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National Library of Medicine, Bethesda, MD.
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THIOPHANATE METHYL
CASRN: 23564-05-8
For other data, click on the Table of Contents
Human Health Effects:
Human Toxicity Excerpts:
Among men who treated citrus with thiophanate-methyl as well as emulsified sulfur and
calcium polysulfide in Kumamoto Prefecture, the incidence of dermatitis was 30.3, 48.2,
and 52.8% in 1972, 1973, and 1974, respectively. The corresponding values for women
were 32.3, 56.3, and 64.8%. The areas affected were the abdomen, back, and waist.
Symptoms included itching, redness, swelling, dryness, and sometimes sensitized
dermatitis. Symptoms frequently appeared 1 wk after exposure. The ocular mucosa was
congested. The incidence of positive patch tests was only about 5%. Medical exam
revealed some abnormalities of hemoglobin.
[Hayes, W.J., Jr., E.R. Laws, Jr., (eds.). Handbook of Pesticide Toxicology. Volume 3.
Classes of Pesticides. New York, NY: Academic Press, Inc., 1991. 1458]**PEER
REVIEWED**
Skin, Eye and Respiratory Irritations:
Mild skin & eye irritant.
[Tomlin, C.D.S. (ed.). The Pesticide Manual - World Compendium. 10th ed. Surrey, UK:
The British Crop Protection Council, 1994. 988]**PEER REVIEWED**
Probable Routes of Human Exposure:
Occupational exposure to thiophanate-methyl may occur through inhalation and dermal
contact with this compound at workplaces where thiophanate-methyl is produced or
used(SRC). Worker re-entry exposure to pesticides residues in greenhouses is a probable
exposure route based upon a study in which thiophanate-methyl was applied to
carnations via high-volume spraying at application rates of 150 and 325 g ai/1000 sq m,
showing half-lives of 22 and 41 days, respectively(1). Dermal exposure of greenhouse
workers to thiophanate-methyl (applied by spraying) on carnations cultured in
greenhouses was found to be 64 mg/day (during cutting operations) and 23 mg/day
(during sorting and bundling)(2).
[(1) Brouwer DH et al; Bull Environ Contam Toxicol 58: 976-84 (1997) (2) Van
Hemmen JJ et al; Med Fac Landbouww Univ Gent 57/3b: 1271-1283 (1992)]**PEER
REVIEWED**
Emergency Medical Treatment:
Animal Toxicity Studies:
Non-Human Toxicity Excerpts:
Flow cytometric technique was used to study the effects of the fungicide Thiophanatemethyl on cell proliferation, micronucleus induction, and apoptosis in human peripheral
blood lymphocytes treated in vitro. Most micronuclei induced by Thiophanate-methyl
did not reveal any centromeric signal, thus demonstrating clastogenic action of this
fungicide. Moreover, it was found that as a function of the concentration of
Thiophanate-methyl, cellular proliferation was delayed and the frequency of apoptotic
cells was increased.
[Fimognari C et al; Environ Mol Mutagen 33 (2): 173-6 (1999)]**PEER REVIEWED**
No observable effect level (2 yr) for rats & mice 160 mg/kg diet.
[Tomlin, C.D.S. (ed.). The Pesticide Manual - World Compendium. 10th ed. Surrey, UK:
The British Crop Protection Council, 1994. 988]**PEER REVIEWED**
Single exposures of mice for 30, 60, or 120 min to an aerosol of 70% wettable powder
under dynamic conditions at a nominal concn of 100,000 mg/cu m caused lacrimation,
salivation, & nasal exudation within 5-6 min after exposure began. For a few days after
exposure the mice wheezed, & a crust was present around their eyes. However, they
recovered completely & showed no change in growth compared to controls.
[Hayes, W.J., Jr., E.R. Laws, Jr., (eds.). Handbook of Pesticide Toxicology. Volume 3.
Classes of Pesticides. New York, NY: Academic Press, Inc., 1991. 1457]**PEER
REVIEWED**
Large oral doses caused tremor beginning 1-2 hr later; the animals became sensitive to
touch & had tonic or clonic convulsions. Rabbits & dogs showed a slight decr in
respiratory rate, lethargy, loss of tone of the abdominal muscles, discharge from the eyes,
& mydriasis prior to death.
[Hayes, W.J., Jr., E.R. Laws, Jr., (eds.). Handbook of Pesticide Toxicology. Volume 3.
Classes of Pesticides. New York, NY: Academic Press, Inc., 1991. 1457]**PEER
REVIEWED**
When mice were fed thiophanate-methyl for 6 months, there was a slight retardation of
growth in those receiving 8000 ppm, and, when killed, these rats had slight enlargement
of the liver with enlargement of some liver cells. The no-effect level was 1600 ppm
(about 250 mg/kg/day). Similar results were obtained in rats; the no-effect level of 1600
ppm in this species corresponds to about 78 mg/kg/day.
[Hayes, W.J., Jr., E.R. Laws, Jr., (eds.). Handbook of Pesticide Toxicology. Volume 3.
Classes of Pesticides. New York, NY: Academic Press, Inc., 1991. 1457]**PEER
REVIEWED**
A 2 yr study in rats showed that a dietary level of 640 ppm caused a slight reduction in
growth in both male & female rats & a slight incr in the relative weight of the kidneys in
males. There was no indication of incr thyroid or liver weight such as had been seen in an
earlier, briefer study; however, at the end of 2 yr there was some enlargement of thyroid
epithelial cells, especially in the males. Food consumption, survival, behavior, laboratory
findings, and, with the exception of the thyroid, gross & microscopic morphology did not
differ from those of the controls. A dietary level of 160 ppm (about 8 mg/kg/day) was a
no-effect level.
[Hayes, W.J., Jr., E.R. Laws, Jr., (eds.). Handbook of Pesticide Toxicology. Volume 3.
Classes of Pesticides. New York, NY: Academic Press, Inc., 1991. 1457]**PEER
REVIEWED**
When dogs were fed capsules of thiophanate-methyl 7 days a week for 2 yr, those
receiving 250 mg/kg/day showed a marginal effect on thyroid weight; those that received
10 mg/kg/day or less showed no effect. Even the highest dosage did not affect survival or
the gross or microscopic morphology of any tissue other than the thyroid.
