acute T.C of sodium arsenitc for various species
of fish: iU
LC
Fish Species , Ivxposure (hr) 50 o
1
Rainbow Trout 24 100
/I
Bluegill 24 / 58
2
Spottail Minnow 24 45
3
Lake Emerald Shiner 24 13.5
4
Channel Catfish 24 27.6
. • 5
Rainbow Trout . 48 36.5
6
Chum Salmon Fry 48 8.4
4
Channel Catfish 48,72 v-15
1
Cope, O.B. 1965. Sports Fisheries Investigation, pp. 51-63. In
Pesticide Wildlife Studies, U.S. Fish * Widl. Serv. Circ. 226.
2
Boschetti, M.M. , and T.F. McLoughlin. 1957, Toxicity of Sodium
arsenite to minnows. Sanitaik S: 14-18.
3
Swabey, J.H., and C.H. Schemk. 1963. Studies related to the use of
algacides and aquatic herbicides in Ontario. Aquatic Weed Control
Soc. Meeting, Proc., 3: 20-28.
4
Clemens, H.P., and K.E. Sneed. 1959. Lethal doses of several commer-
cial chemicals for fingerling channel catfish. Special Scientific
Report Fisheries No. 316, U.S. Dept. Interior.
5
FWPCA. 1968. Water quality criteria. Report of the National Tech.
Adm. Comm. to Seer, of the. Interior. Fed. Water Pollution Control
Adm. U.S.D.I. 234 pp.
6
Alderice, D.F. and J.R. Breh. 1957. Toxicity'of Sodium arsenite to
young chum salmon. Progress Report Pacific Coast Station Fisheries
Res. Board, Canada. No. 108, 27.
-78-
-------
(1966) stated that sodium o.rsenite at 4 ppra caused Iclcncy and
liver damage to hluegills. Johns->n (19GrO indicate.-' that Fodium
arsenite applicJ at 5 ppm in ponds haH no effect ca. rainbow or brook
trout populations. Sodium arsenite at 4 ppm had mo effect ou
phytoplanktoa, but produced significant reductions in zooplankton >')
(Cowell, 1965). Zischkale (1952) determined minizsim lethal dosages (ppm)
of sodium arsenite to produce a kill of 25 percent or better of the
following fish food organisms: Daphnia, 3.0; Eucyp-ris, 6.0; Hyallella,
2.5; Culex, Ades, Anopheles, 6.0; and Chironomus, 10.0. Walker (1962)
reported that dosages of sodium arsenite from 2.5 to 20 ppm caused a
50 percent reduction in phantom midges, water bugs,, and snails.
Springer (1957) listed 1.9-3.0 ppm as the toxic lev/el for midges and
mayflies. McKee and Wolf (1963) stated that fish ff:ood organisms are
susceptible at concentrations as low as 1.0 rug/liter.
III.A. 2. Sodium Arsenate
III. A. 2.a. Mammals and Birds - The acute oral .UD^Q for the rat is
112 mg/kg and by interperitoneal injection, 21 mg/feg (Merck, 1960).
No adverse effects have noted for birds.
III. A, 2.b. Fish and Other Aquatic Organisms - Sodium arsenate is not
highly toxic to fish or to other aquatic organisms.,, The lethal
concentration of sodium arsenate for minnows is 234; ppm as arsenic.
.' III. A. 3. Copper Acetarsenite, Paris Green
III. A. 3.a. Mammals and Birds - The acute oral 1^50 for the rat. is 22 mg/kg
(FCH, 1970). The lethal value for hares is 30 mg/lkg (Chappellier and Rancort,
1936). Paris green when applied at 4 pounds/acre liiad no adverse effect on
muskrats feeding on treated vegetation (Stearns, «t_ _al.', 1947). The LC^Q
for mallards was 5000 ppm; for pheasants, 1000 to 1100 ppm; for bobwhite,
500 to 600 ppm; and for coturnix, 1200 to 1400 ppm when fed a diet for five
days followed by a three day observation period {'leath, at jl. , 1970).
The acute lethal value for gray partridge is approximately 30 mg/kg
(Chappellier and Rancort, 1936).
III. A. 3.b. Fish and Other Aquatic Organisms - Paris green had no
apparent effect on oysters, shrimp and fish at application of rates
100 pounds per acre.7 Minute quantities of Paris green appear to have
no effect upon top minnows or other fish (Barber, 1941) , but excessive
dosages may have ill effects on fish (Hackett, 1925). McCormick (1940)
found arsenic in the bodies of Gambusia and catfisii, but there were no
evidence of fish mortality.
III. A. 4. Cacodylic Acid
]_l Unpublished data. Gulf Breeze, 1965.
-79-
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III. A, 4. a. Mammals and birds - The LD5Q for the rat was 1280-1400 mg/kg
when fed orally (House et al., 1967). Acute toxicity data are available
for birds.
#
III. A. 4. b. Fish and other aquatic organisms - Oliver (1966) exposed
mosquito fish, largemouth bass, and taillight shiners to concentrations
of 100 ppm for 72 hr with all fish surviving. Some mortality was observed '
when concentrations reached 631 ppm at 72 hr. Cacodylic acid at 40 ppm in
water for 48 hr. had no noticeable effect on shell growth of oysters. Pink
shrimp exposed to 40 ppm in water for 48 hr. showed no effect (USDI, 1966)
and dragon fly nymphs exposed to 1000 ppm of cacodylic acid in water for 72 hr.
showed no noticeable effects (Oliver et al. , 1966).
III. A. 5 Monosodium methanearsonate , MSMA
III. A. 5. a. Mammals and birds - The acute oral LD5Q for MSMA to albino
rats is 1800 mg/kg (Barrier, 1970). No acute toxicity data are available
for birds.
III. A. 5. b. Fish and other aquatic organisms - The acute LC^Q for
bluegills after 24 and 48 hr. exposure in water was greater than 2000 ppm.
MSMA at 1 ppm had no effect on killifish or pink shrimp after 24 and 48 hr.
exposure. There was no effect on shell growth in oysters with 96 hr exposure
to 1 ppm MSMA in water.
- III. A. 6. Disodium methanearsonajte , DSMA.
III. A. 6. a. Mammals and birds - The acute oral LD5Q for DSMA to rats is
approximately 1000 mg/kg (FCH, 1970). No acute toxicity data are available
for birds.
III. A. 6. b. Fish and other aquatic organisms - DSMA toxicity data for
fish, shrimp, and oyster are approximately the same as MSMA. 8
III. A. 7. Lead arsenate
III. A. 7. a. Mammals - The acute oral LD5Q for lead arsenate to rats has
been reported to be 800 mg/kg (Merck, 1960). Lead arsenate was found to
have an acute oral LI>50 of 192 mg/kg to sheep (St John et al., 1940).
Metcalf et al. (1962) have reported the acute oral LD^Q for rabbits to be
125 mg/kg.
III. A. 7. b. Fish
A concentration of 25 mg lead arsenat'e/liter of water ha5 killed trout
within 24 hours and a concentration of 17.1 mg lead arsenate/liter of
stabilized tap water did not harm minnows during a 1 hour exposure
(McKee and Wolf, 1963).
8 Unpublished data, Ansul Chemical Company.
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III. A. 8. Comparative ToxicT try of 1 Bivalent and ff.^ntavalent Arsenic -
Two'forms of arsenic axist in the e ..v'iroriraent, tribsalent (arsenite) and
pentavalent (arsenate). Pentavalenc arsenic as arssaiate is relatively
nontoxic in normal concentrations, ?.-.;£ trivalent arsenic (arsenite) is
toxic and is the principal form prov;.-;,.ced commercially,. Schroeder and
Balassa (1966) compiled comparative Lexicological data for sodium arsenite
and sodium arsenate (Table 2).
. - Tsc ie 2
Relative Toxicity of Sodium Arsenic'-
Item Arsenite. (;
Bacteria
Algae
Yeast
Daphnia magna
Flatworms
Minnows
Minnows
Minnows
Rat, acute oral LD5Q
290
4C
20
17. E
11. fi-
ll.2
_aiid_ Sodium Arsenate to Selected Organisms
As)
(ppm As)
10,000
1,000
300
12.5
361
250
234
60
112
Several important factors to keep ±r: aiind when examiining the implications
of arsenic in the environment are: the greatly Increased toxicity of the
trivalent (arsenite) compared to pc.-.iavalent (arsenate); the x^idespread
distribution of arsenic in naturef .--nd the misconception that all arsenic
compounds are highly poisonous.
III. B. Residues in Fish and Wildliio from Environroantal Exposure
It has been indicated that all living things contain* arsenic with the
marine invertebrates and other aqu::;:ic organisms hawing the largest
amounts. Very limited work has-apparently been dons-: on the determination
of arsenic in wild animals and bir-'.s. Shroeder arrfl Balassa (1966) trapped
several wild animals and analyzed them for arsenic i'n specific tissues.
Laboratory mice and rats, fed a di-::r; of naturally ccE'curring arsenic of
0.053 ug/g and water containing 0.51. ug/liter, wer:e also included in the
investigation.
-8.1-
-------
The tiaCrj in Table 3 demon;-: LrnLcs the pi ese.ru: c of arsenic in most of the wild
animal tissues analyzed. ?'he laboratory an:u._1Rbad small amounts of arsenic
in most tissues, but a lar^e quantity in the spltra.
Tabl» 3
Natural Levels of Arsenic in Aaimals
Tissue .
Kidney
mice, lab
rats, lab
mice, wild
fox, cross, wild
Liver
mice, lab
rat, lab
rat, lab
rat, lab
• mice, wild
woodchuck
Heart
mice, lab
mice, wild
fox, cross, wild
Pg/8 As
1.30
0.0
0.0
0.39
0.0
0.49
0.0
0.52
0.74
0.52
0.0
1.10
0.25
Tissue
Lungs /
mice, lab
mice, lab
fox, cross, wild
Spleen
mice, lab
Tumor
mouse, lab
Brain
rats
rat
0.11
1.53
0.69
5.60
0.93
0.0
0.31
Coulsori et al. (1935) investigated the arsenic residue in rats fed 17.9 ppm
natural arsenic in shrimp (assumed to be pentavalent) . He found that the
pentavalent was only slightly (0.7 percent) retained in the tissue, whereas,
the dose of sodium arsenite accumulated up to 18 percent of the amount given.
Overby and Frost (1962) recovered in the excreta only one-half of the arsenite
fed. to rats, but virtually all the pentavalent fom of arsenic. Chickens fed
livers of pigs that had been given arsenite showed accumulation in muscle,
whereas, those given arsenilic acid (an organic arsenical) had none (Overby and
Staube, 1965)-. Schreiber and Brouwer (1964) demonstrated that pentavalent
arsenic was much more readily excreted than trivalent arsenic. Peoples (1964)
fed cows arsenate (1.25 mg/kg) without finding increases of arsenic in milk,
indicating the existence of some mammary barrier and rapid elimination.
However, the rat accumulates arsenates by binding it to' hemoglobin and
depositing it in the spleen, liver, kidney and heart to a much greater extent
than cows, hamsters, guinea pigs and rabbits.
Experimental results indicate that there is a homeostatic'mechanism for
excretion of arsenates. As a general rule, pentavalent ccmpounds are
excreted by the intestines, some of them in the bile. This serves as a possible
explanation as to why sodium arsenate and cacodylate are relatively nontoxic
(Schrocder and Balassa, 1966). Frost (1967) indicated that arsenite has a
-82-
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preference for kidney, liver, hair, nails and skiff. Arf.en.ite accumulates
in tissues upon continued exposure up to o balarirw or c.o toxic levels,
depending upon the dose and the degree of toxicity of the artenical and is
reflected in the levels of arsenic in vital tissues.
Ehman (1967), concluded that organic ^entavalent aarsenicals, even though
having relatively low mammalian toxicity, are definitely toxic when in
sufficient quantities or are potentially toxic in small quantities through
possible breakdown to other arsenicals.
III. B-. 1. Teratogenic Studies
Perm, et al. (1971) stated, after investigating tine teratogenic profile >
of sodium arsenite in the golden hamster, that it is possible that either
cumulative or accidental peak exposure of human or other animal populations
to arsenic might have profound effects on reproduction mechanisms. Such
effects might include lox^ered reproductive rates, or detectable increases
in incidences of specific embryonic malformations* Several investigators
(Boutwell, 1963; Perm, et al., 1971; and Perm and Carpenter, 1968) have
examined the possible teratogenic effects caused by arsenic.
III. B. 2..Documented Arsenical Poisonings
Arsenical poisonings to both domestic and wild animals are well documented
(Booth, 1964; Boyce and Verme, 1954; Clough, 1927; Cook, 1953; Glover, 1952;
Hatch and Funnell, 1969; Jones, 1958; Motham and Camp, 1968; Peoples, 1964;
Schreiber and Brouwer, 1964; Sutherland, et al., 1364; Towers, 1949; and
Weaver, 1962). Many of these poisonings have resulted from the uses of
sodium arsenite to debark trees, destroy trees and stumps, preserve wood,
and as a herbicide, .dessicant, or insecticide. Because of the extreme
toxicity of this compound, many of the former uses of sodium arsenite have
been cancelled.
III. B.3. Natural Arsenic Residue Levels in Marine or Aquatic Animals and Fish-
Arsenic is widely distributed in biologically significant quantities in sea
water (2-5ppb). Table 5 presents arsenic residue levels for a number of
marine animals and fish. Assuming the arsenic concentration of sea water
as 5 ppb (2-5 ppb average), the corresponding concentration factors for various
fish and other aquatic organisms has been calculated (Table 5). The assumed
concentration factors illustrate the accumulative capabilities of organisms
and it is readily apparent that arsenic in the form present in these animals
has a relatively low toxicity. Vinogradov (1953) reported the following
accumulations of arsenic in marine animals: sponges (8-24 ppm), molluscs
(1-68 ppm), coelenterates (16 ppm), echinoderms (0..37-1.5 ppm), crustacea
(10-79 ppm) and fish (0.2-15 ppm by wet weight and 2-25 ppm by dry weight).
The whole fat, muscle fat, intestinal'fat and liver fat of the marine fish
contained 1.8-30.4 ppm arsenic with the highest level in the liver. McKee and
Wolf (1963) indicate the arsenic trioxide concentrations in water that will kill
food organisms and fish are lower than the concentrations of arsenic actually
found in marine invertebrates and fish. Sodium arsenate at 100 times those
concentrations exhibits little or no toxic .effects tlo such organisms.
-83-
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TABLE 5
Natural levels of arsenic in fish and other aquatic orgur..isms
Species
Haddock
King fish
Oyster, fresh
Oyster, frozen
Scallops, fresh
Shrimp, fresh, frozen
Shrimp shells
V 1
Clams, fresh frozen
• Conch, fresh
1
Conch, dried, whole
2
Escallops *
2 ^
Mussels
Cockles
Whelks2
2
Lobsters
2
Prawns
2
. Crabs
Plaice2
Soles2
2
Dabs
\
*
mg/kg
2.17
8.86
2.9
2.7
1.67
1.50
15.3
, 2.52
3.1
5.63
44
- 80
. -' 26
24
37
.72
46
10
7
4
Cone, factor
430
1770
580
-\
330
300
3060
500
620
8800
lepoo
5200
. 4800
7400
12400
9200
2000
1400
• 800
-••£2:r!£...£.s per.!
Schroeder end Balsssn (1966).
2
Chapman (1926) , Analyst: 543.
-84-
-------
III. C. Food Chain Buildup - The trivalent arsenic as arsenide
accumulates and is slowly oxidised to l.he pcntsvaleat form in i:he
mammalian body (Schreiber and Rrouwer, 196'-t; and Scuroeder and
Balassa, 1966). The pentaval; nt arseiu_c. as arsenate is rapidly *> •
excreted and probably docs not accumulate in tissue. A possible
exception exists with the rat since arsenate accumulation has been
noted in studies with rats (Coulson,_et_al., lS35j Schroeder and
Balassa, 1966).
In the terrestrial environment the arsenites will accumulate in
mammalian and avain tissues (Overby and Fredericfcson, 1963; Schroeder
and Balassa, 1966). Macek (1969) stated that itt arder to be bio-
magnified, "a compound must be persistent in the physical environment,
available to the organism and persistent once assimilated into the
biological system." Sodium arsenite is persistent in water and is
available to fish. Gilderhus (1966) concluded fram his study that sodium
arsenite is persistent (50 percent) in fish for greater than 16 weeks
and that pools treated with sodium arsenite retained 20-40 percent of the
arsenic after 16 weeks. Organisms present in this system would be
subjected to long-term exposure.
The potential exists for a food-chain buildup of amsenic in both the
aquatic and terrestrial environment, but it must foe recognized that
higher members of the food chains have not shown residue levels as
high as the lower forms in the chains. This woul€ indicate that in
actuality bio-magnification probably does not take place.
III. D. Fate and Movement in Terrestrial acd' Aquatic Systems -
Remembering that arsenicals are ubiquitous - existing in water, soil,
air, plant and animal life - Frost (1967) proposed! an As cycle in .
nature (Fig. i).
Fig. 1. Arsenic Cycle in Nat-tare
Arsenic comoounds in
soil, .land, wat^r and the sea
rain - '
^•^
Volatile Micrdbial " Arsenicals in
_______________ ........ _ plants, microbes,
— — - — • ---------- — •• ------------- " ' '
r^
decomposition crustaceams
•„ excreta
decomposition
All cr.i:n-l life
(organic arsenicals)
-85-
-------
Tue earliest arsenical herbicide: i-;as sodium arsenire ann it proved t^ bo
an excellent -30il sterilant altaough ii_ could slsjj be use:l for selec. Livo
weed control. Sodiuir, calcium, and lead arseiu±s i.ave been used for
pre-emer;ence control in grasses. Calcium and Ie.-ad arsenate have alsg
been used .^or insect control on turf and fruit, respectfully. Two organic
arsenicals, monosodium methanearsonate (MSMA: aZLso the disodium salt DSMA)
arid hydroxydimethylarsinic oxide (cacodylic acid) have been used extensively
for weed control. Paris green has been widely tiseS in aquatic areas as a
mosquito larvicide and as an insecticide bait in -'terres trial sites. Repeated
applications of arsenicals to crops have resulted in an increase in the level
of soil arsenic (Bishop and Chisholm, 1962; Ehnan, 1967; Jones and Hatch,
1945; and Vandecaveye, 1936).
Heavy lead arsenate sprays have produced extremely high accumulation of
arsenic residues in soils, especially orchards of Che Pacific Northwest.
Most of the arsenic residues in these specific soils were confined to the
top 6-8 inches. Arsenic residues below 8 inches rarely exceed the natural
occurrence level for arsenic (Boswell, 1952). Leaii arsenate applied up to
30 pounds/1000 ft~- in 1937 was highly effective far controlling white grubs
in turf and after 10 years the arsenic content was still high enough to
give very high control of white grubs (Neiswander, 1951).
The importance of the microflora for pesticide decomposition is well
documented for many arsenicals (Dickens and HoltbcQd, 1967; Thorn and P«.aper,
1932; and USDI, 1963). The arsenic herbicides, arsenic acid, methanearsonic
acid, and dimethylarsinic acid are reportedly absented by soil surfaces.
This would lead to the conclusion that high levels of arsenic would accumulate
with repeated applications. This apparently does -rot happen and is indicative
of the presence of some type of degrading mechanise Microorganisms appear
to have the ability to degrade arsenic (Alexander, 1961; Bird, 1948;
Challenger, 1947; Thorn and Raper, 1932; and Zussman et al. , 1961). Thorn
and Raper concluded that an accumulation of arsenic in soil would be expected
only when massive amounts were used or under speciaT conditions unfavorable to
the microflora. Further studies demonstrated that soil microorganisms are
capable of degrading monosodium methanearsonic aciH at the level of 1000 ppm.
Dickens and Holtbold (1967) concluded that methaneaasonates are decomposed
under aerobic soil conditions and the rate of decomposition is directly
dependent upon the availability of organic matter for microbial degradation.
Duble, Holt, and McBee (1969) found less than 0.1% of the 14c-applied as
DSMA released as volatile 14^ 10 days after treatment of Bermudagrass and
they concluded that the carbon-arsenic bond was stable in Bermudagrass.
In soils, however, the carbon-arsenic bond is subject to biological systems.
Von Endt, et al. (1968) found a rapid loss of 14c :rrom lAc^MSMA which
supported degradation by the microflora. Vineland Ghemieal Company " stated
" ... . since MSMA contains only 1 carbon atom, and the arsenic recovered is
arsenate, and no other -"-^C products appeared, that the probable course of
reaction and fate of the arsonate in the soil is oxidation by microorganisms
of the methyl groups to C02 and arsenate as end products." Ehman (1967)
also reported rapid inactivatzion of cacodylic acid and MSMA in soils. It.
"has "been suggested that inactivation may be due to bonding to some mineral
structure, and ion exchange phenomenon, or biologic*I degradation. The
complete cheuical fate of MSMA and cacodylic acid is not known.
9 Vineland Chemical Company; MSMA-DMA Weed Control.
-86-
-------
Much work lias been done on the fate ol the inox:;7_iiic arsenical, sodium
arsenite, since it was previously registered for -aquatic wo.ccl control.
Cowell (1965) stated thai: appliv-di-lon of sodiuE sssenite may have cumulative
effectb on zooplankton. Gilderhaus (1966) cp.tcrraiinecl the effects of long-
term exposures of sodium arsenite to fish ar.d the acuatic environment. Fish,
water and bottom soils were analyzed f determine tiK-; fate of arsenic. Fish
suffered acute symptoms and the bottom fc-.una was -substantially reduced".
Arsenic from sodium arsenite is removed very slowly from the water and
Gilderhaus interpolated that a single treatment of. 4 ppm sodium arsenite
would deposit about 50 ppm arsenic in the top iacla of bottom soil.
Several explanations have been suggested concerning the fate of paris green.
Benedetti (1934) claimed that arsenic is buried im the bottom mud. Misseroli
(1917) found that accumulation of arsenic did not take place because any
dissolved arsenic was volatilized by the microflora of the water. Morin
et al (1933) explained that no accumulation occurs because the aquatic
flora converts the arsenic to ethylarsenine. Kerns and Gray (1940) stated
"In the quantities effective for control of mosquito larvae, Paris green
appears to have no effect on aquatic plants or anamal life or upon livestock
and repeated applications do not appear to result in any accumulative effect.
Rathburn (1966) however, stated that small quantities of arsenic are added to
the soil as a result of applications of granular jaris green. He further
.stated that Paris green ". . . may occur unchanged as cupric acetqarsenite
or as various breakdown products caused by hydrolysis and the action of
chemicals present in the soil." Persistence of 2 percent paris green
applications is 24-25 days (Bendetti, 1934).
In a recent article, "Trace metals: unknown, unseen pollution threat"
(Anonymous, 1971), the health hazards of trace metals in the environment
were discussed. The author raised the question about arsenic and possible
hazards when arsenic undergoes methylation. ". . . microorganisms in
sediments containing arsenic convert the arsenic 'into deadly poisonous
dimethylars.ine. . . ." This methylarsenic compoetod xcill go through the
water just the same as methylmercury does [accurolite in fish, and ] cause
another problem: . . . As 5+ is first reduced to A's3+. Arsenite is then
methylated to form dimethylarsenic acid (As5^ ) . . . pollution hazards exist
when arsenic and its derivatives are introduced ±mEo environments where
anaerobic organisms are growing." (Fig. 2).
