丙硫克百威及其主要代谢物在棉田中的残留降解研究

将20% 丙硫克百威乳油施于棉田, 采用气相色谱分析技术研究了丙硫克百威及其主要代谢产物在棉田中的残留降解情况。结果表明: 1) 丙硫克百威在棉田土壤和棉叶中可很快降解转化为克百威, 克百威在棉叶中的最大残留值出现在施药后当天, 在棉田土壤中出现在施药后3d, 说明丙硫克百威在棉叶中的降解速率快于在棉田土壤中; 2) 克百威可进一步转化为3-羟基克百威, 后者在棉叶和棉田土壤中的残留量表现为先升后降, 到第10 天才达最大值,明显滞后于克百威最大值出现的时间; 3) 丙硫克百威和克百威在棉叶和棉田土壤中的降解过程符合Ct= C0·e-kt方程, 它们在棉叶中的降解半衰期为3.6～4.4d, 在棉田土壤中则为10.4～11.9d; 4) 当丙硫克百威的用量按有效成份计为200～400g/hm2, 每季棉花施药3～4 次(每次间隔7d) , 最后一次施药距采收时间分别为20、30d时, 丙硫克百威(含克百威和3-羟基克百威) 在棉籽和棉田耕层土壤中的残留量均小于0. 5 mg/kg。     

气相色谱-质谱法测定烟叶和土壤中丁硫克百威及其代谢产物的残留

建立了气相色谱-质谱法同时检测烟叶和土壤中丁硫克百威及其代谢产物(克百威和3-羟基克百威)残留量的分析方法。土壤样品用丙酮-石油醚[V(丙酮)∶V(石油醚)=1∶4]混合溶液提取,无需净化;鲜烟叶样品用丙酮-乙腈[V(丙酮)∶V(乙腈)=1∶9]混合溶液提取;烤后烟叶用乙腈提取。鲜烟叶和烤后烟叶提取液经旋转蒸发浓缩后,用弗罗里硅土柱净化。结果表明:在0.05~1 mg/kg添加水平下,丁硫克百威及其代谢产物的平均回收率在74%~99%之间,相对标准偏差(RSD,n=5)在1.5%~9.2%之间。该方法的前处理相对于萃取过程较简单,其准确度、精密度和灵敏度均符合农药残留分析与检测的技术要求,适合于丁硫克百威及其代谢产物在烟叶和土壤中的残留分析与检测。     

A comparative study of carbofuran metabolism in treated and untreated soils

Soils which have been pretreated with carbofuran can degrade the insecticide more rapidly than untreated soils, with a consequent loss of efficacy. In laboratory studies, soils pretreated with carbofuran were found to degrade the chemical more rapidly than soils which were not so pretreated. When pretreated soils were sterilised, the rate of carbofuran degradation was much reduced, indicating that most of it was due to microbial action. Incubation of pretreated soil with [phenyl-U-¹⁴C]carbofuran led to the rapid disappearance of the parent compound (3 % left after seven days). Most of the ¹⁴C was accounted for as bound residue after seven days, whilst smaller amounts were recovered as carbon dioxide, 3-hydroxycarbofuran, 3-ketocarbofuran, and an unknown metabolite. Incubation of pretreated soil with [carbonyl-¹⁴C]carbofuran led to rapid loss of the parent compound and the recovery of 73% of ¹⁴C as carbon dioxide by five days. Most of the bound ¹⁴C (>90%) arising from [phenyl-U-¹⁴C]carbofuran treatment of pretreated soil was extracted by 1 M sodium hydroxide and about half of the extracted ¹⁴C was precipitated with ‘humic acids’ after acidification. These and other results suggest that the major metabolic route for carbofuran in pretreated soils involves hydrolysis of the ester bond leading to (1) release of carbofuran phenol which rapidly binds to soil organic matter and, (2) release of the carbonyl moiety which quickly degrades to generate carbon dioxide.     

