S-Ethyl-1-perhydroazepinthioat

Pesticide -> EPA IRIS

Herbicides

Active substance -> EU Pesticides database: Not approved

Pesticides -> Herbicides, Thiocarbamate

Pesticide (Molinate) -> USDA PDB

Pesticide

log Kow = 3.21

2.49

Clear liquid

Amber liquid

Miscible with acetone, ethanol, kerosene, 4-methylpentan-2-one, xylene

In water, 970 mg/l @ 25 °C

0.0056 [mmHg]

5.6X10-3 mm Hg @ 25 °C

Warning

H302: Harmful if swallowed [Warning Acute toxicity, oral]

P203, P260, P261, P264, P270, P271, P272, P273, P280, P301+P317, P302+P352, P304+P340, P317, P318, P319, P321, P330, P333+P317, P362+P364, P391, P405, and P501 (click each P-code to see the statement)

Warning

H302+H332 (36.7%): Harmful if swallowed or if inhaled [Warning Acute toxicity, oral; acute toxicity, inhalation]

P203, P260, P261, P264, P270, P271, P272, P273, P280, P301+P317, P302+P352, P304+P340, P317, P318, P319, P321, P330, P333+P317, P362+P364, P391, P405, and P501 (click each P-code to see the statement)

Hazard Traits - Carcinogenicity; Developmental Toxicity; Reproductive Toxicity

Regulation (EC) No 1107/2009 (amended)

03/81/EC, Reg. (EU) No 2015/408, Reg. (EU) 2022/801, Reg. (EU) No 540/2011

The New Jersey Worker and Community Right to Know Act requires public and private employers to provide information about hazardous substances at their workplaces. (N.J.S.A. 34:5A-1 et. seq.)

A skin and eye irritant; [HSDB] High-dose animal studies: Reproductive toxicity at 4 mg/kg/day; Increased thyroid weights at 45 mg/kg/day in 13-week feeding study of dogs; May cause skin sensitization; [eChemPortal: ESIS] May cause irritation; May cause skin sensitization; Targets the thyroid; [MSDSonline] See Diallate and Thiobencarb.

Tolerances are established for negligible residues of the herbicide S-ethyl hexahydro-1H-azepine-1-carbothioate in or on the raw agcultural commodities rice and rice straw.

As the federal pesticide law FIFRA directs, EPA is conducting a comprehensive review of older pesticides to consider their health and environmental effects and make decisions about their future use. Under this pesticide reregistration program, EPA examines health and safety data for pesticide active ingredients initially registered before November 1, 1984, and determines whether they are eligible for reregistration. In addition, all pesticides must meet the new safety standard of the Food Quality Protection Act of 1996. Pesticides for which EPA had not issued Registration Standards prior to the effective date of FIFRA, as amended in 1988, were divided into three lists based upon their potential for human exposure and other factors, with List B containing pesticides of greater concern and List D pesticides of less concern. Molinate is found on List B. Case No: 2435; Pesticide type: herbicide; Case Status: OPP is reviewing data from the pesticide's producers regarding its human health and/or environmental effects, or OPP is determining the pesticide's eligibility for reregistration and developing the Reregistration Eligibility Decision (RED) document.; Active ingredient (AI): S-Ethyl hexahydro-1H-azepine-1-carbothioate; Data Call-in (DCI) Date(s): 06/11/91, 10/13/95; AI Status: The producers of the pesticide has made commitments to conduct the studies and pay the fees required for reregistration, and are meeting those commitments in a timely manner.

MOLINATE is a thiocarbamate. Flammable gases are generated by the combination of thiocarbamates and dithiocarbamates with aldehydes, nitrides, and hydrides. Thiocarbamates and dithiocarbamates are incompatible with acids, peroxides, and acid halides.

Acute Tox. 4 (100%)

Carcinogenicity - category 2

Acute toxicity (Oral) - Category 4

Acute toxicity (Oral) - Category 4

Carc. 2

SRP: At the time of review, criteria for land treatment or burial (sanitary landfill) disposal practices are subject to significant revision. Prior to implementing land disposal of waste residue (including waste sludge), consult with environmental regulatory agencies for guidance on acceptable disposal practices.

Incinerate in a unit equipped with an effluent gas scrubber to absorb polluting combustion product (sulfur dioxide). Incineration temp about 1000 °C for 1-2 sec. Recommendable methods: Incineration /of treated residual/.

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.

Avoid contact and inhalation. Wash hands and exposed skin before eating, drinking or smoking and after work.

SRP: Contaminated protective clothing should be segregated in such a manner so that there is no direct personal contact by personnel who handle, dispose, or clean the clothing. Quality assurance to ascertain the completeness of the cleaning procedures should be implemented before the decontaminated protective clothing is returned for reuse by the workers. Contaminated clothing should not be taken home at end of shift, but should remain at employee's place of work for cleaning.