Fig. 2. Arsenic is Methylated by Microorganisms in Waterways
- 11
.0
Arsenite t Methylaosonic
CH3 Acid
CH3 - B12 "1 B12r HO - As * CH3 Ae _ ^ m3
N "" 11 &s - CH
0
acid
tvc ]Mkethylarsine
-87-
-------
Arsenic pesticides such as tedium methylarscnatc 'and calcium aaJ lead
ars'.nate cculd eventually iri-ij thc.ii ,;ay into anaerobic aquatic or
terrcstr;.,-il environments. Angino et al. (1970) questioned existing
evidence !"hat arsenic, remains in the same oxidation state af,"cr enter lug
sewage or the environment. They further stated, 'VJhcn the amount of ""
dissolved oxygen in many streams or in portions of certain streams is zero
or nearly so, then we must consider the real possibility that arsenic present
in water as the arsenate stands a good chance of bring reduced to the arsenite
form." Ehman (1967) also introduced the possibility of pentavalent arsenicals
breaking down into other arsenicals.
III.E. Summary - Since arsenicals differ widely, ',v.e must be cautious about
generalized statements. However, the following stannary can be made:
1. Arsenic is widely distributed in water, seLl, air, and plant
and animals life.
2. Soils are capable of inactivating the arsenicals, but prolonged
use of arsenicals have resulted in an accunulation of arsenic in
the top layers of the soil.
3.^ Organic arsenicals are much less toxic thai inorganic arsenicals;
• and, the pentavalent inorganic less toxic than trivalent inorganic
arsenicals.
4. Substantial levels of arsenic have been frond in fish and shellfish
when compared to the natural level of ars.rn.ic in sea water. This
would indicate that arsenic accumulates in aquatic organisms.
5. Pathological changes resulting from long-tterm exposure to sodium
arsenite have been observed in fish; substantial residues of
• arsenic have been found in water, bottom ;soil and in fish; and
bottom fauna and plankton populations have been reduced by arsenic
( sodium arsenite) in the aquatic environment..
6. There appears to be a homeostatic mechanise x^ithin mammals for the
arsenates. Arsenates are excreted relatively fast, but the arsenites
accumulate in animal tissues.
7. The possibility exists that hazards may develop from the methylation
of arsenic.
-oo-
-------
CHAPiT.il III
(v/if-s of Arserp.c in Envirrnr.•u:-':)
ITBLIOru A PHY
Alexander, M. Introduction to Soil Microbiology. Ssv York, Wiley and
and Sons. 472,p., 1961
Angino, E.E., Magnuson, L.M., Waugh, T.C., Galle, OX., Bredfeldt, J.
Arsenic and Water Pollution Hazard. Science, Vol.. 170: 870-872. 1970.
Anonymous. Trace metals: Unknown, Unseen Pollution Threat. Chemical
and. News. pp. 29, 30, 33. (July 9, 1971). ''
Barber, M.A. Paris Green and Other Stomach Poisons ;es Larvicides Against
Mosquito Larvae. In Human Malaria by Moulton. Am.. Assoc. Adv. Sci.,
Wash., B.C. 398 pp. 1941.
Barrier, G. E., Chairman. Herbicide Handbook of the Weed Society of America.
Prepared by Weed Science Society of America, Monographs and Annual Reviews
Committee. 368 pp. 1970.
Benedetti, A. de. Persistence of Paris Green TreateB by the De Benedetti
Method on the Surface of the Water. Riv. Mol. 13(?4: 211-216. 1934.
Bird, M.L., Challenger, F., Charlton, T.T., and Smith,, J.O. Studies on
.' Biological Methylation. The action of Molds on Inoaganic and Organic
Compounds of Arsenic. Biochemical Journal 43: 73-8". 1948.
Bishop, R.F. and Chisholm, D. Arsenic Accumulation mt Annapolis Valley
Orchard Soils. Canadian Soil Sci. 42: 77-80. L'932.
Booth, E. Arsenical Poisoning of Racehorses_. Vet. Bac. 76(11): 331. 1964.
Boswell, V.R. Residues, Soils, and Plants, p. 284-297.. In: .A. Stefferud (ed} ,
Insects-The Yearbook of Agriculture. U.S. Govt. Printing Office, Washington. 1952.
Boutwell. R.K. A Carcinogenicity Evaluation of Potassium Arsenite and
Arsanilic Acid. J. Agric. Food Chem. 11(5): pp. 381-385. 1963.
Boyce, A.P. and Verme, L.J. Toxicity of Arsenite Delarkers to Deer in
Michigan. 16th Midwest Wildlife Conf., St. Louis, Ho., Dec. 1-3, 1954;
Mineo, 9p. with lp. suppl. 1954.
Challenger, F. Biological Methylation. Science Progiess 35: 396-416. 1947.
&
Chappellier, A. and Rancort, M. Les Treatments Insecticides Arsenicaux
Soils Dangereaux Pour le Gibier et Pour les Animaux de la Ferm?
Ann. Epiphyties et Pytogenecique 2(2): 191-239. 1936.
Clough, C.W. Arsenical Poisoning in Domestic Animals.. Vet. Rec. 7: 209-211. 1927.
-8y-
-------
Cock, D.B. CheiTU-Peeling and Wildlife. Hew YorkS^-cc Conferva tic?^i s'c
7(6): 8. 1953.
, O.B. Contamination of Fresh-Water Ecosystems lly Pesticides. J. Appl.
Eco. 3(Suppleraeut on Pesticides in the Environment aid Their Effects on
Wildlife): 33-34. 1966.
Coulson, E.J., Remington, R.E., Lynch, K.M. Metabolism in the Rat of the
Naturally Occurring Arsenic of Shrimp as Compared -M/th Arsenic Trioxide.
J. Nutrition 10: 225, 270. 1935.
i
Cowell; B.C. The Effects of Sodium Arsenite and Sil^ex on the Plankton
Population in Farm Ponds. Trans. Amer. Fish. Soc. 94(4): 371-377. 1965.
Dickens, P. and Holtbold, A.E. Movement and Resistance of Methanearsonate
in Soils. Weeds 15(4); 299-304. 1967.
Duble, R.L., Holt, E.G., and McBee, G.G. Translocatdon and Breakdown of
Disodium Methanearsonate (DSMA) in Coastal Bermudagpass . J. Agr. Food
Chem. 17: 1247:1250. 1969.
Ehman, P.J. Effects of Arsenical Build-up in the So'dT on Subsequent Growth
and Residue Content of Crops. Proceedings 18th Southern Weed Conference,
685-687. 1967.
FCH. Farm Chemicals Handbook. Meister Publ. Co., WiUloughby, Ohio, 472 p. 1970.
Ferm, V.H., Saxon, A., -Smith, B.M. Teratogenic Profile of Sodium Arsenite
in the Golden Hamster. Arch. Environ. Health, 22CJJ);: 557-560. 1971.
Ferm, V.H. and Carpenter, S.J. Malformations Indue ell by Sodium Arsenate
J. Reprod. Fert. 17: 199-201. 1968.
Frost, D.V. Arsenicals in Biology-Retrospect and Prospect. Federation
Proceedings. 26(1): 194-208. 1967.
Gilderhus, P. A'. Some effects of Sublethal Concentrations of Sodium Arsenite
on Bluegills and the Aquatic Environment. Trans. A'mer. Fish. Soc. 95(3):
289-296. 1966.
Glover, R. C. Deaths of cattle from lead arsenate prisoning. Vet. Rec .
64: 548-550-. 1952.
Hackett, L.W. The Importance and Uses of Paris Grean as an Anopheles
Larvicide. Compete-Render du Premier Congres Intemat. du Paludisme Rome. 158 pi
Hatch, R.C. and Funnell, H.S. Inorganic Arsenic Levels in Tissues and Ingesta
of Poisoned Cattle: An Eight-Year Survey. Can Vett. J. 10(5): 117-120. 1969.
-90-
-------
Heath, R.C. ft al. Cou;paiacive dietary Toxicities of Pesticides to
Birds in Chert-Term Tests. U/S. Bur. Sport Fish., Wildlife, Faf.uxeiu:
Wildlife Research Center. Unpublished dafa. 1.93Q.
o ••
Herms, W.B. and Gray, H.F. Mosquito Control. The ffibmmonwealth Fund,
New York, New York 317 pp. 1940.
House, W.B., Goodson, L.H., Gadberry, H.M., and Dodfcter, K. Assessment
of Ecological Effects of Extensive or Repeated Use of Herbicides.
Midwest Res. Ins tit., Kansas City, Mo. 369 pp. 1367.
Johnson, M.G. Control of Aquatic Plants in Farm Poids in Ontario.
U.S. Fish Wildlife Serv., Progr. Fish. Cult. 27: 23-30. 1965.
Jones, J.S. and Hatch, M.B. Spray Residues and Crqp Assimilation of
Arsenic and Lead. Soil Sci. 60: 277-288. 1945.
Jones, W.G. Some Cases of Arsenical Poisoning. Vet. Rec. 70: 785-786. 1958.
Macek, K.J. Biological Manification of Pesticide Residues in Food Chains,
p. 17-21. In; The Biological Impact of Pesticide* in the Environment.
Environ. Health Ser. 1, Oregon State Univ. 210 ;„ 1969.
McCormick, E.M. The Relation Between the Amount of .Arsenic a Fish Gets
from Mosquito Control Dusting and the Lethal Dose.. J. Tenn. Acad.
; Sci. 15: 343. 1940.
McKee, J.E. and Wolf, H.W. Water Quality Criteria. No. 3-A, State Water
Quality Control Board, California. 1963.
Meliere, K.A. Cacodylic Acid. U.S. Army Engineering Command, Army
Chemical Center (Maryland) ENCR No. 34, June 1959, AD 318 626. 1959.
The Merck Index of Chemicals and Drugs. Merck and Go., Inc. 1960.
Misseroli, A. Nuove Richerche Sulla Rolatilizzatione Fermentiva Deu
Arsenico. Boll. R. Acad. Med. Roma, 43: Fasco V. 1917.
Metcalf, R.L., Flint, W.P., and Metcalf, C.L. Destructive and Useful
Insexts. McGraw-Hill, New York, 1087 pp. 1962.
Morin H.G.S. et al. The Mode of Action of Paris Gresn. Bui. Soc. Path.
Exot. 26(10): 1267-1273. 1933.
Motham, J.W. and Coup, M. Arsenic Poisoning of Cattfla and Other Domestic
Animals. New Zealand Vet. J. 16: 161-165.
Neiswander, C.R. Duration of the Effectiveness of Lxnd Arsenate
Applied to Turf for White Grub Control. J. Econ. .Bitomol. 44: °.21-224.
1951.
-51-
-------
Oliver, K.H. An Ecological Study of the Effects cof Certain Concentrations
of Cacodylic Acid on Selected Fauna and Flora. Dept. of the Army, Fort
' Detrick, CDTL 45644. 1966.
\
Oliver, K.H.,Jr., Parsons, G.H., Hyffstetler, C.T- An Ecological Study
on the Effects of Certain Concentrations of Cacrcrdylic Acid on Selected
Fauna and Flora. APGC-TR-66-54. Elgin Air Fence Base, Florida. 1966.
Overby, L.R. and Frederickson, R.L. Metabolic Stability of Radioactive
Arsanilic Acid in Chickens. J. Agric. Food Chem.. 11:378. 1963.
Overby, L.R. and Frost, D.V. Nonavailability of tth'e Rat of the Arsenic in
Tissues of Swince Fed Arsanilic Acid. Toxicol. Appl. Pharmacol. 4:38.
1962.
Overby, L.R. and Staube, L. Metabolism of Arsanilic Acid. II. Local-
ization and Type of Arsenic Excreted and Retained by Chickens. Toxic.
Appl. Pharmac. 7: 855-867. 1965.
Peoples, S.A. Arsenic Toxicity in Cattle. Ann.. 'JSew York Acad. Sci. 11(2):
644-649. 1964.
Pimentel, D. Ecological Effects of Pesticides'on Son-target Species.
Executive Office of the President. Office of S,ct'ence and Technology,
220pp. 1971.
Rathburn, C.B. The Arsenic Content in Soils Following Repeat Applications
of Granular Paris Green. Mosquito News 26(4): 537-539. 1966.
Rudd, R.L. and Genelly, R.E. Pesticides: Their Use and Toxicity in
Relation to Wildlife. Calif. Dept. Fish and Cans, Game Bull. No. 7. 1956.
St. John, J.L., McCullock, E.G. Sotola, J., Todhuntter, E.N. Toxicity to
Sheep of Lead Arsenate and Lead Arsenate Spray Residues. J. Agri.
Research 60: 317-329. 1940.
Schreiber, M. and Breuwer, E.A. Metabolism and Tcsicity of Arsenicals.
I. Excretion and Distribution Patters in Rats. In: 48th Meeting of the
Federation of American Societies for Experimental!. Biology, Chicago. 1964.
Schroeder, H.A. and Balassa, J.J. Abnormal Trace ELementfs in Man: Arsenic.
J. Chronic Diseases 19: 85-106. 1966.
Springer, P.F. Effects of Herbicides and Fungicid.es on Wildlife. N. Carolina
Pesticide Manual, N. C. State College, Raleigh, pp. 87-106. 1957.
Stearns, L.A., Lynch, E.E., Krafchick, B., Woodmansee, C.W. Report of the
Use of DDT and Paris Green on Muskrat Marshes. 3?roc. 34th Ann. Meeting
N.J. Mosquito Extermination Assoc. 1947.
-92-
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Sutherland, G.N., Faweil, E.V., Brown, J.K. Arsenical Poisoning of # •
Racehorses. Vet. Rec. 76(10): 275-278. 1964.
Thorn, C. and Raper, K.B. The Arsenic Fungi of Gosio. Science 76 (1980):
548-550. 1932.
Towers, K.G. Acute Arsenical Poisoning in Cattle. Brit. Vet. J. 105:
18-22. 1949.
Tucker, R.K. and Crabtree, D.G. Handbook of Toxicity of Pesticides to
Wildlife. U.S. Fish Wildl. Serv., Bur. Sport Fish. Wildl., Resource
Publ. No. 84, 131p. 1970.
USDI 1963. U. S. Department of the Interior. Pesticide Wildlife Studies
Circ. 199. 1963.
USDI 1966. Bureau of Commercial Fisheries Biological Laboratory. Bio-
assay Screening Test on Cacodylic Acid (Gulf Breeze, Florida),
January 1966.
Vandecaveye, S.C., Horner, G.M. , Keaton, C.M. Unproductiveness of Certain
Orchard Soils as Related to Lead Arsenate Spray Accumulations. Soil
Sci. 42: 203. 1936.
Vinogradov, A.P. The Elementary Chemical Composition of Marine Organisms.
Sears Foundation for Marine Research, Yale Univ., New Haven, Conn. 1953.
Von Endt, D.W., Kearney, P.C., Kaufman, D.D. Degradation of Monosodium
Methanearsonic Acid by Soil Microorganisms. Agricultural and Food
Chemistry, Vol. 16, No. 1, 17-20. 1969.
Walker, C.R. Toxicological Effects of Herbicides on the Fish Environment.
Ann. Air. Poll. Conf. (Nov. 12, 1962) (Columbia, Missouri). 1962.
Weaver, A.D. Arsenic Poisoning in Cattle Following Pasture Contamination
by Drift of Spray. Vet. Rec. 74: 249-251. 1962.
Zischkale, M. Effects of Rotenone and Some Common Herbicides on Fish-Food
Organisms. Field Lab 20: 18-24. 1952.
Zussman, R.A., Vicher, E.E., Lyon, I. Arsine Production by Grichlphyton Rubrum.
Journal of Bacteriology 81:157. 1961.
-93-
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CHAPTER IV
SIGNIFICANCE OF Al
-------
is established that the use of disodium m£ tnanearsrcuite and nvnosodium
acid, methansarFonate to control weeds o:' cotton a;iJ n.0ii~crop areas
has Increased greatly during the past decade (Arle said Hamilton, 1971).
The following table summarizes pounds of the major
-------
This use is of special importance to tbe types of i?.ottoo grown i'- [. ->rts
of Arkansas, in the Texas High Plain:- and Black Lands, and Oklahoma
that require a stripper harvester.
••
IV. B. Arseiiic in the Aii - "Maximum permissible cxncentrations" of
arsenic as a dust or fume or as arsirie in v/orking atmospheres have
been a matter of some importance to workers in the field of industrial
hygiene for some time. An international symposium under the auspices of
W.H.O./I.L.O. , discussed various aspects of the prcb'lem in 1959. -Values
set by this symposium were such that when averaged over an 8-hour work-
ing day, no demonstrable effect on the health may b?. expected for those
exposed. The value proposed for inorganic arsenic in the form of vapor
fume or dust was 0.5 mg/cubic meter of air (America! Conference of
Governmental Industrial Hygienists 1959) and 0.5 mg calculated as
arsenious oxide (Imperial Chemical Industries, GreaS Britain). For
calcium and lead arsenate lower values of 0.1 mg anl> 0.15 mg per cubic
meter were adopted (Buchanan, 1962). Presence of arsenic in the air
following use of either an insecticidal or herbicide! arsenic compound
is not considered a factor of primary concern with .ofispect to environ-
mental impact.
The lead and arsenic content of air following use oil" lead arsenate in
orchards of the State of Washington are presented ir Table 2. (Neal,
et_.al., 1941).
IV. C. Arsenic in Water - There are relatively lit tile direct or document-
able bits of information about the effect of lateral movement of scil
and water from fields treated with methanearsonic arid herbicides or from
orchards with accumulations of arsenic. Being highHy soluble in water,
it may be theorized that disodium methanearsonate and monosodium acid,
methanearsonate tend to move downward into the soil in the initial
stages of the first rain rather than remain with the surface soil that
may be washed from the field as runoff beings. Once leached into the
soil, the methanearsonates change to less soluble Inorganic compounds
that are tightly adsorbed by soil colloids and organic matter. It is
considered that this adsorption inhibits downward msvement of the
arsenic toward the water table (Arnott and Leaf, 1967; Dickens and
Hiltbolt, 1967).
Sodium arsenite has been used to control submerged plants in ponds and
lakes. Findlay Lake, New York was sprayed with sodoum arsenite during
May 17-20, 1958, resulting in a miximum arsenic coricsntration of 7.0
mg/1 liter of water. Arsenic content of the water had dropped to 1.5
rag/liter of water one week after treatment and in diminishing amounts
during the balance of the summer. The herbicide was applied again on
May 29, 1959. In none of the fish caught from FindJay Lake on May 29,
1959, and June 19, 1959, was an amount of arsenic fcund equal to that
-96-
-------
.-•
Mixing . ...-••
i
Burning containers
Spraying-
Thinning"
picking ' ;
Dumping:
• October
i
December
Sorting and Packing (October)
Blanks
Milligram par
Lead
Average
57,4
35.8
4.5
3,0
29.3
1.9
0.3
0.16
•0.011
Range
0.9 r467c3
10.2 -H.S-
1.3 -14.33
0.4 -17 JX
7.7 -75,2?.
0.4 - 6,3)
0.01 -ML
0.07- QM;
0.001-o.iB
10 s'.ibic no l ..TO
Arsenic
Average
18.5
166.7
1,4
•0.8
8.8
0.6
0.1
0.06
0.003
Range
0.2 -110.7
48.6 -261.2
0.4 - 4.8
0.1 - 3.2
2.6 - 19.0
0.1 -1.9
0.02-0.2
0.03-0.03
0.001-0.01
Kote:' Factors influencing exposure ware:- (1) dcfsj.ee of care used, in opening
and shaking containers; (2) amount of material anfi number of bags.used per
nix; (3) amount and direction of breeze; (4)-dry JQC wet mixing; and (5) location
in shed or outdoors.
V
-------
present in edible salt water fist.. The maximum fawnc. was i.O^j
of viscera from fish on June 19, 1959, Jllman, et i£. , 1961),
Recent worK by Dr. B. C. McBride and Dr. R. S. Wolfe:, University of /;
Illinois has shown that arsenic, as well as seleniuir, may be acted on
by bacteria in nature to produce highly poisonous sainpounds. Micro-
organisms in sediments that contain arsenic convert the arsenic into.
the highly toxic dimethyl arsine. The work evidently showed that
methanobacteria act upon a variety of arsenic compomds to produce the
dimethyl arsine. Thus, this recent work warns that pollution hazards
exist for acquatic and terrestrial environments thatt have large amounts
of arsenic introduced where anaerobic organisms are growing (Anonymous,
July 1971).
IV. D. Arsenic in Soil - It has been indicated that one of the beneficial
environmental aspects of using methanearsonic acid Jterbicides includes
lessening of the need for other herbicides with greater residual phyto-
toxicity. However, review of papers cited for this section would
indicate continued extensive use of arsenic insecticides and herbicides
in soil may represent a serious potential phytotoxir hazard that eventu-
ally will reduce the productivity of land, especialDy in the cotton belt.
In an extensive review of pesticide residues in soills, there was a report
that one commercial apple orchard received more than 3,500 pounds of
lead arsenate per acre over a 25-year period. Accumulation of this
form of the arsenic was not too surprising and explainable because of
its immobility and insolubility. Further, apple tEffis usually grew
unaffected in soil containing relatively high levels? of inorganic arsenic
residues because the arsenic remained largely in thse upper six or eight
inches of soil (Sheets and Harris, 1965). It has teen found that recovery
of old orchard soils for forage or food-crop production is difficult
and slow and many remain unproductive. ' ~ . •)
(r'L* k-^-'i'.^'i-::-, £*.!$;»:•,< i-tz-:*-----'
Before emergence of DDT and more recent modern insezticides, inorganic
arsenicals^ were used extensively on cotton and tobacco for insect control.
Undocumented reports from the lower Mississippi ValDey have implicated
arsenic residues in abnormalities that occur sporadically in rice
growing on old cotton land. The recently -introduced} organic arsenicals,
especially monosodium acid, methanearsonate, may adil to the arsenic
residues already present in the soils of this area ((Sheets and Harris,
1.965).
It has recently been reported that arsenic buildup iin soils after years
of pesticidal use reached 1.8 - 830 ppm arsenic whiQe untreated areas
ranged from 0.5 to 14 ppm arsenic in areas tested wiithin'North America.
-98-
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Further, arsenic residues in 58 surf^o soil sairr~i.e;» taken from soils
with a histoiy of arcenic applicatic,:. averaged 1§S ypm arsenic.
(Woolsor., Axley, and Kearney, in
A review of arsenic applied to experimental fields jfrom three states
provides valuable information. A variety of organic arsenicals were
applied to Alabama soils, and two years after the last treatment, 95
percent of that applied was recovered in the surface 15 cm. Cao (As
04)- was applied to Mississippi soils around 1930 ami only 28 percent
of the amount applied was recovered. The Mississippi soil had a history
of flooding and silting. In Wisconsin, 72 percent of applied Na As Q~
was recovered about four months after application (.IHnolson, Axley and
Kearney, in press).
Such factors as soil texture and presence of iron, aluminum, calcium,
phosphorus and humus might be expected to affect fixation of arsenic in
soil and thus its phytotoxicity . There have been numerous reports that
the presence of small arsenic concentrations in soil have been beneficial
to the growth of peas, radishes, wheat, corn sorghum, soybeans, cotton
and potatoes (Woolson, Axley, and Kearney, 1971a).
It has been reported that loss of methanearsonic acod from soil via
photodecomposition and/or volatilization is none (Barrier, 1970).
It has been shown that organic arsenicals have about the same leaching
and fixing characteristics in the soil as inorganic arsenates . In
addition, it has been shown that the monosodium aciH, inethanearsonate
(MSMA) goes to the inorganic arsenate form so that -.ultimately the
behavior and fate- of inorganic arsenate is of prime importance regard-
less of the source of the arsenic (Woolson, Kearney and Axley, 1971).