溴氰菊酯对马铃薯腐烂茎线虫的毒力及对其运动和摄食的影响

采用药液浸渍法、沙柱法以及与荧光染料Cy3共孵育的方法,以丙溴磷、克百威和阿维菌素为对照药剂,测定了溴氰菊酯对马铃薯腐烂茎线虫Ditylenchus destructor的毒力以及对其运动扩散和摄食的影响。结果表明:溴氰菊酯对马铃薯腐烂茎线虫具有一定的杀灭活性,其LC50值为459.8mg/L,活性低于丙溴磷(159.9mg/L)、克百威(331.9mg/L)和阿维菌素(257.3mg/L);溴氰菊酯对马铃薯腐烂茎线虫运动扩散的抑制作用IC50值为3.1mg/L,其活性低于阿维菌素(0.8mg/L),但高于丙溴磷(8.3mg/L)和克百威(16.1mg/L)。当丙溴磷和克百威质量浓度分别低至0.6和40mg/L时,可刺激90%以上的线虫摄食;当丙溴磷和克百威质量浓度最低分别为360和300mg/L时,可抑制全部线虫的摄食;溴氰菊酯与阿维菌素则对线虫的摄食无刺激作用;用10mg/L的丙溴磷处理线虫2h后再分别用阿维菌素和溴氰菊酯处理,发现阿维菌素和溴氰菊酯质量浓度最低分别为20和200mg/L时可抑制全部马铃薯腐烂茎线虫的摄食。研究表明,溴氰菊酯对马铃薯腐烂茎线虫具有较高的活性,其在线虫防治领域的开发应用潜力较好。     

高效液相色谱串联质谱法测定小麦和土壤中的丁硫克百威及其代谢物

建立高效液相色谱-四级杆串联质谱快速测定小麦植株、土壤和麦粒中的丁硫克百威、克百威以及土壤中3-羟基克百威的检测方法。样品经提取、分散固相萃取净化后采用同位素内标法进行多反应监测模式测定。结果表明,该方法目标物在三种基质中的定量限为5μg/kg,回收率在73.7%~98.6%之间,变异系数在1.3%~3.3%之间,满足残留检测方法的要求。     

Metabolism of 2,3-dihydro-2,2-dimethyl-7-benzofuranyl (di-n-butylaminosulfenyl)(methyl)carbamate and 2,3-dihydro-2,2-dimethyl-7-benzofuranyl (morpholinosulfenyl)(methyl)carbamate in cotton and corn plants

The absorption, translocation, and metabolism of two new, selectively toxic derivatives of carbofuran, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl (di-n-butylaminosulfenyl)(methyl)carbamate and 2,3-dihydro-2,2-dimethyl-7-benzofuranyl (morpholinosulfenyl)(methyl)carbamate, were studied in cotton and corn plants 1, 3, 6, and 10 days following both stem injection and foliage treatment. Both carbamates were readily translocated to all plant parts following stem injection, but translocation following leaf application was restricted to within the leaf. In cotton plants, the dibutylaminosulfenyl derivative was easily hydrolyzed to form carbofuran which, in turn, was oxidized at the 3-position of the ring and the N-methyl group. These oxidized metabolites were then converted to plant conjugates. Major metabolites were carbofuran and 3-hydroxy-carbofuran followed by 3-keto-carbofuran phenol and N-hydroxymethyl-carbofuran. Five minor metabolites also were detected. In corn plants, the dibutylaminosulfenyl derivative gave the same metabolites, although the metabolism rate was significantly slower in corn relative to cotton. Overall, the results showed that there were no fundamental differences in the metabolism of the morpholinosulfenyl and dibutylaminosulfenyl derivatives. The stability of both carbamate derivatives in different solvent systems also was investigated.     

