Simultaneous determination of benzimidazole fungicides by HPLC on apples,pears and their pulps

The simultaneous HPLC determination of carbendazim, thiabendazole and thiophanate-methyl in apples, pears and their pulps is described. The method is based on a clean-up procedure carried out on an Extrelut 20 cartridge followed by HPLC analysis on a Diol column using hexune+isopropanol as mobile phase. Average recoveries of 83.8% for carbendazim, 82.9% for thiabendazole and 68.8% for thiophanate-methyl on apple matrix were obtained; recoveries on pear matrix were in the same range. Detection limits with UV detection at 285 nm of 100 ng ml^?1 for carbendazim, 140 ng ml^?1 for thiabendazole and 500 ng ml^?1 for thiophanate-methyl were achieved.     

Determination of tricyclohexyltin hydroxide residues in apples and pears

Plictran (tricyclohexyltin hydroxide, Cy₃SnOH) residues in Stark Delicious apples and Passacrassana pears were determined. Field applications were carried out 7, 16 and 28 days before harvest. The analyses were carried out by two procedures: selective determination of the various Sn forms and determination of total Sn. The final spectrophotometric determinations were made as inorganic Sn using dithiol reagent. Average data obtained for apples were from 0.26 to 0.32 ppm of Sn (0.84–1.00 ppm Cy₃SnOH) and for pears from 0.12 to 0.30 ppm of Sn (040–0.99 ppm Cy₃SnOH). A residues half-life of 5–6 weeks for the apples and of 2 weeks for the pears was found.     

进境水果重要真菌病害——星裂壳孢梨果腐病和苹果果腐病

星裂壳孢梨果腐病和苹果果腐病分别由Phacidiopycnis(缩写:Ph.)pyri和Ph.washingtonensis侵染所致,这两种真菌性病害在我国尚未有发生为害的报道,前者在欧洲和北美梨和苹果产区为害严重,而目前后者则仅在美国报道.本文介绍了以上两种病害的发生分布、寄主范围、病原菌及其形态特征、侵染特点及为害症状、病原菌培养性状、生物学特性、分离和鉴定方法、致病性测定及简要的防治方法;初步分析了病害的传播途径.自2008年4月起首次并连续3次从佛山澜石口岸截获的美国进境苹果中截获星裂壳孢苹果果腐病(Ph.washingtonensis),根据此疫情本文阐述了梨果腐病和苹果果腐病在我国口岸检疫的重要性.     

山东主产区苹果和梨中农药残留风险因子排序

风险排序是风险评估或管理中的重要一环,是对风险因子进行排序从而确定管控优先顺序的重要手段。2014-2015年连续两年对山东省主产区苹果、梨进行102种农药残留风险监测。利用农产品质量安全风险排序系统对苹果和梨中检出的农药残留进行风险得分计算和排序。结果显示:苹果中检出27种农药,风险得分较高的有三唑磷、毒死蜱、氰戊菊酯、联苯菊酯、吡虫啉、戊唑醇、唑螨酯7种农药;梨中检出37种农药,风险得分从高到低分别有氧乐果、克百威、水胺硫磷、苯醚甲环唑、毒死蜱、唑螨酯、灭多威、氟硅唑8种农药。建议对上述风险得分较高的农药予以优先管控。     

Multiresidue method for captan,folpet, captafol,vinclozolin and iprodione on italian apples and pears by capillary gas–liquid chromatography with electron-capture detection

A method is described for the simultaneous determination of residues of five fungicides used for foliar treatment of apple and pear trees, and for postharvest application. After extraction, the mixture of these fungicides is cleaned-up on a ‘SEP PAK C₁₈’ cartridge and the components determined by gas-liquid chromatography with electron-capture detection. The minimum detectable amounts in apples and pears, on a fresh weight basis, were 0.005mg kg⁻¹ for vinclozolin, 0.010mg kg⁻¹ for captan, folpet and iprodione, and 0.020 mg kg⁻¹ for captafol. The percentage recovery for each fungicide (calculated by analysing four samples of untreated apples and pears, to which varying concentrations of each active ingredient had been added) varied for vinclozolin between 70.0 and 89.2, for captan between 72.0 and 83.8, for folpet between 73.0 and 93.0, for captafol between 70.8 and 91.8, and for iprodione between 75.1 and 97.1.     

Determination of residues in apples and pears following treatment with the acaricide fenazaflor I. Routine method for fenazaflor and major metabolites

A method is described for the determination of residues of fenazaflor (I), its hydrolysis product 5,6-dichloro-2-trifluoromethylbenzimidazole (II) and the metabolite 5,6-dichloro-4-hydroxy-2-trifluoromethylbenzimidazole (III) in apples and pears. These chemicals may be present in the crop as a result of the application of the acaricide fenazaflor, formulated as a wettable powder and known by the trade name ‘Lovozal’. Total residues of I and II are determined as II, and III is determined after methylation, both by GLC with electron capture detection. The limit of detection for each compound is 0.02parts/million (based on a 50 g sample weight). Recoveries are over 80%. Using apples sprayed with radio-labelled fenazaflor it was shown that approximately 20% of the total radioactivity present in the fruit was not extracted by the routine method. Further investigation showed much of this to be present as trifluoroacetic acid in a tightly bound form. No problems were encountered with interference from a number of commonly used orchard pesticides.     