The metabolism of cacodylic acid applied to soil unfer aerobic conditions
appeared to proceed through C - arsenic cleavage as well as through a
volatile arsine production. The metabolism of cacoilylic acid under
anaerobic conditions appeared to proceed through reiuction to arsine or
dimethylarsine (Kearney and Woolson, 1971b).
A fungus, several actinomycetes and bacteria have been isolated and
shown to metabolize monosodium acid, methanearsonate. Further studies
with cacodylic acid demonstrated metabolism by soil microorganisms .
Some of the soil organisms were arsine producing (Rrarney and Woolson,
1971a).
Hurtig recently reported on a survey of different sril and crop types
of 32 farms in Southwestern Ontario, Canada, relative to occurrence of
arsenic following use of lead arsenate for insect control. The survey
included five field crops tobacco, pasture, greenhoj.se and orchards.
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Gen-iralj..- ail soils examined has less than 10 ppm arsenic except the.
highest, recorded Jor v--"getabl£s (26.6 ppm) and orichards which ranged
• from 10.2 to 121 ppm (llurtig, 1969), # ,
IV. E. Arsenic in Plants - In plants, 10-12 ppm arsenic by dry weight
have been regularly reported. Certain azotobacter, yeast, fungi and
' molds, including species of aspergillis, can exist in high concentra-
tions and reduce the arsenic to volatile hydrides.. On a dry weight
basis algae have been found to contain 0.1 - 2.6 ppm arsenic and other
seaweeds 0.7 - 12 ppm arsenic. Certain English, Japanese, New Zealand
and California marine algae, have been found to comttain 17-95 ppm of
arsenic whereas freshwater algae have less (Schroeder and Balassa,
1967).
Organic arsenicals are translocated in many plant species. Studies
have shown that in crabgrass and soybeans monosodimm acid, methane-
arsonate ^" As translocated to a greater extent at 85°F. than at 60°F.
Other investigators reported that ammonium arsenate. 77 As moved through-
out the bean plant whether applied to leaves or roasts. Disodium
methanearsonate is taken up from nutrient solution by roots of Johnson
grass and translocated to all part of the plant.
In cotton, various levels of arsenic residues derived from organic
• arsenicals are found throughout the plant depending; on the stage of
development of the plant at the time of application'.. Arsenic residues
in cotton seed are low when applications are made Before development of
the first flower bud. However, if applications are made after square
formation, residues increase and may reach 40 ppm in seed from bolls
closed at time of application and sampled at maturity (Duble jet_ al., 1968).
A comparative study of absorption, transport and metabolism in beans
revealed that cacodylic acid and monosodium acid, methanearsonate (MSMA)
were transported about equally from the leaves to tthe terminal bud and
expanding leaves whereas negligible amounts of saflium'arsenite and
arsenate were translocated. The latter two compounds caused more rapid
contact injury to the treated leaves than either cmganic arsenical.
Both cacodylic acid and MSMA were more phytotoxic j>er mole of tissue
arsenic when foliarly-applied than when root-appliad (Sachs and Michael,
1971).
Arsenic sprays are often applied to grapefruit trees in Florida to reduce
the acid content of the fruit in order to improve flavor and permit early
harvest. Symptoms of arsenic toxicity frequently appear when the treat-
ment Is used repeatedly in consecutive years. The foliar1 symptoms of
toxicity appears first on the south and southwest side of the trees.
The first leaf symptoms are a slight mottling with darker green areas
adjacent to the lateral veins. This resembl'is manganese deficiency except
-100-
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that the symptoms of manganese deficiency appear 'first on the young
leaves, wherein symptoms of arsenic toxicity appeals on mature leaves
in the summer and fall. Arsenic toxicity to grap'diruit can be presented
by several means: (1) spray vi.th recoiiunended amouvts of arsenic during> •.
alternate seasons only; (2) in serious cases of arsenic toxicity
eliminate use for several seasons until the trees iiegain their vigor;
and, (3) application of an adequate amounts of bonx tends to reduce
symptoms of arsenic toxicity (Deszyck, 1958).
-------
CHAPTER IV
SIGNIFICANCE OF ARSENICAL PESTICIDES
.IN THE EMIR(j:iMFNT
BIBLIOGRAPHY
'Annonymous. Trace raetals: unknown, unseen pollution threat. Chemical
and Eng. News. pp. 29, 30, 33. July 19, 1971.
Arle, H. F. and Hamilton, K. C. Topical applications of DSMA and MSMA
in irrigated cotton. Weed Science 19(5):545-541. 1971.
Arnott, J. T. and Leaf, A. L. The determination and distribution of
toxic levels of arsenic in silt loam soil. Wee:i Sci. 15(2) :121-124.
1967.
Baker, R. S., Arle, H. F., Miller, J. H. and Holstum, Jr., J. T. Effects
of organic arsenical herbicides on cotton respoiose and chemical
residues. Weed Sci. 17(1) 37-40. 1969.
Barrier, G. E., Chawman. Herbicide handbook of the Weed Society of
America, 2nd Ed. W. F. Humphrey Press, Geneva, 1LY. 368 pp. 1970.
Batjer, L. P. and Benson, N. R. Effect of metal cHrelates in overcoming
arsenic toxicity to peach trees. Proc. Am. Soc~ Hort. Sci. 72:74.
1958.
Benson, N. R. Can profitable orchards be grown on old orchard soils?
Washington State Hort. Assoc. Proc. 64:109-114. 1968.
Blodgett, E. C. A systemic arsenic toxicity of p.each and apricot on old
apple land. Plant Disease Reporter 25:549. 1941.
Bradicich, R. , Foster, N. E., Hons, F. E., Jeffers, M. T. and Kenner, C. T.
Arsenic in cottonseed products and various commoxiities. Pesticides
Monit. Jour. 363:139-141. 1969.
Buchanan, W. D. Toxicity of Arsenic Compounds. Elsevier Publishing
Company. Amsterdam, London, New York. 151pp. 1962.
Deszyck, E. J. Arsenic toxicity. pp. 66-67. From Florida guide to
citrus insects, diseases, and nutritional disorders in color. Pratt,
R. M. (Editor). Florida Agricultural Experiment Station. Gainesville,
Florida. 191 pp. 1958.
0
Dickens, R. and Hiltbolt, A. E. Movement and persistence of methanearsonates
in soil. Weed Sci. 15 (4):299-304. 1967.
Duble, R. L. , Holt, E. C. and McBee, G. G. The translocation of two organic
arsenicals in purple, nutsedge. ..Weed Science 16 (-4) : 421-424. 1968.
-102-
-------
Fairhall, L. T. Industrial toxicology, 2nd ed. IHiiiiam and Wilkinj
Co. Baltimore. 1957. ^
Havelka, U. D. , and Merkle, M. G. Arsenic residues, in cotton and
johnsongrass. South. Weed Sci. Soc. Proc. 22:51-57. 1969.
Hurtig, H. Ecological chemistry implications of "tike use of pesticides.
Presented at International Symposium "Chemical and Toxicological
Aspects of Environmental Quality." Munich. July 1969.
Kearney, P. C. and Woolson, E. A. Cacodylic acid metabolism in soils.
Paper No. 29, Pesticide Division, presented at 102nd meeting, American
Chemical Society, Washington, D.C. September, 3S71a.
Kearney. P. C. and Woolson, E. A. Chemical distribution and persistence
of C^-Cacodylic acid in soil. Paper No. 29, Pesticide Division, 162
National Meeting American Chemical Society. Waslkington, D.C.
September 1971b.
Keeley,. P. E. and Thullen, R. J. Cotton response to temperature and
organic arsenicals. Weed Sci. 19(3) :297-300. 33)71.
Neal, P. A., Dreessen, W. C. } Edwards, T. I., Reiiftart, W. H. , Webster, S. H. ,
Castberg, H. T., and Fairhall, L. T. A study of the effect of lead
arsenate exposure on orchardists and consumers oif sprayed fruit. Federal
Security Adm. Public Health Service. Public Health Bulletin No. 267.
31 pp. 1941.
Sachs, R. M. and Michaels, J. L. Comparative phyferotoxicity among four
arsenical herbicides. Weed Science 19(5): 558-SfA. 1971.
Schroeder, H. A. and Balassa, J. J. Abnormal trace metals in man: arsenic.
Arsenic News No. 15. Arsenic Development Commititee 26, Rue La Fayette,
Paris 9. 16 pp. Sept. 1967.
Sheets,. T. J. and Harris, C. J. Herbicide Residues in soils and their
phytotoxicities to crops grown in rotation, pp. 119-140. [From Residue
Reviews. Gunther, F. A., Editor. Vol. II. Springer-Verlag, New York.
• 1965.. I
Thompson, A. H. , and Batjer, L. P. Effect of vari'ms soil treatments for
correcting arsenic injury of peach trees. Soil Sci. 69, ( ):281. 1950.
Ulltnan,, W. W. , Schaefer, R. W. , and Sanderson, W. 'W. Arsenic accumulation
by fish in lakes treated with sodium arsenite. Water Pollution Control
Federation Jour. 33(4) :416-418. 1961.
-103-
-------
U.S. Department: of Conferee, Current Industrial Rtpcrts - inorganic Chemi-
cals, j.969. Series: M28A(69)-14, Bureau of the Census. 28 pp. March 29,
1971.
United States Tariff Commission. Synthetic Organic Chemicals - United
States Production and Sales of Pesticides and Rdlated Products, 1970.
11 pp. September 1971.
Vallee, B. L. , Ulmer, D. D., and Wacker, W. E. C. Arsenic toxicology and
biochemistry. Arch. Ind. Health 21(2): 132-151. 1960.
Von Endt, D. W. , Kearney, P. C., and Kaufman, D. Du Degradation of
nlonosodium methanearsonic acid by soil microorganisms. Agr. and Food
. Chem. 16( ):17-20. 1968.
Wiese, A. F. , and Hudspeth, E. B. , Jr. Effects of HSMA and MSMA on
cotton yield and arsenic content of cotton seed. Texas Agr. Expt.
Sta. MP-877. 1968.
Woolson, E. A., Axley, J. H. , and Kearney, P. C. Its' chemistry and
phytotoxicity of arsenic in soils. I. Contaminated field soils.
Scientific Article No. A-1691 and Contribution No.. 4448 of Maryland
Ag. Exp. Sta., Dept. of Agronomy. 17 pp. 2 tables. In Press.
1971a.
Woolson, E. A., Axley, J. H. , and Kearney, P. C. Graiparison of a color-
imetric and a colorometric method for the deternnnation of arsenic in
soil digests. Soil Sci. 111(3):158-162. 1971b.
Woolson, E. A., Axley, J. H. , and Kearney, P. C. Correlation between
available soil arsenic, estimated by six methods, and response of cron
(zea mays L.). Soil Sci. Soc. of Am. Proc. 35(l}:i01-105. 1971c.
Woolson, E.A., Kearney, P. C., and Axley, J. H. Chnnical distribution
of arsenic-in soils. Unpublished. 6pp. Slides. [1971].
-104-
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CHAPTER V
RLS7DUES IN CROPS AOT) FOOD ITEMS
According to Lehman (1965), the toxicology of arsenic has been exhaus-
tively studied. It has been shown that as an average, natural foods
contain 0.6 ppm arsenic calculated on a dry-weight basis. The daily
urinary excretion of arsenic is an index of the amount ingested and
estimated to be up to 0.5 mgx A third important aspect is arsenic's
cumulative properties. Based on data reported for a rat study (Morris
and Wallace, 1938), 4.36% of ingested arsenic (as the arsenate) could
be expected to be retained in the body.
V. A. Tolerances
V. A, 1. Established Tolerances - Following are the established toler-
ances presented in this chapter (for more details see exhibits 1-10):
a. A tolerance of 4 ppm of combined As203 for residues of the
defoliant orthoarsenic (arsenic) acid in or on cotton (420.180).
b. A tolerance of 0.7 ppm (expressed as As-O-) for residues of
the herbicide methanearsonic acid in or on cotton, from application of
the disodium and monosodium salts of methanearsonic acid in the produc-
tion of cotton (420.289),
c. Tolerances of 3.5 ppm of combined AsoOn for residues of the
insecticides calcium arsenate, copper arsenate, magnesium arsenate and
sodium arsenate on specified raw agricultural commodities (420.192,
420.193, 420.195, and 420.196, respectively). Tolerances for lead
arsenate (420.194) on vegetables and tree"fruits were based mainly .on
the cumulative action of lead.
d. Tolerances for total residues of combined arsenic (calculated
as As), contributed in food by veterinary medicine uses under Sections
121.253, 121.254, 121.262, and 121.310 are established under Section
135g.33 as follows: 0.5 ppm in muscle and eggs and 1 ppm in edible
by-products of chickens and turkeys; and, 2 ppm in liver and kidney of
swine, and 0.5 ppm in muscle and by-products of swine other than liver
and kidney.
V. A. 2. Tolerances Pending - The following arsenic tolerances are now
under consideration:
»
a. Tolerances for residues of elemental arsenic at 2 ppm in or on
cotton, 1 ppm in liver and kidney and 0.5 ppm in meat, fat, and meat
by-products (except liver and kidney) of cattle from use of the defoliant
cacodylic acid (dimethylarsinic acid) on cottonseed.
-------
b. Tolerances of 0.5 ppm residues of arsenic (as As) in meat, fat,
ancl meat by-products of cattle and horc-es (except liver and kidney);
and 2 pptr. in the kidney and liver of < at tie and hoars es resulting from
fne dermaA application of arsenical dip solutions (sodium arsenite) fo* •
tick control of these livestock imported from Mexico and in the tick
eradication program in the Texas area. The use of the. arsenical solu-
tions are to be supervised by authorized personnel according to prescribed
ARS (USDA) procedures. The animals may remain in (the Texas quarantine
area from 3 weeks to 10 months and are subject to repeated dip treatments
during this time. Such animals are usually range-fed and are shipped to
feed lots for feeding for periods from 3 to 6 months prior to slaughter.
All animals recieve a final dip before leaving the quarantine area.
Horsemeat is not generally available in the U.S. fo-r human consumption.
Arsenic residues in cattle result mainly from feed rations containing
cottonseed meal which are fed to cattle in feed lots or on the farm.
V. A. 3. Policy Considerations for Arsenic Residues. - Section 420.3 (d) (4),
21 CFR revised as of January 1, 1971, states: "When a tolerance is
established for more than one pesticide containing arsenic found in, or
on a raw agricultural commodity, the total amount
-------
was 0.1 ppm. Residue levels of arsenic (As-^O^) fi.or each of tne follow-
ing class of lood items (6 composite samples at reach of the 5 sampling
sites) were found to be:
ft ••
Dairy products: 1/6 composites (Boston, Mirneapolis) - 0.1 ppm
Meat, fish, and poultry: 4/6 composites (Beston - average 0.2 ppm
range from 0.2 to 0.4 ppm); 4/6 composites (Los i&igeles - average 0,1
ppm, range from 0.1 to 0.4 ppm); 4/6 composites ^altimore - average
0.4 ppm, range from 0.2 to 1.0 ppm); 3/6 composites (Minneapolis. -
average 0.1 ppm, .0.1 ppm).
Grain and cereal products: 4/6 composites '(Jlbston. - 0.1 ppm)
1/6 composites (Los Angeles - 0.1 ppm); 2/6 composites (Minneapolis -
0.1 to 0.2 ppm).
Potatoes: 1/6 composites (Boston, Los AngeQas, Minneapolis) -
0.1 ppm.
Leafy vegetables: 2/6 composites (Boston; Q//6 composites), (Los
Angeles, Minneapolis) - 0.1 ppm.
Legume vegetables: 2/6 composites (Boston)s 1/6 composites (Los
Angeles) - 0.1 ppm.
Root vegetables: 2/6 composites (Boston); Q//6 composites (Minneapolis)
0.1 ppm.
Garden fruits: 3/6 composites (Boston); 1/6 composites (Los Angeles) -
0.1 ppm. . ' .
Fruits: 2/6 composites (Boston, Los Angeles)); 1/6 composites-
(Minneapolis) - 0.1 ppm.
Oils, fats and shortenings: 1/6 composites ((Boston, Minneapolis) -
0.1 ppm.
Sugars and adjuncts: 3/6 composites (Boston;)); 1/6 composites
(Baltimore Minneapolis) - 0.1 ppm.
Beverages: 2/6 composites (Boston); 1/6 congosites (Baltimore) -
0.1 ppm.
In this report, as in earlier reports, the arsenic values were reported
on an "as in" basis for 3 food classes: Dairy pmducts, meat, fish and
poultry, and, oils, fats, and shortening, even thnigh the earlier tabu-
lations (Duggan, et al., 1967) indicated a "fat basis."
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V. C. 2. US DA.Consumer and Markt t ing Se rvice Surra ^t
V. C. 2. a. Arseni_c_ Residues in Beef: - The Meat and 1-oultry Inspection
Program is conducting a survey (1971) to determine the nature, extents
and levels of mercury, lead, cadmium, selenium, arsenic, antimony,
copper and zinc in beef. This is to evaluate any present or potential
public health hazard that may exist and to deterniSne background levels
of these elements. The survey is to include:
(1) Analyses of 3000 samples randomly obtained from beef slaughter-
ing plants throughout the U.S. The number of samples to be taken at
each plant is based on the seasonal production -capacity of the plant.
(2) Analyses of 50 samples to be obtained froan beef slaughtering
plants in each of five geographical areas selected on the basis of
known data regarding heavy metals. The data collected for the random
samples (2176/3000) through June 28, 1971, are sunmarized in TABLE IV. 2.
The data on the samples from selected areas have .rot been fully evaluated.
The analytical data for the' random samples indicate that lead, cadmium
and copper are present in all the samples analyzed and that arsenic
occurs randomly at relativelylow levels. Arsenic residues in beef
result mainly from feed containing cottonseed meal and from arsenical
dips used for tick control of cattle imported from Mexico. It will be
necessary to obtain more residue data during subs'efuent yearly surveys
to ascertain if the arsenic residues in tissues wall increase appreciably
following more extensive use of arsenicals as herbicides for cotton or
in cattle dips.
V. C. 2. b. Arsenic Residues in Poultry and Swine - Surveys were con-
ducted for arsenic residues in 1966, 1968, and 19'70>. in swine and in
1968, 1969, and 1970, in young chickens. Tolerance limits were set at
1.5 ppm in chicken livers and 2.0 ppm in swine liters. Violative residues,
found mainly in the livers, were more pronounced -on. chickens than swine
and were attributed to lack of proper withdrawal. In 1970, about 5% of
liver samples in 261 swine and 7.4% of liver sarapOes in 431 young
chickens were found to contain violative residues..
-108-
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TABLE 1 - RESIDUES OF SEVERAL METALS IN BEEF -.-'-.
' LIVER
MUSCLE (DIAPHRAGM)
KIDHEY
ALL TISSUES
METALS -
ARSENIC (AS)
PDMIUM (CD) •
MERCUKY (HC)
LEAD (PB)
ANTE-.OIiY (SB)
COPPER (CU)**
H
1 •':.•>
212!
39!;
215,'.
()
20.1 1
ItJCIDE.
RATE
6.664
97.518
18.153
99.081
0.0
99.904
AVE.
(PPM)
0.093
0.207
0.023
0.536
0.0
34.923
LOW
(PPM)
0.02
0.01
0.01
0.01
0.0
1.30
HIGH
(PPM)
0.22 '
3.17
1.79
3.74
0.0
115.30
INCIDE.' AVE.
LOW
COPPER (CU)** 3?.' 100.000 42.494 3.90 104.10
N RATE (PPM) (PPM)
0 0.0 0.0 0.0
1765 81.112 0.082 0.01
566 26.011 0.028 0.01
2080 95.588 0.361 • 0.01
0 0.0 0.0 0.0
2081 99.904 1.818 0.03 29.90
322 100.000 1.816 0.60
nicH
(PPM)
O.Q
0.90
1.85
2.96
0.0
!9.90
3.70
N
21
2153
1164
2145
0
2081
: 322
' .INCIDE.
RATE
0.965
93.943
53.493
98.575
0.0
99.904
100.000 ',
AVE. .
(PPM)
0.077
0.546
0.026
0.625
o.o ......
4.176
4.155
LOW
(PPM)
0.05
0.01
0.01
0.02.
0.0
0.08
0.08
HIGH
(PPM)
0.17 .
. 7.82
5.25
3.38 '
0.0".
24.20
20.30 .
••H
U5
XJ.71
•1456
I1 176
. 0
2032.
322
•7
..'9
6G
100
• o
99
100
Aii,
.:.-3
.r?S
.912
. COO
.0
.952
.COO
COFFER V..\:, !;..•. ;.:!/\LYZEU- IN TilE FIRST 4 SAMPLES
Y;L Ki'.:. :R i•:' A-MlHAbS - 2176
:A COn •VT. .. ;.:HOUGH 6/28/71
-------
CHAPTER V
Bibliography (Residue.--:)
/;>
Anonymous, - Symposium on feed additives and Gignifii-ance of their residues
in animal tissues, Agr. & Food Chemistry, 11:362, (U63) .
Byron, W.R. ; Bierbower, G.W. ; Brouwer, J.B.; and Hanson, W.H.:
Pathologic changes in rats and dogs from two-year feeding of sodium arsenite
and sodium arsenate, Toxicol. Appl. Pharmaccl., 10:122 (1967).
Calvery, H.O.; Laug, E.P.; and Morris, H.J.; The chronic effects on dogs
of feeding diets containing lead acetate, lead arsereatie, and arsenic trioxide
in varying concentrations, J. Pharm. Exper, Ther. 6'4:364 (1938).
Corneliussen, P.F.: Pesticide residues in total dieSt samples (V); Pesticides
Monit. J., 4 (3): 89 (1970).
Duggan, R.E.; Barry, H.C.; and Johnson, L.Y.: Pesticide residues in total
diet.samples (II), Pesticides Monit. J. , 1 (2): 2(19'S7/).
FAO/WHO 1968: Evaluations of some pesticide residues in food. FAO/PL: 1968
M/9/1; WHO/Food Add./69.35.
Lehman, A.J.: Summaries of pesticide toxicity. The Association of Food and
Drug Officials of the U.S., Topeka, Kansas, (1965),
Morris, H.P.; Laug, E.P:; Morris, H.J.; and Grant, R..E. : The growth and
reproduction of rats fed diets containing lead acetate and arsenic trioxide
and the lead and arsenic content of newborn and suckling rats. J. Pharm. Exper.
Ther. , 64:420 (1938).
Morris, H.J., and Wallace, E.W.: The storage of arssnic in rats fed a diet
containing calcium arsenate and arsenic trioxide. J.. Pharm. Exper. Ther.,
64: 411 (1938).
Schroeder, H.A. -and Balassa, J.J.: Abnormal trace me&als in man: Arsenic,
J. Chronic Dis., 19:85 (1966).
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(§5 120.180 thru 120.182)
f
hnant m.blished in Federal Register: SUBPART C-PESTICIDE REGULATIONS --Page
"or'c-nher 1 1970; 33 r'.R. 13830 Remove old page 36 and insert this new
September ?.3, 1970; 35 F.R. 14768 paga in your reprint.
Orlhoarscnic ncid.
. A -tolerance of 4 parts per million of
combined Az,O, Is established for residues
of the defo!L~,nt orthoarsonJc acid In or
on the raw agricultural commodity cot-
tonseed.
§ 120.181 CIPC; tolerance for residues.