[Hayes, W.J., Jr., E.R. Laws, Jr., (eds.). Handbook of Pesticide Toxicology. Volume 3.
Classes of Pesticides. New York, NY: Academic Press, Inc., 1991. 1457]**PEER
REVIEWED**
Repeated dermal application of a 10% concn to rabbits caused slight erythema, but this
disappeared a few days after the last treatment. A 1% suspension was not irritating. Even
the 10% suspension produced no clinical effect and no change in histology of the tissues.
Studies in guinea pigs with repeated sensitizing injections and a delayed challenge dose
indicated that thiophanate-methyl produced no primary irritation and only slight
sensitization. The compound showed no phototoxic property.
[Hayes, W.J., Jr., E.R. Laws, Jr., (eds.). Handbook of Pesticide Toxicology. Volume 3.
Classes of Pesticides. New York, NY: Academic Press, Inc., 1991. 1457]**PEER
REVIEWED**
This study was conducted to evaluate the relationship between Benomyl, Carbendazim,
Topsin-M, Dimethoate, and TPTA administrated by gavage, and the external and skeletal
changes of fetuses in rats. Results showed that Benomyl and Carbendazim could cause
external malformations and skeletal malformations, anomalies, and variations, but similar
changes were not found in Topsin-M, Dimethoate, and TPTA. The Carbendaziminducing skeletal changes in rats had a dose-response relationship. The external
malformations observed in Benomyl-treated fetuses induced exencephaly and
gastroschisis. Exencephaly, rhinocephaly, anury, kinky or bent tail, edema, astomia, and
fetal death occurred in Carbendazim-treated fetuses. The skeletal anomalies revealed in
Benomyl and Carbendazim-treated rats were absence (< 7) of arch, bifurcated arches,
extra ossification on an arch, fused arches/centers, hypoplastic arches/centers, variation in
shapes/size, reduction in the number (< 13) of ribs, small 13th rib, fused ribs, dumbbellshaped center, wavy and variations in shape.
[Lu SY et al; J of the Chinese Society of Veterinary Science 22 (6): 402-12
(1996)]**PEER REVIEWED**
Non-Human Toxicity Values:
LD50 Rat oral 6640 mg/kg
[Lewis, R.J. Sax's Dangerous Properties of Industrial Materials. 9th ed. Volumes 1-3.
New York, NY: Van Nostrand Reinhold, 1996. 2653]**PEER REVIEWED**
LD50 Rat ip 1140 mg/kg
[Lewis, R.J. Sax's Dangerous Properties of Industrial Materials. 9th ed. Volumes 1-3.
New York, NY: Van Nostrand Reinhold, 1996. 2653]**PEER REVIEWED**
LD50 Mouse oral 3400 mg/kg
[Lewis, R.J. Sax's Dangerous Properties of Industrial Materials. 9th ed. Volumes 1-3.
New York, NY: Van Nostrand Reinhold, 1996. 2653]**PEER REVIEWED**
LD50 Mouse ip 790 mg/kg
[Lewis, R.J. Sax's Dangerous Properties of Industrial Materials. 9th ed. Volumes 1-3.
New York, NY: Van Nostrand Reinhold, 1996. 2653]**PEER REVIEWED**
LD50 Rabbit oral 2270 mg/kg
[Lewis, R.J. Sax's Dangerous Properties of Industrial Materials. 9th ed. Volumes 1-3.
New York, NY: Van Nostrand Reinhold, 1996. 2653]**PEER REVIEWED**
LD50 Guinea pig oral 3640 mg/kg
[Lewis, R.J. Sax's Dangerous Properties of Industrial Materials. 9th ed. Volumes 1-3.
New York, NY: Van Nostrand Reinhold, 1996. 2653]**PEER REVIEWED**
LD50 Rat (male) oral 7500 mg/kg
[Tomlin, C.D.S. (ed.). The Pesticide Manual - World Compendium. 10th ed. Surrey, UK:
The British Crop Protection Council, 1994. 988]**PEER REVIEWED**
LD50 Rat (female) oral 6640 mg/kg
[Tomlin, C.D.S. (ed.). The Pesticide Manual - World Compendium. 10th ed. Surrey, UK:
The British Crop Protection Council, 1994. 988]**PEER REVIEWED**
LD50 Mouse (male) oral 3510 mg/kg
[Tomlin, C.D.S. (ed.). The Pesticide Manual - World Compendium. 10th ed. Surrey, UK:
The British Crop Protection Council, 1994. 988]**PEER REVIEWED**
LD50 Rabbit (male) oral 2270 mg/kg
[Tomlin, C.D.S. (ed.). The Pesticide Manual - World Compendium. 10th ed. Surrey, UK:
The British Crop Protection Council, 1994. 988]**PEER REVIEWED**
LD50 Rat percutaneous > 10,000 mg/kg
[Tomlin, C.D.S. (ed.). The Pesticide Manual - World Compendium. 10th ed. Surrey, UK:
The British Crop Protection Council, 1994. 988]**PEER REVIEWED**
LC50 Rat inhalation 1.7 mg/l air/4 hr
[Tomlin, C.D.S. (ed.). The Pesticide Manual - World Compendium. 10th ed. Surrey, UK:
The British Crop Protection Council, 1994. 988]**PEER REVIEWED**
LD50 Rat (male) ip 1640 mg/kg /from table/
[Hayes, W.J., Jr., E.R. Laws, Jr., (eds.). Handbook of Pesticide Toxicology. Volume 3.
Classes of Pesticides. New York, NY: Academic Press, Inc., 1991. 1457]**PEER
REVIEWED**
LD50 Rat (female) ip 1140 mg/kg /from table/
[Hayes, W.J., Jr., E.R. Laws, Jr., (eds.). Handbook of Pesticide Toxicology. Volume 3.
Classes of Pesticides. New York, NY: Academic Press, Inc., 1991. 1457]**PEER
REVIEWED**
LD50 Mouse (female) oral 3400 mg/kg /from table/
[Hayes, W.J., Jr., E.R. Laws, Jr., (eds.). Handbook of Pesticide Toxicology. Volume 3.
