Thionazin

Nematicides

Active substance -> EU Pesticides database: Not approved

Pesticides -> Organophosphate Insecticides

Pesticide (Thionazin) -> USDA PDB

1.204-1.210 @ 25 °C

1.204-1.210 @25 °C

MISCIBLE WITH MOST ORG SOLVENTS

1140 PPM IN WATER @ 24.8 °C

MISCIBLE WITH POLYETHYLENE GLYCOLS & DIMETYL FORMAMIDE

176 °F at 0.001 mmHg (EPA, 1998)

80 °C

80 °C @760 [mm Hg]

29 °F (EPA, 1998)

-1.7 °C

-1.7 °C

0.003 mmHg at 86 °F (EPA, 1998)

0.003 [mmHg]

3X10-3 MM HG @ 30 °C

0.003 [mm Hg] @30 °C

Thionazin is an amber liquid. Pure compound is almost colorless; technical product is light brown to tan. Used in insecticides, fungicides, and nematocides. Not registered as a pesticide in the U.S. (EPA, 1998)

Nearly colorless liquid when pure; Technical product: Light brown to tan liquid; [HSDB] Clear very deep brown liquid; [MSDSonline]

HYDROLYZED BY ALKALI TO SODIUM PYRAZINOLATE

TECHNICAL PRODUCT IS LIGHT BROWN TO TAN, RELATIVELY MOBILE LIQUID

Danger

H300: Fatal if swallowed [Danger Acute toxicity, oral]

P262, P264, P270, P280, P301+P316, P302+P352, P316, P321, P330, P361+P364, P405, and P501 (click each P-code to see the statement)

Danger

H300+H310 (20%): Fatal if swallowed or in contact with skin [Danger Acute toxicity, oral; acute toxicity, dermal]

P262, P264, P270, P280, P301+P316, P302+P352, P316, P321, P330, P361+P364, P405, and P501 (click each P-code to see the statement)

2002/2076

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 cholinesterase inhibitor; [CAMEO] The average of two baseline respective cholinesterase activity determinations three days apart, with no exposures to enzyme inhibiting pesticides for at least 30 days, is recommended for each worker prior to exposure to cholinesterase inhibitors because of large inter-individual differences in published baseline values. To be established at least once a year. Removal from workplace exposures is recommended until the cholinesterase activity returns to within 20% of baseline. [TLVs and BEIs]

As stipulated in 40 CFR 261.33, when O,O-diethyl O-pyrazinyl phosphate, 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 container or inner liner used to hold this waste or 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(e)).

Organothiophosphates, such as THIONAZIN, are susceptible to formation of highly toxic and flammable phosphine gas in the presence of strong reducing agents such as hydrides. Partial oxidation by oxidizing agents may result in the release of toxic phosphorus oxides.

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 reportable quantity of 100 lb or 45.4 kg. 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).

Releases of CERCLA hazardous substances are subject to the release reporting requirement of CERCLA section 103, codified at 40 CFR part 302, in addition to the requirements of 40 CFR part 355. Thionazin is an extremely hazardous substance (EHS) subject to reporting requirements when stored in amounts in excess of its threshold planning quantity (TPQ) of 500 lbs.

Acute Tox. 2 (100%)

Acute toxicity (dermal) - category 1

Acute toxicity (Oral) - Category 2

Acute Tox. 1

(Non-Specific -- Organic Phosphate Compound, Liquid, Poison B). Keep unnecessary people away; stay upwind; wear positive pressure breathing apparatus and special protective clothing; remove and isolate contaminated clothing. (Non-Specific -- Organic Phosphate Mixture, Liquid, Poison B). Do not extinguish fire unless flow can be stopped. (Non-Specific -- Parathion) Avoid breathing dusts, and fumes from burning materials. Avoid body contact with materials. Wear full protective clothing.

Biological Exposure Indices (BEI) [ACGIH] - Acetylcholinesterase activity in red blood cells = 70% of individual's baseline; Butylcholinesterase activity in serum or plasma = 60% of individual's baseline; Sample at end of shift; [TLVs and BEIs]

(Non-Specific -- Organic Phosphate Compound, Liquid, Poison B). Do not touch spilled material; stop leak if possible; use water spray to reduce vapors. Small spill: take up with sand or other noncombustible absorbent material and place into container for later disposal.