A tolerance of 60 parts per million
Is established for residues of the plant
regulator CIPC (isopropyl tf(3-cliloro-
phenyl) c'arbamate) In or on potatoes
from postharvest application.
g 120.182 Endosulfan; tolerances for
residues.
Tolerances are established for the total
residues of the insecticide endosulfan
(6.7,8,9,10,10 - hexachloro - l,5,5a,6,9,Da -
hexahydro-6,9-methano - 2,4,3 - benzodi-
oxathiepin-S-ortlde) and its metabolite
end'osulfan sulfate (6,7,8,9,10,10-hesa-.
chloro - l,5,5a,8,9,9a-h e x ft li y d r o-3,9- .
methano-2,4,3-ben2odloxathlepta-3,3-dl-
oxlds) In or on raw agricultural
commodities as follows:
2 parts p-c-r nUUon in or an apples,.
apricots, nrUchokes, beans, broccoli,
brussals sprouts, cabbage, cauliflower,
celery, cherries, collnrds, cucumbers, Cj3-
plants, grapes, tale, lettuce, melons,
mustard greeia, nectarines, peaches,
pears, peaa (succulant type), peppers,
pineapples, plunn, prunes, pumpkins,
spinach, Btrartsrries, summer squa-^h,
cuniloTver seed, tomatoes, turnip creens,
watercress, and wlnt-sr sauash.
* 1 part per iniilion in or on ai.ctfa hay
srxl cottonread. vV
0.5 part per million In mlTi fat (re-
flecting; negligible residues In nllk) and
In or on sugarcane.
0.3 part per million in or on alfalfa
(fresh).
0.2 part per million In or on carrots,
sweet corn (kernels plus cob with huslis
removed), sTvsatpctatoes; and in meat,
fat, and meat byproducts of catUe, goats,
hcus, horses, and ;heep.
••It-It 0.2 part p-jr-million (negligiWs resi-
dues) in or on fijterts, tnacadamla nuts,
pecans, potatoes, safflower seeiT, and
walnuts. 4-A
u. s. C':P;?T,''.~NT OF
HEALTH, ECT'JCAT.;.-!, /.; iD'..JLT.'.
FOOD AMD D.VUG ApyiN!ST«ATiCM
-110-
-------
($8 ;?').282 ftlini 420.289)
Anenctasnt yuMished in Federal Register
ft' Septeaber 9, 1971; 35 F.R. 18079
SUBPAKT C—PSSTIC1DF. iJEGULATIOHG— Page 5
Renove oH page 59 und insert '-this new
page in ystur reprint.
tnide; tolerances for residues.
Tolerances arc established for ESslLjl-
ble residues of the herbicide 2-chloro-
A'JV-diallylacetamlde In or on the raw
agricultural commodltlja cabbage, castor
beans, celery, com groin (Includes pop-
corn), fresh com including sr,ve-3t corn
(kernels phis cobs v/ith husk removed),
com forage or fodder (Including STveut
cpm, field corn, and popcorn), driod
beans, lima beans, lima bean forajj,
onions, peas, pea forase, potatoes, snap
beans, snap bean forage, sorghum grain,
sorghum forage, soybeans, soybean for-
ase, oc-jarcanc, sweetpotaloea. and to-
matoes at 0.05 part per million.
§ 420.233 2,3,6-Trlr5i!orophenylscetk
cddj tolerances for residues,
A tolaro.nc3 of 0.1 part per million Is
established for ne^lislble residue* of tlis
herbicide 2, 3, G-irichlorophcnylacetle
ccld la or en E^rr,rerJa3, ouch rcjlduu
resultlnj from application of Its dlmeth-
ylamins or sodium julta. ft
6^20.23-J ZI»e pJioaphltlej toleronces
A tolcranca cf 0.01 part per million Is
estabU^hM for rc:-ldui3 of phc:phin-3 In
or on the rs,w cjrlcultursJ ccniinccUty
aujarcias from u;j of ths rccf^ntlcide
Eiiic phcophlO.2 In
tor
ara ejb.bllihcd fc? ccm-
jid'.-] of tli3 ln.;:ct!:ldj W'-(4-
ehlsro-o-tcl?!) - W^V-dimjlhjL'onnaral-
dlca W3d Jt3 rr.ot"iboUt;3 contMalnj thj 4-
chlorov^>luld!no moiety (cilcul^t:d EJ ths
-frora a.-:pllcitJcn o/ tha In-
to a f .'13 bicj or aa th j hydro-
in o.- ca raw agricultural
ecnur.cT(:.V3'C- 2.7,01 (i'?-.s:j
.
ca tia ri'a1 ic;il7:-jJuKd - isa
e?
g 450^37
BQCthcaoSII-cyc'Dliula [ tcJ ] penlutcn-
g-onei Uj-!zcci-ce for residues.
A'tolsranca of »J501 p.->,rt por million Is
established for r^-l^blD realnxiaj of tMa
-
metheno - 3H-c;a2'3iJui,
ons in or oa CID rr,-^ agricultural com-
modity banansa.
0 ^SO.203
for ircilJv.ca.
A to!r?acc3 s2 0.1 port p-;r mUlica y
v-.;'.au:j cf thj
in cr.
A
•prc.-",:
-------
namJIi.^iit: puM.-" ;ih-:-d In VvJcral F;rj,.i
November 18, 1.970; 33 F.R. 17703
§120.l!'f-' Coumuplux; ii>Ieranc:-M for
residual.
Tolerances, are establislied fo. residues
of the insecticide coumaphoo (O,O-
dlethyl O-3-chloro-l,:mcthyl-2-oxo-2II-
l-benzopyran-7-yl phosphorothioatc)
and its oxygen an.ilo:,' (O,O-d!ethyl
O-3-chlorO"i-methyl-2-oxo-2H-l-benzo-
pyran-7-yl phosphate) In or on raw
agricultural commodities as follows:
1 part per million In or on meat, fat,
and meat byproducts of cattle, goats,
hogs, horses, poultry, and sheep.
0.5 part per million In milk-fat reflect-
ing negligible residues In milk.
0.1 part per million in eggs.
(See also § 121.304 of this chapter.)
Remove; old page 39 and inaerl:
new ;>•:.;;-; e tn your reprint,
25 pt:~ts rcr miHIon In or ou rrr^c"
avOiiHfl&s, bUaikb.virles, blueberries, boy-
"...nberrlcs, cr'.bapples, cranberries, cur-
rants, dewberries, ECKiseberrlCo, crapes,
hi'd-i'i'-berries,, loganberries, raspberries,
strawberries, iromatoej.
* 15 parts par million in or on citrus
fruits, cucumbers, garlic, melons, onions
(dry bulb), pnunpkins, summer sqilash,
winter squash,A-
,4-
3
| 120.190 Diphenylamiuc; tolerances
for residue1*.
Tolerances for residues of the fungi-
cide dlphcnylomlne are established as
follows:
10 parts per million In or on apples
from prohar/est or posthnrvest u^a, In-
cluding U52 of Irnpregruited wraps, for
scald control.
Zero in milk and meat.
Folpat; tolerances for
resi-
§ 120.191
dues.
Tolerances for residues cf the fungi-
cide folpet W-(trlchloromethylthio)
phthallmide) in or on raw agricultural
commodities are established as follows:
60 parts per million in or on celery,
cherries, leeks, lettuce, onions (green),
shallots.
§ 120.192 Cilciuin nrocnalo; tolerances
for rcjJ
for
A tolerance sf 3.5 parts per million of
combined Ass'Oi 13 established fcr resi-
dues of the lasscticlde calcium arf-snato
in or on each atf the following raw agri-
cultural comiEadJties: Asparasrus, be.'irj,
blackberries, Blusberriea (hucltlcbsr-
rles), boyssntai-ries, broccoli, bnr^sla
sprouts, cabiase, carrots, c^ullI3ov7er,
cslery, colidsl', ooru, cucumbsrs, claw-
berri3s, e^splazits, krJe, kohlrabi, lccrr>n-
berrles, taelorui,p-3p>2r3, pumpldas, rr.o>-
berrles, nitsbaras (with or without tops)
or rutabaga tcrjas, spinach, squash, s'.raw-
beiTlu, summ£F squash, tomatoos, tur-
nlpa (v/ith or without topa) or turnip
fjreens, younshsrlea.
\ 120.191 JH. amended by deleting the
Per e
-112-
-------
(SS 120.193 t:n:,<. UCJf5)
-r.r. published in reJar/il Register: RUBPART C—PESTICIDE I fiGULiVnOtTS'-roge 40
December 14, 1958; 33 F.R. 18578 Re-ove old pc.fj 40 an-1 insert this new
pigc in yojr rcnrint.
* '/i_- ^
§120.193 Copper nrsenatc; tolermscja
for •'
A tolerance of 3.5 pirta per million «£ /
combined AsjOj i3.pstn.b!l5hed for M-i- /
dues ol the Insecticide and lunsic'.fe
copper arsanate iu or on each of lh-i
followlcs raw agricultural commodiUi';.''
Eru«cls sprouts, cabbie, cari-oU , caaili- '
flower, koiilrabl. txsmatoes.
•>-i-i>
§ 120.194 Lead arscnule; tolerances fer
residues.
Tolerances for residues of lead ar-
senata (primarily an Insecticide) in esr
.on raw agricultural commodities are e»-
/tablished as follows: ' /
7 parts per million of cotnblnafl *
lead in or on apples, apricots, aspara-
ETos, p.vocados, blackberries, blueberrier,
(huckleberries), boys^nberries, celery,,
cherries, cranberries, currants, dewbsr-
ries, egyplants, gooseberries, grap33i,
loganberries, mangoes, nectarines;,
peaches, pears, peppers, plums (frwla
prunes) , quinces, ro^pbeiries, strawber-
ries, tomatoes, youugberrles.
1 part p«r million of combined lead tm
or .on citrus fruits.
§120.195 Magnesium nrsenate;
ance for residues, /
A tolerance of 3.5 parU per million of
combined AsuOs is estab'.isheci for resi-
dues of the insecticide magnesium ar-
senate in or on the raw agricultural
commodity beans.
§ 12^.196 Sodium nrsenalc; tolerance
for residues. ,
A tolerance of 3.5 part? per million •
of combined AsiOj is established for resi-
duer. of the insecticide sodium arsenats
in or on the raw agricultural commodity
grapes.
Jn $ 120.193, "(with or without
or carrot tops" Is deleted.
-113-
-------
Amendrr.cn f.s pub I j.:.ih<.:d i.n Fedc.ral Regi.-U'e.i
* May 13, 197 '• 36 F.R. »/'"!
* * June 19, 1971; -6 F.R. 11811-
FART 135g--TOLCRAnCES FOR Pa;;e L,'
RESIDUES OF NEW ANIMAL DRUGS III FOC
Remove old page 17 and insert this
new pogc in your reprint.
§ 135g.29 TcMostu'-onc proplvnalc.
(a) No residues of testosterone pro-
pionate mny he found in the uncooked
edible tissues of heifers.
(b) The method of examination pre-
scribed for the quantitative determina-
tion of testosterone propionate is as fol-
lows: Prepare an extract of the tissues as
described in § 135s.28tb) <1) and (2) and
bioassay the extractive in an ethyl
alcohol vehicle by inunction on the day-
old chick's comb by the method published
in "Methods in Hormone Research." New
York, Academic Press, volume II. page
286 (19G2).
§ 135g.30 Eslrudiol bcnzoale.
(a) No residues of estradiol benzoate
may be found in the uncooked edible tis-
sues of heifers, larflbs, and steers.
(b) The method of examination pre-
scribed for the quantitative determina-
tion of estradiol berLzoate is as follows:
Incorporate the finely ground tissues in
the diet of immature mice, and assay by
the mouse uterine weight method of
E. J. Umberger, G. H. Gass, and J. M.
Curtis, published in "Endocrinology,"
volume 63, page 806 (1958).
§ 135R.31 Chlorobutanol.
A tolerance of zero is established for
residues of chlorobutanol in milk from
dairy animals.
'§ 135fC.32 Salicylic acid.
A tolerance of zero is established for
residues of salicylic acid in milk from
dairy animals.
§ 135g,33 Arsenic.
Tolerances for total residues of com-
bined arsenic (calculated as As) in food
are established as follows:
(a) In edible tissues and in eggs of
chickens and turkeys:
(1) 0.5 part per million in uncooked
muscle tissue.
(2) 1 part per million in uncooked edi-
ble byproducts.
(3) 0.5 part per million in eggs.
(b) In edible tissues of swine:
(1) 2 parts per million in uncooked
liver and kidney.
(2) 0.5 part per million in uncooked
muscle tissue and byproducts other than
liver and kidney.
if •fi
§ 135g.34 ErYlhromycin.
Tolerances for residues of erythromy-
cin In food are established as follows:
(a) 0.1 part per rr-'uUon (n^lijible res-
idue) in uncooked edible tissues of swine.
(b) Zero in unccoked edible tissues
of chickens, turkeys, and b™f cattle; in
ur.coehed e^; an I ::i milk. ~v *
"§ i'3"o!,'.'^>j biiVr.-.i''i"">'»v';,vri(!.-..'.ine.
A tolerance oi r. TJ is e-U-ibMsbed for
residue o." rjlf-ir: •.-:vpyridazi.--? in the
uncooked e-Jiblc tU-.--.ie;; of .iwine rind Cdt-
tif and in milk.
§ 135V..16 Fum/o!ii!orio.
A tolerance of zero is established for •*#
residues of lunu'.olidone in the uncooked
odiblu tissues of swine.
o' 13:ijr.S7 Prt'dnipoloiic.
A tolerance of zero is established for
residues of predniiolone in milk from
dairy animals.
§ 13j£.3u Eslr;'.i!iol ii!oiiOp:i!miiatc.
(a) No residues of estradiol monopal-
mitate may be found in the uncooked
edible tissues of chickens.
(b) The method of examination pre-
scribed for the quantitative determina-
tion of estradiol rnonopalmitate is as fol-
lows: Incorporate finely ground tissues
of the treated chickens in the diet of im-
mature mice and assay by the mouse
uterine weight method of E. J. Umbercer,
J. K. Gass, and J. M. Curtis published in
"Endocrinolgoy," volume 63, page 80G
(1958).
§ 133s-39 Tliiubemlazolc.
Tolerances are established at 0.1 part
per million for neglisible residues of thia-
bendazole in uncooked edible tissues of
cattle, goats, sheep, and swine, and at
0.05 part per million for negligible resi-
dues in milk.
§ 133g.40 Predniso:ie.
A tolerance of zero is established for
residues of prednisone in milk from dairy
animals.
§ 135g.41 Mctliylpnraben.
A tolerance of zero is established for
residues of methylparaben in milk from
•dairy animals.
§ 135;;.42 Propylparabcn.
A tolerance of zero is established for
residues of propylparabcn in milk from
dairy animals.
§ 135g.43 Iproniduzolc.
No residues of Ipronidazole (2-isopro-
pyl-l-methyl-5-nltroimidazole) and its
metabolite d-methyl-5-nitroinn'dazole-
2-lsopropanci.i are found in the uncooked
edible tissues of turkeys as determined
by the following method of analysis:
I. METHOD or ANALYSIS
A. Tho assay procedure Is aultable for tho
recovery and analy.-.Ls of "Jproold.izole (l-
mctiiyl-3-lsopropyl-5-nUrolmldr.2olo) and Its
metabolite l-mcthyl-5-rUtrolm!c!:ibo!o-2-!.K>-
prop-inol from turkey ti^ue with 3 lover
Umlt of 2 part.5 per blUlon using a lOO-srrt'-in
ef-aiple. IprorUdi.-.olo and Its me';abo!lto aro
cxtracc'-d from mu'X'.e, liver. Xldai:/, a'.: In.
1 :• ',. ai'.ii b! vxl -.vC.h So-:?.c::5 In '.hi r>::•"::'..•)
of lx;ra.T. Th-j ns:r:io: is pur'.Iied by colu.Tia
ci.ro:r..'.U.*^"j.;Vay on aillc-. g-jl a_::'J t'as t~'0
co;r.rou:id;i r-re clitjr.Tijrii'd jcTi.-.i:ely by ja,"!-
li. nu :'v'.!o•.•,•:,••-; -..-ooui of tlia pvcooluro
ni:t^» ba c.uofully o.; :.?ri'c
-------
'eissuecJ July 29, 1964
§ ]21.253
SUBPART C--F03D ADCl/IVES— •P.-.ig.n 39
Remove old. page 39 and insert this new
page in your reprint.
§121.253 Arwnllicacid.
Arsanllic add may be safely used !n
Dnlmal feed when Incorporated therein
In accordance with the following condi-
tions;
(a) The additive is the chemical p-
aminchenzenearsonlc acid (CeHiAsNOj)
conforming to the following specifica-
tions (on the dry brwls):
(1) The additive contains not less
than 2'S percent and not more thrvn 34.8
percent of arsenic (A/,), equivalent to
not leas thr.n 93.5 percent a:irt not more
than 100.8 psrcant CsHjAs^Oj.
(11) The additive contains not more
than 0.025 parccnt ai-Eenic as inorganic
orsenito. ctJoulatod EI Aa:O3 and not
more tlian 0.03 percent rrsenlc as in-
orcanic arssnate, calculated as AsO^.
(b) Permitted uses of arsanillc acid
alone and with certain other additives
are described in tabular form in this sec-
tion, and these tables are to be read as
follows:
(1) The numbered line Items establish
the required limitations and Indications
for use of the principal ingredient as the
medicament alone or with an additional
Ingredient added for Increased effective-
ness.
(2) The lettered Ine items establish
the required ilmitat-ians and Indications
for use of secondaiy ingredients that
may be added to the indicated principal
Ingredient. Where principal and sec-
ondary ingredients have been mixed, the
applicable limitations and Indications for
use from both the mim'bered Items and
lettered items apply.. If duplicate limi-
tations occur, these may be appropri-
ately combined.
(3) Permitted conbLnatlons of princi-
pal ingredient and :a?condary Insredlents
are Individually listed. Unisys specifi-
cally provided by the regulations, the
principal infrredicu't may not be mixed
with two or more secondary ingredients.
(4) Where cross-references specify a
partlculr.r table and item numbsr of an-
other section, use >aS. only the principal
ingredient of the rnonbered item is au-
thorized thereby.
(5) The term "pdnclpal Ingredient"
as used in this sectlccr refers to the addi-
tive named In the teiding of this section
and is not Intandei! to imply that the
ingredient Is of a gisater value than any
other additives nancd In. this section.
(c) It Is used or Ih.ter.deti for use in
feeds, as follows:
-115-
-------
(§ 121 253)
Amendment published in Federal Register:
* November 6, "1968; 33 F. P.. 16272
SURPAKT C--FOOD ADDITIVES--Faae 39.1
Remove old page 39.1 at.'l insert this
oew page in your reprint.
! Cmcxrv • .,a TURXET Fira>-
Print! pa!
Ingredient
L 1 Ar? \nlilc
6dd.
Grams per
•ton
9?
CoTiM-nod
with-—
(a 01%)
~» u
1.2 ArauiUlcadd. BO (0.01%) Amprollum..
L8 Aremlllo
tcJd.
L« AmnUUj
odd.
I.I ArvmUlc
field.
1.9 Arsnnillc
Kid.
90
(a 01%)
90
(0.01%)
90
(0.01%)
90
(a 01%)
Atnprollura...
•f-
cthopaL-uto.
Amprolium...
Zoalenc ----
Zoaleno
Orarr.j p«r
ton
Lln,,,^,
F .. ,
....
dnya bc.'ora slai:;hter; m
solo sourco of O.-;;A.I'C
ar3?^ic.
...... 113. 6-7:7"] Xorbroilrr
(O.Girji^- repl^Ci'Ci
O.OCi%) whcro IIT
chkiros; fo?
>T! cl'.lcfccns
;-u-;Uy to
eocc!d!ci!j b r.rt d*-
tirtd; wl
before sin
&OUTC6 Ol
113. 5-127*
(d Oi'.1j'/J»-
a K'/,%)
3.6
(a cc»i%)
3-5. 3-1 11. 5
(0. ci-i?V-
O.OI23Vc)
hO.~i-.r 5 da5
s
u;h'.:.- ta tjto
C7,anlc
For broiler chlcVsns; with-
draw 6 days bdcro
slaughter.
For replacement eWcVeas;
wltfn;raw 5
da7J ^J.'cro
slwjhter; M soli; :ource
of organic axsealc; as
follows:
lodlcntlor.j for ass
Oro'.'th promotioo Md
icvd c£fic!jncy; Im-
provlnj pl^menta-
lion.
Qrowtb promotion
6.
id fw
d ei'.lcl»r.cy:
Unrrovlr.s pl™in?n-
t.i:icn;
a
xcidl
Do.
\ Orovtb
i r
d
1
Mi C:
pras-cctloa of
osls. ,
^roi^".Oi^03 IU3^
lci'r.cv; 1m-
'rovl.-ij pljnwutatlor
CTClopmeat of active
nmu
ilty to
" cocdd (oils.
Growing con-
ditions
Severe exposure
to cocddlosls.
Moderate ex-
posure to coo-
cldlosls.
Ellsht etposuro
to coccidiosls.
Arncantofniasroliumla
Ijyase grou
Up toB
n&jiisof
sje
Orawptr
(on
113.8
(0.0128%)
72. 6-113. i.
(0 &"a
fed to blrds_
\voek5 o?r.:j
doys beior'j
sole soorc-a
V over 14
fi; withdraw
5l3'igh'.c.-; a.
of on;cmic
S
food tor birds,
s
Overs
WEt-is of
OJ0
Orami pir
ten
M.3-1I3.S
^3~"ll3. 5
(0/£-4%—
o. bi:>vi)
3S. 3-113. 3
(O.CCH%-
0.012^)
nuftH nnv.nrtHftn «n/l
fsed cfiic!ency;lm.
r
rovln
" uknjL'nLstlon
prevention and coatr
o
f COC'
t(iiCSi3.
Deve'opinent of active
Immunity tococddl-
osis; growth promo-
tion nacl .'ted e;7J-
cienc>
; Improving
pigmentaticn.
CJ^enic; as follows:
Orowlnj conditions EUrtar
8*jyarg expos
Light to mcx
eipo^uro.
mtion
Qromt jar
t
jre...-
on
113.J.
(a 0125,2):
eret« 75. *-H3.ff.
(aCC83%-
a 012J13,
Oro»'cr
ration
Orqnt per
73.
(0.
0.
(on
4-113.8
0 'K'V
012.5-7,)
38. 3-Ti. 4
(0 WJA
a oaw%)
* In § 121.253(c), the words "under 5 1/2 weeks of age nor" are
deleted from item 1.6 under "Limitations" itm the table.
•* i ^
-O..LU-
-------
121.233)
A'Dtnilment published in Federal Register:
* lebruary 17s
33 F.R. 3112
SUBPAHT C--FC9D ADDITIVES
Reraow. old p^.;e 39,2 and
n-";v page in 'yxar reprint*
39.2
this
Ansintuc ACID IN COHPLE-TH CHICEIN AND TonKEt FEW—Conttoed
Principal
Ingredient
Orams per
tea
Combined
with—
hains per
too.
Limitations
Idfiatlona for uso
l.TArsanillcacid...
L8 Arsanlllc
odd..
O. 1.1, 1.2,
1.3, 1.4,1.5
or 1,0.
6. I.I, 1.1.
1.3 or 1.4..
C. 1.8 or 1.6.
d. 1.5 or 1.6.
e. 1.1, 1.5,or
. 1.8.
M (0.01%)
eo
(a 01%)
Amprolluiii.
72. C-113. 6
(0. COS%)
0.0125%)
BuQulnolaio..
