Mancozeb 代森锰锌

代森锰锌

代森锰锌纯品为白色粉末，工业品为灰白色或淡黄色粉末，有臭鸡蛋味，难溶于水，不溶于大多数有机溶剂，但能溶于吡啶中，对光、热、潮湿不稳定，易分解出二硫化碳，遇碱性物质或铜、汞等物质均易分解放出二硫化碳而减效，挥发性小。所谓保护，就是为植物提供Zn元素，除解决缺锌的症状外，给植物增强抵抗病害的能力，从而相对地起到杀菌作用。

[中文名称]:代森锰锌
[英文名称]：Mancozeb
[化学名称]:乙撑双二硫代氨基甲酰锰和锌的络盐
[应用解释]：该产品为广谱的保护性杀菌剂，防治麦类，水果蔬菜等的多种真菌病害。
[成分组成]：
代森锌80%WP
CAS # 8018-01-7
化学名称：亚乙基双—（二硫代氨基甲酸锌）
英文名称（IUPAC Name）： manganese ethylenebis(dithiocarbamate) (polymeric) complex with zinc salt
英文名称(CA name）： [[1,2-ethanediylbis[carbamodithioato]](2-)]manganese mixture with [[1,2-ethanediylbis[carbamodithioato]](2-)]zinc
分子式：
[C4H6MnN2S4]xZny, x:y = 1 : 0.091
分子量：271.2（基于组成成分）
组成：The ISO definition is ‘a complex of zinc and maneb containing 20% of manganese and 2.55% of zinc, the salt present being stated (for instance mancozeb chloride)’. A manufacturer gives c. 20% Mn and 2.2% Zn.
[质量规格] ：
代森锌含量，% ≥ 80
水份，% ≤ 1.2
悬浮率，% ≥ 83
润湿时间，S ≤ 40
细度（325目），% ≥ 98
PH值范围 8.4
[市场剂型]：70%和80%代森锰锌可湿性粉剂，80%喷克、大生M-45、新万生可湿性粉剂。

防治对象和使用方法
代森猛锌主要用于防治蔬菜霜霉病、炭疽病、褐斑病等。目前是防治西红柿早疫病和马铃薯晚疫病理想药剂，防效分别为80%和90%左右。对多菌灵产生抗性的病害，改用代森猛锌可收到良好的防治效果。一般作叶面喷洒，隔10－15天喷1次。
（1）防治西红柿、茄子、马铃薯疫病、炭疽病、叶斑病，用80%可湿性粉剂400-600倍液．发病初期喷洒，连喷3－5次。
（2）防治蔬菜苗期立枯病、猝倒病，用80%可湿性粉剂，按种子重量的0．1－0．5%拌种。
（3）防治瓜类霜霉病、炭疽病、褐斑病，用400－500倍液喷雾，连喷3－5次。
（4）防治白菜、甘蓝霜霉病，芹菜斑点病，用500一600倍液喷雾，连喷3－5次。
（5）防治菜豆炭疽病、赤斑病，用400－700倍液喷雾，连喷2－3次。

注意事项
（1）贮藏时，应注意防止高温，并要保持干燥，以免在高温、潮湿条件下使药剂分解，降低药效。
（2）为提高防治效果，可与多种农药、化肥混合使用，但不能与碱性农药、化肥和含铜的溶液混用。
（3）药剂对皮肤、粘膜有刺激作用，使用时留意保护。
（4）不能与碱性或含铜药剂混用。对鱼有毒，不可污染水源。