Generators of waste (equal to or greater than 100 kg/mo) containing this contaminant, EPA hazardous waste number P040, must conform with USEPA regulations in storage, transportation, treatment and disposal of waste.

Good candidate for liquid injection incineration with a temperature range of 650 to 1600 °C with a residence time of 0.1 to 2 seconds. Also, a good candidate for rotary kiln incineration with a temperature range of 820 to 1600 °C with a residence times for liquids and gases: seconds, solids: hours. Also, a good candidate for fluidized bed incineration with a temperature range of 450 to 980 °C with residence times for liquids and gases: seconds; solids: longer.

Group I Containers: Combustible containers from organic or metallo-organic pesticides (except organic mercury, lead, cadmium, or arsenic compounds) should be disposed of in pesticide incinerators or in specified landfill sites. /Organic or metallo-organic pesticides/

Group II Containers: Non-combustible containers from organic or metallo-organic pesticides (except organic mercury, lead, cadmium, or arsenic compounds) must first be triple-rinsed. Containers that are in good condition may be returned to the manufacturer or formulator of the pesticide product, or to a drum reconditioner for reuse with the same type of pesticide product, if such reuse is legal under Department of Transportation regulations (eg 49 CFR 173.28). Containers that are not to be reused should be punctured ... and transported to a scrap metal facility for recycling, disposal or burial in a designated landfill. /Organic or metallo-organic pesticides/

0.011 [mg/m3]

0.12 [mg/m3]

0.69 [mg/m3]

For emergency situations, wear a positive pressure, pressure-demand, full facepiece self-contained breathing apparatus (SCBA) or pressure- demand supplied air respirator with escape SCBA and a fully-encapsulating, chemical resistant suit. (EPA, 1998)

LC50 Colinus virginianus (Bobwhite quail) oral 65 ppm, (in 5 day diet), age 14 days (technical grade)

LC50 Coturnix japonica (Japanese quail) oral 58 ppm, (in 5 day diet), age 14 days (technical grade)

LD50 Phasianus colchicus (ring-necked pheasant) oral 72 ppm, (in 5 day diet), age 10 days (technical grade)

LD50 Anas platyrhynchos (mallard ducks) oral approx 420 ppm (in 5 day diet), age 10 days (technical grade)

TERRESTRIAL FATE: SOIL WAS TREATED WITH ZINOPHOS SHORTLY AFTER PLANTING. ... DETECTABLE AMT REMAINED FOR 1 YR IN CHURCH FIELD SOIL (PH 5.4) BUT IN HIGH FIELD (PH 7.3) NO RESIDUES ... DETECTED AFTER THIS PERIOD. ZINOPHOS HALF-LIFE IN SOILS VARIED FROM ABOUT 5-12 DAYS @ LOW DOSAGE (5 PPM) TO ABOUT 9-22 DAYS @ HIGH DOSAGE (20 PPM).

TERRESTRIAL FATE: Thionazin was described as slightly persistent in soil, with a given half-life of 2-6 weeks encompassing removal by leaching, hydrolysis, and biodegradation(1). Commercial formulations of 10 ppm thionazin applied to the top or broadcast 4 inches into a sandy loam soil (pH= 6.1) resulted in a removal half-life of 23 days(2). The initial loss rate when thionazin was applied at 250 ppm was much slower, and traces of thionazin remained after 2 years(2). In a laboratory assay, 100 ppm thionazin lost 95% of its biological activity in 100 days(3). Thionazin was found in soil up to one year after its application to an acidic sandy loam field, but this compound was not detected after 10 weeks in alkaline clay soil(4).

AQUATIC FATE: If released to water, thionazin is expected to undergo hydrolysis. An experimentally determined half-life for the hydrolysis of thionazin at 25 °C under neutal conditions was given as 29 days at pH 7(1,2). A half-life of approximately 40 and 4 days at pH 10 and pH 11, respectively, can be calculated(SRC) from a basic hydrolysis rate constant of 7.3 L/mole-hr(1,2). Thionazin was reported as having a half-life of 14 weeks in natural water at pH 6.8(3).