Classes of Pesticides. New York, NY: Academic Press, Inc., 1991. 1457]**PEER
REVIEWED**
LD50 Mouse (male) ip 790 mg/kg /from table/
[Hayes, W.J., Jr., E.R. Laws, Jr., (eds.). Handbook of Pesticide Toxicology. Volume 3.
Classes of Pesticides. New York, NY: Academic Press, Inc., 1991. 1457]**PEER
REVIEWED**
LD50 Mouse (female) ip 1110 mg/kg /from table/
[Hayes, W.J., Jr., E.R. Laws, Jr., (eds.). Handbook of Pesticide Toxicology. Volume 3.
Classes of Pesticides. New York, NY: Academic Press, Inc., 1991. 1457]**PEER
REVIEWED**
LD50 Guinea pig (male) oral 3640 mg/kg /from table/
[Hayes, W.J., Jr., E.R. Laws, Jr., (eds.). Handbook of Pesticide Toxicology. Volume 3.
Classes of Pesticides. New York, NY: Academic Press, Inc., 1991. 1457]**PEER
REVIEWED**
LD50 Guinea pig (female) oral 6700 mg/kg /from table/
[Hayes, W.J., Jr., E.R. Laws, Jr., (eds.). Handbook of Pesticide Toxicology. Volume 3.
Classes of Pesticides. New York, NY: Academic Press, Inc., 1991. 1457]**PEER
REVIEWED**
LD50 Rabbit (female) oral 2250 mg/kg /from table/
[Hayes, W.J., Jr., E.R. Laws, Jr., (eds.). Handbook of Pesticide Toxicology. Volume 3.
Classes of Pesticides. New York, NY: Academic Press, Inc., 1991. 1457]**PEER
REVIEWED**
Metabolism/Pharmacokinetics:
Metabolism/Metabolites:
Studies in mice with four radioactive forms of the molecule (14C in the ring or as the
thiourea carbon of the methyl carbon and 35S) showed that the C=S bond was cleaved to
a great extent prior to absorption from the gastrointestinal tract. Some of the methyl
carbon apparently is metabolized to carbon dioxide. The major urinary metabolites are
carbendazim and its 6-hydroxy derivative; these are excreted as O- or N-glucuronides. A
compound in which the two =S's of thiophanate-methyl are replaced by =O's is a minor
metabolite. Some other metabolites detectable by thin-layer chromatography of
radioactive material remain unidentified.
[Hayes, W.J., Jr., E.R. Laws, Jr., (eds.). Handbook of Pesticide Toxicology. Volume 3.
Classes of Pesticides. New York, NY: Academic Press, Inc., 1991. 1457]**PEER
REVIEWED**
Absorption, Distribution & Excretion:
Nearly all thiophanate-methyl is eliminated from the body in 24 hr; that left in tissues
after 24 hr is largely eliminated within 96 hr.
[Hayes, W.J., Jr., E.R. Laws, Jr., (eds.). Handbook of Pesticide Toxicology. Volume 3.
Classes of Pesticides. New York, NY: Academic Press, Inc., 1991. 1457]**PEER
REVIEWED**
Pharmacology:
Environmental Fate & Exposure:
Environmental Fate/Exposure Summary:
Thiophanate-methyl's production and use as a fungicide is expected to result in its
direct release to the environment. If released to air, a vapor pressure of 7.13X10-8 mm
Hg at 25 deg C indicates thiophanate-methyl will exist in both the vapor and particulate
phases in the ambient atmosphere. Vapor-phase thiophanate-methyl will be degraded in
the atmosphere by reaction with photochemically-produced hydroxyl radicals; the halflife for this reaction in air is estimated to be 5 hours. Particulate-phase thiophanatemethyl will be removed from the atmosphere by wet and dry deposition. If released to
soil, thiophanate-methyl is expected to have high mobility based upon an estimated Koc
of 137. Volatilization from moist soil surfaces is not expected to be an important fate
process based upon an estimated Henry's Law constant of 1.2X10-9 atm-cu m/mole.
Thiophanate-methyl degrades rapidly in soils of various textures to methyl 2benzimidazolecarbamate and the rate of degradation is four times faster in soil at pH 7.4
than in soil at pH 5.6. Thiophanate-methyl degraded by 90% during a 6-18 week period
in soils of various textures (humus 2-4%; pH 5.5-6.5). A half-life of 28 days was
estimated for thiophanate-methyl applied to leaves of green house crops. If released into
water, thiophanate-methyl is not expected to adsorb to suspended solids and sediment
based upon the estimated Koc. Volatilization from water surfaces is not expected to be an
important fate process based upon this compound's estimated Henry's Law constant.
Thiophanate-methyl degrades in aqueous solution (25 deg C; 48 hr) by 60% to methyl
benzimidazole-2-yl carbamate (MBC). An estimated BCF of 2.4 suggests the potential
for bioconcentration in aquatic organisms is low. Occupational exposure to thiophanatemethyl may occur through inhalation and dermal contact with this compound at
workplaces where thiophanate-methyl is produced or used. (SRC)
**PEER REVIEWED**
Probable Routes of Human Exposure:
Occupational exposure to thiophanate-methyl may occur through inhalation and dermal
contact with this compound at workplaces where thiophanate-methyl is produced or
used(SRC). Worker re-entry exposure to pesticides residues in greenhouses is a probable
exposure route based upon a study in which thiophanate-methyl was applied to
carnations via high-volume spraying at application rates of 150 and 325 g ai/1000 sq m,
showing half-lives of 22 and 41 days, respectively(1). Dermal exposure of greenhouse
workers to thiophanate-methyl (applied by spraying) on carnations cultured in
greenhouses was found to be 64 mg/day (during cutting operations) and 23 mg/day
(during sorting and bundling)(2).