Excerpt from ERG Guide 151 [Substances - Toxic (Non-Combustible)]:

Wear protective clothing; wash it thoroughly after use.

Treatment of carbamate poisoning is similar to that of organophosphate poisoning in that atropine sulfate injections readily reverse the effects. For acute exposures and first aid: EYES: irrigate opened eyes for several minutes under running water. INGESTION: do not induce vomiting. Rinse mouth with water (never give anything by mouth to an unconscious person). Seek immediate medical advice. SKIN: should be treated immediately by rinsing the affected parts in cold running water for at least 15 minutes, followed by thorough washing with soap and water. If necessary, the person should shower and change contaminated clothing and shoes, and then must seek medical attention. INHALATION: supply fresh air. If required provide artificial respiration.

Data concerning the effects of thiocarbamates on man are scarce. However, cases of irritation and sensitization have been observed among agricultural workers. Some thiocarbamates, e.g., molinate, have an effect on sperm morphology and, consequently, on reproduction. However, no teratogenic effects have been observed. The results of mutagenicity studies have shown that thiocarbamates containing dichloroallyl groups are highly mutagenic. Some thiocarbamates are acetylcholine esterase inhibitors. Acute exposure to cholinesterase inhibitors can cause a cholinergic crisis characterized by severe nausea/vomiting, salivation, sweating, bradycardia, hypotension, collapse, and convulsions. Increasing muscle weakness is a possibility and may result in death if respiratory muscles are involved.

LC50 CRAYFISH 14 MG/L/96 HR

LC50 Gammarus fasciatus 4.5 mg/l/96 hr @ 21 °C (95% confidence limit 3.5-5.8 mg/l), mature. Static bioassay without aeration, pH 7.2-7.5, water hardness 40-50 mg/l as calcium carbonate and alkalinity of 30-35 mg/l. /Technical, 98.6%/

LC50 Pteronarcys 0.34 mg/l/96 hr @ 15 °C (95% confidence limit 0.24-0.47 mg/l), mature. Static bioassay without aeration, pH 7.2-7.5, water hardness 40-50 mg/l as calcium carbonate and alkalinity of 30-35 mg/l. /Technical, 98.6%/

LC50 Salmo gairdneri (Rainbow trout) 0.21 mg/l/96 hr @ 12 °C (95% confidence limit 0.16-0.29 mg/l), wt 1.6 g. Static bioassay without aeration, pH 7.2-7.5, water hardness 40-50 mg/l as calcium carbonate and alkalinity of 30-35 mg/l. /Technical, 98.6%/

For more Ecotoxicity Values (Complete) data for MOLINATE (10 total), please visit the HSDB record page.

Ordram was applied in granular form to flooded rice paddy. The half-life of Ordram was less than 100 hr. No significant residues were present in the water after 192 hr. In a rice field, Ordram was half gone in 3 days. About 80% of the Ordram was lost by vaporization. Field studies conducted under flooded rice cultivation indicated that molinate has a half-life of 74 to 118 hr in intermittent flow plots and 37 to 71 hr in continuous flow plots. The half-life was not dependent on application rate.

TERRESTRIAL FATE: Based on a classification scheme(1), Koc values ranging from 80-120(2,3) indicates that molinate is expected to have high mobility in soil(SRC). Volatilization of molinate from moist soil surfaces is expected to be an important fate process(SRC) given a estimated Henry's Law constant of 4.10X10-6 atm-cu m/mole(4). Molinate is not expected to volatilize from dry soil surfaces(SRC) based upon a vapor pressure of 5.6X10-3 mm Hg(5). Molinate residues do not persist long enough to injure susceptible crops planted 1 yr after application(6). Field studies have shown that volatilization can be the dominant removal process for molinate applications to soil and flooded rice field surfaces(9-11). The half-life in most loam soils (at 21-27 °C) is approximately 3 weeks(6); the US Dept of Agric's Pesticide Properties Database lists a soil half-life of 21 days(5). Volatilization half-lives of applications to flooded rice fields are reported to range from about 1 to 6 days(8,9,12). Biodegradation is an important environmental fate process. Degradation studies have shown that molinate will degrade more rapidly in non-sterile soil than in sterile soil; >90% of initial molinate degraded while only 10-20% degraded in the sterile controls(7). Degradation under anaerobic soil conditions is reported to be slower than under aerobic conditions(7,8); half-lives were 8-25 days under upland conditions and about 40-160 days under flooded conditions(7).

