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新《生活饮用水卫生标准》GB5749-  项目解读(1):呋喃丹

                  中国水质网

一、呋喃丹农药
carbofuran


氨基甲酸酯类杀虫剂和杀线虫剂。1963年由美国创制,1967年推广。纯品为白色结晶,25℃时水中溶解度为700ppm,在中性和酸性条件下较稳定,在碱性介质中不稳定,水解速度随pH值和温度的升高而加快,在水田中半衰期为1~2天 ,土壤中为30~60天。是内吸剂,兼有触杀作用,能被植物根、茎、叶吸收,并在体内传导。杀虫谱广,对稻、棉、甜菜、烟草、大豆等多种作物及林木、花卉上的多种害虫和线虫有效。持效期长,一般可达30~40天。剂型主要是颗粒剂。防治地上害虫亩用有效成分35~60克,防治地下害虫和线虫用200~250克。防治稻虫采用土壤或水面施药法,防治旱田作物害虫和地下害虫、线虫时随种子播入土中,作物生长期可将药条施或沟施入土中,不能将颗粒剂浸水后喷雾。

二、、呋喃丹特性
 

[毒害品]有机毒害品.一级有机毒害品.
[英]Furadan Carbofuran
[别]虫螨威;克百威
[缩]FND  

【化学特性】
纯品为无臭白色结晶. 不易溶于水. 遇碱不稳定. 不易燃烧. 大鼠经口半数致死量为11毫克/千克. 相对密度: 1.180 熔点: 153~154℃(纯品);150~152℃(工业品)
【火灾危险】
剧毒, 可燃.
【处置方法】
水、泡沫、二氧化碳、砂土
 

三、呋喃丹详解

英文:

