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Zineb

Zineb structure

Zineb 

structure
  • CAS No:

    12122-67-7

  • Formula:

    C4H6N2S4Zn

  • Chemical Name:

    Zineb

  • Synonyms:

    Zinc,[N-[2-[(dithiocarboxy)amino]ethyl]carbamodithioato(2-)-κS,κS′]-;Zinc,[ethylenebis[dithiocarbamato]]-;Zinc,[[1,2-ethanediylbis[carbamodithioato]](2-)]-;Zinc,[[2-[(dithiocarboxy)amino]ethyl]carbamodithioato(2-)-κS,κS′]-;Carbamodithioic acid,1,2-ethanediylbis-,zinc complex;[N-[2-[(Dithiocarboxy)amino]ethyl]carbamodithioato(2-)-κS,κS′]zinc;Aspor;Blizene;Carbadine;Dithane Z 78;Lirotan;Lonacol;Novozir N;Parzate zineb;Zineb;Cynkotox;Hexathane;Asporum;Crittox;Micide 55;Zineb 80;Carbamodithioic acid,1,2-ethanediylbis-,zinc salt;Zebenide;Dithane Z;Novozir N 50;Novozir;Daisen;Dithane 65;Perozine;Perozin;Zinc ethylenebis[dithiocarbamate];Discon;Perozine 75B;Perozin 75B;Ethylenebis[dithiocarbamato]zinc;Ethylenebis[dithiocarbamic acid] zinc salt;Zinc N,N′-ethylenebisdithiocarbamate;Aaphytora;Aphytora;Deikusol;Fungo-Pulvit;Thionic M;Pilzol SZ;Unizeb;Zinosan;Aspor C;Funjeb;Polyram Z;Phytox;Dipher;Tiezene;Zebtox;Tritoftorol;Curit;Turbair Zineb Fungicide;Bonzeb 10;Bonzeb;Indofil Z 78;Azzurro;NSC 49513;142-14-3;1360-39-0;12673-65-3;14039-25-9;14242-12-7;14460-17-4;20316-44-3;21512-95-8;39357-09-0;70066-35-2;84653-18-9;1135443-09-2

  • Categories:

    Agrochemicals  >  Fungicides

Description

Light-tan solid. Insoluble in water; soluble in pyridine; decomposes on heating.ChEBI: A polymeric complex of zinc with the ethylene bis(dithiocarbamate) anionic ligand. Formerly used as an agricultural fungicide for the control of downy mildews and rusts, its use is no longer permitted in the US or the EU.Zineb is a light-coloured powder/crystal and insoluble in water. Zineb is one of the nonsystemic (surface-acting) fungicides of the group ethylenebisdithiocarbamates (EBDCs). Zineb is a po


Zineb appears as an off-white powder. Used as a fungicide.|YELLOW POWDER.|An off-white, or pale yellow powder.


Zineb appears as an off-white powder. Used as a fungicide.

Zineb Basic Attributes

275.75

273.870514

235-180-1

0350

2771

DTXSID5021465

Powder or crystals from chloroform + alcohol|Light-tan solid|WHITE POWDER OR CRYSTALS|Pale yellow powder

29309090

Characteristics

88.24000

0.60850

Water-Insoluble Powder

1.74 g/cm3 (approx) @ Temp: 20 °C

157 °C (decomp)

308.2ºC at 760mmHg

90℃

ca.10 mg l -1 (room temperature)Decomposes gradually, accelerated by exposure to air, moisture, and heat. Insoluble in water. Thio and dithiocarbamates slowly decompose in aqueous solution to form carbon disulfide and methylamine or other amines. Such decompositions are accelerated by acids.

2-8°C

<1x l0 -5 at 20 °C

Oral-rat LD50: 267 mg/kg; Oral-Mouse LD50: 480 mg/kg

Flammable; burning produces toxic nitrogen oxides and sulfur oxide fumes; strongly irritates eyes, nose and throat

Practically odorless

Henry's Law constant = <2.7X10-9 atm-cu m/mole (est)

The powder spreads easily on water, also forms aqueous suspensions|Fungicidal activity is due to degradation products, principally ethylenethiuram monosulfide.|When precipitated from concentrated solution a polymer is formed which is less fungicidal.|Incompatible with alkaline or mercury-containing compounds.|Unstable to light, moisture, and heat on prolonged storage (decomposition is reduced by stabilizers).

Decomposes gradually, accelerated by exposure to air, moisture, and heat. Insoluble in water. Thio and dithiocarbamates slowly decompose in aqueous solution to form carbon disulfide and methylamine or other amines. Such decompositions are accelerated by acids.

Thiocarbamate Esters and Salts/Dithiocarbamate Esters and Salts

ZINEB is a zinc salt of a dithiocarbamic acid. May generate flammable gases with aldehydes, nitrides, and hydrides. Incompatible with acids, peroxides, and acid halides.

149 °C

Dust explosion possible if in powder or granular form, mixed with air.

Safety Information

I; II; III

6.1

UN 3077 9 / PGIII

3

37-43

8-24/25-46

ZH3325000

Xi

The warehouse is ventilated, low temperature and dry; stored and transported separately from food materials

Unstable to light, moisture and heat on prolonged storage ...