直接竞争酶联免疫吸附分析法测定甘蔗中的克百威残留

采用包被抗体直接竞争酶联免疫吸附分析(ELISA)法测定了甘蔗中的克百威残留量。在优化条件下,对克百威标样检测的线性范围为0.000 1~1 mg/L,抑制中浓度(IC50)=3.09 μ g/L,5次重复测定的相对标准偏差(RSD)为9.3%, IC20值为0.085 μ g/L。甘蔗中分别添加克百威标样1,0.1,0.01 mg/kg,直接竞争ELISA法测定的回收率分别为86.3% ~99.1%,89.0% ~101% 和70.7% ~90.6%,RSD(n=5)分别为5.4% ,5.2% 和10.7%。ELISA法对甘蔗中克百威残留的最小检出量为6.3×10-11g,定量限可达1.26 μ g/kg。而同样前处理条件下高效液相色谱-紫外检测器(HPLC-UV)法对克百威的最小检出量为5×10-8 g,检测甘蔗中克百威残留的定量限仅为2.5 mg/kg。     

The metabolism of chlorotoluron in the rat

The metabolic fate of ¹⁴C-labeled chlorotoluron, i.e., 1-(3-chloro-4-methyl[⁴C]-phenyl)-3,3-dimethyl urea, was followed in rats. After a single oral dose the radioactivity was preferably excreted with the urine. Nine of the eleven urinary metabolites isolated, were identified by spectroscopic and derivatization techniques, whereas the structure of the remaining two metabolites was only partially elucidated. N-Demethylation and stepwise oxidation of the ring methyl group to hydroxymethyl and carboxyl derivatives were found as the major metabolic mechanisms. Both mechanisms proceeded simultaneously so that the isolated metabolites showed all combinations of N-demethylation and ring methyl group oxidation in their structures. One of these metabolites was an N-formyl derivative, being probably an intermediate product of demethylation. In the urine of rats fed doses of [¹⁴C]chlorotoluron higher than 50 mg/kg three additional metabolites with different degrees of N-dealkylation were found, the ring methyl group of which was transformed to a methylthio methyl group. The metabolites identified in the faeces were of the same type as those found in the urine. Based on the structures of the metabolites elucidated, a metabolic pathway of chlorotoluron in the rat is presented.     

Residues of carbofuran and 2,3-dihydro-3-hydroxy- 2,2-dimethylbenzofuran-7-yl methylcarbamate in the mushroom,agaricus bisporus,cultivated in casing soils treated with the insecticide

Residues of carbofuran ( 1 ) and 2,3-dihydro-3-hydroxy-2,2-dimethylbenzofuran-7-yl methylcarbamate ( 2 ) in and on mushrooms, cultivated on casing soils containing added carbofuran granular insecticide, were determined. The quantitative estimations in cleaned mushroom extracts were done on thin-layer plates using a cholinesterase inhibition method. Samples were analysed, which had been harvested at different times from cultures, to which different amounts of carbofuran were added. Residues in washed and unwashed mushroom samples were compared. Residues did not exceed 0.5 mg (carbofuran) kg^?1 and 0.25 mg (compound 2 ) kg^?1 for fresh unwashed mushrooms grown on casing soil treated with carbofuran granules 1 g (a.i.) m^?2.     

Carbofuran occupational dermal toxicity, exposure and risk assessment

BACKGROUND: Carbofuran is a carbamate insecticide that inhibits AChE. Although toxic by ingestion in mammals, it has low dermal toxicity, with relatively few confirmed worker illnesses. This risk assessment describes its time of onset, time to peak effect and time to recovery in rats using brain AChE inhibition in acute and 21 day dermal studies; in vitro rat/human relative dermal absorption for granular (5G) and liquid (4F) formulations; occupational exposure estimates using the Pesticide Handlers' Exposure Database and Agricultural Handlers' Exposure Database (PHED/AHED). RESULTS: The point of departure for acute risk calculation (BMDL₁₀) was 6.7 mg kg^?1 day^?1 for brain AChE inhibition after 6 h exposure. In a 21 day study, the BMDL₁₀ was 6.8 mg kg^?1 day^?1, indicating reversibility. At 75 mg kg^?1 day^?1, time of onset was ?30 min and time to peak effect was 6–12 h. Rat skin had ca tenfold greater dermal absorption of carbofuran (Furadan^® 5G or 4F) than human skin. Exposure estimates for 5G in rice and 4F in ten crops had adequate margins of exposure (>100). CONCLUSION: Rat dermal carbofuran toxicity was assessed in terms of dose and time‐related inhibition of AChE. Comparative dermal absorption in rats was greater than in humans. Worker exposure estimates indicated acceptable risk for granular and liquid formulations of carbofuran. Copyright © 2011 Society of Chemical Industry     