Synonyms Carbofuran
Furadan
Carbamic acid, methyl-, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl ester
7-Benzofuranyl, 2,3-dihydro-2,2-dimethyl-, methylcarbamate
Analytical Methods EPA Method 531.1
EPA Method 632
Molecular Formula C12H15NO3
Use BROAD SPECTRUM INSECTICIDE, NEMATOCIDE, MITICIDE SYSTEMIC ACARICIDE FURADAN CONTROLS CORN ROOTWORM IN FIELD CORN; MOST SOIL & FOLIAR PESTS; ALFALFA WEEVIL, APHIDS & LYGUS BUGS; NEMATODES, SOIL, FOLIAGE FEEDING INSECTS IN TOBACCO; NEMATODES, THRIPS IN PEANUTS; RICE WATER WEEVIL; NEMATODES, WIREWORMS, SUGARCANE BORER IN SUGARCANE; GREENBUG IN SORGHUM; COLORADO POTATO BEETLE, LEAFHOPPERS, FLEA BEETLES IN POTATOES; NEMATODES, MEXICAN BEAN BEETLE IN SOYBEANS; SOIL, FOLIAR FEEDING INSECTS, NEMATODES IN SWEET CORN; THRIPS IN COTTON; NEMATODES, PHYLLOXERA IN GRAPES; GRASSHOPPERS, CEREAL LEAF BEETLE IN SMALL GRAINS; NEMATODES IN CUCURBITS; GRASSHOPPERS, STEM WEEVILS, SUNFLOWER BEETLES IN SUNFLOWERS CARBOFURAN IS EFFECTIVE AGAINST A NUMBER OF MITES WITH THE EXCEPTION OF SOME TETRANYCHUS OUTSIDE USA: OVERSEAS USES INCLUDE BANANAS, COFFEE AND SUGAR BEETS. GRANULES ARE USED IN LOWLAND RICE AGAINST LEAFHOPPERS, STEMBORERS, & CERTAIN OTHER INSECTS. In Canada carbofuran is registered for use in control of out-breaks of grasshoppers using aerial applications of carbofuran up to 140 g active ingredient/hectare. Canada: Highest rate of carbofuran registered for the control of wireworms in potatoes at 5.6 kg active ingredient/hectare. Registered uses of carbofuran in Canada: Limitations are as follows: Do not apply to crops within the following pre-harvest intervals (days): alfalfa (7); barley (21); corn (7); flax (21); mustard (21); oats (21); pastures ; pepper, green ; potato (7); rape (60); rutabaga (40); sweet clover (28); sunflower (60); tomato, field (30); turnip (40); wheat (21). Do not feed foliage of treated turnips to livestock; mature roots may be fed. On alfalfa, do not apply during bloom, or allow spray to drift toward beehives. Do not graze or feed to livestock within the following intervals (days) after application: alfalfa (7); barley (21); corn ; oats (21); mustardseed (21); pastures ; rape seed (60); sweet clover (28); wheat (21). Do not make more than the following number of applications per season: barley ; flax ; mustard (1 at 140 g ai/ha or 2 at 70 g ai/ha); oats ; pastures ; pepper, green (6); rape (1 at 140 g ai/ha or 2 at 70 g ai/ha); sunflower ; sweet clover ; tomato, field ; wheat . Do not permit livestock to graze on road sides or headlands within 1 day after application. Commercial class products limited to a maximum carbofuran content of 10%. For registered uses of carbofuran in Canada, limitations are as follows: Do not apply to crops within the following pre-harvest intervals (days): alfalfa (7); barley (21); corn (7); flax (21); mustard (21); oats (21); pastures ; pepper, green ; potato (7); rape (60); rutabaga (40); sweet clover (28); sunflower (60); tomato, field (30); turnip (40); wheat (21); Do not feed foliage of treated turnips to livestock; mature roots may be fed. On alfalfa, do not apply during bloom, or allow spray to drift toward beehives. Do not graze or feed to livestock within the following intervals (days) after application: alfalfa (7); barley (21); corn ; oats (21); mustardseed (21); pastures ; rape seed (60); sweet clover (28); wheat (21). Do not make more than the following number of applications per season: barley ; flax ; mustard (1 at 140 g ai/ha or 2 at 70 g ai/ha); oats ; pastures ; pepper, green (6); rape (1 at 140 g ai/ha or 2 at 70 g ai/ha); sunflower ; sweet clover ; tomato, field ; wheat . Do not permit livestock to graze on road sides or headlands within 1 day after application. Commercial class products limited to a maximum carbofuran content of 10%. UNREVIEW
Consumption Patterns ABOUT 82% AS AN INSECTICIDE ON CORN; ABOUT 15% AS AN INSECTICIDE ON ALFALFA; AND THE BALANCE ON TOBACCO AND OTHER FIELD CROPS (1974) Applied to Alfalfa, 47.1%; Rice, 42.2%; Turf, 6.7%; Grapes, 2.4% Remainder on other grains, fruits and vegetables, and non-food crops (1984) California use, calculated from table (1984) 9.35X10 7 g California use, calculated from table
Apparent Color WHITE, CRYSTALLINE SOLID
Odor ODORLESS (PURE MATERIAL); Slightly phenolic.
Melting Point 153-154 deg C (pure)
Molecular Weight 221.26
Density 1.180 AT 20 DEG C/20 DEG C
Environmental Impact The dominant source of carbofuran emission to the environment is the application of the compound as an insecticide. If released to soil, chemical hydrolysis and microbial degradation appear to be the important degradation processes. Chemical hydrolysis is expected to occur more rapidly in alkaline soil as compared to neutral or acidic soils. Results of various degradation studies comparing sterile versus nonsterile soil suggest that soil biodegradation may be important. The rate of degradation of carbofuran in soil is greatly increased by pretreatment with carbofuran. The major metabolites of carbofuran degradation in soil are 3-hydroxycarbofuran, 3-ketocarbofuran and carbofuran phenol. Experimentally measured Koc values ranging from 14 to 160 indicate that carbofuran may leach significantly