P261-P280

H317-H335

Generators of waste (equal to or greater than 100 kg/mo) containing this contaminant, EPA hazardous waste number U114, must conform with USEPA regulations in storage, transportation, treatment and disposal of waste.|A potential candidate for liquid injection incineration at a temperature range of 650 to 1,600 °C and a residence time of 0.1 to 2 seconds. A potential candidate for rotary kiln incineration at a temperature range of 820 to 1,600 °C and residence times of seconds for liquids and gases, and hours for solids. A potential candidate for fluidized bed incineration at a temperature range of 450 to 980 °C and residence times of seconds for liquids and gases, and longer for solids. /Ethylenebisdithiocarbamate/

Zineb is an indirect food additive for use only as a component of adhesives.

WHO; Environmental Health Criteria 78: Dithiocarbamate Pesticides, Ethylenethiourea and Propylenethiourea (1988). EHC documents are designed for scientists and administrators responsible for the establishment of safety standards and regulations and provide basic scientific risk evaluations of a wide range of chemicals and groups of chemicals.[Available from, as of March 4, 2010: http://www.inchem.org/documents/ehc/ehc/ehc78.htm]

Flash point data for this chemical are not available, but it is probably combustible. (NTP, 1992)|Combustible. Gives off irritating or toxic fumes (or gases) in a fire. Finely dispersed particles form explosive mixtures in air.

|Warning|H317: May cause an allergic skin reaction [Warning Sensitization, Skin]|P261, P271, P272, P280, P302+P352, P304+P340, P312, P321, P333+P313, P363, P403+P233, P405, and P501|H317 (100%): May cause an allergic skin reaction [Warning Sensitization, Skin]|Aggregated GHS information provided by 261 companies from 6 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies.|Danger|H316: Causes mild skin irritation [Warning Skin corrosion/irritation]|P260, P261, P264, P270, P271, P272, P280, P302+P352, P304+P340, P312, P314, P321, P332+P313, P333+P313, P363, P403+P233, P405, and P501|P260, P261, P264, P270, P271, P272, P273, P280, P302+P352, P304+P340, P311, P312, P314, P321, P333+P313, P363, P391, P403+P233, P405, and P501

Excerpt from ERG Guide 151 [Substances - Toxic (Non-combustible)]: As an immediate precautionary measure, isolate spill or leak area in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids. SPILL: Increase, in the downwind direction, as necessary, the isolation distance shown above. FIRE: If tank, rail car or tank truck is involved in a fire, ISOLATE for 800 meters (1/2 mile) in all directions; also, consider initial evacuation for 800 meters (1/2 mile) in all directions. (ERG, 2016)

SMALL SPILLS AND LEAKAGE: If you spill this chemical, FIRST REMOVE ALL SOURCES OF IGNITION, then dampen the solid spill material with toluene, then transfer the dampened material to a suitable container. Use absorbent paper dampened with toluene to pick up any remaining material. Your contaminated clothing and absorbent paper should be sealed in a vapor-tight plastic bag for eventual disposal. Solvent-wash all contaminated surfaces with toluene followed by washing with a soap and water solution. Do not reenter the contaminated area until the Safety Officer (or other responsible person) has verified that the area has been properly cleaned. STORAGE PRECAUTIONS: You should store this material in a refrigerator. (NTP, 1992)

RECOMMENDED RESPIRATOR: Where the neat test chemical is weighed and diluted, wear a NIOSH-approved half face respirator equipped with an organic vapor/acid gas cartridge (specific for organic vapors, HCl, acid gas and SO2) with a dust/mist filter. (NTP, 1992)|Personal protective equipment should be issued to workers engaged in prodn of carbamates or in their agricultural use, in particular eye protections and respirators to those who spray crops. /Carbamates and thiocarbamates/

Combustible.

Finely dispersed particles form explosive mixtures in air.

Water spray, foam, powder, carbon dioxide ... Keep drums, etc., cool by spraying with water.

SRP: Wastewater from contaminant suppression, cleaning of protective clothing/equipment, or contaminated sites should be contained and evaluated for subject chemical or decomposition product concentrations. Concentrations shall be lower than applicable environmental discharge or disposal criteria. Alternatively, pretreatment and/or discharge to a permitted wastewater treatment facility is acceptable only after review by the governing authority and assurance that "pass through" violations will not occur. Due consideration shall be given to remediation worker exposure (inhalation, dermal and ingestion) as well as fate during treatment, transfer and disposal. If it is not practicable to manage the chemical in this fashion, it must be evaluated in accordance with EPA 40 CFR Part 261, specifically Subpart B, in order to determine the appropriate local, state and federal requirements for disposal.|Do NOT wash away into sewer. Sweep spilled substance into containers; if appropriate, moisten first to prevent dusting. Carefully collect remainder, then remove to safe place.