The metabolism of the herbicide flamprop-methyl in rats and some comparative data for dogs,mice and rabbits

[¹⁴C]Flamprop-methyl administered orally to rats (3-4 mg kg^?1 body weight) was excreted mostly via the faeces (78.7 and 61.6% in males and females, respectively). Elimination was rapid and 90% of the dose of ¹⁴C was excreted in faeces and urine 0-48 h after dosing. The distribution of ¹⁴C between faeces and urine was different in males and females. No expired [¹⁴C]carbon dioxide was detected and less than 2% of the dose remained in the animals 4 days after dosing. The predominant metabolic pathway was hydrolysis of the ester bond to afford the carboxylic acid which was excreted unchanged and as its glucuronide conjugate. Aromatic hydroxylation occurred at the para- and meta-positions of the N-benzoyl ring. N-(3)-Chloro- 4-fluorophenyl-N-(3,4-dihydroxybenzoyl)-DL -alaninate was also formed. This hydroxylated form of flamprop-methyl was partially O-methylated at the 3-hydroxy group. Flamprop-methyl was also metabolised and eliminated rapidly by dogs, mice and rabbits. The last of these three species afforded very little aromatic hydroxylation and also differed from the others in that the metabolites were eliminated mostly in the urine. Aromatic hydroxylation lay in the order: male rat = female rat > dog= mouse>rabbit (female).     

The effect of initial concentration of carbofuran on the development and stability of its enhanced biodegradation in top‐soil and sub‐soil

Carbofuran was incubated in top‐soil and sub‐soil samples from a pesticide‐free site at a range of initial concentrations from 0.1 to 10 mg kg⁻¹. Amounts of the incubated soils were removed at intervals over the subsequent 12 months, and the rate of degradation of a second carbofuran dose at 10 mg kg⁻¹ was assessed. An applied concentration as low as 0.1 mg kg⁻¹ to top‐soil resulted in more rapid degradation of the fresh addition of carbofuran for at least 12 months. The degree of enhancement was generally more pronounced with the higher initial concentrations. When the same study was conducted in sub‐soil samples from the same site, an initial dose of carbofuran at 0.1 mg kg⁻¹ resulted in only small increases in rates of degradation of a second carbofuran dose. However, degradation rates in the sub‐soil samples were, in many instances, considerably greater than in the corresponding top‐soil samples, irrespective of pre‐treatment concentration or pre‐incubation period. Initial doses of 0.5 mg kg⁻¹ and higher applied to sub‐soil successfully activated the sub‐soil microflora. Application of the VARLEACH model to simulate carbofuran movement through the soil profile indicated that approximately 0.01 mg kg⁻¹ of carbofuran may reach a depth of 70 cm 400 days after a standard field application. The results therefore imply that adaptation of the sub‐soil microflora (c 1 m depth) by normal field rate applications of carbofuran is unlikely to occur. In experiments to investigate this in soils exposed to carbofuran in the field, there was no apparent relationship between top‐soil exposure and degradation rates in the corresponding sub‐soils. The results further confirmed that some sub‐soil samples have an inherent capacity for rapid biodegradation of carbofuran. The high levels of variability observed between replicates in some of the sub‐soil samples were attributed to the uneven distribution of a low population of carbofuran‐degrading micro‐organisms in sub‐surface soil. There was no apparent relationship between soil microbial biomass and degradation rates within or between top‐soil and sub‐soil samples. © 2001 Society of Chemical Industry     