75
For broiler chickens;
withdraw 5 Jays
before slaughter;..
snlo
on fro of organic
Arsenic.
Jforbroiler chicieiu;
withdraw 5 dap beloro
sKiu£ht«r; do not fe«l to
hens; u aolo
of organic arsoolc.
Orsrth pmraotfon
'.nd food efflclincy;
iiliTiroviii" plgincu-
Ltl!oa; prevention
.dfcocc:ilioslj cauxxl
•V;i.'. Untlla only.
s MI eJdrhthe prevention
of cocdflS'i ir.in«u1iil promotion and '
ferktfllcieucy; irnprov-
in^^ipnent.'ttioo; pre-
veuirin of coccl'llt>r>ls.
Gro»!t'.prorBotlon ajid
forVl'.iricit.'ncy; im-
prouti: pii;^ient;it!oD;
p.-csai.icin and control
ofcotidiosu.
'.d) To assure safe use, the label and
labeling of the additive, any combina-
tion of additives, and any feed additive'
supplement, feed additive concentrate,
feed additive premix, or co.mplete feed
prepared therefrom shall bear, in ad-
dition to the other information required
by the net, the following:
(1) The name of the additive or addi-
tives.
(2> A statement of the quantity or
quxp.'.l'.^'s .:•. v\;:ne<1 (.herein.
'••' S'.'.'.i'ji-.i'.?. cl.cc'.Iorvs and v/aroinss
for u.v:.
>.<.•' Section "U'.'li.iS c.iinljllihes tii«
l,^k:r:,in fu- ;':.•(•:•>.{ -jl r!>r :>.d:iu:vo
In 'or-,; ;or ;:.i::-.:.i:i con.sumpll'::i.
-117-
-------
Reissued July '29, 1964
-"•*••*
L-
7
§ 121 o.254
SUDPART C-FOOi! ADDITlViiS—Pa-n 40
Remove old page 40 and insert this
new page ;ii your reprint. °
121.254 Sodium arsanilale.
Sodium srsanilate may be safely used
In animal feed when Incorporated there-
in in accordance with the following
conditions.
(a) The additive Is the ' chemical
sodium p-aminobenienearsonate (CsHi-
AsNNaO,) conforming to the following
specifications (on the dry basis):
(i) The additive contains not less
than 30.87 percent and not more than
31.65 percent of arsenic (Aa), equivalent
to not less than 98.5 percent and not
more than 101 percent of CuHiAsIfNaOj.
(11) The additive contains not more
than 0.025 percent arsenic as inorganic
arsenite. calculated as AsaO: -and not
more than 0.05 percent arsenic,as inor-
ganic arsenate, calculated as AsO< = .
(b) Permitted use of sodium arsanll-
ate alone and with certain other addi-
tives is described in tabular form In
this section and this table is to be read
as follows:
(1) The numbered line items establish
the required limitations and Indications
for use of the principal ingredient as
the medicament alone or with an addi-
tional ingredient added for Increased
effectiveness.
(2) The lettered line items establish
the required limitatons and Indications
for use of seconds-y ingredients that
may be added to tlicindlcated principal
ingredient. Where principal and sec-
ondary ingredients lave been mixed, the
applicable limitations and indications
for use from both ;tie numbered items
and lettered items apply. If duplicate
limitations occur, tlese may be appro-
priately combined.
(3) Permitted combinations of prin-
cipal Ingredient andsecondary insredi-
ents are Individudly listed. Unless
specifically provided by the regulations,
the principal ingreh'ent may not be
mixed with two or more secondary in-
gredients.
(4) Where cross-Eferences specify a
particular table anditem number of on-
other section, use of only the principal
ingredient of the nunbered item is au-
thorized thereby.
(5) The term "pihcipal Ingredient"
as used in this sectiorrefers to the add!-'
tive named in the healing of this section
and is not intended.tximply that the in-
gredient Is of a grerter value than any
other additives naniet in this section.
(c) It is used or intended for use in
feeds, as follows:
-113-
-------
-jh-d in i\-.vvil Ro
* Octobor 3.1, i;07: 32 F.R. 15012
SU13PAS1 C---FCOD /J)DI1TVP;:> -P.^a 40,1
Remove. old page 40.1 and inocrt thio
new pa^e in your r-rprlut ,
SODIUM ARSAMI.A7E IN COMPLETE CHXKEN AND TURKEY FL'ED
Principal Ingredient drums per
ton
1. &jtam ursanil-
QM. .
CO (0.01%)
t
Cc^bttTM Onjjps per
with— ton
.17~:
Llmiuuiojis
For cl.i;kt'n.i ond tur-
keys; witlidrmv5(hiys
bcforp slJtishtP".*.
Indications for use
UrowUi jAy^mprl/jn and
fmt ejli«l''>tiN
j 121.207, table, items
1. 3. 3. . '
5121J2IO.
items 1
'5121 .*:;
Nil. 2, 3.'
table 1
i. 2.i.'3.r, 4.1.
r V.if '
tablo. Items'
?
(d) To assure safe use, the label and
labeling of the additive, any combina-
tion of additives, and any feed additive
supplement, feed additive concentrate,
feed additive premlx, or complete feed
prepared therefrom shall bear, in ad-
dition to the other informatloij required
by the act, the following:
(1) The name of the additive or addi-
tives.'
(2) A statement of the quantity or
quantities contained therein.
(3) Adequate directions and warnings
for use.
-------
or -I lit: p
»:«ior 25,
.vrod In Fc'Ju
1964j 29 F,R.
1':^~\f*-t "^(^"^r- CTrf1^ W': r* T^/^OTv
i.^ji-Jtorr oulu A-lx W--J.-GOU
15815 Insert thta iv:::/ ).-.".30 in your roorinc,
§ 121.262 3.Nitro.4-Lydros7plien7lar-
oonic acid.
S-Nltro-l-hydroxyphenylarsonlc acid
may be safely-used In onlmal feed when
incorporated therein Ln accordance with
the following conditions:
(a) The additive Li the chemical
^-hydrorcy-S-nitrobenzcne srconlc- acid
• CtHsAsNOj, conforming to tha foUowias
specifications, on a dry b?.sis:
(1) TTis additive contains not lc;a
than 23.0 percent and not more than
28.7 percent arsenic, equivalent to not
less than 03.3 percent and not more than'
100.8 percent of CtHjAsNGj.
(2) The additive contains not more
than 0.025 percent arcsnlc as Inorganic
araenlte, calculated aa AI.-OJ, and not
more th?Ji 0.05 percent arconic aj Inor-
ganic arscmite, crJculatcd as AcO»=.
-------
(§ 121.262)
Amendment published in federal Register; SUfiPART C--FOOD ADDITIVES--Page. 48
Remove oid j^ngc ^8 an& insert this new
I'^c in. your reprint.
TABLE I—3-N:T;«i-4-llvi!u>XYi'neniLAii»ONic Acn IN CojrmTK Ui VKKN *':ND TunntT KEKD
* March 31, 1971; 36 F.K, 5906
Principal
Ingredient
1.1 3-Nltro-4-hy-
droxyphenyl-
arsonic acid .
1.23-Nitrc-4-hy.
droxyiihcnyl-
nrfonic acid.
1.8 3-N!trc~4-by-
droiypbenyl-
arsonic r.cla.
1.4 3-Nltro-4-hy-
droiyphenyl-
orsonlcacla.
1.8 S-Nltro-4-by-
droiyphonyl-
ersonlcacla.
1 .8 3-Nitro-4-
bydroiy-
phenyl-
arsonlc
acid.
1.7 3-NltnM-
hydroiy-
pneaylarsonlc
add.
IS 3-Nltro-4-
hyd.-oiy-
ii:j.%-
o. 005%:
45.4
(0. uos7i)
22.7-45.4
(0. 0025%-
0. 005%)
27.7-45.4
(0. 0025%-
0. 005%)
22.7-45.4
(0. 0025%-
0. 005%)
22.7-45.4
(0.0025%-
O.OC5%)
22.7-45.4
(0.0015%-
0.005%)
22. 7-45. 4
(0. Ci.'.V"-
i). ' •). '; i
Combined with—
3,5-Dinilrol'enza-
niiiiu *
SuJfuiiitran
Zo alecs
do
Qrarys per
ton
rVl-
(0. 02.5%)
•v^o
(0. 03%)
113.6
(0. 0125%)
38.3-113.5
(0. 004%-
a 0125%)
Limitations
For chickens; with-
draw 5 (:l(in.'?l:ni'.i.'h-
ti-r; (rum f'ji'il nil<(U-
Livu priMni-xes cuni-
luinnic nut inoiv
tluiii V.r> ]n'rci'.nt 3:,.-ri-
ilinitro trii7nitU'.!i!'..
3o pcrrrnt siiHnn^-
tr:iit. :ui'l 5; pi-rv'i'i.tt
.1-iiil.r
i
Orami '>.-T it/.
sure.. - - . 'j.'S.
>derato cipos
1S1.6
(0.02%)
227
(0.025%)
227
(0.025%)
113.5-227
(o. or^v
0. OWi)
1 13. .V7--1-
(0.1)11'.-;.-
'j. 10' ' )
(•i. •/.• ; " •
(0. Oli*/i
ure . 75. 4r-!n3.
(0. OCC3%
0. OE.?5%
For chickens; not tm
bo fed to laying
chickens; withdnruw
6 days before slaugh-
ter; from feed ad 11-
tlvo premiies con-
taining not more:
than 20 percant
sulfanitran, 25 pt'-r-
centailomirta, ar.'ii2.5
percent to S.o poj-
cent 3-nitro-4-hy-
droi/phenyl.ir-
sonlc acid; as sol's
source of organic
^ arsenic.
For broiler chickens
oniyj
withdraw 5 days b°!3ore
sliuj>htp.r;cj solei^nrc*
of organic oraenlc, ^
For broi er chlctcrms;
for rcpla.vmt'ni:
chicki as '.rn-T" sinniu-
nlly to coccidloafo
Is not dosirsd;
withdraw 5 days
before sl'iusrhur,; as
so!-- 30 jre<: of o.-^-iiiii:
nrs.'nio.
For broiler clncki-rs^;
(or rr;/ ..•I'jn.-n L
i - '.;''' ••: n. •'lf..T, \i<
•<•.••• %/:.'' • •'. • r : -i:-.'
.-;:i.-n,.
i Oramt p:r /on
) 75. 4-113. S
(0. 0023%-
0. 0125%)
S 36. 3-75. 4
(0. 004%-
0. OCSi%)
Asana'.dlnt ho pre-
vention of coccidiosls
caused by E. l:n.
tlla, K. ntccJrir,
and F.. oijrra/rna.'
growth promotion
and feed efficiency;
Improving pig-
mentation.
Aid In the prevention
of coccld-losls caused
by E. Imt'.la sud K.
TifC&Tif.: Kro'.vth pro-
motlin ami foed of-
flc'.eocy; ImprovlnR
pigmentation.
Prevention of cocci-
diosis; growth
promotion and
fo-jd eili^it-ncy;
lmpfovln« pig-
mentation.
Do.
esliuoi. ar- cl-Mc'-cd tj LLo
..: /:,. ..U
e :r.l.c:3 (a).
-121-
-------
(3 J21.262)
Ame.'idment published in Fade, a! Register'
* May 20, 1970; 35 F.». 7734
* * June 2J, 1970; 33 F.?x, 10146
SUBPART C—FOOD ADDITIVES --Page 48.1
R.er.:ove ol.$ page 48.1 and insert this
new page in your reprint.-
l— J-N"nao-4-ETnaoir33>rn.iR.'!Osrfl Aon in Coaruiz Ciunr::*
Frsr>— Continued
Principal
Ingredient
l.« 3-Mtro-4-
liydrojy-
pnenyl-
arsonlc odd.
*
U03-Nltrc~»-I)y-
clroiypbonyl-
ursomc acid.
Ill 3-Nltro-4"
hydioiy-
pnenyl-
anoolo
odd.
1.12 >-Nltro-«-
hydroiyphcnyl-
tsrsonli- ocid.
W3 3-Nltro-4-
hydroxyphp.nyl
arsonic acid.
Oraras pw
ton
22. 7-45. 4
(U. 0015%-
o. KaK'i
22. 7-45. «
'or replacement chlcicias
intendixl for use as
caged layc
do not f«
over 18 wi
Over Sweets
of ago
Crami j>tr
ton
30.3-113.5
(0.004%-
0.0125%)
38.3-113.5
(0.004%-
0. 0125%)
30.3-113.5
(0. 004%-
0. 0125%)
As an aid In the pre-
vention of coccldioslj
caused by E. tmlla.
E, maifniQ, E. f.fico-
/rlr, ai
id K. acfrm-
/irw; growth promo-
tion ar
d feed
efficiency; Improving
pigmentation.
rowth pro
m.'ittrtn anrt
feed elficloncy; Im-
proving pigmenta-
tion; aid
n the
prevention of coccl-
dlosts cnusod by E.
trntlla, E
acerrttllna
K. brunc:
E. mltall.
riicc.'rtr, S.
, E. maibna.
1, and
Aid In tho prevention
of cotcldios'-J caused
rs; by E. tcrk-Ua, K.
1 tochlckerai
•cks of age;
withdraw 5 d iys tc/ora
alaughter;
of organic
as 3ole sourn*
arr-enlc.
— » "^~^ *"
rnrJi-t ^"l"'1""' 57. 2 For hrolle.- chickms-
(n-00j/r) (0. 0037c) do not f^d lo
•"^•fc-
•ft 1.H 3-Nltro-f-hydroiy-
phenylanonk acid.
—
1
lay
iij? ciiicictns;
withdraw 5 day*
before slushies,
/i ^
*** PI ,~T-.f
source ofor;;iso.
alien ic. « «.
f "
JJ;4 ^'onensLn 110 (13 For bro!!«r ch!cisra;
(U. wj,0) monen- -do no' I^ed lo 1^.; n
olc acid ch!c)c.>nj; crlthttiaw
act
IV- 5 £
Ity). BU
->
sou
IJ'3 Oo.'.x»
«.'iUr; ai sdb>
rrd of ori"inii:
a/soiijc.
niccjrur,
E. maiir
1C. ceerzidina,
fl'3. E. &TU-
tuili, and K. mi'mfi,'
growth promotion
and feed
1 ' 'orovi
(.Ion.
oITiclency;
ig plgrnonta-
i
A? an aid In the
prevention of
ooccki
in.7t.» CJIIKAH
by E. tsr.elia.
K. neczlri;. K.
mirati
;;.
cccrrt;/ir.o, 1\.
maxima, and K.
brunt:
promo
d; growth
tlon an.1 he<\
efficiency; Improving:
pitf'ne
ntrttlon.
1 • - -
Orowt i promotion
g acj Iw..| eiQcliincj;
Unrsrovlr.i; iiinnoiv-
ta:ion
; M jn aid In
th.i prevention of
C'XV.'j
by /•:
t/n/U"
piii?"
r-us c;'.turd
nc:i:t\i E.
. K. a«rruJiru,
iT'/-''. m.'ul,',in.
-122-
-------
/,jn:;"idi''iant pvb ]!:•'•"'::d in Federal.
* May 27, 1971; 36 i- .R. 96 2 o
SUSP AST C--FOOD ADDITIVES --?;'.cf- 48 ,2
Remove o;.lc! page 48.2 and insert fchlo
new pagi' in. your reprint.
L!; 1—3 Niiiic-' llvytoiYFii!,' •.•u.inso-.'h' Acii> ix
w.-.Tn CIIICXES *:«) TURKEY FKEP— Continued
Principal
Ingredient
1.153-NTltrc-l-
hydroJy-
phonyl-
arsonlc acid.
l.I63-Nltro-4-
bydroiy-
pnenyl-
arsonlc acid.
*1.17 3-Nitrc~4-
hydroiy-
phenyl-
'arsonlc acid.
tt. 1.1,1.3,1.4
h. I.l
o.l.l
d. LI
e. 1.1
Grams
per ton
2-.'. 7
(0.00!5%)
«.4
(0. 003%)
4.m
(a 005%)
22.7-45. 4
22.7-45.4
2J.7-15.4
23.7-43.4
22.7-^5.4
Combin?-'! with —
Sul'adimeth-
oilne-l-
ortnctoprlm
Amprollum
Ethopabate .
Llncornycin.
Neaumate
Penicillin.
do
Penlclllln+
atreptomydn.
ChlortetracycUns
do
Grams
per ton
113.5
(0.0125%)
f». I
(0. 0075%)
113 5
(0. 0125%)
3 6
(0.0004%)
2-4
18. 16
(0. 002%)
2.4-50
60-100
14.4-50
10-50
60-200
Limitations
For broiler chitons;
not for It'.yinp.
chickens; diwin-
tinue ILSC of :nul-
cated feed 5-lhya
before sliagliar; as
solo source of
organic arsen'lj.
For floor-mlspd
broiler chiclcms;
not for laying
chickens; as ilico-
mycln hydro-
chloride mondiy-
drate; wltbdrav 5
days before
slaughter; as aie
source of ampnllum
and organic anifinlc.
Kor broiler chlotins
only; food coniinu-
ously as sole rrt.'lon
throughout thn
starting period; "
withdraw 5 dajs.
before slaughtra;; 'is
sole source of o;;unlc
-arsenic.
As procatao pojtcllllr
5 121.2JS, tabb'.
item 3.1.
As procaine poriclllli
andstreptomscla
sultete.
As chlortetracyillnQ
hydrochloridu
{ 121.208, tablall.
Items 2, fl.
Indications for uso
As an aid In the pre-
vention of coccMlosU
Musod by all
Elmcrla S|>;cles
known to be
pathogenic to
chickens, mmely,
E. tcnclla. K.
nccolrix.Fj. acer-
eulina, E. bruntttl,
E. micali. and E.
mazima and bacterial
Injections duo to
//. gallinarurn
(InftKtlous coryza)
and E. cod', growth
promotion and fe-ed
efficiency; Improving
pigmentation.
For increase In rate
of weight gain;
Improved feed
efficiency and pig-
mentation; as an
aid In the prevention
of coccldios'.s In
floor-raised broiler
chickens.
An aid in the prevention
of coccMlos'j caus'Jd by
E. Unell-i, E. titM.'rtr,
E. acerrvlina, E. maxima,
E. brvnttti, and £•'.
mire.'/ In brollej
chickens; growth
promotion and feed
efficiency; for Improving
•piirmentatlon. .
Growth promotion and
feod ediclcncy.
9 121. 25v table 1
Item 3.1.
feed efficiency.
Do.
} 121.203 table 1
Items i.6.
-123-
-------
Araeudmc.-.1; publinhcd in Fcue/ul Resistor: SUMi^T C--FOOD Ab.TrirVES--Page 49
* July 9, 1970; 35 F.K.. 11.01.9 Remove old! page ur, and insert thiri
new page in your reprint.
TABLE l--'!.N!Tv.O"!-nYr.'.oxvFUBSTL.\!isoNic ' CID ix d K-LITE L.PICKUK *:•': TVi'RrT Fxto--Con'.lr;ucJ
Principal Gr.viu J Cumblr.ed with— Gi •-•>, : Limitations
ingredient • p-.r tun P?r ton ,
t. !,i, 1.3, >.<
8. LI ...
h 1 1
1. 1 1 1.3, 1 4. 1.8
J. 1.1
* *-U1
2.1 3-NHro-t-hy-
droiyphenyl-
tsrsonlc acid.
3.J 3-NltrM-
hydroxy-
phenylarjonlc
tcld.
t. 2.1
b. 2.1
e, S.l
4. 2.1
e. 2.1
f. J.l
e. 2.1
h. 2.1
L 2.1
J. 2.1
k. 2.1
22.7-4;-. 4
22. 7-ij. «
22.7-15.4
22. 7-15. «
22. 7-45. 4
Sac"
22. 7-45. 4 n
(0. 0024%-
0.005%)
22.7-)5.4
(0. 002i%-
0. 005%)
22-7-45. 4
22.7-45.4
22. ?-«. 4
22. 7-45. 1
22.7-45.4
22. 7-S5. 4
22. 7-«S. 4
22. 7-W. 4
22. 7-45.4
23.7-44.4
2L7-i5.«
?tinlcir.l!l4-
bacltracln.
. ...do
Bacltrsdn „
do
OiytetracycUae...
tracln
o
Zoal&ne
Panldllln
do
PerJclllin+
streptomycin.
ChlorUjtrscyclIn^.
do
Fea!c!Hln+
bacltiscln.
do
Bicltracin
to
Ozytatrscjctoo...
3. 6-M
60-100
60-100
4-50
50-100
4 Tor br
03 bs
dlsa
113.5-170.3
(0. 01257n-
0.01370)
2.4-60
40-100
li.4-iO
10-60
60-200
8.8-50
W-IM
4-M
80-100
50-100
113.4-227
As proc.'Uiic p<:n!t"iin
plus baci!r:iclf),
or.clfriicln nitHhy'^-
eua divUlcylatP.
marigancso h^^itrj-
cln. or ilnc bad-
tracln.
I 131.2.1X Uble 1.
Ileni52.2, 5.2;
{ 121.233. toblo 1,
Items 2.2. 5.2;
; 121.032, table 1,
Items 2.2. 5.2.
i 121.232. tublo 1,
(terns 2.1. 5.1:
i 121.233, table 1,
Items 2.1, 5.1;
} 121.252, table 1,
It*ros2.1, 5.1.
As bacltracln, bacl-
tracln iTicthyleno
dls.illcylate, line
bacitructn. or msa-
ganese bacUracio,
{ 121.251, toblo 1,
item 6. i
oMtrctilckonj; JSro
cltnvrln methylon* ;j fe
Icylnto. il
For turkeys; with-
draw 5 days before*
alaUfehter; as sole
source of organic
&rs«nlc.
For turkeys grownibr
meat purposes odli;
withdraw 5 days tor-
fore slaughter; as
cole sourcs of or-
(janle arsenic.
As procalue penlcUlfc.
I 121.256, table 1,
item 4.1.
As procslr.c pep.lcllla
and streptomydis
sulfaW.
As chlortetracydUB.
hydrocWc.-ida.
1 121.203. tab'.e 1,
Items 3, 7.
Not less than 0.6 ga.
of penicillin Dorlca
than 3.0 gm. of bad-
• trac'.n; as procnlnB
penicillin plus brf-
tracln, bacltracln
methy'.ene dlis.ll-
cylato, mangojic^s
bacltracln, or rlnr
bscltrictn.
i 121. X-J, labial,
Itea 4.2.
Aa b-icUrstlu, b^icl-
trocSa c'.5'.byl-!ss
dJ;-sUcyi»'«, iniD;>
nj« bacltricln, ca
il-'ic bicliracla.
I 121.203. table 1,
Item 3.1; 5 121.233,,
tabij 1, Itam 3,1,
1 121.25'J, table I,
Itzin 3.1.
H21.251, table 1,
1U3! 3.
I 121.210, tabla 1,
lUci 1.1.
Indlcatloiu for ax
Growth promotion and
feed elllcli;ncy.
5 121.212, table 1,
Items 22, 5.2;
5 121.233, table 1,
Items 2,2. 5.2;
i 121.252, table 1,
Hem' 2. 2. 5.2.
[ 1S1.232, Libia 1,
Itorns2.l, 5.1:
4 121.233, table 1,
Items 2.1, 5.1:
{ 121.252, tabis 1,
tt«nu2.1, 6.1.
Growth promotion
and feed efficiency.
1 121.251, table 1, Item
0.
wth promotion and
'.d o.liciency. ^.
Growth promotion and
feed eJTlctency; Im-
proving pigmenta-
tion.