分散固相萃取-超高效液相色谱-串联质谱法同时检测大豆植株及土壤中烟嘧磺隆、莠去津及其代谢物残留

土壤中烟嘧磺隆和莠去津的高残留往往会导致后茬大豆药害问题。本研究建立了一种分散固相萃取-超高效液相色谱-串联质谱法同时检测大豆植株及土壤中烟嘧磺隆、莠去津及其代谢物残留方法。样品经含2%甲酸的乙腈提取, 经分散固相萃取净化, 以乙腈和0.2%甲酸水为流动相, 采用Poroshell 120 EC-C18色谱柱梯度洗脱, 基质匹配标准曲线外标法定量分析。结果表明:在0.01、0.10 mg/kg和1.00 mg/kg添加水平下, 烟嘧磺隆、莠去津及其代谢物的平均回收率为70%~113%, 相对标准偏差为0.3%~11.8%, 目标化合物质量浓度与对应的峰面积之间在0.001~1 mg/kg范围内线性关系良好, 决定系数R2≥0.984 1, 方法的定量限为0.01 mg/kg。该方法简便、快捷、准确, 适用于土壤和幼苗期至鼓粒期大豆植株中烟嘧磺隆、莠去津及其代谢物的检测。本研究为烟嘧磺隆和莠去津的科学使用及后茬作物的安全种植提供有效监测方法。     

印楝素和阿维菌素的液相色谱法同时测定

提出了一种可同时测定印楝素·阿维菌素乳油中印楝素和阿维菌素B1a的液相色谱法。该方法使用Hypersil ODS C18(250 mm×4 mm,5 μm)色谱柱和紫外检测器(印楝素λ 215 nm,阿维菌素B1a λ 240 nm),印楝素和阿维菌素B1a的回收率分别为97.5%~105.0% 和98.0%~107.5%,相对标准偏差分别为1.70%和1.60%,达到了简便、快速、准确的目的。     

Spectrophotometric determination of ferric dimethyldithiocarbamate (ferbam) in formulations,grain and apples using 1, 10-phenanthroline

A procedure has been developed for the determination of ferbam (ferric dimethyldithiocarbamate) by converting it into ferbam-phenanthroline complex, which is dissolved in acetone + water (1 + 1 by volume), and the absorbance measured at 490 nm against a reagent blank. Beer's law is obeyed over the concentration range 0–8–20-0 mg litre^?1 in the final solution. The method is sensitive, selective and can be used for the direct determination of ferbam in commercial samples, in mixtures with various other dithiocarbamates (ziram, zineb, maneb, etc.) and from grains (rice and wheat) and apples. The limit of determination from foodstuffs is 0–4 mg kg^?1.     

气相色谱法同时检测水果中氟吡菌酰胺、肟菌酯及其代谢物肟菌酸的残留量

采用气相色谱法建立了水果中氟吡菌酰胺、肟菌酯及其代谢物肟菌酸残留的分析方法。样品用乙腈匀浆提取,氯化钠和无水硫酸镁盐析后,经N-丙基乙二胺（PSA）分散固相萃取净化,气相色谱-电子捕获检测器（GC-ECD）检测。结果表明:在0.05~1 mg/kg添加水平下,氟吡菌酰胺、肟菌酯及其代谢物肟菌酸的平均回收率为79%~120%,相对标准偏差（RSD）为0.7%~16%。氟吡菌酰胺、肟菌酯及其代谢物肟菌酸在不同水果样品中的检出限（LOD）分别为0.01、0.015和0.01 mg/kg,定量限（LOQ）均为0.05 mg/kg。该方法快速、简单和稳定,可以满足水果中氟吡菌酰胺、肟菌酯及其代谢物肟菌酸残留量的检测要求。     

分散固相萃取-超高效液相色谱-串联质谱法同时检测玉米及其土壤中烟嘧磺隆、莠去津及氯氟吡氧乙酸残留

采用QuEChERS法结合超高效液相色谱-串联质谱法(UPLC-MS/MS)建立了玉米及其土壤中同时检测烟嘧磺隆、莠去津和氯氟吡氧乙酸残留的分析方法。样品采用乙腈(含体积分数为2%的甲酸)提取,基质固相分散净化后,用UPLC-MS/MS外标法检测定量。结果表明:该方法具有灵敏度高、简便、快速等优点;在0.01~1.0 mg/L质量浓度范围内,3种除草剂的仪器响应值与其质量浓度呈良好线性相关,相关系数大于0.990 6;玉米和土壤样品中3种除草剂的添加水平在0.02~0.5 mg/kg时,平均回收率均为78.9%~117.7%,日内相对标准偏差(RSD)均小于11.6%,日间 RSD 均小于13.9%。 3种除草剂在玉米籽粒、玉米植株和土壤中的定量限(LOQ)均小于7.1μg/kg。     