SRP: The scientific literature for the use of contact lenses by industrial workers is inconsistent. The benefits 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.|SRP: Contaminated protective clothing should be segregated in a manner that results in no direct personal contact by personnel who handle, dispose of, or clean the clothing. Quality assurance procedures to confirm the efficacy of the cleaning procedures should be implemented prior to the decontaminated protective clothing being returned for reuse by the workers. Contaminated clothing (including shoes/socks) should not be taken home at end of shift, but should remain at employee's place of work for cleaning.|Production equipment must be enclosed and provided with exhaust ventilation. No workers must be authorized to enter reactor for syntheses of this compound before it has been purged, cleaned, checked and certified safe for entry. ... Showers should be provided, and their regular use should be encouraged. /Carbamates and thiocarbamates/

No person may /transport,/ offer or accept a hazardous material for transportation in commerce unless that person is registered in conformance ... and the hazardous material is properly classed, described, packaged, marked, labeled, and in condition for shipment as required or authorized by ... /the hazardous materials regulations (49 CFR 171-177)./|The International Air Transport Association (IATA) Dangerous Goods Regulations are published by the IATA Dangerous Goods Board pursuant to IATA Resolutions 618 and 619 and constitute a manual of industry carrier regulations to be followed by all IATA Member airlines when transporting hazardous materials.|The International Maritime Dangerous Goods Code lays down basic principles for transporting hazardous chemicals. Detailed recommendations for individual substances and a number of recommendations for good practice are included in the classes dealing with such substances. A general index of technical names has also been compiled. This index should always be consulted when attempting to locate the appropriate procedures to be used when shipping any substance or article.

... Can cause irritation to eyes, nose and larynx ...|Some irritation of skin and mucous membranes has been reported in man.

Personal protection: particulate filter respirator adapted to the airborne concentration of the substance. Do NOT let this chemical enter the environment. Sweep spilled substance into covered labelled containers. If appropriate, moisten first to prevent dusting. Then store and dispose of according to local regulations.

Separated from food and feedstuffs, strong bases, amines, amides, acids and strong oxidizers. Store only in original container. Provision to contain effluent from fire extinguishing. Cool. Dry. Keep in the dark. Keep in a well-ventilated room.

A harmful concentration of airborne particles can be reached quickly when dispersed, especially if powdered.

The substance is irritating to the eyes, skin and respiratory tract.

Repeated or prolonged contact with skin may cause dermatitis. Repeated or prolonged contact may cause skin sensitization. The substance may have effects on the blood, nervous system, liver and thyroid. May cause an increase in cholinesterase activity. Animal tests show that this substance possibly causes toxic effects upon human reproduction.

NO open flames. Closed system, dust explosion-proof electrical equipment and lighting. Prevent deposition of dust.

PREVENT DISPERSION OF DUST!

Use local exhaust or breathing protection.

Protective gloves.

Wear safety goggles.

U114; A toxic waste when a discarded commercial chemical product or manufacturing chemical intermediate or an off-specification commercial chemical product or manufacturing chemical intermediate. /Ethylenebisdithiocarbamic acid, salts & esters/

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 5000 lb or 2270 kg. The toll free number of the NRC is (800) 424-8802. The rule for determining when notification is required is stated in 40 CFR 302.4 (section IV. D.3.b). /Ethylenebisdithiocarbamic acid, salts and esters/

U114; As stipulated in 40 CFR 261.33, when ethylenebisdithiocarbamic acid, salts & esters, 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). /Ethylenebisdithiocarbamic acid, salts and esters/

SOIL: The residues of zineb in a soil planted with forage crops decreased from 11.0 ppm to 0.03 ppm within 4 months after surface spraying with 20 kg zineb/ha(1).

Toxicity

highly toxic

Estimated lethal dose for humans 5-15 g/kg.

LD50 Rat oral >5200 mg/kg|LD50 Rat oral 1850 mg/kg|LD50 Rat percutaneous >6000 mg/kg|LD50 Rat dermal > 10,000 mg/kg bw|For more Non-Human Toxicity Values (Complete) data for Zineb (12 total), please visit the HSDB record page.

/BIRDS and MAMMALS/ Signs of intoxication /in mallards and pheasants administered Ziram (LD50 >2000 mg/kg, orally)/: goose-stepping ataxia, wings crossed over back, general myasthenia from first hr up to 1 or 2 days. /Sample purity 95%/|/AQUATIC SPECIES/ Dithane and Zineb were potent teratogens inducing formation of large, wavy notochord in embryo of Microhyla ornata /(ornate narrow-mouth frog)/. Cysteine was protective against these fungicides. Ethylenethiourea a degradation product of bisdithiocarbamates, was also a potent teratogen with the same effects as Dithane or Zineb. Urea and thiourea were not teratogenic whereas carbon disulfide, another degradation product of dithiocarbamates induced moderate changes in the morphogenesis of the notochord. Sodium thiocyanate and D-penicillamine were without any effect on survival or development of the embryo. Apparently, teratogenic effects of dithiocarbamates are caused by oxidative damage to embryonic cells; chelation probably does not play any significant role.|/AQUATIC SPECIES/ The dithiocarbamate fungicides sodium diethyldithiocarbamate, Dithane M-45, and Zineb were teratogenic to Lymnaea luteola (freshwater snail) at very low concentration. The concentration inducing 100% teratogenesis were < 10 ppm for Zineb. Swollen balloon like embryos resulted from these treatments.|/OTHER TERRESTRIAL SPECIES/ Not toxic to bees.|/PLANTS/ Phytotoxicity: Non-phytotoxic, except for zinc-sensitive plants such as tobacco and cucurbits.