性质与作用
代森锰锌是一种优良的保护性杀菌剂，属低毒农药。由于其杀菌范围广、不易产生抗性，防治效果明显优于其他同类杀菌剂，所以在国际上用量一直是大吨位产品。目前，国内多数复配杀菌剂都以代森锰锌加工配制而成，锰、锌微量元素对作物有明显的促壮、增产作用，通过十几年田间应用，对防治梨黑星病、苹果斑点落叶病、瓜菜类疫病、霜霉病、大田作物锈病等效果显著，不用其他任何杀菌剂完全可有效控制病害发生，质量稳定、可靠。
主要防治对象：梨黑星病，柑橘疮痂病、溃疡病，苹果斑点落叶病，葡萄霜霉病，荔枝霜霉病、疫霉病，青椒疫病，黄瓜、香瓜、西瓜霜霉病，番茄疫病，棉花烂铃病，小麦锈病、白粉病，玉米大斑、条斑病，烟草黑胫病，山药炭疽病、褐腐病、根颈腐病、斑点落叶病等。

使用方法
（1）防治枣树、苹果、梨等果树的叶斑病、锈病、黑星病、霜霉病等病害，于发病初期开始喷洒800倍80%代森锰锌可湿性粉剂（爱诺艾生）+1000倍“天达2116”（果树专用型），每10-15天1次，连续喷洒2-3次。注意与波尔多液交替使用。
（2）防治瓜菜类疫病、霜霉病、炭疽病，用600-800倍80%代森锰锌可湿性粉剂（爱诺艾生）+600倍天达2116（瓜茄果型），每7-14天一次，中间交替喷洒其他农药。
（3）防治大田作物霜霉病、白粉病、叶斑病、根腐病等病害，在发病初期用700-1000倍80%代森锰锌可湿性粉剂（爱诺艾生）+600倍天达2116壮苗灵，每7-14天一次，中间交替喷洒其他农药。

mancozeb
Fungicide
FRAC M3; multi-site: alkylenebis(dithiocarbamate)

NOMENCLATURE
Common name mancozeb (BSI, E-ISO); mancozèbe ((m) F-ISO); manzeb (JMAF)
IUPAC name manganese ethylenebis(dithiocarbamate) (polymeric) complex with zinc salt
Chemical Abstracts name [[1,2-ethanediylbis[carbamodithioato]](2-)]manganese mixture with [[1,2-ethanediylbis[carbamodithioato]](2-)]zinc
CAS RN [8018-01-7] (formerly [8065-67-6]); number also applies to other mixed manganese and zinc ethylenebis(dithiocarbamate) complexes

PHYSICAL CHEMISTRY
Composition The ISO definition is 'a complex of zinc and maneb containing 20% of manganese and 2.55% of zinc, the salt present being stated (for instance mancozeb chloride)'. A manufacturer gives the ratio of maneb to zinc as 1:0.091, i.e. 20% Mn and 2.2% Zn. Mol. wt. 271.2 (based on Composition) M.f. [C4H6MnN2S4]xZny Form Greyish-yellow, free flowing powder with a slight odour of hydrogen sulfide. M.p. Decomposes at 172 °C V.p. <1.33 ´ 10-2 mPa (20 °C) KOW logP = 0.26 S.g./density 1.92 Solubility In water 6.2 ppm (pH 7.5, 25 °C). Insoluble in most organic solvents; dissolves in solutions of powerful chelating agents but cannot be recovered from them. Stability Stable under normal, dry storage conditions. Slowly decomposed by heat and moisture. On hydrolysis (25 ºC), DT50 20 d (pH 5), 17 h (pH 7), 34 h (pH 9). Mancozeb a.i. is unstable and the tech. not isolated; the formulated product is produced in continuous process. F.p. 137.8 ºC (Tag open cup)

COMMERCIALISATION
History Fungicide reported in Fungic. Nematic. Tests, 1961, 17.Introduced by Rohm & Haas Co. (now Dow AgroSciences) and by E. I. du Pont de Nemours and Co. (who no longer manufacture or market it). Patents GB 996264; US 3379610; US 2974156 all to Rohm & Haas Manufacturers Agrochem; Aimco; CAC; Cerexagri; Crystal; Dow AgroSciences; Griffin; Hindustan; Indofil; United Phosphorus