加速溶剂萃取-液相色谱-串联质谱法同步检测白菜中的丁硫克百威及其代谢物残留

建立了白菜中丁硫克百威及其代谢物克百威、3-羟基克百威和3-酮基克百威的同步检测方法。白菜样品匀浆后用硅藻土混合分散,经加速溶剂萃取仪(ASE)用二氯甲烷萃取,固相萃取柱净化,在液相色谱-串联质谱(LC-MS/MS)仪上采用正电离方式以多反应监测模式(MRM)检测,内标法定量。丁硫克百威及其3种代谢物在白菜中的平均回收率在85%～122%之间,相对标准偏差为2.3%～12.5%,检出限为0.002～0.01 mg/kg,定量限为0.005～0.02 mg/kg。采用该方法测定的消解动态结果表明:丁硫克百威在白菜中的消解半衰期为0.9 d,代谢物克百威在施药当天即达到最大值,并在1 d内消解70%以上,而3-羟基克百威与3-酮基克百威的浓度则在1 d时达到最大值,然后呈现快速降低的趋势。     

The metabolism of tefluthrin in the goat

A goat was dosed orally with [¹⁴C]tefluthrin, twice daily for 4 days, at a rate equivalent to 10.9 mg kg^?1 in its diet. Within 16 h of the final dose, 70.1% of the dose had been excreted (urine 41.4%, faeces 28.7%). Extensive metabolism occurred in the goat by ester cleavage and oxidation at a variety of positions on the molecule. Low radioactive residues were detected in the milk (0.076 mg kg^?1), fat (0.076 mg kg^?1) and muscle (0.016 mg kg^?1), with tefluthrin as the largest individual component of the residue (milk 66.5%, fat 76.7%, muscle 34.2%). Higher residues were present in the kidney (0.3 mg kg^?1) and liver (1.0 mg kg^?1) and only a small percentage of this residue was due to tefluthrin (kidney 3.4%, liver 6.1%). The remainder of the residue in the kidney and liver was a complex mixture of metabolites. Most of the kidney metabolites were identified, but a high proportion of the liver residue was due to six unidentified polar compounds.     

高效液相色谱柱后衍生化法检测蔬菜中涕灭威和克百威残留的方法研究

建立了蔬菜中涕灭威和克百威残留的分析方法。样品以乙腈提取,以氨基固相萃取柱净化,甲醇∶二氯甲烷=1∶99（V/V）洗脱,以高效液相色谱柱后衍生系统,荧光检测器检测。在最佳分离条件下,涕灭威和克百威在浓度0.01～1.0mg/L范围内线性关系良好;方法检出限涕灭威为1.4μg/kg,克百威为1.7μg/kg。蔬菜样品中3个添加水平的平均回收率为涕灭威70.6%～82.0%,RSD为5.1%～12.2%;克百威88.0%～98.0%,RSD为1.3%～14.0%。该方法灵敏,准确,适用于蔬菜中涕灭威和克百威的残留检测。     

The metabolism of [14C] cymoxanil in the rat

A rat, given a single oral dose of [¹⁴C] cymoxanil, 1-(2-cyano-2-methoxyimino-[2-¹⁴C]-acetyl)-3-ethylurea, eliminated 91% of the radioactivity within 72 h. The urine contained 71%, the faeces 11%, and the expired air about 7% of the radiolabel; no ¹⁴C residue was found in the internal organs. Greater than 70% of the radioactivity in the urine was identified. The major metabolite was characterised as glycine, both free and conjugated, as hippuric acid and phenylaceturic acid [N-(phenylacetyl)-glycine], and probably in the form of polypeptides of low molecular weight. The other metabolites identified included 2-cyano-2-methoxyiminoacetic acid, 2-cyano-2-hydroxyiminoacetic acid and 1-ethylimidazolidine-2, 4, 5-trione. The minor metabolites included succinic acid and 2-oxoglutaric acid which indicated reincorporation of metabolic ¹⁴C. Cymoxanil, as such, was not detected in the urine.     