Growth promotion and
fe«d eElctency; Im-
provlns plsir.enta-
tlon; prevention and
control of coccldlosli
Growth promotion add
feed erncleocy.
! 121.240, table 1,
Itom 4.1.
Growth promotion and
feed efficiency.
Do.
J 121.208, table 1,
Items 3. 7.
Qrowthpromotlon and
fe«d eificlency.
} 121.2M, tab'.e 1,
Item 4.2.
Gro-:.'tb crozioMon and
fasd e^'clmcy.
5121.232. tablsl,
IWra 3.1: } 121. 2i3,
taal3 1, 1'.i;ci3.1;
} 121.112, t«Vl» 1,
lM:n 3.1. .
( 131. Ml, table 1,
Itsm 3.
{121.210, Ublsl,
Iteia 1.1.
(d) To osrore safe me, the label and by the act, the 1
labeling of the additives, any corr.binr.-
tlon oJ addltlvis, nr.d s.ny ^c-3d additive
feed additive prjmia;. c~ co!r.-;h'-e f;.:d
prep.-\T;ti ii>f-r:-/rcrr :'TvU tear. In a rill -
tion to lha ci>.:r Li-'cnr.i:;l.in rcquirt-d
(1) The narae of -de additive or adcll-
Urea.
(2) A st^teaien4; af tho quantity or
qujntitlo.} contained therein.
(3) Adequate dirscllorj and
for iu;.
-124-
-------
(S 120.3)
Amendment published HM Federal Register:
* December 3, 1970; 35 F.R. 1x570
sirB?/:ivr A--JESTICIDS REGULATIONS--Pace 3
Remove old «::3£ 3 auU insert this
new page in your reprint.
(?) Where tolerances are established
In terms of tnor;nuilc bromide r:siducs
only from usa of ors^nic bromide
fumijanto on ra\v agricultural commodi-
ties, such tolerances are sufacisut to pro-
tsct the public health and no r.dtiltional
concurrent tolerances for the organic
pesticide chemicals from such use are
necessary. This conclusion is based on
evidence of the dissipation of the organic
pesticide or its conversion to inorganic
bromide residues in the food when'ready
to eat.
(d) (1) Where tolerances are estab-
lished for both calcium cyanide and
hydrogen cyanide on the same raw
"agricultural tommodity, the total amount
of such pesticides shall not yield more
residue than that permitted by the
larger of the two tolerances, calculated
as hydrogen cyanide.
(2) Where tolerances Hre established
for residues of both O,O-dlethyl S-[2-
(ethylthlo) ethyl] phosphorodithioate
and demeton (a mixture of O,O-dlcthyl
O-(and S-H2-(ethylthlo) ethyl] phos-
phorothloates) on the same raw agri-
cultural commodity, the total amount of
such pesticides shall not yield more resi-
due than that permitted by the larger
Of the two tolerances, calculated as
demeton.
(3) Where tolerances are established
for both terpene polychlorinates (chlori-
nated mixture of camphene, pinene, and
related terpenes, containing 65-66 per-
cent chlorine) and toxaphene (chlori-
nated camphene containing 67-69 per-
cent chlorine) on the same raw agricul-
tural commodities, the total amount of
such' pesticides shall not yield more resi-
due than that permitted by the larger of
the two tolerances, calculated as a
chlorinated terpene of molecular v/eJght
393.8 containing 67 percent chlorine.
*<4) Where a tolerance is established
for mere than cno pesticide containing
arsenic found In, or on a raw ajricultural
commodity, tha total amount of such
pesticide shall not exceed the hishest
established tolerance calculated as
(5) Where tolerances are established
for more than one member of the class
of dithiocarbamates listed In paragraph
(e) (3) of this section on the same raw
agricultural commodity, the total resi-
due of such pesticides shall not exceed,
that permitted by the highest tolerance
established for any one member of the
clr.£j, calculated as zinc ethyleneblsdl-
thlocarbomate.
(6) Where tolerances are established
•c- r '. ' •-.:•: v •.•'•. T " S-Tr'.i1:1:?; ".':."-
such pesticides ETUI! not yieM more
residue than that 'prmitted oy the
hi slier of the two tcfcv-.nces, calculated
as S^S/S-trlbulyl pbr.phorotrithloato.
(c) Itcc2pt as rsotdiin subparacr^plis
(1) arid (2) of this p.irajraph, where
residues from tvro 'cr moro chemicals
in the came clr.rj c,rappc-::nt in or on a
raw agricultural cc^irtcuiiy tho tolerance
for the total of such rclc'.usa shall b? the
same as that for the chrjalcal havinj
too lowest nuir.srlcrd tolcr.-Jico in this
cla?s, unle^ rv fc\ab2r toliranca Icval 13
epccLQc-diy pro7id:d icr the combined
residues by a rc3Ubtl.cn in this port.
(1) Where residues Ircm t~fo or more
chemicals in the ciinr clacs ara pr«.:ant
in or on a raw ajriotiiural commodity-
and there are nviilila methods that
penait quantitative {J^tsrralnatlon of
each residue, the Quantity of combined
re::!du£3 that are vrt£iirx the tolerance
may' bo' det-ermtaed as foUows:
(1) Determine tits quantity of each
residue prc;snt.
(11) Divide tha qrrutity of each resi-
due by the tolorancs Jtiat would epply
if it occurred alone, ani multiply by 100
to determine tha percoita^e of the per-
mitted amount of refills precsnt.
(lii) Add the percsifcvjca so obtained
for all residuea prepare;
(iv) Thi siim cf tbepsrcentajrca shall
not exceed ICO percsi;.
(2) Where residuaSrora two or more
chemicals in tha c.i;ne cb.sa are pre;-mt
in or on a raw a^rlcillural commcclifcy
and there are avaUrffla methods that
permit quantitative ^terminations of
one or more, but not &\ of ths residues,
the amounts of such rc!du33 as may bo
determinable shall ba-fcuucted from tha
total amount of rcjiduia pr;-ent ar;d the
remainder eh all have tie coztio tolsrancs
as that for the cbiraicd'havlzsj ths low-
est numerical toI=iT^2j in that clr.ii.
The quantity 01 compiled reslduca that
are v/ithin the tdararae may bj ditor-
mined as follows:
(1) Determine the fliontity of each
determinable residue pcessnt.
(11) Deduct the emomts of such resi-
dues from the tot^i r.nount of rsddues
present and consider iffie remainder to
have the same tolerance as that for the
chemical having the )bwest numerical
tolerance in that cl-isa.
(ill) Divide ths quaxaty of each deter-
mlnable residue by tie tolerance thnt
wculd apply if it occumd alcne aid the
quantity of the rer.ainhj residue by ths
tolerr.nc-j for th; ch?nical ha-.-lr.T ths
UJ
DT
•f *
fell
ai < S
S: 5? a
^3 g <
< t- e
lu r5 s
?§
_l O
< u.
LU
z
tr.'.".." - : ;.i o; i,.'. ; •;.-..• ..... ..-.. —-
tu.-.l C3~.T.c<.U"y, tha Vito.l amount of
present.
-------
CHAPTER VI
THE TOXICOI.nGY OF ARSESE
Although the less toxic arsenicals have had a therapeutic use for over
2,000 years, the toxic nature of the soluble inorginic compounds has
been known and exploited for much longer. Industrial applications for
arsenic compounds have increased the total of the tloxic experiences but
it was not until the 20th century that the fundameital mechanisms of
the action of arsenic were beginning to be brought to light. In the
past half century, first stimulated by the interesLt in the mode of action
of the organic arsenical drugs used in the treatmeit of syphilis then
by the need to combat the possible use of offensive arsenical warfare
agents by discovering effective antidotes, a great deal has come to be
known about the action of arsenic on biological systems (Buchanan, 1962).
VI. A. Absorption - Systemic poisoning has been produced by the absorption
of. arsenic compounds from the lungs, the gastrointestinal tract, and across
the skin.
VI. A.I. Oral Absorption - The degree of absorption from the gastrointestinal
tract and the toxicity of the ingested arsenical is closely related to the
.'solubility at the pH of the stomach and the intestonal tract. Arsenic sulfides,
found in ores, are very insoluble and are not toxic.. Elemental arsenic is
considered by most authorities to be nonpoisonous aid after ingestion, appears
to pass through the alimentary tract largely unchained, though it is possible
that a small amount may be changed info the irritate trioxide (Buchanan, 1962).
Buchanan (1962) states that arsenic trioxide is absirbed across the gastro-
intestinal tract and that absorption is more rapid Jb'f the oxide is in finely
divided form. Hox^ever, Harrison, et_ _al. (1958), in comparing the toxicities
of the crude arsenic trioxide and pure arsenic triocide, found the pure
compound to be more toxic than the crude form. The particle size distribution
of the two samples indicated that the pure arsenic ttrioxide contained many
more large particles than the crude white arsenic.
The absorption of the arsenates is probably similar to the corresponding
phosphate compound but no quantitative information iis available (Clarkson
and Distefano, 1971).
VI. 2. Dermal Absorption - The percutaneous absorption of arsenicals
resulting in systemic toxicity is generally not considered important
although poisonings have been reported' by this route. Ars'enic may be
absorbed through the skin when it is applied in oinlments or lotions.
The soluble arsenic compounds are readily absorbed Team all mucous membranes,
including the lung surfaces, at a rate and to an extent dependent upon the
form in which they are ingested (Stewart and Stol-ian, 1960).
-127-
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VI. 3. Respiratory Absorption - Approximately 75 pec cent of inhaled
arsenic trioxide is retained in the lungs (CJ.arkson and Distefauo, 1971).
Ciliary movement may remove inhaled ar^anic from the bronchial passages
and introduce them into the alimentary canal. Therefore, some of the •£
effects noted from inhalation exposure may be derived from gastrointestinal
absorption. Rozenshtein (1970) demonstrated that as little as 4 ug/m^ of
arsenic trioxide in the inspired air has untoward effects on the unconditioned
feflexes and cholinesterase levels in rats. All levels of 1 ug/m^ was shown to
have no effect. Benko (1970) demonstrated systemic absorption in mice from
the inhalation exposure to 180 ug/m^ arsenic triox'ii'e dust. Arsine, which
is a gas, may readily be absorbed through the lungs and produces very toxic
effects.
VLB. Distribution - Utilizing radiqlabeled arsendee, Lanz, jet_ _al. (1950),
demonstrated that 95 to 99 percent of the arsenic ol whole blood is combined
with the globin of hemoglobin in the erythrocytes. This study was carried
out in rats and confirms the findings of Hunter, _et^_al- (1942). However,
this does not hold true for other animals and humans (Hunter, _et _ajL. , 1942).
Almost all of the arsenic of serum is bound to the serum proteins (Stewart
'and Stollman, 1960).
After acute exposure arsenic is deposited in descending order in the liver,
kidney, intestine, spleen, and lung (Clarkson and Diistefano, 1971). Arsenic
appears in the hair about two weeks after the first exposure where it is
/bound to the -SH linkage of keratin. Chronic exposure leads to accumulation
in hair, bone, and skin. Arsenic may be found in h'dgh concentrations in the
hair years after cessation of exposure and after most of the metal has been
removed from the soft tissues (Clarkson and Distefaro, 1971).
Apparently arsenic levels do not remain high in tissues after the cessation
of arsenic intake. Inorganic arsenic fed to cows raised the arsenic levels
of the liver and kidney during an 8 week'feeding peiiod, but 15 days after
the last feeding the levels returned to normal (Peqples, 1962; 1964).
Arsenic fed in low levels (5 ppm) to mice failed to accumulate in the tissues.
At high levels the arsenic content of tissues first increased then declined
(Benko, 1968-70). Schroeder (1968) demonstrated that arsenic accumulated
in the-aortas of rats. In humans who had Salvarsan treatments, the liver
levels of arsenic were found to be normal.
The estimates of the "normal" arsenic content of haiir, nails, and urine
have been made by various investigators and show a treasonable measure of
agreement. Watrous and McCaughey (1945) have quotei. a normal range of
arsenic in the urine of 0.014 to 0.046(mg/l. Buchanan (1962) cites arsenic
values found in human tissues and fluids by Smales and Pate as follows:
Urine 0.013 - 0.33mg/l
Blood 0.09 - 0.50mg/l
Hair 0.5 - 2.1 rjpm
*
Fingernails 0.82 - 3.5,Tpm
Toenails 0.52 - S.S.jpm
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Normal fasting serum level:-: of human males and females range from 3.5 to
7.2 ug of arsenic per .100 i.i!1 . From autopsy samples arsenic levels measured
in ug/100 g in kidney ranged from 2.6 to 3./; liver 3.0 to 3.9; heart 2.4
to 3.7; brain 2.4 to 3.7; lung 1.8 to 2.9; and thigh muscle 3.1 to 5.S
(Kingsley and Schaffert, 1951). # •.
Arsenic passes the blood-brain barrier only slowly.. Brain levels are
.among the lowest in the body. Arsenic in brain tissue, however, is retained
for longer periods than it is in other soft tissues and is associated with
the mesoglial mesenchyma, where it may cause degenerative changes (Clarkson
and Distefano, 1971).
VI. C. Metabolism and Excretion - There is evidence indicating pentavalent
arsenic is reduced in the tissues to the trivalent state. Ehrlich first
advanced this theory to explain the action of pentawalent arsonic acids
which are relatively nontoxic to trypanosomes in vitro but are active in vivo.
In 1923, Voegtlin, ej: jd., demonstrated that although the organic pentavalent
compounds of arsenic were toxic in vivo, the time required for this toxic
action to appear was longer than in the case of triwalent compounds. This
latter theory may not be tenable due to the different mechanism of toxicity
of the two types of compounds.
Winkler (1962) found that arsenic is stored in tissues of rats in the pentavalent
form even when fed as trivalent arsenic. This indicates there may be an
oxidation of trivalent arsenic to the pentavalent state.
• Overby and Frost (1962) and McChesney and Banks (19:62) have demonstrated
that there is no cleavage of organically found arsemic in the body. The
'reverse, the conversion of inorganic arsenic to organically bound arsenic
probably occurs.
Excretion occurs by all physiologic routes - feces, urine, sweat, and milk.
Some volatile arsenic may be exhaled from the lungs. Arsenic is also removed
from the body by the normal loss of hair and skin, .especially in cases of
chronic poisoning. The urine and feces contain most of the excreted arsenic.
In general, the arsenite salts are lost mainly via itSie feces and the arsenates
via the urine. Arsenate excretion is more rapid than arsenite excretion and
probably occurs via the phosphate excretory mechanisms. Approximately 10
days are required to eliminate a single dose of arsenic from the body and
as much as 70 days are needed to eliminate the body Tburden after cessation
of repeated exposure (Sollman, 1957).
The arsenic in the urine is in the inorganic form if elemental arsenic has
been administered. About 10 to 15 percent of the arsenic found in the bile
is in the trivalent form. None of the arsenic is d-etected in the organic
-129-
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form or as a complex or conjugated compound. Since Phe rate of excretion
of arsenic is important in determining toxicity, it lias been found that*
when various arsenicals are administered intravenously to rats the trivalent
sodium arsenite was excreted less readily than the pmtavalent arsenical
(Schreiber and Brouwer,- 1964). The rate of excretioi of pentavalent
arsenic was 41 to 64 percent, found predominantly in the urine. Only 9 to
24 percent of trivalent arsenic was excreted in the urine,
VI. D. The Biochemical Basis for Toxicity - Trivafent arsenic compounds,
inorganic and organic, possess a high affinity of neighboring thiol (SH)
groups. The reactions are of the following type:
R A:
R—As 0 + HS CH -)> ^^S CH + H20
HS CH0
This reaction of arsenic with the essential components? of enzyme systems
is the basis for the toxic action of trivalent arsenir in the body. Exper-
iments with arsenical compounds have shown them to hare a marked effect on
,'a wide range of enzyme systems and the pyruvate oxidiss system, e.g. that
of brain cells, in particular, is greatly inhibited.-ty>low concentrations
of trivalent arsenic compounds (Peters, Sinclair, andThomspon, 1946).
An important means by which trivalent arsenic exerts its poisonous effects
is by the inhibition of pyruvate oxidation which is-tan essential stage of
the mechanism of energy transformation in the, livingaell. Strong support
for this view is provided by the finding an increase in the blood level of
pyruvate in cases of experimental poisoning. This hiss: also been observed
in man (Buchanan, 1962).
A great many other enzyme systems in the body are al» affected by arsenic
in this manner'. D-amino acid oxidase, 2-glutamic acift oxidase, monoamine
oxidase and transaminase are all inhibited by trival-eit arsenic and are
reactivated by glutathione. Urease is highly sensitu/e to trivalent arsenic
as are also choline oxidase, choline dehydrogenase aide glucose oxidase.
All of these enzymes possess thiol groups as a commomfactor in this
inactivation. On the other hand, enzymes not possesahg thiol groups
essential to their activity, are not inactivated by itrivalent arsenic
(Buchanan, 1962).
Unlike trivalent arsenic, the toxicity of pentavalentarsenic is not due to
its binding to thiol (SH) groups. Therefore, the arsnate ion does not
affect enzyme systems in the way the arsenite ion do.es (Johnstone, 1963).
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Rather, the unstable arsenyl icns may replace the cure, stable phospkoryl
ions in a number of systems resulting in the uncoupling of oxidative 'J
phosphorylation. This substitution has been shown to take place in vitro.
Under certain conditions, arsenic can substitute fa; nitrogen in choline
and lecithin. It may be seen, therefore, that the Coxicity of pentavalent
arsenic does not necessarily depend on its reductioi to trivalent arsenic
in the body as postulated by Ehrlich.
VI. E. Toxicity to Laboratory Animals - The absorption, distribution,
metabolism, excretion, and the action of arsenic at cellular and subcellular
levels has previously been discussed. This section will deal with the
toxic effects of arsenic on the intact animal.
VI. E. 1. Acute Toxicity - In general, the inorgmic arsenicals are more
toxic than the organic compounds. Of the inorganic arsenic compounds, the
trivalent compounds are more toxic than the pentavaQent compounds.
Frost (1967) reported that at their respective LD^Q levels of 700, 16, and
0.8 mg/kg, tryparsamide, benzenearsonic acid, and btnaenearsenoxide gave
similar levels of arsenic in rabbit tissues. This has been confirmed in
other-species with other arsenicals. It appears that target enzymes,
although farm more susceptible to trivalent than to pentavalent arsenicals,
bind a similar level of arsenic at the point of dea'.th.
The first and principal symptoms of acute arsenic tocicity are those of
inflammation of the digestive tract. Autopsy rarely shows extensive
corrosion, and the gastroenteritis may be obtained b>; intravenous or sub-
cutaneous administration. This does not exclude all local action, since
some arsenic is excreted into the alimentary canal., but the quantity is
not sufficient to account, for the symptoms. The inflammation is due 'to
the systemic action on the capillaries, which is strongest in the intestines,
regardless of the route of arsenic administration. Capillary paralysis
results in the production of exudation into the conmctive tissue. This
raises the epithelium and causes it to be thrown off in shreds or false
membranes. The exudation is then poured into the,,lunen of the intestine
and largely coagulates. This distention, as well^tha circulatory changes, •<-
causes increased peristalsis and watery diarrhea, lie vessels of the
kidney participate in the capillary dilatation. The glomercular capillaries
are. swollen and fill the capsule; the urine is albuminous and scanty.
Nephritis results.
Table 1 lists the acute LDcQ of various, arsenic compounds.,
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Table 1. Acute Oral Toxicityes of Ar.-.enical Pesticides in Rats
Compound LDrg (mg/kg)
Inorganic
/
Arsenic trioxide 138
Arsenic pentoxide 8
Calcium arsenate 10-100
Paris green (copper acetoarsenite) 20-100
Lead arsenate • 10-100
Sodium arsenite . " 10- 50
Organic
Cacodylic acid 1350
Methanearsonic acids:
Calcium hydrogen salt (CMS) 4000
Ammonium salt (AMA) 749
Disodium salt (DSMA) 2800
Monoammonium salt (MAMA) 750
Monosodium salt (MSMA) 1800
*Gaines (personal communication)
VI. E. 2. Subacute Toxicity - Von Glahn, .et, al_. «L~938) reviewed the
subacute toxicity studies of arsenicals. They state that the earliest
reported experiment was that of Ziegler and Obolonsiy in 1888. In this
experiments small doses of arsenic were administered subcutaneously and
orally to dogs and rabbits. In the rabbits, fatty '.'changes of the liver
cells in the central part of the lobule was observetl after a few days; at
the end of 9 days, shrinking and hyaline degeneration of individual liver
cells, with fragmentation of the nuclei, were presertu After 14 days, in
addition to the fat droplets, there were necroses, iflie necrotic liver
cells having a spongy appearance. In the livers of the rabbits surviving
for 16 days, small groups of swollen liver cells BfilHout nuclei, an
increase of connective tissue and proliferation of bile ducts were found.
One of the rabbits survived for 20 days-. In addition to the alterations
described, many multinucleated cells ware present In the sinusoids.
Another rabbit remained alive for 25 days; degeneration of single hepatic
cells and numerous giant cells were seen. The only Hepatic lesion produced
in dogs following the administration of arsenic in cb.ses from 0.01 to 0.1
gm over a period of 90 days was vascular degeneratloi of liver cells and
fatty degeneration of liver cells and fatty infiltration. The fat was net
-132-
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abundant SB in the liver of rabbits. Podvyssotzfoy, in the same year,
reported somewhat similar results in <*uinea pigs .after subcutaneous
injection of sodium arsenite in. amounts from 0.005 to 0.1 gm. Some of'-'-1 ••
the animals lived but a short time - from 3 to 6 cbys. Necrotic areas
were found in the livers, the connective tissues SHS increased, and
bile ducts were proliferating. Mitoses were presert in fibroblasts
and the epithelium of bile ducts. Later the masses of necrotic liver
cells were sharply delimited, as though sequestrated, and were invaded
by newly formed bile ducts and connective tissue. In the animals whose
period of survival was from 15 to 25 days, the neorotic liver cells had
disappeared for the most part and were replaced by recently formed liver
cells and scar tissue.
Wolkow (cited by Von Glahn, et al. 1938) administered a solution of potas-
sium arsenite by subcutaneous injection to eighteen, rabbits. Doses of
from 0.003 to 0.003 to 0.005 gm of arsenious. acid'«2re well tolerated;
following large doses of from 0.1 to 0.02 gm, the "aiimals lived only a
few days. Nine of the animals were put to death aft varying intervals,
the longest period being 36 days. The other nine rabbits were allowed
to succumb from the effects of the arsenic. In th'is' group the longest
period of survival after the beginning of the experiment was 60 days.
The most constant finding was fatty degeneration of the liver cells and
-Kupffer cells, usually in all parts of the lobule. Areas of necrosis of
liver cells were found as early as the second day "'it five of the animals
given the larger doses. The necroses were situated most often at the
periphery of the lobule; the necrotic cells were frequently swollen, the
cytoplasm was clear and transparent, and their imcQai stained faintly and
were scarcely visible. Leukocytes had collected ait the periphery of
each area of necrosis and had also penetrated betsrean the necrotic cells.
These foci of necrosis were sharply defined from tie surrounding cells.
The stroma remained in the necrotic areas; fine fat droplets were not
conspicuous in the necrotic cells. Mitoses were observed in a few of the
liver cells, and in three of the animals multinucifated liver cells were
found. Inflammatory reactions in the bile ducts srer
-------
were found scattered throughout the lobule but were more frequent cl:se
'to the efferent vein and portal area. The Kupffer cells were well ^
preserved in these areas. After from 3 to 6 weeks, the liver cell layer
bordering tne portal area was irregular. The epithelial cells of the
precapillary bile ducts contained fine droplets of fat, and these ducts
were surrounded by sparse numbers of leukocytes.