APPLICATIONS
Biochemistry Reacts with, and inactivates the sulfhydryl groups of amino acids and enzymes of fungal cells, resulting in disruption of lipid metabolism, respiration and production of ATP. Mode of action Fungicide with protective action. Uses Control of many fungal diseases in a wide range of field crops, fruit, nuts, vegetables, ornamentals, etc. More frequent uses include control of early and late blights (Phytophthora infestans and Alternaria solani) of potatoes and tomatoes; downy mildew (Plasmopara viticola) and black rot (Guignardia bidwellii) of vines; downy mildew (Pseudoperonospora cubensis) of cucurbits; scab (Venturia inaequalis) of apple; sigatoka (Mycosphaerella spp.) of banana and melanose (Diaporthe citri) of citrus. Typical application rates are 1500-2000 g/ha. Used for foliar application or as a seed treatment. Formulation types DP; DS; OD; SC; WG; WP. Selected products: 'Dithane M-45' (Dow AgroSciences); 'Dithane' (Dow AgroSciences); 'Fore' (Dow AgroSciences); 'Manconex' (Griffin); 'Manex II' (Griffin); 'Manzate' (Griffin); 'Sancozeb' (Dow AgroSciences); 'Aimcozeb' (Aimco); 'Caiman' (Calliope); 'Crittox' (Siapa); 'Defend M 45' (Crop Health); 'Devidayal M-45' (Devidayal); 'Hilthane' (Hindustan); 'Indofil M-45' (Indofil); 'Ivory' (Calliope); 'Kifung' (Inquiport); 'Lucazeb' (Lucava); 'Mancosol' (Ingeniería Industrial); 'Mancothane' (Vapco); 'Manzeb' (Barclay); 'Micene' (Sipcam); 'Policar MZ' (Cequisa); 'Saver' (Sanonda); 'Uthane' (United Phosphorus); 'Vimancoz' (Vipesco); 'Zeb' (Nagarjuna Agrichem); mixtures: 'Electis' (+ zoxamide) (Dow AgroSciences); 'Equation Contact' (+ famoxadone) (DuPont); 'Gavel' (+ zoxamide) (Dow AgroSciences); 'Manex C-8' (+ cymoxanil) (Griffin); 'Sygan PM' (+ cymoxanil+ folpet) (Griffin); 'Syphal PM' (+ copper oxychloride+ cymoxanil+ folpet) (Griffin); 'Curtine-V' (+ cymoxanil) (Vapco); 'Duett' (+ cymoxanil) (Cequisa); 'Hawaii' (+ metalaxyl) (Rocca); 'Micexanil' (+ cymoxanil) (Sipcam); 'Mike' (+ flumorph) (Shenyang); 'Milor' (+ metalaxyl) (Rotam); 'Pulsan' (+ oxadixyl+ cymoxanil) (Syngenta); 'Roxam' (+ zoxamide) (Interfarm); 'Sandofan' (+ oxadixyl) (Syngenta); 'Tairel' (+ benalaxyl) (Sipcam); 'Talman-combi' (+ metalaxyl) (Cequisa); 'Trecatol' (+ benalaxyl) (Isagro)