ATMOSPHERIC FATE: If released to the atmosphere, the vapor pressure, 3X10-3 mm Hg at 30 °C(1), suggests that thionazin may exist entirely in the vapor phase in the ambient atmosphere(2). Thionazin is expected to undergo rapid destruction by the gas phase reaction with photochemically produced hydroxyl radicals; the half-life for the reaction can be estimated at 4.3 hr(2,SRC). The water solubility, 1140 mg/l at 25 °C(1), suggests that wet deposition may occur(SRC).

A calculated soil adsorption coefficient of 100 has been reported for thionazin(1). This value suggests that thionazin will display high mobility in soil(2). In a laboratory study measuring the water induced movement of insecticides in packed soil columns, thionazin was found to have a relative mobility factor of 3.2 on a scale from 1 to 6(3).

POISONOUS BY SKIN CONTACT, INHALATION, OR /INGESTION/

SYMPTOMATOLOGY: 1. Nausea is often the first symptom, followed by vomiting, abdominal cramps, diarrhea, and excessive salivation (sialorrhea). Hypothermia has been reported in animals and at least once in man as an early sign. 2. Headache, giddiness, vertigo, and weakness. 3. Rhinorrhea and a sensation of tightness in the chest are common in inhalation exposures. 4. Blurring or dimness of vision, miosis (with fixed pinpoint pupils), tearing, ciliary muscle spasm, loss of accommodation, and ocular pain. None of these ocular effects are diagnostically dependable except in primary ocular exposures. Indeed, mydriasis is sometimes seen, probably due to sympatho-adrenal discharge. 5. Bradycardia or tachycardia. Varying degrees of AV heart block are described, as well as atrial arrhythmias. 6. Loss of muscle coordination, slurring of speech, fasciculations and twitching of muscles (particularly of the tongue and eyelids), and generalized profound weakness. 7. Mental confusion, disorientation, and drowsiness. 8. Difficulty in breathing, excessive secretion of saliva and of respiratory tract mucus, oronasal frothing, cyanosis, pulmonary rales and rhonchi, and hypertension presumably due to asphyxia. 9. Random jerky movements, incontinence, convulsions and coma. 10. Death primarily due to respiratory arrest arising from failure of the respiratory muscles, intense bronchoconstriction, or all three. /Parathion/

Thionazin was used as a soil insecticide and nematicide for the control of free living and plant parasitic nematodes, foliar insects, root maggots, and symphilids(1). It may have been released to the environment by fugitive emissions during its production, formulation, and application as an insecticide(SRC).

... Zinophos degraded faster in non-autoclaved soil ...

When 10 and 100 ppm thionazin was added to soil, the oxygen consumption was found to increase proportionally over the endogenous level(1). The author concluded that microbial degradation was indicated(1). Thionazin at these concentrations was not found to be permanently deleterious to the microbiota(1). Thionazin was listed as being degradable by microbiological means(2). The oxygen consumption of a sandy loam soil was found to increase significantly above the level of endogenous respiration when 5 or 10 ug/g of thionazin was added(3). When applied to a sultan silty loam, thionazin was found to undergo removal at rates faster than those observed in autoclaved samples; the half-lives for removal were 2 weeks of the soil sample and 9 weeks for the autoclaved sample (25 °C, pH 6.3, 20% water moisture)(4). Thionazin was most persistent at pH 5.5, and least persistent at pH 8.1, however, the author concluded that this was due to a change in the biological species responsible for degradation, and not from abiotic processes(4). The persistence of thionazin was also found to decrease with increasing moisture content of the soil(4). In a related study, thionazin underwent 68%, 23%, 31%, and 22% degradation in sultan silty loam, autoclaved sample, irradiated sample, and irradiated and autoclaved sample, respectively(5). The difference between the degradation in the autoclaved and irradiated sample was attributed to presence of a heat labile substance, which could not be identified(5).

A calculated bioconcentration factor for thionazin of 13 has been reported using the water solubility and a regression equation(1). This value suggests that bioconcentration in fish and aquatic organisms is not expected to be a significant fate process(SRC).

A calculated Henry's Law constant of 8.19X10-7 atm cu-m/mol at 20 °C has been reported for thionazin(1). Based on this value, the estimated volatilization half life for a model river 1 m deep, flowing at 1 m/sec, and a wind velocity of 3 m/sec is 69 days(2,SRC). Volatilization of thionazin from water to the atmosphere is, thus, not expected to be a significant fate process(SRC). Thionazin was described as being volatile from soil at 20 °C(3), however, the Henry's Law constant suggests that volatilization from moist soil is not expected to be a significant process(SRC).