AQUATIC FATE: Based on a classification scheme(1), Koc values ranging from 80-120(2,3), indicate that molinate is not expected to adsorb to suspended solids and sediment(SRC). Volatilization from water surfaces is expected(4) based upon a Henry's Law constant of 4.10X10-6 atm-cu m/mole(5). Using this Henry's Law constant and an estimation method(4), volatilization half-lives for a model river and model lake are 12 and 94 days, respectively(SRC). The major loss route from water is by volatilization, with a reported half-life of 84 hrs from rice paddies in the Sacramento Valley in California(6). The half-life of molinate in natural waters collected from rice paddies or rivers fed by rice paddy runoff ranged from 0.6 to 6.6 days(12). Molinate can degrade in water through photooxidation(13). Molinate has been shown to undergo photo-sensitized degradation (via reaction with photochemically formed species such as hydroxyl radicals) in natural water(14,15); photodegradation rates will depend upon sunlight intensity and availability of sensitizing agents such as humic materials, amino acids, etc(SRC). According to a classification scheme(7), measured BCF values of 13 to 48(8-11), suggests bioconcentration in aquatic organisms is low to moderate. Molinate can degrade in water through biodegradation(13). Anaerobic conditions retard microbial degradation in aqueous media(13); therefore, persistence is expected to increase in anaerobic conditions with no sunlight exposure(SRC).

ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), molinate, which has a vapor pressure of 5.6X10-3 mm Hg at 25 °C(2), is expected to exist solely as a vapor in the ambient atmosphere. Vapor-phase molinate 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 12 hrs(SRC), calculated from its rate constant of 3.0X10-11 cu cm/molecule-sec at 25 °C(SRC), determined using a structure estimation method(3).

Some thiocarbamates (EPTC, Molinate, Pebulate, and Cycloate) share a common mechanism of toxicity, i.e. the inhibition of acetylcholinesterase. An acetylcholinesterase inhibitor suppresses the action of acetylcholine esterase. Because of its essential function, chemicals that interfere with the action of acetylcholine esterase are potent neurotoxins, causing excessive salivation and eye-watering in low doses. Headache, salivation, nausea, vomiting, abdominal pain and diarrhea are often prominent at higher levels of exposure. Acetylcholine esterase breaks down the neurotransmitter acetylcholine, which is released at nerve and muscle junctions, in order to allow the muscle or organ to relax. The result of acetylcholine esterase inhibition is that acetylcholine builds up and continues to act so that any nerve impulses are continually transmitted and muscle contractions do not stop.

As with organophosphates, the signs and symptoms are based on excessive cholinergic stimulation. Unlike organophosphate poisoning, carbamate poisonings tend to be of shorter duration because the inhibition of nervous tissue acetylcholinesterase is reversible, and carbamates are more rapidly metabolized. Muscle weakness, dizziness, sweating and slight body discomfort are commonly reported early symptoms. Headache, salivation, nausea, vomiting, abdominal pain and diarrhea are often prominent at higher levels of exposure. Contraction of the pupils with blurred vision, incoordination, muscle twitching and slurred speech have been reported. (L795)

Stormwater runoff in the Sacramento River Basin, CA sampled during a storm in January, 1994 contained molinate at a concn range of 91 to 475 ng/l post-rainfall(1). In a 1988-1989 agricultural field runoff study conducted in Greece, it was estimated that 0.3% of field applied molinate was transported to the Gulf of Thermaikos via the Loudias River(2).

Tolerances are established for negligible residues of the herbicide S-ethyl hexahydro-1H-azepine-1-carbothioate in or on the raw agcultural commodities rice and rice straw.

As the federal pesticide law FIFRA directs, EPA is conducting a comprehensive review of older pesticides to consider their health and environmental effects and make decisions about their future use. Under this pesticide reregistration program, EPA examines health and safety data for pesticide active ingredients initially registered before November 1, 1984, and determines whether they are eligible for reregistration. In addition, all pesticides must meet the new safety standard of the Food Quality Protection Act of 1996. Pesticides for which EPA had not issued Registration Standards prior to the effective date of FIFRA, as amended in 1988, were divided into three lists based upon their potential for human exposure and other factors, with List B containing pesticides of greater concern and List D pesticides of less concern. Molinate is found on List B. Case No: 2435; Pesticide type: herbicide; Case Status: OPP is reviewing data from the pesticide's producers regarding its human health and/or environmental effects, or OPP is determining the pesticide's eligibility for reregistration and developing the Reregistration Eligibility Decision (RED) document.; Active ingredient (AI): S-Ethyl hexahydro-1H-azepine-1-carbothioate; Data Call-in (DCI) Date(s): 06/11/91, 10/13/95; AI Status: The producers of the pesticide has made commitments to conduct the studies and pay the fees required for reregistration, and are meeting those commitments in a timely manner.