OTHER PRODUCTS
'Baronet' (Dow AgroSciences); 'Cobrethane' (with copper) (Dow AgroSciences); 'Cuprozeb' (with copper) (Dow AgroSciences); 'Dithane 60' (Dow AgroSciences); 'Dithane DF' (Dow AgroSciences); 'Dithane F 448' (Dow AgroSciences); 'Dithane F MB' (Dow AgroSciences); 'Dithane F-45' (Dow AgroSciences); 'Dithane Neotec' (Dow AgroSciences); 'Dithane NT' (Dow AgroSciences); 'Karamate' (Dow AgroSciences); 'Manzate 200' (Griffin); 'Persist' (Dow AgroSciences); 'Titan' (Dow AgroSciences); 'Ziman-Dithane' (Dow AgroSciences); 'Acarie M' (Siapa); 'Chemispor' (Chemiplant); 'Dicozeb' (Agrochem); 'Dithane SH' (Philagro); 'Emthan-M-45' (Sabero); 'Man Gard' (Agricultura Nacional); 'Mankotam' (AgroSan); 'P.S.T. 6' (Simplot); 'Penncozeb' (Cerexagri, Nufarm UK); 'Pennfluid' (Cerexagri); 'Quell Flo' (Interfarm); 'R 6 Erresei' (Bayer CropScience); 'Sparsh' (Biostadt) mixtures: 'Aderio' (+ zoxamide) (Dow AgroSciences); 'Artimon' (+ fosetyl-aluminium) (Dow AgroSciences); 'Besiege WSB' (+ cymoxanil) (DuPont); 'Clip' (+ famoxadone) (DuPont); 'Curathane' (+ cymoxanil) (Dow AgroSciences); 'Curzate M68' (+ cymoxanil) (DuPont); 'Dikar' (+ dinocap) (Dow AgroSciences); 'Kocide Combi' (+ copper hydroxide) (Griffin); 'ManKocide' (+ copper hydroxide) (Griffin); 'Metasan' (+ metalaxyl) (Dow AgroSciences); 'Midas' (+ famoxadone) (DuPont); 'Rhodax Express' (+ fosetyl-aluminium) (Dow AgroSciences); 'Stimo' (+ zoxamide) (Dow AgroSciences); 'Sygan LS' (+ cymoxanil+ folpet) (DuPont); 'Syphal LS' (+ copper oxychloride+ cymoxanil+ folpet) (DuPont); 'Systol M' (+ cymoxanil) (DuPont); 'Trustan' (+ oxadixyl+ cymoxanil) (DuPont); 'Unikat' (+ zoxamide) (Dow AgroSciences); 'Acrobat MZ' (+ dimethomorph) (BASF); 'Adagio' (+ chlorothalonil) (Interfarm); 'Armetil M' (+ metalaxyl) (IQV); 'CL 197509' (+ dimethomorph) (BASF); 'Cupertine M' (+ Bordeaux mixture) (IQV); 'Cure-M' (+ metalaxyl) (Agrochem); 'Cymoxeb' (+ cymoxanil) (Me2); 'Fubol Gold' (+ metalaxyl-M) (Syngenta); 'Galben M' (+ benalaxyl) (Isagro); 'Guru' (+ chlorothalonil) (Interfarm); 'Invader' (+ dimethomorph) (BASF); 'Konkret' (+ copper oxychloride) (Azot); 'Mandore' (+ iprovalicarb) (France) (Bayer CropScience); 'Manhandle' (+ myclobutanil) (Lesco); 'Manoxil' (+ cymoxanil) (AgroSan); 'Mantox' (+ copper oxychloride) (Vapco); 'Mantox-Forte' (+ copper oxychloride+ copper sulfate) (Vapco); 'Maxim