VI. E. 3. Chronic Toxicity - Sollmann (1921) studied the effects of
chronically administered daily doses of arsenic trioxide on albino rats.
The doses ranged, in mg/kg/day from 0.0000475 to 0.0049, while the duration
of the studies ranged from 9 to 24 weeks.
It was found that when arsenic trioxide was administered to the rats over
this time period, a distinct retardation of growth and checking of appetite
resulted from small doses; i.e., 0.00005 to 0.0005 Eg/kg; and a more
marked ioss of weight with doses of 0.0015 to 0.005 ,mg/kg. No mortality
was attributable to arsenic trioxide in this experiment.
Utilizing dogs, Joachimoglu (1916) found that more arcsenic was absorbed
from the gastrointestinal tract when increasing doses were given. One
dog, for example, received daily doses of arsenic which were increased
weekly from 10 mg to 400 mg. When the dog received 40 mg of arsenic
irioxide, it excreted 4.58 mg arsenic daily in his urine. When the
dose was increased to 400 mg arsenic daily, it excreted 19.8 mg in the
urine. However, these figures show that the percent of urinary excretion
decreases with increasing oral doses and more is excreted in the feces.
On microscopic examination, the gastrointestinal tract was either normal
or showed degenerative changes. The amount of arsenic absorbed varied
greatly with the animals. Apparently decreased absorption of arsenic by
the gastrointestinal tract is not responsible for the tolerance to
arsenic.
Von Glahn,_e_t_al. (1938), in studying the effects of various diets on the
liver of rabbits, fed ten animals a diet of cabbage only. Pigment was
increased in the liver cells of most of the animals,, and in many of them
large phagocytes containing pigment were present in the sinusoids. The
experiment was repeated three times, but similar changes were not produced.
Thinking that the cabbage fed to the first series of rabbits may have con-
tained an arsenical pesticide, the authors attempts to repeat their results
by feeding low levels of copper arsenate, sodium arsenate, or lead arsenate.
The arsenic level in the diets was adjusted to the arsenic levels found in
their analysis of cabbage (4.32 rag/kg). Copper arsenate w,as administered
at levels of 5.6 mg (1.4 mg arsenic) and 9.3 mg (2.33 mg arsenic); sodium
arsenate was administered at 6.8 mg (.5 mg arsenic); lead arsenate was
administered at 7.2 mg (1.4 mg arsenic) and 12 ing (2.33 mg arsenic).
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Of the forty-six rabbits fed hay and oats and given a daily dose O.L one
of the arsenates only four-9 percent-failed to acquire cirrhosis. Two #
of these four lived only a short time. That the arcenate did, however,
produce damage in the livers of three of these four animals was indicated
by the presence of necrosis. The analyses for the arsenic contents of
the livers of the rabbits that received the arsenates show clearly that
the extent of the damage done was directly related to the arsenic present.
It was determined that arsenic alone was responsible and that the lead
and copper did not play any part in the production of the lesions.
Morris, e_t_ al. (1938) studied the storage of arsenic when low levels of
arsenic were fed as either calcium arsenate or arsenic trioxide. In this
study 215 mg of arsenic per kilogram, of body weight, as either arsenic
trioxide or calcium arsenate, was added to the control diet of albino
rats. The average number of days on the diet was 54 for those on calcium
arsenate and 42 for those on arsenic trioxide. In both the calcium
arsenate and arsenic trioxide groups, large quantities of arsenic were
stored in the various organs. The liver and kidneys store°d by far the
largest amount per gram of dry weight. The livers -of the experimental
animals of the calcium arsenate series were 41 percent larger than those
of the controls, while the brains were 8 percent smaller. Much larger
amounts of arsenic were stored in animals receiving calcium arsenate than
in those receiving arsenic trioxide when fed at the same level.
In a study of the effect of several abnormal trace elements (germanium, tin,
and arsenic) on rats, Schroeder, jet_ _al. (1968) fed .albino rats 5 jug/ml of
sodium arsenite in their drinking water for over two years. Arsenic, in
this experiment, was not found to be carcinogenic. No arsenic keratoses
appeared, and this element was not toxic in terms of growth and life span.
In evaluating the differences between the test and -control animals, the
following criteria were considered: limited growth,, lessened survival and
longevity, elevated serum cholesterol and glucose levels, excess proteinuria,
excess number of tumors, fatty changes in the liver and renal lesions. In
this light, femalerats fed arsenic showed no significant differences from
the controls; .male rats and elevated serum cholesterol levels only. Glucose
levels, however, were lower than; the controls. These very few changes
occurred in the presence of a remarkable accumulation of arsenic in the
tissues, demonstrating that arsenite, given at this level is not toxic to
rats.
Calvery, et al. (1938) studied the chronic effects cm dogs of feeding diets
containing lead acetate, lead arsenate, and arsenic ttrioxide. The basic
problem in this study was to determine 'the toxicity s>f lead and arsenic
when used as sprays and spray residues. Dogs were used in the study. Lead
acetate, lead arsenatc or arsenic trioxide was added to the basic diet at
the following levels: lead acetate, 12.8, 38.4, and 64 mg of lead/kg diet;
lead arsenate, 64 mg of lead/kg of diet; arsenic trioxide, 28.8 and 107.5
mg arsenic/kg of diet.
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It was found that the storage, and retention of arsttnic by the dogs when
fed arsenic trioxide and lead arsenat<_ was much les-s than that of the
rats fed arsenic trioxide and calcium arsenate. jQre very low storage
was either due to failure of absorption or rapid elimination, and explains
the low susceptibility of dogs to chronic arsenic itoxicity. At the levels
used in the experiment, there was no difference beitween the toxicity of
lead acetate and lead arsenate. However, earlier .experiments in rats at
higher levels showed that lead arsenate was far more toxic.
Fairhall and Miller (1941) studied the relative toxicity of the molecular
components of lead arsenate. Albino rats were useS in the experiment.
The diets were uniform except that lead arsenate was added to the diet
of one group (10 mg/day), an equivalent amount of lead as lead arsenate
was added to the diet of the second, and an amount of arsenate equivalent
to that of the lead arsenate group was added as calcium arsenate to the
third group. The animals remained on the diets for two years.
Based upon the mortality rates over the 2-year period, the order of
toxicity of the three substances at equivalent leveDs of intake was as
follows: calcium arsenate was most toxic, lead arsmate less, and lead
'carbonate least toxic.
Pathologic studies showed significant changes in thce kidney and spleen.
The large hyperregenerative cells with large vesicular nuclei and
cytoplasmic brown pigment granules in the renal convoluted tubules x-/ere
most frequent in rats fed lead carbonate, less with lead arsenate, and
least with calcium arsenate. The large oxyphil intiranuclear inclusions
appeared in the same order in animals fed lead carbonate and lead arsenate
but were absent in the calcium arsenate group. These changes are typical
of lead toxicity. . -
Splenic hemosiderosis, considered indicative of blosrd destruction, occurred
in the greater amounts in rats fed calcium arsenate and lead arsenate than
in those fed lead carbonate. Splenic myelosis was c&istinctly reduced in
the lead carbonate series but not appreciably diminished in the calcium
arsenate and lead arsenate series or in the control groups. If splenic
hemosiderosis is accepted as signifying blood destruction and splenic
myelosis is accepted as a sign of'blood formation, .lit appears that the
action of lead carbonate on the spleen in rats may lie both hypoplastic and
hemolytic while that of the arsenate radical is priirarily .hemolytic.
The distribution of lead and arsenic in'the tissues of the 1-and 2-year
groups indicated less storage of lead than of arsenic in the soft tissues
of animals fed lead arsenate. The kidney content off arsenic in the calcium
arsenate group was distinctly greater than that of (the lead arsenate group,
both in the 1-year and 2-year animals.
_i
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It would appear that the arsenate rac.ical either decreases the absorption
or increases the excretion of lead. " /;)
VI. E. 4. Teratogenicity Studies - Ferm and Carpenter studied the
teratogenic effects of sodium arsenate in the golden hamster. Virgin
female golden hamsters were mated with male hamsters. On the 8th day of
gestation the pregnant hamsters were injected into the lingual vein with
5 rag/kg or 20 mg/kg of sodium arsenate in distilled water. Exencephaly,
a specific malformation in the heads of the offsprings was produced. The
dosage level appeared to be critical since 5 mg/kg induced no malformations
while a dose of 40 mg/kg kills all embryos in utero. The exencephalic
lesion was markedly consistent and specific and often within a single
litter a majority of the survivors showed a strikingly similar defect.
Secondary effects of this nervous system lesion included occasional bulging
of the eyeballs and a relative protrusion of the tongue and mandible similar
to that seen in hypervitaminosis-A-treated animals. No other gross external
malformations x^ere noted in other organ systems. The maternal animals
tolerated all dose levels of arsenic very well. Maternal weight gain was
normal. Histological examination of the placental Membranes revealed no
abnormality.
Fern and Carpenter (1971) made a more complete study of the teratogenic
-effects of sodium arsenate on the golden hamster in an attempt to deter-
mine the possible mechanism of arsenic as a teratogen.
Virgin female hamsters were bred to males during the night and the day
following the evening of breeding was considered the first day of gestation.
On the eighth day of gestation, the pregnant females were anesthetized and
injected intravenously with dibasic sodium arsenate. The dose varied
between 15 and 25 mg/kg of body weight. The time of injection on this day
was recorded, the day being divided into 6 hour periods. The female animals
were killed on the morning of the 15th day of gestation.
Dibasic sodium arsenate had a marked effect both upan resportion and malforma-
tion rates in- the hamster. The rates increased witfti increasing doses. The
observation that the resorption rate decreases in those litters which are
treated at later stages of development may be best understood in that early
in the-8th day of gestation, the hamster embryo develops very rapidly,
progressing from primitive streak stage to an embryo with a completely
closed neural tube and a beating heart within a 24-fcour period. It is
during this period that the embryo is most susceptible to lethal and
teratogenic influences. Thereafter, this susceptibility decreases with
time. The time of injection had a profound influence on the teratogenic
profile. The overall malformation rate remained constant over the 12-hour
period (8th day) but the frequency with which specific malformations
occurred varied considerably with time. There was .narked increase in rib
-------
malformations in the last six hour period of the 8tb day. However, the
frequency of all other malformations (genitourinary, anencephaly, and ,_•> .
exencephalia) decreased through the 12-hour time span. Malformations of
the cranium were the most common developmental anomaly found.
VI. E. 5. Cancer Studies - Attempts to demonstrable cancer in experimental
animals with arsenic have not been successful. Fro.?t (1967) contends that
no carcinogenesis from arsenic in animals has been ^reported. However,
Kraybill and Shimbin (1964), in a review, indicated that hepatomas had been
induced in trout from the feeding of carbarsone in (the diet. The control
group had zero hepatomas in a group of 300, whereas the carbarsone treated
group had 5 hepatomas in 50 exposed.
VI. F. . Toxicity to Humans - The symptoms and efforts of acute and chronic
arsenical poisoning in man are quite similar to tho-se. found in experimental
animals. Systetnically arsenicals relax the capillaries and increase their
permeability, thus stimulating inflammation. This -change is most con-
spicuous in the splanchnic area. In acute poisoning it results in violent
gastroenteritis. The dilation of capillaries introduces change in the
circulation which cause secondary disturbances in tine function of more
remote organs, particularly in the nervous system. Fatty degeneration
of the cells is seen, especially in glands and muscles, with other dis-
Jturbances of nutrition and metabolism, particularly in chronic poisoning.
There may also be, direct paralysis cf the heart (SoLOmann, 1964).
VI. F. 1. Acute Poisoning - The mortality in clinically acute arsenical
poisoning in people is high, about 50 to 75. percent.. The fatal dose varies,
especially with the solubility of the preparation. Of the trioxide, 5 to
50 mg are toxic; 0.1 to 0.3 gm is usually fatal, but recovery may occur
after much larger quantities (Sollmann, 1957). The arsenites are more
soluble and are more rapidly toxic than the correspmding arsenates.
Even when administered in comparatively large doses,, there is a charac-
teristic delay ranging from half an hour to several hours in the onset of
symptoms following ingestion of•trivalent arsenic. The first symptom is
frequently a feeling of throat constriction, followed by difficulty in
swallowing and epigastric discomfort. Thereafter, violent abdominal pain
accompanied by vomiting and a watery diarrhea occurar. Blood may be present
in the stools or vomitus. These symptoms are accompanied by others of
systemic upset, including a sensation of giddiness,-muscular cramps,
possibly the effect of the severe loss of fluid in tthe watery stools and
headache. In those dying from the acute effects, s'Vock, manifesting itself
by a cold clammy skin, feeble pulse and weak sighing respirations, supervene,
and death may be preceded by terminal convulsions. In these cases, death
usually takes place within 24 hours. In less acute cases, the victim may
survive for two to four days (Buchanan, 1962).
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The number of reported c-jses of arsenical poisoning in the United States
in 1969 is shown in Table 2. It should be noted that, although sodium
'arsenite and arsenic trioxide accounted for about one-fourth ox the ';>
poisonings, they accounted for all of the deaths resulting from identified
arsenical compounds,
\
p
Table 2. Reported Cases of Arsenical Poisoning, U.S.A., 1969*
• Arsenical Reported Reported
Cases Deaths
Lead arsenate .83 0
Sodium arsenate 79 P
Sodium arsenite 38 5
Arsenic (unspecified) 34 1
Arsenic trioxide 23 2
Calcium arsenate 7 0
.Disodium methyl arsenate 5 0
Paris green 2 0
*Poison Control Center Statistics, National Clearing House for Poison
Control Centers, FDA, DHEW.
A number of cases of acute poisonings are summarized with the most pre-
valent symptoms of poisoning and also some unusual findings given.
Barnhart and Weiderkopf (1961) describe a- patient who ingested a large
quantity of an unspecified arsenical insecticide. His stomach was
pumped 45 minutes later. Nevertheless, the patient developed a neuropathy
with pain and impaired function of the hands and feet and full recovery
was incomplete 2 years after the initial poisoning.
Capellini, et_ jil_. (1955) reported 34 cases of lead arsenate poisoning in
workers producing insecticides. The concentration of lead and arsenic in
the workroom air was from 8 to 11 mg/1. The average length of exposure
varied from 2 to 6 months. The symptomology of lead arsenate poisoning
was quite varied since signs of both lead and arsenic intoxication occurred.
Barry and Herndon (1962) found EGG changes in 3 patients that had taken
arsenic trioxide in an attempt to commit suicide. These changes disappeared
within 20 days in the two patients that recovered. Similar EGG changes were
reported by Glazener, e_t_ a_l. (1968).
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Sodium arsenate in the form of "Ant Buttons" was invested ry two children.
'Both recovered after acute symptoms of poisoning. Hhe repot £ states ;:h
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persons her.arae ill and about 70 persons died from drinking contaminated
•beer. The beer contained as much as 15 ppm arsenic and the glucose us 3d'-1
in the fermentation contained about 400 ppm arsenic. The ultimate source
of- the contamination was found to be in the sulfuric acid used in prepara-
tion of the sugar. The sulfuric acid which contains! about 1.4 percent
arsenous acid was manufactured from pyrites containing arsenic impurities.
Smelter operations have commonly been associated wit5i adverse effects
from arsenic exposure. Such a situation was reported in this country
in 1962 when a gold mine and smelter was reopened ami the emission
control equipment was inadequate to control atmospheric pollution from
S0~ and As202 (girminghaia et_al., 1965). In this case, air levels taken
at the plant showed 60 to 13,000 micrograms per cubi?: meter of arsenic.
A study was made of 40 school children in the area. Out of these students,
32 had dermatosis associated with arsenic cutaneous exposure. The systemic
arsenic poisoning was discounted when it was proved (to be a contact
dermatitis. One interesting aspect of this environmental exposure is that
children who were bussed to a high school in a distant town did not have
the continuous exposure of the 40 children in the local elementary school
had no dermatitis. As to the children shoxcLng dermatitis, the skin
irritation was in the folds of skin and where the skin was moist. In a
few cases, the conjunctivae and nasal mucosae were irritated. There were
no cases of keratoses, epitheliomas, or melanodermas present. Among the
refinery workers, there were typical symptoms of arsenic exposure.
A similar air pollution episode was recorded at a cogiper mine in northern
Chile (Oyanguren and Perez, 1966). The air levels off arsenic were quite
high. In .a survey of 124 workers, the symptoms of arsenic exposure were
melanosis - 7.25 percent., arsenical dermatitis - 5.6.5 percent, and
perforation of the nasal septum - 1.65 percent. There were no cutaneous
manifestations encountered among a control group or among members of the
mining community.
Heyman, et_ al. (1956) reviewed 41 cases of peripheral! neuropathy caused by
arsenical intoxication. All of the patients were from North Carolina where
arsenical dusts and sprays are extensively employed as pesticides. Seven
of the victims could relate the onset.of nausea and vomiting with the use
of arsenical pesticides on tobacco. Fourteen others also were employed
around crops utilizing arsenical pesticides. Twenty-two patients in the
study treated with BAL failed to show any dramatic inprovement on an
accelerated recovery of sensory and motor function.
Micks, et_ _aJL. (1956) review four cases of chronic arsenical poisoning in
farmers resulting from the use of arsenic containing pesticides on crops.
-------
They state that the intemnitte.it natui - of the exposures, which occurred
during a period of years, provided optimum conditions for chronic poison-
ing.
The most prominent symptom exhibited was paralysis of the legs and hands,
which occurred in 3 of the patients. The paralysis began in the feet and
involved the hands shortly thereafter. BAL in addition to vitamin therapy
and other symptomatic treatment. By this time, however, the arsenic had
already produced marked pathological changes which were irreversible.
Since all of the patients were farmers, the occupational hazards associated
with arsenical insecticides were pointed out as well as the characteristic
symptoms of chronic arsenic poisoning.
In a study conducted by'the U.S. Public Health Service, Neal _e_t a!L. (1941)
failed to reveal any positive association between lead and arsenic exposure
and certain adverse effects which might have been anticipated from such
exposure by orchard workers applying lead arsenate. Hcwever, Farner, et al.
(1949) in a four month medical study on a group of Mexican Nationals
employed in Washington State's orchard industry durimg 1945, established
a definite health hazard from exposure to lead arsenate. An increasing
incidence of lead intoxication as the season progressed was demonstrated.
VI. F. 3. Cancer - There is considerable confusion in the literature
about the role of arsenicals in carcinogenesis or im the development of
cancer. The earliest published claim of arsenic camcer was made by Paris
(1820) in which he reported occasional cases of cancer of the scrotum in
copper smelters. Huchinson (1887) was the first to report skin cancer
following prolonged internal administration of arsenical preparation.
Neubauer (1947) reported a collection of 143 published cases of arsenic
cancer including a number of workers exposed to pesticides. It appears
that skin cancer resulting from systemic arsenic poisoning is first
manifested in non-malignant keratosis (on palms of bands and soles of
feet) and eventuates into a neoplasm.
Snegireff and Lombard (1951) studied the records of two industrial plants
and found that where workers in one plant were exposed to arsenic, 18 of
146 deaths (12.3 percent) were caused by cancer. IB another plant where
workers were not exposed to arsenic, 12 of 109 deaths (11.0 percent)were
caused by cancer. They concluded that these were not significantly
different.
In another study Pinto and Bennett (196,3) compared nurrtality and cancer
rates for the years 1946-1960 of 38 copper smelting plant workers who were
exposed to arsenic with 191 workers not exposed to arsenic. The percentage
of deaths due to cancer in the arsenic exposed workers was 15.8 percent and
19.4 percent in those not exposed to arsenic. The fact that the workers were
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exposed to arsenic was confirmed by urlnalysis. The mean urine values
of arsenic for the exposed workers was 0.82 ing /I and for the non-exposed
workers 0.13 mg/1. Cancer death rates for men of similar age ranges for
the whole state was 15.9 percent, virtually the same rate as for the
arsenic exposed group.
j2t_ _al. (1941) did not observe any increase in cancer among the 1200
people studied in the Wenatchee, Washington area during extensive use of
lead arsenate.
On the other hand, Braun (1958) and Roth (1956) reported what they con-
sidered an unusually high incidence of internal cancers including malignant
tumors of the liver and lungs. These were apparently always preceded by
benign keratosis of the skin. It appears that the arsenic exposure was
directly connected with the use of arsenical pesticides as well as the
consumption of wine made from grapes contaminated with arsenic. In a
brief review of arsenic cancer, Hueper (1966) concluded there is abundant
and reliable evidence that arsenic is a human carcinogen.
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CHAPTER VI
BIBLIOGRAPHY
ARSENIC TOXICOLOGY
Barry, K. G. and Herndon, E. G. "Electrocardiogrsiphic changes associated
.with acute, arsenic poisoning." Med. Annals D.C. 31;25-27 (1962).
Barnhart, D. and Weiderkopf, S. A. "Arsenic neuropathy." Physical Therapy
Rev. 41:782-3 (1961).
Bencko, V. and Simane, Z. "The effect of chronic (sic) intake of arsenic
on the liver tissue respiration in mice." Experientia 24(7) , 706 (1968a).
Bencko, V. et. al. "Histological picture of several organs after long-term
peroral administration of arsenic to hairless mice," .Cs_'_Hy_S_i. _13_ (1968b).
Bencko, V. and Symon,'K. "Dynamics of arsenic cumndLation in hairless mice
after peroral administration." JN Hyg. Epidemic)!. Immunol. (Prague)
13(2) -:248-253, 1969a.
Bencko, V. and Symon, K. "Suitability of hairless mice for experimental work
and their sensitivity to arsenic." JL Hyg. Epjuiemiol. Microbiol. Immunol.
(Prague) 13(1); 1-6 (1969b).
Bencko, V., et. al. "The cumulation dynamics in soiue tissues of hairless
mice inhaling arsenic." Atmos. Environ. _4_: 157-161 (1970).
Birmingham, D. J. , et. al. "An outbreak of arsenical dermatoses in a mining
community." Arch. Derm. 91: 457-464 (1965).
Braun, W. "Occupational multiple arsenic keratoses of the trunk in vintners."
Dermatologische Wochenschrift Vol. 137;468-73 (3S58).
Buchanan, W. D. Toxicity of Arsenic Compounds, Elsenier Publishing Company,
New York (1962).
Calvery, H. 0., et. al. "The chronic effects on dags of feeding diets con-
taining lead acetate, lead arsenate, and arsenic trioxide in varying con-
centrations." J. Pharm. & Exp. -Therap. 64:364-387 (1938).
Capellini, A., Parmeggiani, L. , Sartorelli, E. , ancf Martelli, G. C. "Thirty-
four cases of lead arsenate poisoning in two factories producing insecti-
cides." Med. Lavoro 46: 147-157 (1955).
Clarkson, T. W. and Distefano, V. "Lead, mercury, arsenic, and chelating
agents." Drills' Pharmacology in Medicine, 4th EH. (19°71).
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Fairhall,. L. T., and Miller. J. W. ''A study of Hie relative toxicity of the
molecular components of lead arsenate." Pub. IHth, Rep. 56: 1610-1625
' (1941).
Earner, L. M, , et. al> "The hazards associated with the use of lead
' arsenate in apple orchards." J_. Ind. Hyg. Toxicol. 31 (3): 162-8 (1949).
Perm, V. H., and Carpenter, S. J. "Malformations induced by sodium
arsenate." J. Reprod. Fert. 17_:199-201 (1968).