Excretion and residues of the herbicides benzoylprop-ethyl flamprop-isopropyl and flamprop-methyl in cows,pigs and hens

Two wild oat herbicides, benzoylprop-ethyl and flamprop-methyl were administered to lactating cows at low dose levels (0.3–3.0 mg/kg in total diet) and the excretion of total metabolites in milk, urine and faeces was measured. Total residues in tissues were also determined. Similarly a third and related herbicide flamprop-isopropyl was fed to cows, pigs and hens (at 0.5 mg/kg in total diet) and the residues were determined in excreta and tissues, including eggs. The amounts of the compounds fed were equivalent to approximately 10–300 times the total residue found in cereal treated in the field. Residues in milk in most cases were well below 0.001 mg/kg; in muscle samples <0.003 mg/kg; and in eggs, 0.0008 mg/kg, decreasing by 50% in approximately 3 days to 0.0001 mg/kg 4 days after the termination of treatment. Elimination of the herbicides from the animals was rapid in every case and this, together with the low residue levels, was attributed to very efficient metabolic de-esterification to the parent carboxylic acid metabolites (benzoylprop and flamprop). These metabolites possess physical properties ideally suited for excretion via the kidneys and bile into urine and faeces and, conversely, unsuited for transport into milk and eggs.     

Metabolites of carbofuran: Effect on indole-3-acetic acid degradation

Oxygen uptake, product formation, and photon emission in the indole-3-acetic acid/peroxidase/O₂ system were inhibited by carbofuran and its metabolites, the 3-ketocarbofuran phenol and carbofuran phenol. These metabolites acted as competitive inhibitors and concomitantly were degraded. Photon emission, together with uv spectrophotometry and oxygen measurements, shows this to be a rapid and reproducible method to study insecticide interaction with the indole-3-acetic oxidase system in vitro. 3-Ketocarbofuran phenol was metabolized by peroxidase with excited-state production.     

The metabolism of the carbamate insecticide bendiocarb in the rat and in man

The metabolism of the carbamate insecticide bendiocarb (2,2-dimethylbenzo-1, 3-dioxol-4-yl methylcarbamate) has been investigated in male and female rats and in a male human volunteer using radiolabelled material. The compound was rapidly and extensively absorbed and completely metabolised following oral administration. In man, absorption was complete, >99% of the dose being excreted in the urine within 22 h. In the rat, > 86% of the radiolabel was excreted in the urine within the first 24 h. Faecal excretion from the rat was minor (3–8% of dose) and a small amount of the compound (1–3%) was metabolised and excreted as [¹⁴C]carbon dioxide. The major metabolic pathway in both species involved cleavage of the carbamate ester group to yield the phenol,2,2-dimethylbenzo-1, 3-dioxol-4-ol (I). This metabolite, occurring as sulphate and glucuronide conjugates, accounted for more than 95% of the dose excreted by the human volunteer. In man, small amounts of conjugates of 2, 2-dimethylbenzo-1, 3-dioxol-4-yl N-(hydroxymethyl)carbamate (II) were also found in early samples. In the rat, the metabolism was more complex with the formation of small amounts of conjugates of II and several minor metabolites, thought to be ring-hydroxylated derivatives of bendiocarb and I.     

Determination of carbofuran in pesticide formulations by flow injection spectrophotometry

A flow injection spectrophotometric method for the determination of carbofuran in commercial pesticide formulations was developed. The determination involves on‐line hydrolysis of the extracted carbofuran at room temperature with sodium hydroxide. The resulting carbofuran‐phenol is coupled with diazotized 4‐aminobenzoic acid in order to achieve an appropriate selectivity and sensitivity for the spectrophotometric measurements. The calibration curve is linear over the range 1–10 mg litre⁻¹ of carbofuran. The proposed method has a detection limit of 0.15 mg litre⁻¹ of carbofuran and a sample frequency of 120 injections per hour. The relative standard deviation of six independent determinations of a sample containing 1 mg litre⁻¹ carbofuran was 0.6%. The suitability of the proposed procedure for the determination of carbofuran in commercial pesticide formulations was studied. The procedure provides results comparable to those obtained by liquid chromatographic analysis. © 2000 Society of Chemical Industry