MZ' (+ fludioxonil) (Syngenta); 'Mefenoxam MZ' (+ metalaxyl-M) (Syngenta); 'Melody Med' (+ iprovalicarb) (Bayer CropScience); 'Metamac' (+ metalaxyl) (AgroSan); 'Moncoat MZ' (+ flutolanil) (Nihon Nohyaku); 'Noblite' (+ fenamidone) (Bayer CropScience); 'Otria Plus' (+ metalaxyl) (Probelte); 'Oxicob Mix' (+ copper oxychloride) (Ingeniería Industrial); 'Patafol' (+ ofurace) (Bayer CropScience); 'Recoil' (+ oxadixyl) (Syngenta); 'Rhodax M' (+ fosetyl-aluminium) (Philagro); 'Rhodax' (+ fosetyl-aluminium) (Bayer CropScience); 'Rhythm' (+ cymoxanil) (Interfarm); 'Ridomil Gold MZ' (+ metalaxyl-M) (Syngenta); 'Ridomil MZ' (+ metalaxyl) (Syngenta); 'Ripost' (+ oxadixyl+ cymoxanil) (Syngenta); 'Sagaie' (+ fenamidone) (Bayer CropScience); 'Sanchar' (+ metalaxyl) (Biostadt); 'Saracen' (+ dimethomorph) (BASF); 'Secure' (+ fenamidone) (Bayer CropScience); 'Sereno' (+ fenamidone) (Bayer CropScience); 'Sonata' (+ fenamidone) (Bayer CropScience); 'Tairel M' (+ benalaxyl) (Isagro); 'Tattoo' (+ propamocarb hydrochloride) (Bayer CropScience); 'Tops MZ' (+ thiophanate-methyl) (Gustafson); 'Tricuproxi' (+ copper oxychloride) (Aragro); 'UC 70' (+ copper oxychloride) (Philagro); 'Vacomil Mz-72' (+ metalaxyl) (Vapco); 'Vimonyl' (+ metalaxyl) (Vipesco); 'Yorel' (+ iprovalicarb) (France) (Bayer CropScience) Discontinued products: 'Fancozeb' * (Agrochem); 'Helm 75' * (PBI); 'Kor DF' * (Headland); 'Kor Flo' * (Headland); 'Kor' * (Headland); 'Mancotan' * (Agro Chemicals); 'Mandate' * (Portman); 'Nemispor' * (Isagro); 'Opie' * (PBI); 'Quell' * (Headland); 'Tariff 75' * (PBI); 'Zebra' * (Headland) mixtures: 'Besiege' * (+ cymoxanil) (DuPont); 'Adagio' * (+ chlorothalonil) (PBI); 'Agromil MZ' * (+ metalaxyl) (Agro Chemicals); 'Agroxyl M' * (+ metalaxyl) (Agrochem); 'Ashlade Solace' * (+ cymoxanil) (Nufarm Whyte, Ashlade); 'Carlit' * (+ benalaxyl+ fosetyl-aluminium) (Aventis); 'Cymotine' * (+ cymoxanil) (Agro Chemicals); 'Despirol Plus' * (+ kelevan) (Spiess); 'Fubol' * (+ metalaxyl) (Syngenta); 'Furado' * (+ pyrifenox) (Ciba); 'Fytospore' * (+ cymoxanil) (Zeneca); 'Kombat' * (+ carbendazim) (AgrEvo, Hoechst, Stefes); 'Mankuprox' * (+ copper oxychloride) (Azot); 'Osprey' * (+ metalaxyl) (Novartis); 'Septal' * (+ carbendazim) (Schering); 'Sibutol MZA' * (+ anthraquinone+ bitertanol) (Bayer); 'Zaron Combi' * (+ anthraquinone+ bitertanol) (Bayer)