IN NINETY DAY FEEDING TESTS, RATS FED ON DIETS CONTAINING 25-50 PPM SHOWED MODERATE DEPRESSION IN GROWTH RATE BUT NO ABNORMAL BEHAVIORAL REACTIONS.

THIRTY ONE & 90 DAY STUDY WITH DOGS FED 0.5 PPM TO 25 PPM /THIONAZIN/ HAVE BEEN CARRIED OUT INDICATING THAT NO DEATHS OCCUR @ THESE LEVELS.

An experimentally determined rate constant for the hydrolysis of thionazin under neutral conditions was given as 1.0X10-3 1/hr at 25 °C, which translates to a half-life of 29 d at pH 7(1,2). An experimental hydrolysis rate constant under basic conditions of 7.3 l/mole-hr (1,2) translates to a calculated half-life of approximately 40 and 4 days at pH 10 and pH 11, respectively(SRC). Thionazin was reported as having a half-life of 14 weeks in natural water at pH 6.8(3). Thionazin had a half-life of 50, 54, and 56 hr at 70 °C in water from the River Thames, the River Irthing, and in Brussels sprout extract, respectively(4). At 20 °C, the rates can be expected to be several hundred times slower(4). The half-life for the gas phase reaction of thionazin with photochemically produced hydroxyl radicals can be estimated to be 4.3 hr(5,SRC).

As stipulated in 40 CFR 261.33, when O,O-diethyl O-pyrazinyl phosphate, 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 container or inner liner used to hold this waste or 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(e)).

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 reportable quantity of 100 lb or 45.4 kg. 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).

Releases of CERCLA hazardous substances are subject to the release reporting requirement of CERCLA section 103, codified at 40 CFR part 302, in addition to the requirements of 40 CFR part 355. Thionazin is an extremely hazardous substance (EHS) subject to reporting requirements when stored in amounts in excess of its threshold planning quantity (TPQ) of 500 lbs.

Organophosphorus derivatives act by combining with and inactivating the enzyme acetylcholinesterase (AChE). ... The inactivation of cholinesterase by cholinesterase inhibitor pesticides allows the accumulation of large amounts of acetylcholine, with resultant widespread effects that may be ... separated into 4 categories: (1) Potentiation of postganglionic parasympathetic activity. ... (2) Persistent depolarization of skeletal muscle ... (3) Initial stimulation following depression of cells of central nervous system ... (4) Variable ganglionic stimulation or blockade ... /Cholinesterase inhibitor pesticides/

Used as soil insecticide and nematocide to protect vegetables, corn, and other crops; No longer commercially produced in the US; [HSDB] Used in insecticides, fungicides, and nematocides; [CAMEO]

Not registered with the EPA for use as pesticide in the US; [CAMEO]

Farming (Pesticides) [Category: Industry]

FORMERLY A SOIL INSECTICIDE ON VEGETABLES; CORN; STRAWBERRIES; MINT

/Former uses/: Thionazin is a soil insecticide and nematocide effective against a number of plant parasitic as well as free living nematodes, including those attacking buds, bulbs, leaves and roots, as well as against soil dwelling pests such as root maggots and symphylids and foliar insects such as aphids and leaf miners. When incorporated in mushroom compost at spawning it is effective against mushroom flies.

Phosphorothioic acid, O,O-diethyl O-2-pyrazinyl ester: ACTIVE

Product discontinued by American Cyanamid.

PREPN: DIXON ET AL; GORDON; MILLER, FORBES; GAGLIARDI; US PATENTS 2,918,468; 2,938,831; 3,091,614; 3,340,262 (1959, 1960, 1963, 1967, ALL TO AMERICAN CYANAMID).

THIONAZIN ... /WAS/ SHOWN TO BE EFFECTIVE AGAINST SEVERAL SPECIES OF PARASITIC NEMATODES WHEN APPLIED TO SOIL & IS ALSO USED AS ROOT DIP. COMBINATION OF THIONAZIN PLUS PHORATE ... /WAS/ BEING USED IN SOME AREAS.