[(1) Brouwer DH et al; Bull Environ Contam Toxicol 58: 976-84 (1997) (2) Van
Hemmen JJ et al; Med Fac Landbouww Univ Gent 57/3b: 1271-1283 (1992)]**PEER
REVIEWED**
Artificial Pollution Sources:
Thiophanate-methyl's production and use as a fungicide(1) is expected to result in its
direct release to the environment(SRC).
[(1) Farm Chemicals Handbook 2000. Willoughby, OH: Meister Pub Co. p. C 383
(2000)]**PEER REVIEWED**
Environmental Fate:
TERRESTRIAL FATE: Based on a classification scheme(1), an estimated Koc value of
137(SRC), determined from a log Kow of 1.4(2) and a regression-derived equation(3),
indicates that thiophanate-methyl is expected to have high mobility in soil(SRC).
Volatilization of thiophanate-methyl from moist soil surfaces is not expected to be an
important fate process(SRC) given an estimated Henry's Law constant of 1.2X10-9 atmcu m/mole(SRC), based upon its vapor pressure, 7.13X01-8 mm Hg(4), and water
solubility, 26.6 mg/l(5). Thiophanate-methyl is not expected to volatilize from dry soil
surfaces(SRC) based upon its vapor pressure(4). Thiophanate-methyl degrades rapidly
in soils of various textures to methyl 2-benzimidazolecarbamate; the rate of conversion is
four times faster in soil at pH 7.4 than in soil at pH 5.6(6). Thiophanate-methyl
degraded by 90% during a 6-18 week period in soils of various textures (humus 2-4%;
pH 5.5-6.5)(7). A half-life of 28 days was estimated for thiophanate-methyl applied to
leaves of green house crops(8).
[(1) Swann RL et al; Res Rev 85: 17-28 (1983) (2) Hansch C et al; Exploring QSAR.
Hydrophobic, Electronic, and Steric Constants. ACS Prof Ref Book. Heller SR, consult.
ed., Washington, DC: Amer Chem Soc p. 101 (1995) (3) Lyman WJ et al; Handbook of
Chemical Property Estimation Methods. Washington, DC: Amer Chem Soc pp. 4-9
(1990) (4) Tomlin C; The Pesticide Manual. 11 ed. Surrey, England: British Crop Protect
Council p. 1201 (1997) (5) Hu JY et al; Water Sci Technol 35: 219-6 (1997) (6) Fleeker
JR et al; J Agr Food Chem 22: 592-595 (1974) (7) Blume HP Ahlsdorf B; Ecotox
Environ Safety 26: 313-332 (1993) (8) Brouwer DH et al; Bull Environ Contam Toxicol
58: 976-984 (1997)]**PEER REVIEWED**
AQUATIC FATE: Based on a classification scheme(1), an estimated Koc value of
137(SRC), determined from a log Kow of 1.4(2) and a regression-derived equation(3),
indicates that thiophanate-methyl is not expected to adsorb to suspended solids and
sediment(SRC). Volatilization from water surfaces is not expected(3) based upon an
estimated Henry's Law constant of 1.2X10-9 atm-cu m/mole(SRC), based upon its vapor
pressure, 7.13X01-8 mm Hg(4), and water solubility, 26.6 mg/l(5). Thiophanate-methyl
degrades in aqueous solution (25 deg C; 48 hr) by 60% to methyl benzimidazole-2-yl
carbamate (MBC)(8). According to a classification scheme(6), an estimated BCF of
2.4(SRC), from its log Kow(2) and a regression-derived equation(7), suggests the
potential for bioconcentration in aquatic organisms is low(SRC).
[(1) Swann RL et al; Res Rev 85: 17-28 (1983) (2) Hansch C et al; Exploring QSAR.
Hydrophobic, Electronic, and Steric Constants. ACS Prof Ref Book. Heller SR, consult.
ed., Washington, DC: Amer Chem Soc p. 101 (1995) (3) Lyman WJ et al; Handbook of
Chemical Property Estimation Methods. Washington, DC: Amer Chem Soc pp. 4-9, 15-1
to 15-29 (1990) (4) Tomlin C; The Pesticide Manual. 11 ed. Surrey, England: British
Crop Protect Council p. 1201 (1997) (5) Hu JY et al; Water Sci Technol 35: 219-6 (1997)
(6) Franke C et al; Chemosphere 29: 1501-14 (1994) (7) Meylan WM et al; Environ
Toxicol Chem 18: 664-72 (1999) (8) Buchenauer H et al; Pestic Sci 4: 343-8
(1973)]**PEER REVIEWED**
ATMOSPHERIC FATE: According to a model of particle partitioning of semivolatile
organic compounds in the atmosphere(1), thiophanate-methyl, which has a vapor
pressure of 7.13X10-8 mm Hg at 25 deg C(2), will exist in both the vapor and particulate
phases. Vapor-phase thiophanate-methyl is degraded in the atmosphere by reaction with
photochemically-produced hydroxyl radicals(SRC); the half-life for this reaction in air is
estimated to be 5 hours(SRC), calculated from its rate constant of 7.6X10-11 cu
cm/molecule-sec at 25 deg C(SRC).
[(1) Bidleman TF; Environ Sci Technol 22: 361-367 (1988) (2) Tomlin C; The Pesticide
Manual. 11 ed. Surrey, England: British Crop Protect Council p. 1201 (1997) (3) Meylan
WM, Howard PH; Chemosphere 26: 2293-99 (1993)]**PEER REVIEWED**
Environmental Biodegradation:
AEROBIC: Thiophanate-methyl degrades rapidly in soils of various textures to methyl
2-benzimidazolecarbamate; the rate of conversion is four times faster in soil at pH 7.4
than in soil at pH 5.6(1). Thiophanate-methyl degraded by 90% during a 6-18 week
period in soils of various textures (humus 2-4%; pH 5.5-6.5)(2). A half-life of 28 days
was estimated for thiophanate-methyl applied to leaves of green house crops(3).
