QuEChERS-超高效液相色谱-串联质谱法同时测定大米、小麦和动物源食品中异丙隆及其代谢物脱甲基异丙隆残留

本研究建立了超高效液相色谱-串联质谱法(UHPLC-MS/MS)同时测定异丙隆及其代谢物脱甲基异丙隆在大米、小麦、牛肉、牛奶、鸡肉和鸡蛋的残留检测方法。样品经2%甲酸乙腈提取,以N-丙基乙二胺(PSA)净化,利用乙腈和0.2%甲酸水作为流动相梯度洗脱,T3色谱柱分离,在多反应监测模式下定量分析,基质外标法定量。结果表明:异丙隆及其代谢物脱甲基异丙隆溶剂标准曲线和基质标准曲线在1~1 000μg/L范围内线性关系良好,相关系数均大于0.99。在4个加标水平下,异丙隆日内平均回收率为74.0%~107.0%,相对标准偏差0.7%~12.9%;日间平均回收率为76.2%~108.7%,相对标准偏差1.1%~19.8%。脱甲基异丙隆日内平均回收率为76.9%~113.5%,相对标准偏差0.6%~13.9%;日间平均回收率为77.7%~107.4%,相对标准偏差2.2%~17.4%。异丙隆和脱甲基异丙隆的定量限均为1.0μg/kg。该方法简便、快捷、准确、灵敏度高,适用于异丙隆和脱甲基异丙隆在大米、小麦、牛肉、牛奶、鸡肉和鸡蛋6种基质中残留的检测,为解决异丙隆和脱甲基异丙隆在食品中残留的安全问题提供技术方法。     

Effects of modified Pb-, Zn-, and Cd- availability on the microbial communities and on the degradation of isoproturon in a heavy metal contaminated soil

The effects of modified heavy metal (HM) availability on the microbial community structure and on the microbe-mediated degradation of herbicide isoproturon (IPU) were evaluated in soil with a long-term HM contamination. The fate of ¹⁴C-ring labelled IPU was investigated for over 60 days under controlled microcosm conditions. Phosphate mineral apatite and a water solution of Pb, Zn, and Cd salts were previously homogeneously mixed into the soil material to reduce and to increase the proportion of bioavailable HM, respectively. The availability of Pb, Zn, and Cd was determined by HM fractionation and plant uptake 110 days after the addition of amendments, shortly before IPU addition. Apatite treatment reduced the availability of HM, but did not affect the microbial biomass and the microbial community structure on the genotype level (total soil DNA-RAPD). However, it changed the microbial community structure on the phenotype level, based on the composition of phospholipid fatty acids (PLFA) at the end of the degradation experiment. The degradation of IPU did not change. In contrast to apatite treatment, HM supplementation increased the bioavailability of Pb, Zn and Cd, which resulted in biomass reduction and changes of microbial community structure on the genotypic (total soil DNA-RAPD) and phenotypic (PLFA) level. Increased bioavailability of HM also significantly reduced the rate of IPU degradation and mineralisation. The total mineralisation over a period of 60 days decreased from 12 to 5% of initial ¹⁴C. Increased HM bioavailability did not influence the degradation pathways and kinetics of IPU.     

Variation of pesticide sorption isotherm in soil at the catchment scale

The variation of the sorption isotherm of pesticides has seldom been explored at the catchment scale. Such a study was conducted at the scale of a 187-ha agricultural catchment for three herbicides: atrazine, isoproturon and metamitron. Partition coefficient (Kd) values were measured in batch experiments on 51 topsoil samples, and showed moderate variability at the catchment scale (coefficient of variation CV approximately 30%). Values of Kd ranged from 0.47 to 1.70 litre kg(-1) for atrazine, 0.47 to 1.81 for isoproturon, and 0.55 to 2.21 for metamitron. A clustering method was used to reduce the number of samples on which to measure sorption isotherms to 14. Sorption isotherms agreed with the Freundlich rather than the linear model. Kf parameters had CV values similar to those for Kd, with values ranging from 0.78 to 2.13 mg(1 - Nf) litre(Nf) kg(-1) for atrazine, 0.61 to 1.82 for isoproturon, and 0.69 and 2.58 for metamitron. Nf exponents showed little variation (CV < 5%). Nf values were between 0.86 and 0.98 for atrazine, 0.85 and 0.90 for isoproturon, and 0.82 and 0.87 for metamitron. More than 97% of the Kf catchment-scale variations could be explained by the variations of the soil organic carbon content.     