Zineb is not known to occur as a natural product(1).

Zineb's former production in the US may have resulted in its release to the environment through various waste streams; its former use in the US as a fungicide(1) resulted in its direct release to the environment.(SRC). Its use in the United States has been cancelled by the EPA and can no longer be used commercially(2).

TERRESTRIAL FATE: Based on a classification scheme(1), Koc values of 308-1158(2) indicate that zineb is expected to have low to moderate mobility in soil(SRC). Volatilization of zineb from moist soil surfaces is not expected to be an important fate process since zineb is a zinc salt(SRC). Zineb is not expected to volatilize from dry soil surfaces(SRC) based upon a vapor pressure of <7.5X10-8 mm Hg(3). Zineb field half-lives range from 23-43 days(4). Dithiocarbamate fungicides undergo rapid decomposition in the presence of moisture(5-6); therefore, zineb decomposition in and on wet soil may be an important fate process(SRC).|TERRESTRIAL FATE: Zineb is hydrolyzable and does not persist long in soil(1). Its persistence in soil is less than that in water so zineb's degradation in soil is probably catalyzed by soil components. Loss in soil, while rapid, was not complete at the end of 45 days(1). Within four months after a field planted with forage was sprayed with zineb, 99.7% of the fungicide was no longer present at effective levels(1). In the laboratory, zineb lost its efficacy in 16 days at 30 or 40 °C and in the field its bioactive half-life was 16 days(2). Since the fungitoxicity of zineb increases for four days before it declines(2), degradative products are probably the active fungicides and the half-life of the zineb is less than what would be inferred from its bioactivity(SRC). In an experiment in a microagricultural chamber containing 19 day old tomato plants, zineb was applied as a spray at day 56 and day 86, the latter spray containing radiolabeled fungicide(3). The experiment was terminated on day 156 and the half-life of the zineb was 23 days. It was primarily confined to the top 1 cm of soil(3). 36% of the zineb was removed through volatilization of low molecular weight degradation products(3).|AQUATIC FATE: Based on a classification scheme(1), Koc values of 308-1159(2) indicate that zineb is expected to adsorb to suspended solids and sediment(SRC). Volatilization from water surfaces is not expected since zineb is a zinc salt(SRC). According to a classification scheme(3), an estimated BCF of 3(SRC), from its log Kow of 1.3(4) and a regression-derived equation(5), suggests the potential for bioconcentration in aquatic organisms is low(SRC). Surface water mixed with sediment produced 70% cumulative radio-labeled carbon dioxide after 50 days incubation(6), suggesting that biodegradation may be an important fate process in water(SRC). Hydrolysis half-lives for zineb in relation to pH are 9 mins at pH 3.8, 6.5 hrs at pH 5.7, 96 hrs at pH 7.0, and 405 hrs at pH 8.0(6). Zineb is unstable in aqueous solutions, producing ethylenethiourea, 5,6-dihydro-3H-imidaz-1,2,4-dithiazole-3-thione, ethylenediamine, ethylenediisothiocyanate, sulfur, carbon disulfide, and hydrogen sulfide(7). Zineb is unstable to moisture on prolonged storage(7). When zineb was spilled into the Rhine River during a warehouse fire, it hydrolyzed very quickly(8). The mass of zinc resulting from the fire was unimportant(8).|ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), zineb, which has a vapor pressure of <7.5X10-8 mm Hg at 20 °C(2), is expected to exist solely in the particulate phase in the ambient atmosphere. Zineb will be lost by gravitational settling(3). Zineb contains chromophores that absorb at wavelengths >290 nm(4) and therefore may be susceptible to direct photolysis by sunlight(SRC).|ATMOSPHERIC FATE: In the atmosphere zineb will exist primarily as dust or an aerosol and be lost by gravitational settling. In an experiment in a microagricultural chamber containing 19 day old tomato plants, in which zineb was applied as a spray, the half-life of zineb in air, as determined by measuring (14)C-zineb and the ethylenediamine derivative, was 11 and 14 days, respectively(1).

The rate constant for the vapor-phase reaction of zineb with photochemically-produced hydroxyl radicals has been estimated as 1.5X10-10 cu cm/molecule-sec at 25 °C(SRC) using a structure estimation method(1). This corresponds to an atmospheric half-life of about 2.5 hrs at an atmospheric concentration of 5X10+5 hydroxyl radicals per cu cm(1). Hydrolysis half-lives for zineb in relation to pH are 9 minutes at pH 3.8, 6.5 hrs at pH 5.7, 96 hrs at pH 7.0, and 405 hrs at pH 8.0(2).|Zineb is unstable in aqueous solutions, producing ethylenethiourea (ETU), 5,6-dihydro-3H-imidazo(2,1-C)-1,2,4-dithiazole-3-thione (DIDT), ethylenediamine, ethylenediisothiocyanate, sulfur, carbon disulfide, and hydrogen sulfide(1). An increase in the pH of the solution increased the production of ETU(1). Zineb decomposes on storage primarily due to exposure to moisture(2). Products of the decomposition were identified as ethylenethiuram monosulfide, zinc sulfide, carbon disulfide and ETU(2). After 19 months in solution, however, zineb was not completely degraded(3). Zineb is somewhat unstable when exposed to light(4). When adsorbed on silica gel and irradiated for 17 hr with irradiation >290 nm, 5.1% of the zineb was degraded(5). However, other investigators found no changes when zineb was exposed to bright sunlight(3). When 6 commercial formulations containing 80% zineb were exposed to conditions of temperature and humidity similar to that found in warehouses and storage sheds in the southeastern USA for 39 days, the percentage of ETU in the product increased from 0.2-2.0% to 3.5-10.4%(6). Zineb is converted to ETU on boiling (3.6% conversion in 15 min)(7).

