丁硫克百威在豇豆不同时期施用的降解代谢研究

为明确丁硫克百威在豇豆播种期、苗期、结荚期使用后的降解代谢,以及可能产生的膳食风险,分别以其在蔬菜上登记的最低剂量、最高剂量、最高剂量的1.5倍3种剂量施药,进行田间模拟残留试验。将采集的成熟豇豆通过乙腈提取、C18分散净化,经超高效液相色谱串联质谱方法检测,测定豇豆中丁硫克百威及其代谢物——克百威和3-羟基克百威的残留量。结果表明,丁硫克百威、克百威和3-羟基克百威在豇豆中的定量限均为0.01 mg·kg^-1,在0.01~1 mg·kg^-1的添加水平下,丁硫克百威、克百威和3-羟基克百威的平均回收率为72%~105%,相对标准偏差为1.4%~20.1%。丁硫克百威使用后的超标风险主要源于其代谢物——克百威和3-羟基克百威。播种期施药后的豇豆样品均无丁硫克百威及其代谢物检出;苗期以最高剂量的1.5倍施药后,第10天的样品中克百威(含3-羟基克百威)的残留值超出中国国家标准中规定的最大允许残留限量(MRL);结荚期2次或3次施药后7 d内克百威(含3-羟基克百威)的残留值超出MRL。结荚期施药时,丁硫克百威在2次施药和3次施药后的慢性膳食摄入风险和急性膳食摄入风险均较低,小于100%;但克百威(含3-羟基克百威)的急性膳食摄入风险较高,以最高剂量的1.5倍2次施药或3次施药后,克百威(含3-羟基克百威)的急性膳食摄入风险于药后7 d才降至100%以下。综上,播种期使用丁硫克百威不会导致豇豆中残留超标,可以安全使用;但苗期和结荚期使用丁硫克百威存在极高的风险,应禁止其在播种期以外的使用。     

Effects of Carbofuran on Availability of Macronutrients and Growth of Tomato Plants in Natural Soils and Soils Amended with Inorganic Fertilizers and Vermicompost

The effects of lower field rate (LFR), field rate (FR), and higher field rate (HFR) applications of carbofuran on ammonium (NH₄)-nitrogen (N), nitrate (NO₃)-N, available phosphorus (P), and available potassium (K) contents in natural soils and those amended with inorganic fertilizers and vermicompost on the growth of tomato plants were studied. The NH₄-N, NO₃-N, available P, and available K contents increased up to FR but the most significant increase in was observed at LFR of carbofuran application. At HFR there was a significant reduction in nutrient availability. With passage of time all these parameters increase up to 30 days; thereafter, a decrease was observed up to the end of the experiment in both unamended and amended soils. The greater plant growth was observed at LFR of carbofuran application and at HFR the plants exhibited phytotoxicity in the form of marginal leaf scorching in both systems. The morphological growth parameters of tomato plants were positively correlated with nutrients availability.     

克百威降解菌CYW-44的分离及其酶促降解研究

为了有效治理克百威农药污染,以克百威为唯一碳源,利用富集培养的方法从农药厂活性污泥中分离到一株克百威降解菌CYW-44,经生理生化、16S rDNA序列分析及API 50CHB鉴定试剂条分析,将菌株鉴定为枯草芽孢杆菌(Bacillus subtilis)。该菌在营养培养基中培养5 d时对100 mg.L-1的克百威降解率为97.72%,6 d能够完全降解克百威。通过液相色谱(HPLC)法检测,发现在降解过程中,克百威降解产物呋喃酚及其他代谢产物不产生累积;研究证实该菌株能分泌胞外降解酶和胞内降解酶高效降解克百威,对克百威的降解率分别达到99.1%和82.63%;通过SDS-PAGE验证了克百威对菌株降解酶活性的诱导作用。     

Dermal pharmacokinetics of the insecticide furathiocarb in rats

The pharmacokinetics of furathiocarb were studied in vivo in male Sprague-Dawley rats following dermal treatment. HPLC and post-column derivatization were used for the analysis of furathiocarb and its metabolites (carbofuran, 3-hydroxycarbofuran and 3-ketocarbofuran). Carbofuran and 3-hydroxycarbofuran were detected in plasma and urine rather than furathiocarb. 3-Ketocarbofuran, another potential metabolite, was not observed in any sample. The concentration of carbofuran was higher than that of 3-hydroxycarbofuran in plasma, but the reverse was the case in urine. The corresponding area under the plasma concentration-time curve, Tmax, and Cmax values of carbofuran and 3-hydroxycarbofuran for 1500 mg kg-1 doses were 2.4-8.0 mg equiv hml-1, 12 h and 0.1-0.4 mg equiv ml-1, respectively. T1/2 was calculated only for 3-hydroxycarbofuran (28 h). Two metabolites were excreted in a dose-dependent manner without saturation.     