Ferm, V.. H. , et. a_l_. "The teratogenic profile of sodium arsenate in the
golden hamster..7' Arch. Environ. Hlth. .22:557-56) (1971).
Frost, D. V. "Arsenicals in biology-retrospect ani prospect." j[e d. Proc.
26>(1):194-208 (1967).
Glazener, F. S. "Electrocardiographic findings v/ilh arsenic poisoning."
• . Calif. Med 109_(2): 158-162 (1968).
Harrison, Jo W. E. , et. al., "Acute oral toxicityraid chemical and physical
properties of arsenic trioxides." AMA Arch. Ind... Hlth. 17, 118-123
(1958)..
Heyman, A., Pfeiffer, J.'B., Willett, R. W., and T,-ylor, H. M. "Peripheral
neuropathy caused by arsenical intoxication." Naf Eng. J. Med. 254 (9):
401-409. (1956).
Hueper, H. C. Occupational and Environmental Gangers of the Respiratory
System, pp 28-38, Springer-Verlag, New York (196J6).
Hunter, F. T., Kip, A. F., Irvine, J. W., Jr. "RaHLoactive tracer studies
on arsenic injected as potassium arsenite." J_. Biarmacol. Exper.
Therap.. 7^: 207-220 (1942).
Hutchinson, J. "Arsenic cancer." Brit. Med_. J_. i±: 1280 (1887).
Jacobiziner, H. and Raybin, H. W. Dexedrine, metalllic mercury, arsenic, and
arnica intoxication." Arch. Ped_. 78: 19-22 (196'J),.
Jenkins^ M. Q. "Accidental poisoning of the month, arsenical insecticide."
J_. S_. Carolina Med. Ass. 6^:53 (1965).
i »
Joachimoglu, G. "Zur Fraee der Gewohnung an Arsenik,"" Arch. Exp. Path, and
Pharm 79:419-442 (1916).
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Johns tone, R. M. , Si'. ? f h y d ry 1 Agent: s , Arsenicals iu Metabolic Inhibitors,
Vol. TI (Ed. by Hoedistler, R. M. and Quastel, J. H.) Academic Press,
New York (1963).
Kingsley, G. R. , and Schaffert, R. R. Anal. Cheat. 23: 915 (1951).
Kraybill, H. F. and Shimkin, M. B. "Carcinogenesis related to foods con-
taminated by processing and fungal metabolites." Advances in Cancer
Research 8; 191-206 (1964).
Lanz, H., Jr., et, al. "The metabolism of arsenic in laboratory animals
using As I1* as a tracer." University Calif. Piife. Pharmacol. _2 (20):
263-282 (1950).
McChesney, E. W. and Banks, W. F. "Toxicity and physiological disposition
of sodium-p-N-glycolylarsanilate" - Toxicol. Apgl. Pharmacol. JK 702-718
(1963).
Micks, E. W., Neal, J., and Nau, C. A. "Arsenic as an occupational hazard
for farmers." Tex. State J. Med. 52;746-748 (15-56).
Morris, H. J. and Wallace, E. W. "The storage of arsenic in rats fed a
diet containing calcium arsenate and arsenic trioxide." J_. Pharmacol.
Exper. Therap. 64:'411-419 (1938).
Neal, P. A., et. al. "A study of the effect of lead arsenate exposure on
orchardist and consumers of sprayed fruit." Pufe. Hlth. Bull. No. 267:
181 pp. (1941)..
Neubauer, 0. "Arsenical cancer: a review" Brit. JL_ Cancer 1^:192 (1946) .
Overby, L. R. and Frost, D. V. "Nonavailability Ito the rat of the arsenic in
tissues of swine fed arsenilic acid." Toxicol. and Appl. Pharm. 4;
38-43 (1962).
Oyanguren, H. and Perez, E. "Poisoning of industrial origin in a community."
Arch. Environ. Hlth. 13: 185-189 (1966).
Paris. J. A. Pharmacologia or the History of Meditclnal Substances with a View
to Establishing the Art of Prescribing, 4th ed.B London, W. Phillips (1820).
Peters, R. A., Sinclair, L. A., and Thompson, R. H. S. "An analysis of the
inhibition of pyruvate oxidation by arsenicals :iin relation' to the enzyme
theory of vesication." Biochem. J. 40: 516 (1946).
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Peoples. S. A, "The metabolic fata of arsenic tcLoxide in the lactating
bovine,." Fed. Proc. 21(2); 183 (1962). o-
Peoples, S. A. "Arsenic toxicity in cattle." Am. N.Y. Acad_. Sci. Ill:
644-649 (1964).
Podwyssotzky, W. W. , Jr., St. Petersburg. Med. Wdinschrz 5: 211 (1888).
Roth, W. "Chronic arsenic poisoning of Mosel vineyard workers, with
special emphasis on arsenic cancer." Z_. Krebs'farsch. '61;287-319 (1956).
Rozenshtein, I. S., "Sanitary toxicological assessment of low concentrations
of arsenic trioxide in the atmosphere." Hyg. & Sanit. 35 (1-3): 16-21
(1970).
Schreiber, M. and Brouwer, E. A. "Metabolism and toxicity of arsenicals."
Fed. Proc. 23(2), 199 Abst. #589 (1964).
Schroeder, H. A., et. gl. "Germanium, tin and arsenic in rats, effects on
growth, survival, pathological lesions, and life span." J. Nutrition 96,
37-45 (1968). ~
Sollman, T. "Studies on chronic intoxication in albino rats v. arsenic
trioxide. _J. Pharmacol. Ex per. Therap. 1
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Supplemental Information For
"Arsenical Pesticides, Man, and the
'Environment." 1972
Prepared for the Office of Pesticides
Programs, Environmental Protection
Agency, March 17, 1972.
-------
g " "eeet.-t meeting relative to the strtus of the
Special Pesticide Review Group's Arsenic Pesticides Report,
several itp.ms of essential intorin^uion were ii'd'icated. Those
attending the meeting with Mr. Ctarles Fabricaaut were: Mr. Harold
Alfoic!, Dr. H. E. roirchild, Dr. 0. G. Fitzhugjhi, Mr. L. E. Miller,^
and Dr. W. M. Upholt.
• This supplemental information report presents the added
material developed to date. This supplement discusses the follow-
ing 'subjects in the order given: (1) significant arsenical pesticide
production history; (2) basic producers of arsenical pesticides;
(3) export-import data for arsenical pesticides; (4) pesticide use
patterns and history of use in the United States—arsenical pesticides;
(5) comparative use costs of arsenical pesticides and the registered
alternative pesticides; and, (6) Environmental Protection Agency
registrants of arsenical pesticides.
PRODUCTION HISTORY
Calcium Arsenate and Lead Arsenate
Table I of this report gives the production records for
calcium arsenate and lead arsenate during the period of 1950 through
1970. These production data go back to the period when DDT and other
more recent chlorinated hydrocarbon pesticides were still in the
development stage.
Note (Table I) that the production srf calcium arsenate
once was well in excess of forty million pounds. Prominent uses of
this pesticide were on cotton and vegetables. STuch of the recent
production is needed for baits to control snails, slugs and other
pests of crops in the West.
Lead arsenate was the principal insecticide used on fruits
prior to the development of DDT. Note the continued decline in use of
lead arsenate from 1950 to the mid-1960's. Recently, entomologists in
several states, especially in the fruit growing areas of the East, have
encouraged a return to the use of lead arsenate for integrated spray
programs. Further explanation of this subject appears in Chapter I of
the Special Pesticide Review Group's Arsenic Rejport.
Methanearsenate Herbicides
Production data for the methanearsomate herbicides (MSMA,
DSMA, AMA) only became publicly available in 1970. The United States
Tariff Commission has reported 30,454,000 pounds-- were»produced in 1970.
More details on production of this class of pesticides will be found on
page 95 of the Special Pesticide Review Group's Arsenic Report.
Principal uses of the methanearsonate herbicides are in cotton and for
industrial weed control, especially pests such as johnsongrass.
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Table I. ]_/ Annual Production for Calcium Arscriate and Lead
and Lead Arsenate in the United S:tates, 1950-1970
Calcium Arsenate Itad Arsenate
(1,000 (1,000
pounds) pounds)
1950 45,348 ' 12,434
1951 40,900 25,416
1952 7,634 14,286
1953 7,212 '14,196
1954 2,758 15,620
1955 3,770 14,776
1956 27,106 Ilr756
1957 19,478 . Ilr920
1958 10,432 14,938
1959 6,424 12,904
1960 6,590 10,062
1961 7,944 10,446
1962 4,660 . 9,930
1963 3,310 7,842
1964 6,958 9,258
1965 4,192 7*098
1966 2,890 7»328
1967 2,008 5>,952
1968 3,398 9,016
1969 1,418 . 9BU2
1970* 3,059 4^,185
^Preliminary and subject to revision
_!/ Taken, from "the Pesticide Reviews," Agricultural Stabilization
and Conservation Service, United States Department of Agriculture,
Washington, D.C. 1950-1970.
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Sodium Arseniif and Miscellaneous /.rseni :ils
Following are the available date, on sodium arsenite as a
pesf-icide in the United States.
0
Stocks of All Manufacturers and Formulators of
Sodium Arsenite
Year 1,000 Pounds
1962 2,809
1963 2,680
•A sodium arsenite report in 1966 from the United States
Department of Agriculture stated "usage in agriculture is declining
because of the hazard from run-off and from the attraction of the salty
taste to livestock. Some is applied to kill off potato foliage before
harvest; small quantities are used as an algaecide in farm ponds."
(U.S.D.A. The Pesticide Review, 1966. 33 pp. October 1966).
Another compilation of data indicating a decline of
inorganic arsenic herbicidal preparations between 1958 and 1963
follows: *
1958 1963
Products Quantity Value Quantity Value
1,000 1,000 .1,000 1,000
pounds dollars pounds dollars
Arsenical preparations
46,681 2,045 24,359 2,326
*U.S.D.A. the Pesticide Review, 1966. 33pp. October 1966.'
There was a brief report in 1968 (U.S.D.A., the Pesticide
Review, 1968) that arsenic trioxide was in short supply in late 1966
and most of 1967. The short supply of arsenic trioxide was due to a
strike in the copper industry and increased denand for production of
organic arsenical herbicides (such as MSMA and DSMA).
The United States Department of Agriculture has reported
(U.S.D.A. the Pesticide Review, 1969) as follows "usage of inorganic
arsenical pesticides has been declining steadily in recent years due
to replacement with more efficient organic pesticides."
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BASIC PRODUCER?—ARSENICAL PECTiCIDES
Lead Arsenate
Following are the basic producers of lead arsenate:
Allied Chemical Corporation
Agricultural Division
40 Rector Street
New York, New York 10006
Chevron Chemical Company
Ortho Division
t200 Bush Street
San Francisco, California 94120
FMC Corporation
Niagara Chemical Division
100 Niagara Street
Middleport, New York 14105
Los Angeles Chemical Company
4545 Ardine Street
South Gate, California 90280
Nihon Nohyaku Company, Ltd.
(Japan Agricultural Chemicals Company, Ltd.)
5th Floor Eitaro Bldg., No. 4, 1-Chome
Nihumbashitori Chuo-Ku, Tokyo, Japan
Procida (Groupe Roussel)
Saint-Marcel
13-Marseille 11°, France
Rhodia Inc., Chipman Division
120 Jersey Avenue
. New Brunswick, New Jersey 08903
The Sherwin-Williams Company
116 St. Clair Avenue
Cleveland, Ohio 44101
Woolfolk Chemical Works, Ltd.
East Main Street
P.O. Box 938
Fort Valley, Georgia 31030
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Calcium n s ena i q
Following are the basic producers of calcium: arsenat'e:
ti
Allied Chemical Corporation
Agricultural Division
40 Rector Street
New York, New York 10006
Commercial Chemical Company
P.O. Box 86
Memphis, Tennessee 38101
Los Angeles Chemical Company
4545 Ardine Street
South Gate, California 90280
Pennwalt Corporation
Agricultural Chemicals Division
2901 Taylor Way
Tacoma, Washington 98401
Rhodia Inc., Chipman Division
120 Jersey Avenue
New Brunswick, New Jersey 08903
Woolfolk Chemical Works, Ltd.
East Main Street
P.O. Box 938
•Fort Valley, Georgia 31030
Basic Copper Arsenate • -
No longer being manufactured because the tolerance has
been cancelled.
Ammonium Arsenite
Basic producer information is not available from usual
sources. Refer to registrants of Pesticides Regulation Division for
those supplying the material for pesticidal purposes.
Arsenic Acid
Following are the basic producers of arsenic acid:
Allied Chemical Corporation
Agricultural Division
40 Rector Street
New York, New York 10005
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Commercial Ch^".i';al Company
P.O. Box 86
Memphis, 'iC'iiness'ee 38101
Pennwalt Corporation
Agricultural Chemicals Division
2901 Taylor Way
Tacoma, Washington 98401
Rhodia Inc. , Chipman Division
120 Jersey Avenue
New Brunswick, New Jersey 08903
The Sherwin-Williams Company
'116 St. Clair Avenue
Cleveland, Ohio 44101
Woolfolk Chemical Works, Ltd.
East Main Street
P.O. Box 938
Fort Valley, Georgia 31030
Arsenic Pentoxide
Basic producer information is not available from the usual
sources. Refer to registrants of the Pesticides Regulation Division
for those supplying the material for pesticidal purposes.
Arsenic Trioxide
Following is a basic supplier of arsenic trioxide:
American Smelting and Refining Company
120 Broadway
New York, New York 10005
Sodium Pyroarsenate
Basic producer information is not available from the usual
sources. Refer to registrants of the Pesticides Regulation Division
for suppliers of the material for pesticidal use.
Wolman Salts
Following is the basic producer of Wolman S<s:
Koppers Company, Inc.
1501 Koppers Building
Pittsburgh, Pennsylvania 15219
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Cacodylic Vid
Following is the basic producer of cseodylic acid:
The Ansul Company
1 StanLon Street
Marinette, Wisconsin 54149
jodium Arsenite
Following are the basic producers of sodium arsenite:
Allied Chemical Corporation
Agricultural Division
40 Rector Street
New York, New York 10006
Chemical Formulators, Inc.
P.O. Box 26
Nitro, West Virginia 25143
Chemical Insecticide Corporation
30 Whitman Avenue
Edison, New Jersey 08817
Chevron Chemical Company
Ortho Division
200 Bush Street
Sari Francisco, California 94120
FMC Corporation
Niagara Chemical Division"
100 Niagara Street
Middleport, New York 14105
Pennwalt Corporation
Agricultural Chemicals Corporation
2901 Taylor Way
Tacoma, Washington 98401
Procida (Groupe Roussel)
Saint-Marcel
13-Marseille 11 , France
Rhodia Inc., Chipman Division *
120 Jersey Avenue
New Brunswick, New Jersey 08903
— 7 —
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The Sherwin-Williams Company
116 St. Clair Avenue
Cleveland, Ohio 44.1.01
'••
I'otassium Arsenite
Basic producer information is not available from the usual
sources. Refer to the registrants of the Pesticides Regulation Division
for suppliers of the material for pesticidal use.
Sodium Arsenate
Following are the basic producers of sodium arsenate:
Procida (Groupe Roussel)
Saint-Marcel
13-Marseille 11°, France
Rhodia Inc., Chipman Division
120 Jersey Avenue
New Brunswick, New Jersey 08903
Paris Green
Following are the basic producers cof Paris green:
Los Angeles Chemical Company
4545 Ardine Street
South Gate, California 90280
Procida (Group Roussel). -
Saint-Marcel
13-Marseille 11°, France
Rhodia Inc., Chipman Division
120 Jersey Avenue
New Brunswick, New Jersey 08903
The Sherwin-Williams Company
116 St. Clair Avenue
Cleveland, Ohio 44101
DSMA (Disodium Methanearsonate)
ft
Following are the basic producers .of DS?1A:
The Ansul Company
1 St.inton Street
Murincttc, Wisconsin 54149
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W. A.. Clea.y Corporation.
P.O. J'ox 749
New Brunswick, New Jersey 08903 ^
Diamond Shamrock Corporation
Agricultural Chemical Division
300 Union Commerce Building
Cleveland, Ohio 44115
Vineland Chemical Company
P.O. Box 745
West Wheat Road
Vineland, New Jersey 08306
MSMA (Monosodium Methanearsonate)
Following are the basic producers of MSMA:
The Ansul Company
1 Stanton Street
Marinette, Wisconsin 54149
Diamond Shamrock Corporation
Agricultural Chemical Division
300 Union Commerce Building
Cleveland, Ohio 44115
Vineland Chemical Company
P.O. Box 745
West Wheat Road
Vineland, New Jersey 08306
AMA (Amine Kethanearsonate)
Following is the basic producer off AMA:
Vineland Chemical Company
P.O. Box 745
West Wheat Road
Vineland, New Jersey 08306
Sodium Hypoarsenate
Basic producer information is not available, from the usual
sources. Refer to registrants of the Pesticides Regulation Division for
suppliers of the material for pesticidal use,. •
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Pi sodium A/sena;.P
Basic producer information is not available f^om the usual
sources. Refer to registrants of the Pesticides Regulation Division
'for suppliers of the material for pesticidal use.
10, lO'-oxybisphenoxarsine
Following is the basic producer of 10,10'-oxybisphenoxarsine:
Scientific Chemicals Division
Ventron Instruments Corporation
3800 South Racine Avenue
Chicago, Illinois 60609
EXPORT-IMPORT DATA FOR ARSENICALS
The available export data for the arsenicals are presented
in the following tables.
Exports of Calcium Arsenate
Year 1,000 1,000
. dollars pounds
1961 58
1962 104 • 942
1963 18 187
1965 II 613 1,430
1966 I/ 805 3,187
1967 _!/ 898 1,580
1968V 782- 2,277.
1969 1,758.2 5,466.7
I/ Inorganic insecticides which includes lead arsenate, calcium
arsenate and inorganic fumigants and rodenticides.
Exports of Lead Arsenate
Year 1,000 1,000
dollars pounds
1961 183
1962 249 1,423
1963 135 » . 803
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Exports of luorrji'nic Hp-.-bici.des, Ti.cLidinj Sodium
Are
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Folx"wing TO r.i.w.'y devo.lupod cur ;•;: native: coctc (per acre
or of!;cvr eonvcn:>\:v" co.'i.,5" Lson.) for: ;'o;;ropriat£ arsenical pesticide
an^ selected altt -,;ates now registered ("ote:" rates ana costs per
acre -./ill not assure grower of equivalent pest control) :
Comparisons for Lead Arsenate Insectj'cide Uses
Cror
Fruit crops
Vegetable
crops,
ornamentals
and field
crops
Pesticide
Lead arsenate.
*? -.. '
Carbaryl .• '•
Guthion
Diazinon
Malathion
Parathion
Methoxychlor
Rotenone
Lead arsenate
Carbaryl
Diazinon
Malathion
Lindane
Parathion
Range of Dosage
Rates (Ibs. per 100
gal, of per acre)
2-6 Ibs. per 1©0 gals.
1/2 -1-1/2 Ibs. per
1.00 gal. '
0.3 - 0.5 Ibs™ per
100 gal.
0.25 - 0.5 Ibs per
100 gal.
0.5 - 1.0 Ibs per
100 gals
0.15 - 0.5 Ibs
per 100 gals
1-1.5 Ibs per
100 gals
1.25 -2.2 Ibs
per 100 gals
3-10 Ibs per .sere
..Total Cost
Per Treatment
(dollars)
$.52 -- $1.56
.50 - 1.50
.84 - 1.40
1.00 - 2.00
.34 -
.06 -
.66 -
.14 -
.68
.20
.99
.24
,78 - 2.60
.5 - .5 - 2 IES per acre . 50 - 2.00
.4 - .5 Ibs pa?, acre 1.60 - 2.00
1-2 Ibs per acre
, 2 - .4 Ibs per
acre
,3-1 Ib. per acre
,68 - 1.36
27 - .548
12 - .40
(continued)
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Crop EeJi!:^£i^L RcUij'.o_ u_f Vi c i'utal Cost
jjj&l. or pc ' . ere)
Toxaphane 2-4 Ibs per acre $.44 - $' .88
Mefchoxychlor 1-2-1/4 Ibs per acre .66 - 1.48
Lawns and
ornamental
turf
•
Lead arsenate
Carbaryl
Chlordane
Diazinon
Heptachlor
Toxaphene
Comparisons for Calcium
Crop
Vegetable
crops
Pesticide
Calcium
arsenate
80-430 Ibs per acre
4-20 Ibs per acre
10 Ibs per acre
2-2/3 - 7-3/4 Ibs
per acre
10 Ibs per acre
25 Ibs per acre
Arsenate Insecticide
Range of Dosage
Rates (Ibs per 100
gal. or per acre.)
3-5-1/2 Ibs per acre
$20.80 - $118.80
4.00 - 20.00
$5,90
6.90 - 19.40
$10.30
$5.50
Uses
Total Cost
Per treatment
(dollars)
$.42 - $.77
For competitive costs see "Comparisons for Lead Arsenate
Insecticide Uses" under "vegetable crops."
Lawns and Calcium 430 Ibs per acre $60.20
ornamental Arsenate
turf
For competitive costs see "Comparisons For Lead Arsenate
Insecticide Uses" under "lawns and ornamental turf."
Miscellaneous Wood Preservative Arsenical Pesticide Uses -
Compared to Alternates
ei
Arsenic Compound Cost Alternate Cost
Arsenic pentoxide $.64/lb. creosote $.25/gal.
pentachlorophenol .17/lb.
"Arsenic" trioxicie '" $.04//'i'b. 'Same as for arsenic pentoxide.
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Comparisons iV- MSuA and JDSMA I'Vr.-Crp|', InJuctrial
Sites , Ulght-'.-of-V.'ay j., rrlveways and Sidewalks
Pesticide Range £f_ Dosage Rates Totc'l Cost pp_r Tre-itmen!^
(Ibs per acre) (dollar)'
MSMA* 2-5 Ibs (100 gals, water) $2.75 - $6.88
DSMA* 2-5 Its (100 gals, water) $2.75 - $6.88
Simazine 6-12 Ibs $15 - $30
Monuron 6-12 Ibs $12 - $24
*Usually-used to supplement other herbicides for johnsongrass control.
Comparisons of Arsenical Pesticides For Lawns
and Ornamentaj. Turf
Pesticide Range _of_ Dosage Rates Total Cost P^er Treatment
(Ibs of actual per acre) (dollar)
MSMA 2-5 Ibs $2.75 - $6.88
DSMA 5-15 Ibs $6.88 - $20.63
Lead arsenate 70-200 Ibs $18.20 - $52.00
Calcium arsenate 80-600 Ibs $11.20 - $84.00
Comparisons for MSMA and DSMA to Comtrol Weeds
in Cotton (Post-Emergence)
Pesticide Range of Dosage Rates Total Cost Per Treatment
(Ibs of actual/acre) (dollar)
MSMA* 1-2 Ibs $1.38 -$2.75
DSMA* 2-3 Ibs , $2.75 - $4.13
Treflan 3 Ibs $13.95
Monuron 2-2-1/2 Ibs $4.00 - $5.00
- 0
*Primary use is supplement to other herbicides for johnsongrass control.
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REGISTRANTS OF ARSENICAL PESTICIDES
The Pesticides Regulation Division has nade a preliminary
.review of the arsenical pejticides now registered. Mr. Harold Alfthrd
has indicated in a recent letter to Dr. Willian; Upholt that approxi-
mately 700 products are currently registered containing one or more
of approximately 34 arsenical compounds. The Pesticides Regulation
Division has initiated a summarization of the ;arsenical pesticide
registrants.
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