The BCF for zineb in golden ide (Leuciscus idus melantus) after 3 days was reported as <10(1). According to a classification scheme(2), this BCF suggests the potential for bioconcentration in aquatic organisms is low(SRC). Zineb's BCF in algae (Chlorella fuscavar vacuolata) after 1 day was reported as 170(1).

1.00e+03 L/kg|The Koc value for zineb can range from 308-1159(1) depending on the type of soil. According to a classification scheme(2), these Koc values suggest that zineb is expected to have low to moderate mobility in soil. A pesticide leaching potential for zineb was determined to be 36 based on its persistence (measured as half-life in days), rate of application, Koc value, and fraction of pesticide reaching soil during application(3). Depending upon the soil conditions (texture, pH and organic matter content), zineb has a soil leaching potential ranging from very low risk to a moderate risk(3). Zineb was immobile in soil thin-layer chromatography experiments (Rf= 0-0.16) as well as in leaching tests in a 10-cm column filled with an artificial peat moss mixture (0-2.5 cm)(4). Another investigator reported that zineb penetrated 5 cm in loamy sand and <1 cm in peat moss(5). In an experiment in a microagricultural chamber, the amount of zineb in the leachate water was negligible(6). It was estimated that zineb would leach <20 cm through agricultural soil with an annual rainfall of 150 cm(6).

The Henry's Law constant for zineb is estimated as <2.7X10-9 atm-cu m/mole(1). This Henry's Law constant and zineb being a zinc salt indicate that zineb is essentially nonvolatile from water surfaces(2). It is estimated that vapor losses of zineb from agricultural land would be low, <0.1 kg/ha/yr(3). Zineb is not expected to volatilize from dry soil surfaces(SRC) based upon a vapor pressure of <7.5X10-8 mm Hg(1).

GROUNDWATER: Out of 9 groundwater samples taken from California in 1985, none tested positive for zineb(1).

Zineb residues of 0.57 and 0.77 ppm were found in grapes sprayed 5 times and harvested 20 days after the last spraying(1). Similarly, another study reported residues of 1.02-2.05 ppm in grapes sprayed 11-13 times and harvested <20 days after the last spraying(1). A Food and Drug Administration study of pesticide residues in ready-to-eat foods in 1968-1972 indicates that zineb is an infrequent contaminant with concentrations of 0.7-1.4 ppm being reported in onions and 3.0 ppm in celery(3). Of the 1522 samples of leaf and stem vegetables analyzed for zineb in FY1970-1976 in the FDA Total Diet Program, zineb was found in 10% of samples, of which 8% exceeded 0.04 ppm and 2.7% exceeded 2.00 ppm(5). The average zineb concn was 0.461 ppm(5). No zineb residues were reported in tested composite samples of cherries, peaches and strawberries delivered to farmer's wholesale markets in Leamington and Toronto, Ontario between 1980-1984(2). Samples of canned pears and baby food contained no zineb, although the latter contained ETU(4). Zineb was detected in crops from Cuba; 3.6-7.2 ug/kg in tomato, below detection limit in onion and pepper, and not detected in cucumber and citrus(6).|Zineb was detected in 0.057% of 13,980 food sampled for pesticides in fiscal year 1988(1). Out of 710 domestic and 949 imported pears sampled for various pesticides from 1991-1992, zineb was not found as a residue(2). Ethylene bis-dithiocarbamate (EBDCs) fungicides, which includes zineb, were found to be the most prevalent residue found on fruits and vegetables analyzed in Switzerland in 1989-90(3). Out of 461 salads analyzed in Geneva, 23 samples had levels of EBDCs exceeding tolerance values(3). In 1989, 18,798 food samples were analyzed by the FDA for pesticide residues(4). Of these, only 1278 samples were analyzed for EBDCs in which zineb was detected (percent positive and concentrations not specified)(4). Vegetables analyzed included peppers, leafy vegetables, cantaloupe, squash and peas(4). In 1990, the same study was conducted by the FDA but with 1472 samples being analyzed for EBDCs(5). Once again, zineb was detected (percent positive and concentrations not specified)(5).