[(1) Fleeker JR et al; J Agr Food Chem 22: 592-595 (1974) (2) Blume HP Ahlsdorf B;
Ecotox Environ Safety 26: 313-332 (1993) (3) Brouwer DH et al; Bull Environ Contam
Toxicol 58: 976-984 (1997)]**PEER REVIEWED**
Environmental Abiotic Degradation:
The rate constant for the vapor-phase reaction of thiophanate-methyl with
photochemically-produced hydroxyl radicals has been estimated as 7.6X10-11 cu
cm/molecule-sec at 25 deg C(SRC) using a structure estimation method(1). This
corresponds to an atmospheric half-life of about 5 hours at an atmospheric concentration
of 5X10+5 hydroxyl radicals per cu cm(1). Thiophanate-methyl is stable in neutral,
aqueous solution at room temperature and is stable to air and sunlight(2). Thiophanates
have an absorption maximum of 263 nm (range was 220-310 nm); thiophanate-methyl
degrades in aqueous solution (25 deg C; 48 hr) by 60% to methyl benzimidazole-2-yl
carbamate (MBC)(3). MBC is more toxic than the thiophenates. Degradation was not
observed in dark controls. An aqueous solution of thiophenate-methyl applied to plant
foliage exposed to sunlight was found to degrade at a similar rate under the same
environmental conditions(3).
[(1) Meylan WM, Howard PH; Chemosphere 26: 2293-99 (1993) (2) Tomlin CDS, ed;
The Pesticide Manual World Compendium. 11th ed., Surrey, England: British Crop
Protect Council p. 1201 (1997) (3) Buchenauer H et al; Pestic Sci 4: 343-8
(1973)]**PEER REVIEWED**
Environmental Bioconcentration:
An estimated BCF of 2.4 was calculated for thiophanate-methyl(SRC), using a log Kow
of 1.4(1) and a regression-derived equation(2). According to a classification scheme(3),
this BCF suggests the potential for bioconcentration in aquatic organisms is low(SRC).
[(1) Hansch C et al; Exploring QSAR. Hydrophobic, Electronic, and Steric Constants.
ACS Prof Ref Book. Heller SR, consult. ed., Washington, DC: Amer Chem Soc p. 101
(1995) (2) Meylan WM et al; Environ Toxicol Chem 18: 664-72 (1999) (3) Franke C et
al; Chemosphere 29: 1501-14 (1994)]**PEER REVIEWED**
Soil Adsorption/Mobility:
The Koc of thiophanate-methyl is estimated as 137(SRC), using a log Kow of 1.4(1)
and a regression-derived equation(2). According to a classification scheme(3), this
estimated Koc value suggests that thiophanate-methyl is expected to have high mobility
in soil.
[(1) Hansch C et al; Exploring QSAR. Hydrophobic, Electronic, and Steric Constants.
ACS Prof Ref Book. Heller SR, consult. ed., Washington, DC: Amer Chem Soc. p. 101
(1995) (2) Lyman WJ et al; Handbook of Chemical Property Estimation Methods.
Washington, DC: Amer Chem Soc pp. 4-9 (1990) (3) Swann RL et al; Res Rev 85: 17-28
(1983)]**PEER REVIEWED**
Volatilization from Water/Soil:
The Henry's Law constant for thiophanate-methyl is estimated as 1.2X10-9 atm-cu
m/mole(SRC) derived from its vapor pressure, 7.13X10-8 mm Hg(1), and water
solubility, 26.6 mg/l(2). This Henry's Law constant indicates that thiophanate-methyl is
expected to be essentially nonvolatile from water surfaces(3). Thiophanate-methyl's
estimated Henry's Law constant indicates that volatilization from moist soil surfaces will
not occur(SRC). Thiophanate-methyl is not expected to volatilize from dry soil
surfaces(SRC) based upon its vapor pressure(1).
[(1) Tomlin C; The Pesticide Manual. 11 ed. Surrey, England: British Crop Protect
Council p. 1201 (1997) (2) Hu JY et al; Water Sci Technol 35: 219-6 (1997) (3) Lyman
WJ et al; Handbook of Chemical Property Estimation Methods. Washington, DC: Amer
Chem Soc pp. 15-1 to 15-29 (1990)]**PEER REVIEWED**
Environmental Water Concentrations:
GROUNDWATER: Thiophanate-methyl was detected in 0 of 3 groundwater samples
collected in California in 1988(1).
[(1) USEPA; Pesticides in Ground Water Database. Washington, DC: USEPA Off Pest
Programs. Prevention Pesticides and Toxic Substances. (H7507C) USEPA-734-12-92001 (1992)]**PEER REVIEWED**
Plant Concentrations:
Thiophanate-methyl applied to soil at an unspecified concn was taken up in tomatoes,
peppers, and eggplants and persisted up to 8 weeks following application(1).
[(1) Netzer D, Dishon I; Phytoparasitica 1: 33-7 (1973)]**PEER REVIEWED**
Environmental Standards & Regulations:
FIFRA Requirements:
Tolerances are established for residues of the fungicide thiophanate-methyl
(dimethyl[(1,2-phenylene)-bis(iminocarbonothioyl)]bis[carbamate]), its oxygen analogue
dimethyl-4,4-o-phenylene bis(allophonate), and its benzimidazole-containing metabolites
(calculated as thiophanate-methyl) in or on the following food commodities: almonds
(pre-H); almonds (hulls) pre-H; apple, dried pomace; apples (pre- and post-H); apricots
(pre- and post-H); bananas (pre-H); bananas, pulp (pre-H); beans (snap and dry) (pre-H);
bean (forage and hay) (pre-H); cattle, fat; cattle, kidney; cattle, liver; cattle, meat
byproducts (exc. kidney and liver); cattle, meat; celery (pre-H); cherries (pre- and postH); cucumbers; eggs; goats, fat; goats, kidney; goats, liver; goat, meat byproducts (exc.
kidney and liver); goat, meat; hogs, fat; hogs, liver; hogs, meat byproducts (exc. liver);
hogs, meat; horses, fat; horses, liver; horses, meat byproducts (exc. liver); horses, meat;
melons; milk; nectarines (pre- and post-H); onion, dry; onion, green; pecans (pre-H);
peaches (pre- and post-H); peanuts (pre-H); peanuts (forage and hay) (pre-H); plums
(pre- and post-H); potatoes (seed treatment); poultry, fat; poultry, liver; poultry, meat
byproducts (exc. liver); poultry, meat; prunes (pre- and post-H); pumpkins; sheep, fat;
sheep, kidney; sheep, liver; sheep, meat byproducts (exc. kidney and liver); sheep, meat;
soybeans (pre-H); squash; strawberries (pre-H); sugar beets (roots pre-H); sugar beets
(tops pre-H); sugarcane (seed piece treatment pre-H); wheat, grain; wheat, hay; and
wheat, straw.