长江流域农药面源多介质归趋评估

为明确长江流域典型农药面源时空分布,本研究基于逸度理论,构建了适合大尺度、多区域、长时期的农药面源多介质环境归趋模型,量化了1991—2020年长江流域克百威农药在水、土、气、沉积物等环境介质中的累积水平、赋存浓度及传输通量。结果表明：长江流域的克百威总残留量呈现先上升后下降的趋势,在2010年达到峰值（1 647 t）;水体和土壤为克百威的主要赋存介质,其范围分别为0.278~135 ng·L^-1和0.052 2~16.7 ng·g^-1;长江流域中下游地区为热点区域,尤其是赣江流域;每年施用的农药约5.40%会残留在环境中,主要去除方式为降解,其次是输移到近海（2017年约109 t·a^-1）。研究表明,农药面源在大时空尺度的累积和传输作用不容忽视,模型改进使得面源模拟结果更加合理,为长江流域农药面源的科学管控提供了重要的数据参考和技术支持。     

Production and Identification of High Affinity Monoclonal Antibodies Against Pesticide Carbofuran

To produce high-affinity monoclonal antibodies against pesticide carbofuran, and the develop immunochemical assays for people＇s health and environmental protection, the hapten 4-[[（2,3-dihydro-2,2-dimethyl-7-benzofuranyloxy） carbonyl]- amino]-butanoic acid （BFNB） of carbofuran was synthesized and Balb/c mice were immunized by the hapten-carrier （BFNB-bovine serum albumin, BFNB-BSA） conjugates. The splenocytes of immunized mice were fused with Sp2/0 cells and the cultural supernatants of hybridoma cells were screened by the indirect enzyme-linked immunoabsorbent assay （ELISA）, based on BFNB-ovoalbumin conjugates （BFNB-OVA）. Purified monoclonal antibody （McAb） was obtained from fluids of ascites, deposited by octanoic acid and ammonium sulfate. The affinity and the specificity of McAb were characterized by ELISA or indirect competitive ELISA. A hybridoma cell line （5D3） secreting anti-carbofuran McAb had been established. The titer of culture medium and ascites was up to 1：2.048 × 10^3 and 1：1.024 × 10^6, respectively, and the subtype of the McAb was IgG1. The affinity constant of the McAb was about 2.54 × 10×9 L mol^-1, with an IC50 value of 1.18 ng mL^-1 and a detection limit of 0.01 ng mL^-1. Cross-reactivity studies showed that the McAb was quiet specific for carbofuran, as among the four analogous compounds, they were all hardly recognized （4.59 × 10^-4% for 2,3-dihydro-2,2- dimethyl-7-benzofuranol and less than 3.0 × 10^4% for others）. The prepared McAb had a very high affinity and specificity, and it could be used to develop ELISA for rapid determination of carbofuran.     

种衣剂中不同浓度杀虫剂成分对玉米苗期生长的安全性评价

选择克百威、丙硫克百威和丁硫克百威3种杀虫剂作为种衣剂有效杀虫成分,每种杀虫剂设置1%、2%、3%、…10%共10种浓度梯度,春天播种期进行玉米包衣播种,20 d后调查苗期植株的根长、根数、叶数和株高,验证3种杀虫剂不同浓度对玉米苗期的生长安全性。结果表明：在10%浓度以下,3种杀虫剂进行种子包衣处理,玉米苗期生长均未产生药害,植株生长正常。     

Co‐solvent effects on the adsorption of carbofuran by two Indian soils

The adsorption of carbofuran on soils from water‐methanol mixtures has been evaluated by batch shake testing. Two uncontaminated soils having different physicochemical properties were used in these experiments. The volume fraction of methanol in the liquid phase (f_s) was varied from 0.25 to 1.0. Higher adsorption of carbofuran was observed in medium black (silt loam) soil than in alluvial (sandy loam) soil; calculated values of the Freundlich constant (K^m) and distribution coefficient (K_d) showed that adsorption of carbofuran in both soils decreased with increase in f_S values. The decreased carbofuran adsorption in methanol–water mixtures meant a greater potential of ground‐water contamination through leaching from potential sites. The data have been used to evaluate the co‐solvent theory for describing adsorption of carbofuran in methanol–water mixtures. The aqueous phase partition coefficient K_dw (mol g⁻¹) normalized with respect to f_oc and the aqueous phase adsorption constant K_w for carbofuran were evaluated by extrapolating to f_S = 0. © 2000 Society of Chemical Industry     

Gas Chromatography–Mass Spectroscopy Analysis of Carbofuran and Its Metabolite 3-Hydroxy-carbofuran in Maize and Soil in Field

In this article, a simple and efficient method using gas chromatography–mass spectrometry (GC-MS) was developed to determine carbofuran and 3-hydroxy carbofuran in maize and soil. Field experiments were carried out to investigate the dissipation of carbofuran and its metabolite 3-hydroxy carbofuran in soil and maize plants and their accumulation in maize. Results showed that the half-lives of carbofuran were 4.7 and 5.3 days in maize plants and 8.5 and 7.6 days in soil for Beijing and Jinan trial sites, respectively. The final residues of carbofuran and 3- hydroxy carbofuran in the soils and maize grain were not detected. This study suggests that carbofuran is acceptable to apply to maize in the recommended dosage and can be a good alternative to other highly toxic insecticides.