NIOSH (NOES Survey 1981-1983) has statistically estimated that 3,205 workers (none of these were female) were potentially exposed to zineb in the US(1). However, the NOES Survey does not include farm workers. Occupational exposure to zineb may occur through inhalation of dust and dermal contact with this compound at workplaces where zineb was formally produced or used. Monitoring data indicate that the general population may be exposed to zineb via ingestion of food treated with zineb, and dermal contact with fungicide products containing zineb, from sources other than the US(SRC).|Concentrations of dithiocarbamate fungicides in the workroom air of a pesticide residue laboratory were below the provisional threshold level value of 5 mg/cu m(1). This provisional threshold level value of 5 mg/cu m in the workroom air was based on the TLV officially stated for thiram. It has been adopted for all dithiocarbamate fungicides by the company in this study (name of company not disclosed)(1). The levels of dermal exposure of greenhouse workers handling carnations was studied in the Netherlands(2). Average dermal exposure to zineb was 48 mg/task while cutting and 8 mg/task while sorting/bundling(2). Inhalation exposure to zineb was 0.6 mg/task while cutting while no exposure was calculated during sorting/bundling(2).

Drug Information

... Approx 70-75% of ingested zineb passed through the gastrointestinal tract of rats and appeared in the feces within 24-72 hr.|... Only 11 to 17% of an oral dose of zineb is absorbed from the gastrointestinal tract of the rat. Some additional material may be absorbed following breakdown in the intestine. At different dietary levels 68.5 to 74.9% of the ingested material was recovered unchanged in the feces.|In short-term static bioaccumulation experiments with (14)C-labeled zinc ethylenebisidithiocarbamate (zineb) and zinc dimethyldithiocarbamate (ziram) both compounds were rapidly disseminated through the tissues. Whole body elimination was rapid with 45% and 25% of the initial radioactivity from ziram, and zineb, respectively, being retained by the end of the 16 day depuration period. Pigmented tissues appeared to be major distribution sites as well. This may be related to the affinity of the compounds and/or their degradation products to melanin or to complexion with phenoloxidase, a copper containing enzyme involved in melanin synthesis. Autoradiography also revealed a high labeling of thyroid follicles. The results show that dithiocarbamates are selectively localized in various tissues, reported to be the target organs for their toxic actions.|Urinary and fecal excretion of ethylene thiourea, a metabolite of ethylene-bis-dithiocarbamic /acid/ fungicides, was monitored in rats for 16 days after they were administered a single oral dose of zineb. After 48 hr, 86% of the excreted ethylene thiourea was in the urine, 14% in the feces. Urinary excretion peaked at 24 hr after ingestion, at which time 52% of the total urinary ethylene thiourea had been excreted. Low levels of ethylene thiourea excretion continued in urine for the length of the study, by which time 5.1% of the zineb /oral dose/ was excreted as urinary ethylene thiourea. Fecal excretion of ethylene thiourea was complete after 3 days.|For more Absorption, Distribution and Excretion (Complete) data for Zineb (6 total), please visit the HSDB record page.

ETU and DIDT /(5,6-dihydro-3 H-imidazo(2,1-C)-1,2,4-dithiazole-3-thione)/ were the major metabolites found in the urine of rats treated with zineb, and carbon disulfide was detected in the expired air.|The metabolism of the fungicide zineb, (zinc ethylenebisdithiocarbamate), has been studied in the rat and the marmoset. In both species a relatively large proportion (21-22%) of the original zineb administered was detectable in the excreta as ethylenethiourea (ETU) ... A further proportion (2-5%) was determined to be ethyleneurea which is a metabolite of ETU. Results of comparative experiments in marmosets revealed that ETU was photolabile in the presence of excreta, thus showing the importance of conducting the studies in the dark.|Zineb ... Is metabolized in rats to carbon disulfide, which is expired, and to ethylenethiourea ... and ethylenebis(isothiocyanate)sulfide (ebis) ... which are excreted in urine.|Ethylenethiourea is the major metabolite in plants. Ethylenethiuram monosulfide and presumably ethylenethiuram disulfide and sulfur are also formed.|For more Metabolism/Metabolites (Complete) data for Zineb (9 total), please visit the HSDB record page.

Many commercial samples of ... Zineb ... have been shown to contain ethylenethiourea.|After storage of Zineb in darkness, ethylenethiourea, ethylenethiuram mono- and disulfide, trace of sulfur, and one unidentified compound were observed.

SYMPTOMS: Symptoms associated with exposure to this compound include irritation of the skin, eyes and mucous membranes as well as anemia. ACUTE/CHRONIC HAZARDS: This compound is toxic by ingestion and inhalation. It may also cause irritation of the skin, eyes and mucous membranes. Highly toxic fumes are emitted when this material is heated to decomposition. (NTP, 1992)|Mutagens