[40 CFR 180.371 (7/1/2000)]**PEER REVIEWED**
CERCLA Reportable Quantities:
Persons in charge of vessels or facilities are required to notify the National Response
Center (NRC) immediately, when there is a release of this designated hazardous
substance, in an amount equal to or greater than its statutory reportable quantity of 1 lb.
(The Agency may adjust the statutory reportable quantity for this hazardous substance in
a future rulemaking; until then the statutory reportable quantity applies.) The toll free
number of the NRC is (800) 424-8802; In the Washington D.C. metropolitan area (202)
426-2675. The rule for determining when notification is required is stated in 40 CFR
302.4 (section IV. D.3.b).
[40 CFR 302.4 (7/1/2000)]**PEER REVIEWED**
RCRA Requirements:
U409; As stipulated in 40 CFR 261.33, when thiophanate-methyl, as a commercial
chemical product or manufacturing chemical intermediate or an off-specification
commercial chemical product or a manufacturing chemical intermediate, becomes a
waste, it must be managed according to Federal and/or State hazardous waste regulations.
Also defined as a hazardous waste is any residue, contaminated soil, water, or other
debris resulting from the cleanup of a spill, into water or on dry land, of this waste.
Generators of small quantities of this waste may qualify for partial exclusion from
hazardous waste regulations (40 CFR 261.5).
[40 CFR 261.33 (7/1/2000)]**PEER REVIEWED**
Allowable Tolerances:
Tolerances are established for residues of the fungicide thiophanate-methyl
(dimethyl[(1,2-phenylene)-bis(iminocarbonothioyl)]bis[carbamate]), its oxygen analogue
dimethyl-4,4-o-phenylene bis(allophonate), and its benzimidazole-containing metabolites
(calculated as thiophanate-methyl) in or on the following food commodities: almonds
(pre-H), 0.2 (N) ppm; almonds (hulls) pre-H, 1.0 pm; apple, dried pomace, 40.0 ppm;
apples (pre- and post-H), 7.0 ppm; apricots (pre- and post-H), 15.0 ppm; bananas (pre-H),
2.0 ppm; bananas, pulp (pre-H), 0.2 ppm; beans (snap and dry) (pre-H), 2.0 ppm; bean
(forage and hay) (pre-H), 50.0 ppm; cattle, fat, 0.1 ppm; cattle, kidney, 0.2(N) ppm;
cattle, liver, 2.5 ppm; cattle, meat byproducts (exc. kidney and liver), 0.1(N) ppm; cattle,
meat, 0.1(N) ppm; celery (pre-H), 3.0 ppm; cherries (pre- and post-H), 15.0 ppm;
cucumbers, 1.0 ppm; eggs, 0.1(N) ppm; goats, fat, 0.1(N) ppm; goats, kidney 0.2 ppm;
goats, liver, 2.5 ppm; goat, meat byproducts (exc. kidney and liver), 0.1(N) ppm; goat,
meat, 0.1(N) ppm; hogs, fat, 0.1(N) ppm; hogs, liver, 0.1 ppm; hogs, meat byproducts
(exc. liver), 0.1(N) ppm; hogs, meat, 0.1(N) ppm; horses, fat, 0.1(N) ppm; horses, liver,
1.0 ppm; horses, meat byproducts (exc. liver), 0.1(N) ppm; horses, meat, 0.1(N) ppm;
melons, 1.0 ppm; milk, 1.0 ppm; nectarines (pre- and post-H), 15.0 ppm; onion, dry, 3.0
ppm; onion, green, 3.0 ppm; pecans (pre-H), 0.2 ppm; peaches (pre- and post-H), 15.0
ppm; peanuts (pre-H), 0.2(N) ppm; peanuts (forage and hay) (pre-H), 15.0 ppm; plums
(pre- and post-H), 15.0 ppm; potatoes (seed treatment), 0.05 ppm; poultry, fat, 0.1(N)
ppm; poultry, liver, 0.2(N) ppm; poultry, meat byproducts (exc. liver), 0.1(N) ppm;
poultry, meat, 0.1(N) ppm; prunes (pre- and post-H), 15.0 ppm; pumpkins, 1.0 ppm;
sheep, fat, 0.1(N) ppm; sheep, kidney, 0.2 ppm; sheep, liver, 2.5 ppm; sheep, meat
byproducts (exc. kidney and liver), 0.1(N) ppm; sheep, meat, 0.1(N) ppm; soybeans (preH), 0.2 ppm; squash, 1.0 ppm; strawberries (pre-H), 5.0 ppm; sugar beets (roots pre-H),
0.2 ppm; sugar beets (tops pre-H), 15.0 ppm; sugarcane (seed piece treatment pre-H),
0.1(N) ppm; wheat, grain, 0.05 ppm; wheat, hay, 0.10 ppm; and wheat, straw, 0.10 ppm.