in many soils; its detection in water table aquifers beneath sandy soils in NY and WI indicate leaching has occurred. Leaching may not occur, however, in very high organic content soils (65% carbon). Volatilization from soil is not expected to be significant, although some evaporation from plants may occur. A review of literature reported the following half-lives for carbofuran disappearance in soil: 2-72 days in laboratory studies, 2-86 days for flooded soils and 26-110 days for field soil. If released to water, carbofuran will be subject to significant hydrolysis under alkaline conditions. The hydrolysis half-lives in water at 25 deg C are 690, 8.2 and 1.0 weeks at pH 6.0, 7.0 and 8.0, respectively. Direct photolysis and photooxidation (via hydroxyl radicals) may contribute to carbofuran's removal from natural water and may become increasingly important as the acidity of the water increases and the hydrolytic half-life increases. Since carbofuran appears to be susceptible to degradation by soil microbes, aquatic microbes may also be able to degrade carbofuran. Aquatic volatilization, adsorption, and bioconcentration are not expected to be important. The half-lives for degradation of carbofuran in river, lake, and seawater from Greece which was irradiated with sunlight were approximately 2, 6, and 12 hours, respectively. The approximated half-lives observed for degradation of carbofuran in sterilized and non-sterilized natural water (pH = 7.8-8.0 and 7.8, respectively) collected from the Holland Marsh, Ontario, were 2.5 and 3 weeks. If released to air, carbofuran will react in the vapor-phase with photochemically produced hydroxyl radicals at an estimated half-life of 7.8 hr. Direct photolysis may be important removal process for carbofuran in the atmosphere. Occupational and general population exposure to carbofuran may occur by inhalation and dermal routes, particularly in the vicinity of aerial spraying of carbofuran as an insecticide.
Environmental Fate TERRESTRIAL FATE: No appreciable degradation of carbofuran occurred in kari soil (pH 4.8; organic matter 11.8%) until 30 days after flooding, but at the end of 40 days, more than 81% of carbofuran degraded followed by steady increase in recovery of nonextractable soil bound residues. Autoradiographic analysis showed that carbofuran phenol (major) & 3-hydroxycarbofuran were carbofuran metabolites in soil. The mechanism of degradation in flooded soils was studied by using (14)C-carbofuran. TERRESTRIAL FATE: If carbofuran is released to soil, it will be subject to degradation by both chemical and biological processes . A review of available literature reported the half-lives for carbofuran disappearance in soil as follows: 2-72 days in laboratory studies, 2-86 days for flooded soils, and 26-110 days for soil in the field . The rate of degradation of carbofuran in soil is greatly increased by pretreatment with carbofuran(3,4). Chemical hydrolysis (in aqueous solution) occurs much more rapidly under alkaline conditions . Therefore, the pH of the soil is likely to be a major factor in determining the rate of disappearance; several studies have shown that carbofuran is decomposed faster in alkaline soils as compared to neutral or acidic soils . Results of various degradation studies comparing sterile versus nonsterile soil suggest importance of soil biodegradation(6,7). The major metabolites of carbofuran degradation in soil are 3-hydroxycarbofuran, 3-ketocarbofuran and carbofuran phenol . Experimentally measured Koc values ranging from 14 to 160(3,8) indicate that carbofuran may leach significantly in many soils and its detection in water table aquifers beneath sandy soils in NY and WI(9) indicates that leaching has occurred. Leaching did not occur, however, in an onion field containing a high organic matter content (65%) during 10 weeks of monitoring(10). Volatilization from soil is not expected to be significant(11), although some evaporation may occur from plants(12). TERRESTRIAL FATE: Carbofuran was incorporated in soils & its disappearance monitored. Disappearance of 95% of carbofuran varied between 145 & 434 days as a function of temperature, moisture, & soil pH & followed first-order kinetics. TERRESTRIAL FATE: In 4 soils with known insecticide use, the technical carbofuran had a calculated half-life of 11-13 days (pH 6.5) & the granular formulation had a half-life of 60-75 days (pH 6.5). Time of disappearance from the soil at 3.1 to 5.6 kg/hectare was 145 to 434 days. AQUATIC FATE: If carbofuran is released to water, it will not be expected to subject to volatilization, adsorption to sediment or suspended particulate matter(4,5), or to bioconcentration in aquatic organisms(6). The hydrolysis half-lives of carbofuran in water are about 690, 8.2 and 1.0 weeks at pH 6.0, 7.0 and 8.0, respectively, at 25 deg C indicating that hydrolysis in alkaline water will be important . Direct photolysis and photooxidation (via hydroxyl radicals) may contribute to carbofuran's removal from natural water and may become increasingly important as the acidity of the water increases and the hydrolytic half-life increases. Since carbofuran appears to be susceptible to degradation