EYES: First check the victim for contact lenses and remove if present. Flush victim's eyes with water or normal saline solution for 20 to 30 minutes while simultaneously calling a hospital or poison control center. Do not put any ointments, oils, or medication in the victim's eyes without specific instructions from a physician. IMMEDIATELY transport the victim after flushing eyes to a hospital even if no symptoms (such as redness or irritation) develop. SKIN: IMMEDIATELY flood affected skin with water while removing and isolating all contaminated clothing. Gently wash all affected skin areas thoroughly with soap and water. If symptoms such as redness or irritation develop, IMMEDIATELY call a physician and be prepared to transport the victim to a hospital for treatment. INHALATION: IMMEDIATELY leave the contaminated area; take deep breaths of fresh air. If symptoms (such as wheezing, coughing, shortness of breath, or burning in the mouth, throat, or chest) develop, call a physician and be prepared to transport the victim to a hospital. Provide proper respiratory protection to rescuers entering an unknown atmosphere. Whenever possible, Self-Contained Breathing Apparatus (SCBA) should be used; if not available, use a level of protection greater than or equal to that advised under Protective Clothing. INGESTION: Some heavy metals are VERY TOXIC POISONS, especially if their salts are very soluble in water (e.g., lead, chromium, mercury, bismuth, osmium, and arsenic). IMMEDIATELY call a hospital or poison control center and locate activated charcoal, egg whites, or milk in case the medical advisor recommends administering one of them. Also locate Ipecac syrup or a glass of salt water in case the medical advisor recommends inducing vomiting. Usually, this is NOT RECOMMENDED outside of a physician's care. If advice from a physician is not readily available and the victim is conscious and not convulsing, give the victim a glass of activated charcoal slurry in water or, if this is not available, a glass of milk, or beaten egg whites and IMMEDIATELY transport victim to a hospital. If the victim is convulsing or unconscious, do not give anything by mouth, assure that the victim's airway is open and lay the victim on his/her side with the head lower than the body. DO NOT INDUCE VOMITING. IMMEDIATELY transport the victim to a hospital. (NTP, 1992)


Fresh air, rest. Refer for medical attention.


Remove contaminated clothes. Rinse and then wash skin with water and soap.


First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention.

Immediate first aid: Remove patient from contact with the material. Ensure that adequate decontamination has been carried out. If patient is not breathing, start artificial respiration, preferably with a demand-valve resuscitator, bag-valve-mask device, or pocket mask, as trained. Perform CPR as necessary. Immediately flush contaminated eyes with gently flowing water. Do not induce vomiting. If vomiting occurs, lean patient forward or place on left side (head-down position, if possible) to maintain an open airway and prevent aspiration. Keep patient quiet and maintain normal body temperature. Obtain medical attention. /Dithiocarbamates and Related Compounds/|Basic treatment: Establish a patent airway (oropharyngeal or nasopharyngeal airway, if needed). Suction if necessary. Watch for signs of respiratory insufficiency and assist ventilations if necessary. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for shock and treat if necessary ... . Anticipate seizures and treat if necessary ... . For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with 0.9% saline (NS) during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 ml/kg up to 200 ml of water for dilution if the patient can swallow, has a strong gag reflex, and does not drool. Administer activated charcoal ... . /Dithiocarbamates and Related Compounds/|Advanced treatment: Consider orotracheal or nasotracheal intubation for airway control in the patient who is unconscious or is in severe respiratory distress. Use moderate hyperventilation (rate of 20 respirations per minute) if signs of cerebral edema are present. Monitor cardiac rhythm and treat arrhythmias if necessary ... . Start IV administration of D5W /SRP: "To keep open", minimal flow rate/. Use 0.9% saline (NS) or lactated Ringer's (LR) if signs of hypovolemia are present. For hypotension with signs of hypovolemia, administer fluid cautiously. Consider vasopressors if patient is hypotensive with a normal fluid volume. Watch for signs of fluid overload ... . Treat seizures with diazepam or lorazepam ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Dithiocarbamates and Related Compounds/|Gastrointestinal decontamination. If a large amount of the fungicide has been ingested in the last few hours, and if copious vomiting has not already occurred, it may be reasonable to consider GI decontamination. Activated charcoal can be used along with the addition of the cathartic sorbitol to the charcoal slurry. If sorbitol is given separately, it should be diluted with an equal volume of water before administration. No more than one dose of sorbitol is recommended and it should be used with caution in children and the elderly. If contact with the toxicant has been minimal (for example, oral contamination only, promptly flushed out of the mouth), administration of charcoal without a cathartic, followed by careful observation of the patient, probably represents optimal management. /Ethylene bis dithiocarbamates (EBDC compounds)/|For more Antidote and Emergency Treatment (Complete) data for Zineb (6 total), please visit the HSDB record page.

/HUMAN EXPOSURE STUDIES/ The irritant and allergic potential of most dithiocarbamates is evident in occupational exposure. Skin irritation and sensitization were studied in man using a conventional patch test. A cotton square was dipped in 19% nabam solution and placed on the inner surface of the forearm, and, 14 days later, this procedure was repeated on the opposite forearm. Zineb was tested in the same manner, except that the cotton square was dipped in 65% wettable powder. The patches were left in place for 48 hr. Of the 25 subjects included in the nabam study, 2 showed irritation (mild erythema and itching). Thirteen of the 25 reacted to the retest (from mild erythema to severe erythema, edema, and vesiculation), indicating sensitization. Of the 50 subjects used in the zineb study, no reaction at all was seen in 49 of them. One reacted in such a way that it indicated primary irritation rather than sensitization ...|/SIGNS AND SYMPTOMS/ In spray or dust forms, the /ethylenebisdithiocarbamates/ (EBDCs) are moderately irritating to the skin and to respiratory mucous membranes. Poisoning from this class of chemicals includes itching, scratchy throat, sneezing, coughing, inflammation of the nose or throat, and bronchitis ... Early symptoms from exposure of humans to inhalation of zineb include tiredness, dizziness and weakness. More severe symptoms include headache, nausea, fatigue, slurred speech, convulsions, and unconsciousness ...|/SIGNS AND SYMPTOMS/ Occupational exposure to inhalation of zineb can lead to changes in liver enzymes, moderate anemia and other blood changes, increased incidence of poisoning symptoms during pregnancy, and chromosomal changes in the lymphocytes ... Liver functioning was affected in workers exposed to zineb. Moderate anemia and other blood changes were also reported in 150 workers exposed to zineb in a chemical plant ...|/SIGNS AND SYMPTOMS/ Farm workers who were repeatedly exposed to zineb, in fields sprayed with 0.5% suspension of the fungicide, reported severe and extensive contact dermatitis ...|For more Human Toxicity Excerpts (Complete) data for Zineb (16 total), please visit the HSDB record page.