[40 CFR 180.371 (7/1/2000)]**PEER REVIEWED**
Chemical/Physical Properties:
Molecular Formula:
C12-H14-N4-O4-S2
**PEER REVIEWED**
Molecular Weight:
342.40
[Lide, DR (ed.). CRC Handbook of Chemistry and Physics. 81st Edition. CRC Press
LLC, Boca Raton: FL 2000,p. 3-320]**PEER REVIEWED**
Color/Form:
Colorless crystals
[Tomlin, C.D.S. (ed.). The Pesticide Manual - World Compendium. 10th ed. Surrey, UK:
The British Crop Protection Council, 1994. 987]**PEER REVIEWED**
Colorless prisms
[Budavari, S. (ed.). The Merck Index - An Encyclopedia of Chemicals, Drugs, and
Biologicals. Whitehouse Station, NJ: Merck and Co., Inc., 1996. 1595]**PEER
REVIEWED**
Colorless crystaline solid
[Farm Chemicals Handbook 2000. Willoughby, Ohio: Meister 2000.,p. C 384]**PEER
REVIEWED**
Melting Point:
172 deg C (dec)
[Lide, DR (ed.). CRC Handbook of Chemistry and Physics. 81st Edition. CRC Press
LLC, Boca Raton: FL 2000,p. 3-320]**PEER REVIEWED**
Dissociation Constants:
pKa = 7.28
[Tomlin, C.D.S. (ed.). The Pesticide Manual - World Compendium, 11 th ed., British
Crop Protection Council, Surrey, England 1997 1201]**PEER REVIEWED**
Octanol/Water Partition Coefficient:
log Kow = 1.40
[Hansch, C., Leo, A., D. Hoekman. Exploring QSAR - Hydrophobic, Electronic, and
Steric Constants. Washington, DC: American Chemical Society., 1995. 101]**PEER
REVIEWED**
Solubilities:
In acetone 58.1, cyclohexanone 43, methanol 29.2, acetonitrile 24.4, ethyl acetate 11.9
(all in g/kg, 23 deg C). Slightly soluble in hexane.
[Tomlin, C.D.S. (ed.). The Pesticide Manual - World Compendium. 10th ed. Surrey, UK:
The British Crop Protection Council, 1994. 988]**PEER REVIEWED**
Thiophanate methyl is slightly soluble in most organic solvents... .
[Hayes, W.J., Jr., E.R. Laws, Jr., (eds.). Handbook of Pesticide Toxicology. Volume 3.
Classes of Pesticides. New York, NY: Academic Press, Inc., 1991. 1456]**PEER
REVIEWED**
Soluble in acetone, methanol, chloroform and acetonitrile.
[Budavari, S. (ed.). The Merck Index - An Encyclopedia of Chemicals, Drugs, and
Biologicals. Whitehouse Station, NJ: Merck and Co., Inc., 1996. 1595]**PEER
REVIEWED**
Sparingly soluble in most organic solvents.
[Farm Chemicals Handbook 2000. Willoughby, Ohio: Meister 2000.,p. C 384]**PEER
REVIEWED**
In water, 26.6 mg/l @ 20 deg C.
[Hu JY et al; Water Sci Technol 35: 291-26 (1997)]**PEER REVIEWED**
Vapor Pressure:
7.13X10-8 mm Hg @ 25 deg C
[Tomlin, C.D.S. (ed.). The Pesticide Manual - World Compendium, 11 th ed., British
Crop Protection Council, Surrey, England 1997 1201]**PEER REVIEWED**
Other Chemical/Physical Properties:
Unique thioallophanate structure
[Farm Chemicals Handbook 2000. Willoughby, Ohio: Meister 2000.,p. C 384]**PEER
REVIEWED**
MP: 181.5 - 182.5 deg C
[Budavari, S. (ed.). The Merck Index - An Encyclopedia of Chemicals, Drugs, and
Biologicals. Whitehouse Station, NJ: Merck and Co., Inc., 1996. 1595]**PEER
REVIEWED**
Chemical Safety & Handling:
Skin, Eye and Respiratory Irritations:
Mild skin & eye irritant.
[Tomlin, C.D.S. (ed.). The Pesticide Manual - World Compendium. 10th ed. Surrey, UK:
The British Crop Protection Council, 1994. 988]**PEER REVIEWED**
Toxic Combustion Products:
When heated to decomposition it emits very toxic fumes of NOx and SOx /nitrogen
oxides and sulfur oxides/.
[Lewis, R.J. Sax's Dangerous Properties of Industrial Materials. 9th ed. Volumes 1-3.
New York, NY: Van Nostrand Reinhold, 1996. 2653]**PEER REVIEWED**
Hazardous Reactivities & Incompatibilities:
... Incompatible with alkaline & copper-containing compounds.
[Tomlin, C.D.S. (ed.). The Pesticide Manual - World Compendium. 10th ed. Surrey, UK:
The British Crop Protection Council, 1994. 988]**PEER REVIEWED**
Hazardous Decomposition:
When heated to decomposition it emits very toxic fumes of NOx and SOx /nitrogen
oxides and sulfur oxides/.
[Lewis, R.J. Sax's Dangerous Properties of Industrial Materials. 9th ed. Volumes 1-3.
New York, NY: Van Nostrand Reinhold, 1996. 2653]**PEER REVIEWED**
Preventive Measures:
SRP: The scientific literature for the use of contact lenses in industry is conflicting. The
benefit or detrimental effects of wearing contact lenses depend not only upon the
substance, but also on factors including the form of the substance, characteristics and
duration of the exposure, the uses of other eye protection equipment, and the hygiene of
the lenses. However, there may be individual substances whose irritating or corrosive
properties are such that the wearing of contact lenses would be harmful to the eye. In
those specific cases, contact lenses should not be worn. In any event, the usual eye
protection equipment should be worn even when contact lenses are in place.
**PEER REVIEWED**
Stability/Shelf Life:
Stable in neutral, aqueous solution at room temperature. Stable to air & sunlight. Quite
stable in acidic solution at room temperature; unstable in alkaline solution. ... Formulated
product is stable > or = 2 yr below 50 deg C.
[Hayes, W.J., Jr., E.R. Laws, Jr., (eds.). Handbook of Pesticide Toxicology. Volume 3.
Classes of Pesticides. New York, NY: Academic Press, Inc., 1991. 1456]**PEER
REVIEWED**
Disposal Methods:
Generators of waste (equal to or greater than 100 kg/mo) containing this contaminant,
EPA hazardous waste number U409, must conform with USEPA regulations in storage,
transportation, treatment and disposal of waste.