by soil microbes(7), aquatic microbes may also be able to degrade carbofuran. The half-lives for degradation of carbofuran in river, lake, and seawater from Greece which was irradiated with sunlight were approximately 2, 6, and 12 hours, respectively . The approximate half-lives observed for degradation of carbofuran in sterilized and non-sterilizaed natural water (pH = 7.8-8.0 and 7.8, respectively) collected from the Holland Marsh, Ontario, were 2.5 and 3 weeks, respectively, were due primarily to chemical processes . ATMOSPHERIC FATE: If carbofuran is released to the atmosphere, it will be suject to vapor phase photooxidation via reaction with hydroxyl radicals . The half-life for the vapor-phase reaction of carbofuran with photochemically produced hydroxyl radicals has been estimated to be 7.8 hr in a typical atmosphere . Direct photolysis may be an important removal process for carbofuran in the atmosphere . Carbofuran on particulates suspended in air during aerial spraying of the insecticide is subject to dry and wet deposition. TERRESTRIAL FATE: The persistence of carbofuran in the soil will increase as 1) the application rate increases; 2) the clay content of the soil increases; 3) the organic matter content of the soil increases; 4) the pH decreases; 5) the moisture content of soil decreases. TERRESTRIAL FATE: Carbofuran behavior was studied in 2 drained cornfield soils (clay and loamy clay) for 2 successive yr. The persistence values (total residence time) obtained were 56 and 63 days for the first and second yr. Drained water from soil rich in organic matter was found to have a higher carbofuran content, with 7.1-13.7% and 2.5-5.0% of the applied dose for clay and loamy clay soils, respectively. The major part of these percentages arose from the drained waters associated with rainfall occurring during the first 2-3 wk after application. TERRESTRIAL FATE: Half-life in soil is about 30-60 days.
Drinking Water Impact GROUNDWATER: Carbofuran has been found in ground water in WI and NY in areas with sandy soils and water table aquifers at levels typically between 1 and 5 ppb . Carbofuran was detected (detection limit 1 ppb), not quantified, in well water samples taken in 1984 from 5 to 91 farms in Southern Ontario, Canada . The Ground Water Data Base 1988 Interim Report lists three confirmed states (NY, MA, RI) in which carbofuran has been found due to agricultural use and point source contamination . The max concn of the confirmed detections is 176 ppb and the median concn is 5.30 ppb . SURFACE WATER: Carbofuran has been detected (concn not reported) in surface waters associated with Lake Erie and Lake Huron . An overall mean carbofuran concn of less than 0.1 ng/l was detected in 11 agricultural watersheds in Ontario during 1976-77 with the highest monitored concn being 1.80 ng/l; the presence of the carbofuran in the watersheds was thought to have occurred by storm water runoff, soil drainage and spills . Carbofuran was found in samples from the following Michigan Rivers in 1985 at t the indicated concn ranges in the positive samples: Black 0.100-0.473 ppb; Belle, 0.009-0.266 ppb; Pine, 0.056-0.250 ppb; and Clinton, 0.18-0.413 ppb . DRINKING WATER: Between May-July 1986, carbofuran was detected (detection limit 0.1 ppb) in 9 of 33 treated (finished) public water supplies using surface water as a source at a concn of 0.18-14.0 ppb and at an avg concn of positive detections of 3.76 ppb . Carbofuran was detected also in 5 of 15 of the surface water sources at a concn of 0.72-17.0 ppb and at an avg concn of positive detections of 7.1 ppb . The water samples in the above study were taken after rainfall . RAIN/SNOW: Samples of rainwater collected during spring and summer 1985 were analyzed for the presence of carbofuran . Carbofuran was detected at a concn range of 0.1-0.5 ppb in the samples of rainwater from the following locations (number of samples at indicated concn): West Lafayette, IN (2 of 14 samples), Tiffin, OH (1 of 25 samples), Parsons, WV (1 of 20 samples), and Potsdam, NY (1 of 21 samples) . Carbofuran also was detected, not quantified, in 1 of 21 samples from Potsdam, NY . Waters from 21 wells and 2 springs located in a typically farmed, mostly agricultural PA watershed (the Mahantango Creek Watershed) were analyzed for 11 pesticides, including carbofuran. Pesticides were selected according to a farm use survey, and samplings were made during Dec 1985, Aug 1986, and Mar/Apr 1987. Carbofuran was not applied in 1985, but was applied to about 85% of the area at 1.2 kg/ha in 1986. No carbofuran was found in any sampling (< 15 ng/l). EFFL: Carbofuran was detected (detection limit 1 ppb), not quantified, in well water samples taken in 1984 from 5 of 91 farms in Southern Ontario, Canada . Concn of carbofuran in runoff into a hydroelectric lake in GA from a carbofuran-treated pine seed orchard ranged from not detected to 6580 ppb; the runoff event with the maximum detected concn produced a minor fish kill in the lake . Thirty-one tailpits collecting irrigation runoff from corn and sorghum fields in Haskell County KS in 1974 were found to contain a mean concn of 24.1-35.2 ppb carbofuran in the tailpit water .