ANALYSIS
Product analysis CIPAC Handbook, 1998, H,195; in mixture with copper compounds by iodometric titration of liberated carbon disulfide (ibid., 1998, H, 96); determination of manganese by titration, (ibid., 1994, F, 232); ETU content by hplc or paper chromatography (ibid., 1994, F, 399). Residues determined by reaction with acid to form carbon disulfide which is measured by standard methods (Analyst (London), 1981, 106, 782; Pestic. Anal. Man., 1979, II; Manu. Pestic. Residue Anal., 1987, I, S21; Anal. Methods Residues Pestic., 1988, Part II).

MAMMALIAN TOXICOLOGY
Reviews FAO/WHO 68, 70 (see part 2 of the Bibliography). Oral Acute oral LD50 for rats >5000 mg/kg. Skin and eye Acute percutaneous LD50 for rats >10 000, rabbits >5000 mg/kg. No irritation to skin (rabbits); moderate eye irritant (rabbit, EU standards), not an eye irritant (rabbit, U.S. standards) No dermal sensitisation in Buehler test; may cause dermal sensitisation in guinea pig maximisation test. Inhalation LC50 (4 h) for rats >5.14 mg/l. NOEL NOEL for rats 4.0 mg/kg b.w. daily. NOAEL for ethylenethiourea 0.37 mg/kg b.w. daily. Below toxic levels, mancozeb was observed to have no effect on reproduction, on neonatal survival, or on growth. ADI (JMPR) 0.03 mg/kg b.w. (group ADI with maneb, metiram and zineb); ethylenethiourea 0.004 mg/kg b.w. [1993]; mancozeb 0.05 mg/kg b.w. Other At very high, maternally toxic levels, mancozeb has caused birth defects in test animals; ethylenethiourea, a trace contaminant and breakdown product of mancozeb, has caused thyroid effects, tumours and birth defects in laboratory animals. Toxicity class WHO (a.i.) U; EPA (formulation) IV EC classification Xi; R37| R43

ECOTOXICOLOGY
Birds Acute oral LD50 (10 d) for mallard ducks >5500, Japanese quail 5500, English sparrow (Passer domesticus) >1290, European starling (Sturnus vulgaris) >2400 mg/kg. Acute dietary LC50 (8 d) for bobwhite quail and mallard ducks >5200 mg/kg diet. Chronic reproduction NOEL for mallard ducks 125, bobwhite quail 300 mg/kg diet. Fish LC50 (96 h, flow-through) for rainbow trout 1.0, bluegill sunfish >3.6 mg/l; (96 hr static-renewal) for rainbow trout 0.15, 0.088, 0.074, bluegill sunfish 0.083, common carp (Cyprinus carpio) 4.0, 3.3 mg/l; (96 h, static sediment/water microcosm) for rainbow trout 0.073, fathead minnow 0.57, bluegill sunfish 0.84, three-spined stickleback (Gasterosteus aculeatus) 0.93, Zebra fish 0.95, largemouth bass (Micropterus salmoides) 1.0, guppy (Poecilia reticulata) 1.3, Medaka (Oryzias latipes) 1.4, common carp 1.7 mg/l. NOEC (34 d, early life stage) for fathead minnow 0.022 mg/l; extended growth NOEC (14 d) for rainbow trout 0.66 mg/l. Daphnia EC50 (48 h, flow-through) 3.8 mg/l; (48 h static-renewal) 0.073 mg/l; (24 h, static) 0.011 mg/l; (48 h, static) 0.39 mg/l. Algae EC50 (120 h, cell density) for Selenastrum capricornutum 0.044 mg/l. Other aquatic spp. EC50 (24 h) for rotifer (Brachionus calyciflorus) 0.11 mg/l; LC50 (48 h) for snail (Lymnae stagnalis) >113, for amphipod (Gammarus sp.) 3.0, for isopod (Asellus sp.) 4.4 mg/l. Outdoor mesocosm (macroinvertebrates and phytoplankton communities), 11 week, after 8 applications, Ecologically Acceptable Concentration 0.032 mg/l. Bees LD50 (oral) >209 mg/bee; (contact) >400 mg/bee. Worms LC50 (14 d) for Eisenia foetida >1000 mg/kg soil; 56 d reproduction NOEC for Eisenia foetida 20 mg/kg soil.

ENVIRONMENTAL FATE
EHC 78 (WHO, 1988; general review of dithiocarbamates). Mancozeb breaks down rapidly in soil, sediment and water; terminal metabolites are natural products and with mineralisation to carbon dioxide. It does not bioaccumulate. Animals Poorly absorbed and rapidly excreted in animals. The spectrum of metabolites produced was similar in laboratory and farm animals, pointing to two common metabolic pathways, which both lead ultimately to the formation of glycine and to incorporation of the metabolites into natural products. Plants Extensively metabolised in plants, forming ethylenethiourea, ethylenethiuram monosulfide, ethylenethiuram disulfide, and sulfur as transitory intermediates. Terminal metabolites are natural products, especially those derived from glycine. Soil/Environment Rapidly degraded in the environment by hydrolysis, oxidation, photolysis, and metabolism. Soil DT50 <1 d (ave., 20 ºC). Koc 1000 ml/g.