[40 CFR 240-280, 300-306, 702-799 (7/1/2000)]**PEER REVIEWED**
Occupational Exposure Standards:
Manufacturing/Use Information:
Major Uses:
For Thiophanate methyl (USEPA/OPP Pesticide Code: 102001) ACTIVE products with
label matches. /SRP: Registered for use in the U.S. but approved pesticide uses may
change periodically and so federal, state and local authorities must be consulted for
currently approved uses./
[U.S. Environmental Protection Agency/Office of Pesticide Program's Chemical
Ingredients Database on Thiophanate methyl (23564-05-8). Available from the Database
Query page at http://www.cdpr.ca.gov/docs/epa/epamenu.htm as of February 5,
2001.]**PEER REVIEWED**
Used for plant disease control in vegetables, fruits, & turf.
[Lewis, R.J. Sax's Dangerous Properties of Industrial Materials. 9th ed. Volumes 1-3.
New York, NY: Van Nostrand Reinhold, 1996. 2653]**PEER REVIEWED**
Systemic fungicide
[Farm Chemicals Handbook 2000. Willoughby, Ohio: Meister 2000.,p. C 383]**PEER
REVIEWED**
Wound protectant (fruit trees)
[Ashford, R.D. Ashford's Dictionary of Industrial Chemicals. London, England:
Wavelength Publications Ltd., 1994. 886]**PEER REVIEWED**
Preventative and curative fungicide
[Gerhartz, W. (exec ed.). Ullmann's Encyclopedia of Industrial Chemistry. 5th ed.Vol
A1: Deerfield Beach, FL: VCH Publishers, 1985 to Present.,p. VA12 (89) 99]**PEER
REVIEWED**
Manufacturers:
W.A. Cleary Corp., 1049 Somerset St., Somerset, NJ 08873, (732)247-8000; Production
site: Somerset, NJ 08873
[SRI International. 2000 Directory of Chemical Producers -- United States. SRI
Consulting, Menlo Park: CA 2000 792]**PEER REVIEWED**
Methods of Manufacturing:
o-Phenylenediamine + potassium thiocyanate + methyl chloroformate
(addition/dehydrochlorination)
[Ashford, R.D. Ashford's Dictionary of Industrial Chemicals. London, England:
Wavelength Publications Ltd., 1994. 886]**PEER REVIEWED**
Formulations/Preparations:
USEPA/OPP Pesticide Code 102001; Trade Names: Topsin, Cercobin M, Banrot,
component of (with 084701), Fungo, TD-1771, NF-44, Enovit methyl.
[U.S. Environmental Protection Agency/Office of Pesticide Program's Chemical
Ingredients Database on Thiophanate methyl (23564-05-8). Available from the Database
Query page at http://www.cdpr.ca.gov/docs/epa/epamenu.htm as of February 5,
2001.]**PEER REVIEWED**
Laboratory Methods:
Analytic Laboratory Methods:
EPA Method PMD-THO. Determination of Thiophanate-Methyl by UV Spectroscopy.
[USEPA; EMMI. EPA's Environmental Monitoring Methods Index. Version 1.1. PC#
4082. Rockville, MD: Government Institutes (1997)]**PEER REVIEWED**
FDA Method 242.3. Method for Benzimidazole Residues.
[USEPA; EMMI. EPA's Environmental Monitoring Methods Index. Version 1.1. PC#
4082. Rockville, MD: Government Institutes (1997)]**PEER REVIEWED**
Product analysis by hplc. Residue analysis by colorimetry.
[Tomlin, C.D.S. (ed.). The Pesticide Manual - World Compendium, 11 th ed., British
Crop Protection Council, Surrey, England 1997 1202]**PEER REVIEWED**
Special References:
Synonyms and Identifiers:
Synonyms:
BAS 32500F
**PEER REVIEWED**
o-BIS(3-METHOXYCARBONYL-2-THIOUREIDO)BENZENE
**PEER REVIEWED**
1,2-BIS(METHOXYCARBONYLTHIOUREIDO)BENZENE
**PEER REVIEWED**
1,2-BIS(3-(METHOXYCARBONYL)-2-THIOUREIDO)BENZENE
**PEER REVIEWED**
CERCOBIN METHYL
**PEER REVIEWED**
Cycosin
**PEER REVIEWED**
1,2-Di(3-methoxycarbonyl-2-thioureido)benzene
**PEER REVIEWED**
dimethyl [1,2-phenylenebis(iminocarbonothioyl)]bis[carbamate]
**PEER REVIEWED**
dimethyl 4,4'-(o-phenylene)bis(3-thioallophanate)
**PEER REVIEWED**
ENOVIT M
**PEER REVIEWED**
Pesticide Code 102001
**PEER REVIEWED**
FUNGITOX
**PEER REVIEWED**
METHYL THIOPHANATE
**PEER REVIEWED**
Mildothane
**PEER REVIEWED**
NEOTOPSIN
**PEER REVIEWED**
NF 44
**PEER REVIEWED**
PELT-44
**PEER REVIEWED**
4,4'-o-PHENYLENEBIS(3-THIOALLOPHANIC ACID)DIMETHYL ESTER
**PEER REVIEWED**
SIPCAVIT
**PEER REVIEWED**
TD 1771
**PEER REVIEWED**
Tedion V-18
**PEER REVIEWED**
Topsin M
**PEER REVIEWED**
Topsin methyl
**PEER REVIEWED**
TOPSIN WP METHYL
**PEER REVIEWED**
ZYBAN
**PEER REVIEWED**
Formulations/Preparations:
USEPA/OPP Pesticide Code 102001; Trade Names: Topsin, Cercobin M, Banrot,
component of (with 084701), Fungo, TD-1771, NF-44, Enovit methyl.
[U.S. Environmental Protection Agency/Office of Pesticide Program's Chemical
Ingredients Database on Thiophanate methyl (23564-05-8). Available from the Database
Query page at http://www.cdpr.ca.gov/docs/epa/epamenu.htm as of February 5,
2001.]**PEER REVIEWED**
EPA Hazardous Waste Number:
U409; A toxic waste when a discarded commercial chemical product or manufacturing
chemical intermediate or an off-specification commercial chemical product or
manufacturing chemical intermediate.
Administrative Information:
Hazardous Substances Databank Number: 6937
Last Revision Date: 20021011
Last Review Date: Reviewed by SRP on 5/10/2001
Update History:
Complete Update on 10/11/2002, 48 fields added/edited/deleted.