中文:

物质的理化常数:

中文名称 呋喃丹
英文名称 Furadan;Cavbofuran
别    名 克百威;虫螨威;2,3-二氢-2,2-二甲基-7-苯并呋喃基-甲基氨基甲酸酯
分子式 C12H15NO3 外观与性状 纯品为白色无臭结晶,工业品稍有苯酚气味
分子量 221.38 蒸汽压 2.67mPa
熔    点 153℃ 溶解性 微溶于水,溶于多数有机溶剂
密    度 相对密度(水=1)1.18 稳定性 稳定
危险标记 14(有毒品),34(易燃液体) 主要用途 用作农药杀虫剂

对环境的影响:

一、健康危害

  侵入途径:吸入、食入、经皮吸收。
  健康危害:主要抑制体内胆碱酯酶活性,使乙酰胆碱在组织中蓄积而引起中毒。作用机制和有机磷农药中毒相似。中毒表现有流涎、流泪、瞳孔缩小及痉挛。但与有机磷农药相比,抑制胆碱酯酶的作用持续的时间较短。停止接触后,胆碱酯恢复较快。

毒理学资料及环境行为

  毒性:经口属剧毒类;经皮属中等毒类。对人畜高毒。
  急性毒性:LD505.3mg/kg(大鼠经口);885mg/kg(兔经皮);10g/kg(人经皮);LC5085ppm  2小时(哺乳类动物吸入);8~14mg/kg(小鼠经口);

  呋喃丹属高毒农药。对环境生物毒性也很高,在各种环境生物中,呋喃丹对鸟类的危害性最大,一只小鸟只要觅食一粒呋喃丹足以致命。受呋喃中毒致死的小鸟或其它昆虫,被猛禽类、小型兽类或爬行类动物觅食后,可引起二次中毒而致死。在美国曾发现30余起猛禽(鹰、隼、秃鹫)遭呋喃丹二次中毒事故。
呋喃丹的另一个环境行为特点是它在土壤中的残留期较长(降解半衰期为1~2个月)、在土壤中的移动性能较大(水溶解度为700mg/L),在降水量大、地下水位浅的砂土地区易引起对地下水的污染,为此美国对呋喃丹使用作了一些地区性限制。

  危险特性:遇明火、高热可燃。受热分解放出有毒的氧化氮烟气。
  燃烧(分解)产物:一氧化碳、二氧化碳、氧化氮。

现场应急监测方法:

直接进水样气相色谱法

实验室监测方法:

气相色谱法《现代环境监测方法》(水、粮食和土壤)张晓林等主编
气相色谱法(GB/T14877-94,食品)
高效液相色谱法《农药环境毒理学研究》,蔡道基主编

环境标准:

美国(1982) 车间卫生标准 0.1mg/m3
中国(GB11607-89) 渔业水质标准 0.01mg/L
中国(98年修改稿) 地表水环境质量标准(I、II、III类水域特定值) 0.005mg/L
中国(GB14928.7-94) 食品卫生标准 0.5mg/kg(稻谷)

应急处理处置方法:

a.泄漏应急处理

  隔离泄漏污染区,周围设警告标志,建议应急处理人员戴自给式呼吸器,穿化学防护服。用清洁的铲子收集于干燥净洁有盖的容器中,运至废物处理场所。如大量泄漏,收集回收或无害处理后废弃。

b.防护措施

  呼吸系统防护:生产操作或农业使用时,应该佩带防毒口罩。紧急事态抢救或逃生时,建议佩带自给式呼吸器。
  眼睛防护:可采用安全面罩。
  防护服:穿相应的防护服。
  手防护:必要时戴防护手套。
  其它:工作现场禁止吸烟、进食和饮水。工作后,淋浴更衣。保持良好的卫生习惯。

c.急救措施

  皮肤接触:立即脱去污染的衣着,用肥皂水及流动清水彻底冲洗污染的皮肤、头发、指甲等。就医。
  眼睛接触:立即提起眼睑,用流动清水冲洗10分钟或用2%碳酸氢钠液体冲洗。
  吸入:迅速脱离现场至空气新鲜处。注意保暖,呼吸困难时给输氧。呼吸停止时,立即进行人工呼吸。就医。
  食入:患者清醒时给饮大量温水,催吐,可用温水或1:5000高锰酸钾液彻底洗胃。立即就医。

  灭火方法:雾状水、泡沫、二氧化碳、砂土。

 

 

四、对呋喃丹的一些观点:

1.

呋喃丹可经消化道、呼吸道、皮肤吸收中毒。毒物入体后直接与胆碱酯酶活性中心结合,形成氨基甲酰化酶而使胆碱酯酶失去水解乙酰胆碱的活力,而发生内源性乙酰胆碱积蓄,刺激胆碱能神经兴奋而产生相应的临床表现。故症状类似于有机磷农药中毒。但由于其对酶的抑制是可逆的〔1〕,故症状轻、消失快、病程短。

2.

它的生物毒性表现为内吸触杀和胃毒作用,受呋喃丹污染,鱼游动缓慢,翻转打旋,鳃部充血,排泄物不能离开肛门,产生拖属。没有死的鱼大部分身体弯曲畸形。