... RICE SHOOTS HARVESTED 3 DAYS AFTER TREATMENT WITH CHAIN-LABELED MOLINATE SHOWED ... 16 RADIOACTIVE METABOLITES. 7 OF THESE RADIOACTIVE SPOTS COINCIDED WITH AMINO ACIDS ... 5 METABOLITES WERE ORG ACIDS, 2 OF WHICH WERE ... LACTIC & GLYCOLIC ACID.

IN JAPANESE CARP, MAJOR MOLINATE METABOLITES DETECTED WERE MOLINATE SULFOXIDE, 3-HYDROXYMOLINATE, 4-HYDROXYMOLINATE, 4-KETOMOLINATE, & ALPHA KETO HEXAMETHYLENEAMINE.

MOLINATE METABOLITE MOLINATE SULFOXIDE WAS CLEAVED IN VITRO BY JAPANESE CARP LIVER CYTOSOL FRACTION. MOLINATE MERCAPTURATE WAS RECOVERED FROM BILE OF MOLINATE TREATED CARP.

(14)C Molinate ... was metabolized by rats, primarily to the sulfoxide, and thence to the mercapturic acid deriv. Ring hydroxylation, mainly at the 3- and 4- positions, followed by glucuronidation and cleavage of the C--N bond to yieldthe imide, were also observed.

For more Metabolism/Metabolites (Complete) data for MOLINATE (9 total), please visit the HSDB record page.

As a general rule, thiocarbamates can be absorbed via the skin, mucous membranes, and the respiratory and gastrointestinal tracts. They are eliminated quite rapidly, mainly via expired air and urine. Two major pathways exist for the metabolism of thiocarbamates in mammals. One is via sulfoxidation and conjugation with glutathione. The conjugation product is then cleaved to a cysteine derivative, which is metabolized to a mercapturic acid compound. The second route is oxidation of the sulfur to a sulfoxide, which is then oxidized to a sulfone, or hydroxylation to compounds that enter the carbon metabolic pool.

Agents, either mechanical or chemical, which destroy spermatozoa in the male genitalia and block spermatogenesis.

Pesticides used to destroy unwanted vegetation, especially various types of weeds, grasses (POACEAE), and woody plants. Some plants develop HERBICIDE RESISTANCE.

IT IS RAPIDLY METABOLIZED BY RATS, ABOUT 50% TO CARBON DIOXIDE, 25% EXCRETED IN THE URINE AND 7 TO 20% IN THE FECES IN 3 DAYS.

MOLINATE IS RAPIDLY TAKEN UP BY ROOTS & TRANSLOCATED UPWARD TO LEAVES OF PLANTS.

... Not absorbed percutaneously.

Excretion of ring labeled (14)C molinate by rats is 95-96% complete in 48 hr. Approximately 88% was in the urine ... and 11% in the feces. Less than 1% of the dose was found in the expired air. ... Tissue levels were approximately 13.8% of the administered dose after 1 day and 3.7% after 7 days,

Used as selective herbicide for rice; [HSDB]

Farming (Pesticides) [Category: Industry]

For Molinate (USEPA/OPP Pesticide Code: 041402) 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./

Selective herbicide

Herbicide

Thiocarbamates are widely used throughout the world and are produced in great quantities, mainly as herbicides and fungicides.

From ethyl chlorothiolformate and hexamethyleneimine.

Hexamethyleneimine + ethyl chlorothioformate (dehydrochlorination)

USEPA/OPP Pesticide Code 041402; Trade Names: Hydram; Ordram; R-4572; Felan; Jalan; Yulan; and Sakkimol.

ORDRAM 63 (6 LB/GAL); ORDRAM 5G (5% BY WT). GRANULES--5% & 10% ACTIVE INGREDIENT.

Tech. material is 95% pure.

Formulations of this product include an emulsifiable liquid (8 lb active ingredient/gal and granules (10% active ingredient).

Emulsifiable liquid, granules

/MOLINATE/ ... IS APPLIED EITHER BEFORE PLANTING TO WATER-SEEDED OR SHALLOW SOIL-SEEDED RICE OR POST-FLOOD, POST-EMERGENCE ON OTHER TYPES OF RICE CULTURE.

Should be applied and incorporated into the soil with disk or spiketooth harrow before the field is flooded for planting of water seeded rice, or applied after waterseeded or drilled rice is flooded and after the watergrass has emerged at least 2 in and not more than 5 in from the soil, and is at least two-thirds submerged by the water. Rates of application are from 2 to 3 lb per acre. Emulsifiable liquid concentrate are diluted with water so that the recommended rate is applied in the gallonage required for air and ground application.