The substance can be absorbed into the body by inhalation.

Cough. Sore throat. Nausea.


Redness.


Redness. Pain.

Zineb Use and Manufacturing

Methods of Manufacturing

First synthesize Daisen Sodium. One-step or two-step methods can be used. The two-step method is conducive to controlling the formation of by-product sodium trithiocarbonate with good quality and high yield. The reaction temperature is controlled at <35°C, and the drop rate of carbon disulfide is determined by the reaction temperature. Sodium hydroxide solution was added in batches, the temperature of alkali addition was controlled at about 35℃, and the pH of each batch was controlled to be ≤9. The 5% sulfuric acid solution was slowly added dropwise to the above-mentioned aqueous solution of sodium daisen to neutralize the excess sodium hydroxide and sodium trithiocarbonate, a by-product of decomposition, to a pH of 6-7, and to exclude thiohydrogen gas. The neutralized aqueous solution of Dyson sodium was heated to 40-45°C. Zinc sulfate aqueous solution was added under stirring, stirred for 30min, centrifuged, washed with clean water, and dried at 50-60°C under 93kPa to obtain Dyson zinc.

Uses

Agricultural fungicide.

Production

(1975) 1.59 X 10+9 g (est)

Approx 55% as a fungicide for apples; approx 17% as a fungicide for home and garden, lawn, and turf; approx 14% as a fungicide for deciduous fruit; and approx 14% as a fungicide for vegetables (1975)|239 tons are used annually

Grades: commercial dusts & wettable powders usually contain 65% active material.|Dithane Z78 and Parzate Xineb are wettable powders containing 75% Zineb and used generally at 1 1/2 to 2 lb/100 USA gal.|Mancozeb (Dithane M45) is ... a combination of maneb and zineb.|Wettable powder (700 or 750 g ai/kg); dust (Dithane dust). Mixtures include: 'Cupro-phynebe' (Bayer), 'Super Mixy', wettable powder (150 g zineb + 375 g copper (as copper oxychloride)/kg); 'Turbair Dicamate' (zineb + mancozeb).|For more Formulations/Preparations (Complete) data for Zineb (7 total), please visit the HSDB record page.

/Zineb was introduced/ ... by Rohm & Haas Co (& EI du Pont de Nemours & Co who no longer manufacture or market it) (USP 2,457,674; 3,050,439) ...|Generally non-phytotoxic except to zinc-sensitive plants.|In practical application as a fungicide these reactants are mixed in the presence of lime; the zineb is not formed until after reaction of the carbon dioxide of the air with the film of the other chemicals on the leaf or fruit.|Zineb also results from combining nabam (or diammonium or potassium ammonium analogs) with zinc sulfate in the spray tank.|All registrations of zineb were previously voluntarily cancelled by the registrant.

Method: OSHA 107; Procedure: liquid chromatography with ultraviolet detector; Analyte: zineb; Matrix: air; Detection Limit: 103 ug/cu m.|Method: AOAC 965.15; Procedure: carbon disulfide evolution method; Analyte: zineb; Matrix: pesticide formulations; Detection Limit: not provided.|A number of procedures for the quantification of dithiocarbamates are based on high-pressure liquid chromatography. The limits of detection in water solutions for zineb, ziram, and thiram are 0.05, 0.01, and 0.01 mg/kg, respectively. /Dithiocarbamates/|RESIDUES /MAY BE/ DETERMINED BY ACID HYDROLYSIS MEASURING THE CARBON DISULFIDE EVOLVED USING GAS LIQUID CHROMATOGRAPHY OR BY CONVERSION TO A COPPER/AMINE COMPLEX WHICH IS EST BY COLORIMETRY.|For more Analytic Laboratory Methods (Complete) data for Zineb (7 total), please visit the HSDB record page.

Health Hazards -> Mutagens

Computed Properties

Molecular Weight:275.8
Hydrogen Bond Donor Count:2
Hydrogen Bond Acceptor Count:4
Exact Mass:273.870525
Monoisotopic Mass:273.870525
Topological Polar Surface Area:90.2
Heavy Atom Count:11
Complexity:124
Covalently-Bonded Unit Count:2
Compound Is Canonicalized:Yes

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