Effect of recent cropping history and herbicide use on the degradation rates of isoproturon in soils

Five soil samples were taken from each of five fields with different crop management histories. Three of the fields were in an arable rotation, the fourth field was temporary grassland, and the final field was under permanent grass. Of the three arable fields, two had been cropped with winter wheat in three of the preceding 6 years, and the third had last been cropped with winter wheat once only, 6 years previously. With one exception, the winter wheat had been sprayed with the herbicide isoproturon. The rate of isoproturon degradation in laboratory incubations was strongly related to the previous management practices. In the five soils from the field that had been treated most regularly with isoproturon in recent years, <2.5% of the initial dose remained after 14 days, indicating considerable enhancement of degradation. In the soils from the field with two applications of the herbicide in the past 6 years, residues after 27 days varied from 5% to 37% of the amount applied. In soils from the other three sites, residue levels were less variable, and were inversely related to microbial biomass. In studies with selected soils from the field that had received three applications of isoproturon in the previous 6 years, kinetics of degradation were not first‐order but were indicative of microbial adaptation, and the average time to 50% loss of the herbicide (DT₅₀) was 7.5 days. In selected soils from the field that had received just one application of isoproturon, degradation followed first‐order kinetics, indicative of cometabolism. Pre‐incubation of isoproturon in soil from the five fields led to significant enhancement of degradation only in the samples from the two fields that had a recent history of isoproturon application.     

4种助剂对异丙隆防除菵草的增效作用

为了比较4种助剂Silwet 806、红太阳A8、激健、安融乐对异丙隆防除菵草Beckmannia syzigachne的增效作用及机制,采用整株生物测定法测定4种助剂与异丙隆混用后对菵草的生物活性及对小麦的安全性;采用仪器分析法测定4种助剂对异丙隆药液的表面张力、叶面接触角、干燥时间和在叶面上的沉积量的影响。结果表明:添加4种助剂后异丙隆防除菵草的ED90分别降低为553.11、626.31、819.93、841.54 g/hm2,但异丙隆与Silwet 806混用后对小麦安全性下降。添加4种助剂后,异丙隆药液的表面张力和叶面接触角显著降低,药液在叶面上的干燥时间缩短,沉积量增加,其中红太阳A8的上述指标显著优于激健和安融乐,能够较好地实现异丙隆减量增效的目的。     

50%禾草丹·异丙隆WP在直播水稻田中的消解动态

【目的】评价禾草丹和异丙隆在直播水稻田施用后的生态环境和糙米的安全性。【方法】进行2年3地田间试验,采用高效液相色谱-串联质谱法(HPLC-MS/MS)测定稻田土壤中禾草丹和异丙隆的消解动态及其在糙米和土壤中的最终残留。【结果】在0.01~0.5mg/kg添加水平下,禾草丹和异丙隆在土壤和糙米中的平均回收率为80.4%~108.8%,变异系数为0.6%~12.6%。田间试验结果表明:禾草丹和异丙隆在稻田土壤中施药2h后的原始沉积量分别为0.141~1.134mg/kg和0.066~0.543mg/kg,半衰期分别为1.1~4.2d和0.4~4.4d。收获期稻田土壤和糙米中两者的最终残留量均未检出。【结论】禾草丹和异丙隆均属于易降解农药,50%禾草丹·异丙隆WP按推荐剂量(900g a.i./hm2,即1 800g/hm2)施用于直播水稻田中,施药1次,收获的糙米安全。     

Aspects of the adsorption and degradation of isoproturon in a heavy clay soil

Abstract. Degradation of isoproturon in a heavy clay soil followed first-order reaction kinetics with half-lives at 15 °C of 27 and 208 days in the topsoil and subsoil, respectively. Adsorption when shaken with 3 mm sieved samples of the soil fitted the empirical Freundlich relationship with k values of 3.25 in the topsoil and 1.06 in the subsoil. Adsorption in a static system with different sized aggregates of soil did not reach equilibrium, even after 24 hours contact, and the rate of adsorption was slower with larger aggregates. Following an adsorption period of 24 hours, desorption equilibrium was reached more rapidly with larger (6–10 mm) than with smaller (<3 mm) aggregates. Adsorption isotherms measured in a static system with a soil:water ratio typical of field conditions in winter also indicated less adsorption than that measured in shaken, laboratory systems with low soil:water ratios. The rate of change in water extractable residues of the herbicide was more rapid than that of total extract-able residues following application of isoproturon to the heavy clay soil in the field. The implications of the results for isoproturon leaching under field conditions are discussed.     

47%氯吡·丙·异可湿性粉剂对水稻机插秧田杂草防效及安全性

通过大田示范验证47%氯吡·丙·异可湿性粉剂在机插秧田水稻移栽前与移栽后2次土壤封闭处理对杂草的防除效果及水稻的安全性。结果表明:47%氯吡·丙·异可湿性粉剂1 050 g/hm~2在机插秧水稻移栽前1 d毒肥处理结合水稻移栽后10 d 47%氯吡·丙·异可湿性粉剂1 050 g/hm~2毒肥处理对水稻机插秧田稗草、丁香蓼、异型莎草等杂草的株防效和鲜质量防效平均高于90%,且对水稻安全。     

低温和异丙隆处理对分蘖期小麦生理生化特性的影响

为研究异丙隆浓度和低温处理对分蘖期小麦生理生化特性的影响,试验以0,3.0,6.0,9.0 g·L-1的异丙隆对滇11-04进行处理,并测定了SOD活性、POD活性、可溶性蛋白质含量、MDA含量、脯氨酸含量、相对电导率和O.-2产生速率。结果表明：随异丙隆浓度的增加,处理温度降低,小麦受生理性伤害程度逐渐加大,膜脂透性加剧和SOD因加速清除活性氧而活性降低。     

A refined lack‐of‐fit statistic to calibrate pesticide fate models for responsive systems

BACKGROUND: Calibration by inverse modelling was performed with the MACRO transport and fate model using long‐term (>10 years) drainflow and isoproturon (IPU) data from western France. Two lack‐of‐fit (LOF) indices were used to control the inverse modelling: sum of squares (SS) and an alternative statistic called the vertical‐horizontal distance integrator (VHDI), which is designed to account for offsets in observed and predicted arrival times of peak IPU concentration. With these data, SS was artificially inflated because it is limited to comparison of predicted and observed IPU concentrations that are concurrent in time. The LOFs were used along with the index of agreement (d) and the correlation coefficient (r) to ascertain the fit of the calibrated models. RESULTS: Predicted arrival times of peak IPU concentration differed somewhat from observed times. All four indices indicated better model fit for the second of two validation periods when inverse modelling was controlled by VHDI rather than SS (SS = 26.4, d = 0.660, r = 0.606 and VHDI = 1.25). The VHDI statistic was markedly lower compared with the uncalibrated model (38.0) and SS calibration results (24.5). The final maximum predicted IPU concentration (44.5 µg L^?1) for the calibration period was very similar to the observed value (44 µg L^?1). CONCLUSION: VHDI is seen as an effective alternative to SS for calibration and validation of pesticide fate models applied to responsive systems. VHDI provided a more realistic assessment of model performance for the transient flows and short‐lived concentrations observed here, and also effectively substituted for the objective function in inverse modelling. Copyright © 2009 Society of Chemical Industry