气相色谱-串联质谱法快速检测玉米粉中乙草胺、异丙甲草胺和三唑酮残留

建立了玉米粉中乙草胺、异丙甲草胺和三唑酮残留检测的气相色谱-串联质谱(GC-MS/MS)分析方法。样品采用乙腈浸提3 h、过两次0.22μm尼龙66微孔过滤膜后,以气相色谱-串联质谱EI离子源,多反应监测模式(MRM)检测。结果表明:在0.005~1 mg/L范围内,3种供试农药的质量浓度与其相应的峰面积间呈良好的线性关系,决定系数(R2)均大于0.999。在0.025、0.050和0.25 mg/kg 3个添加水平下,3种农药的平均回收率为95%~101%,相对标准偏差(RSD)为0.7%~2.2%(n=6)。3种农药在玉米粉中的定量限(LOQ)分别为0.05、0.05和0.2μg/kg。该方法准确、灵敏、简单,适用于同时快速检测玉米粉中乙草胺、异丙甲草胺和三唑酮的残留量。     

Determination of residues in apples and pears following treatment with the acaricide fenazaflor II. Method for individual residues of fenazaflor and its hydrolysis product

The occasional need for separation of residues of fenazaflor and its hydrolysis product, instead of determination of the total residue by the routine method, is satisfied by partition of the extract between hexane and acidified aqueous methanol. Both residues are subsequently determined as the hydrolysis product by GLC with electron capture detection, after hydrolysis of fenazaflor.     

超高效液相色谱-串联质谱法测定柑橘中的草甘膦及其代谢物残留

本研究首次建立了一种超高效液相色谱-串联质谱法(UHPLC-MS/MS)同时测定柑橘中草甘膦及其代谢物N-乙酰草甘膦?氨甲基磷酸(AMPA)和N-乙酰AMPA?样品经过0.5%甲酸水提取, 以十八烷基硅烷键合硅胶柱(C18)净化, 利用水和200 mmol/L碳酸氢铵溶液(含0.1%氨水)作为流动相梯度洗脱, 在多反应监测模式下定量分析?结果表明, 草甘膦及其代谢物在0.05~1 mg/kg范围内线性关系良好, 相关系数均大于0.99; 草甘膦及其3个代谢物在柑橘全果和果肉基质中3个加标水平下回收率为 70.5%~109.5%, 相对标准偏差(RSD)为0.6%~10.1%, 定量限为0.05 mg/kg?本方法的前处理样品无需衍生, 简便?快捷?高效?准确可靠, 可用于柑橘中草甘膦及其代谢物N-乙酰草甘膦?AMPA和N-乙酰AMPA的定量检测?     

唑草酮20%微囊悬浮剂高效液相色谱分析方法

本文采用高效液相色谱法,以甲醇＋乙腈＋磷酸溶液为流动相,使用以ODS、5μm为填料的不锈钢柱和二极管阵列检测器,在243nm波长下对唑草酮20%微囊悬浮剂进行分离和定量分析。结果表明,该方法的线性相关系数为0.9999;标准偏差为0.11;变异系数为0.54%;平均回收率为99.2%。     

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。     

Daminozide residues in sweet cherries,and their determination by colorimetric and gas-liquid chromatographic methods

Daminozide residues in fruit from sweet cherry trees were determined over a period of 4 years as part of an investigation into the effects of growth regulators. Analysis was by the usual colorimetric method. Additionally, for the 2 final years, a gas-liquid chromatographic method was developed to determine the 1,1- dimethylhydrazine produced by hydrolysis of daminozide residues and to confirm the results from the first method.     

超高效液相色谱-串联质谱法快速检测核桃中戊唑醇､肟菌酯及肟菌酸残留

建立了超高效液相色谱-串联质谱法(UHPLC-MS/MS)同时测定戊唑醇?肟菌酯及其代谢物肟菌酸在核桃中的残留检测方法?样品中待测农药组分采用2%乙酸乙腈溶剂振荡提取, 弗罗里硅土(florisil)净化, 利用乙腈和0.2%甲酸水作为流动相梯度洗脱, C18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:戊唑醇添加水平为5~500 μg/kg时, 戊唑醇在核桃中添加回收率为80.3%~100.8%, 相对标准偏差(RSD)为2.5%~11.7%; 肟菌酯和肟菌酸添加水平为2~200 μg/kg时, 肟菌酯在核桃中添加回收率为91.1%~102.9%, 相对标准偏差(RSD)为1.7%~12.5%; 肟菌酸在核桃中添加回收率为91.7%~101.9%, 相对标准偏差(RSD)为3.7%~9.2%?戊唑醇?肟菌酯和肟菌酸溶剂标准曲线和基质标准曲线在1~1 000 μg/L范围内线性关系良好, 相关系数均大于0.99?戊唑醇定量限为5 μg/kg, 肟菌酯和肟菌酸定量限均为2 μg/kg?实际样品检测中, 戊唑醇残留结果为6~99 μg/kg, 肟菌酯残留结果为<2~103 μg/kg, 肟菌酸均小于检测限?该方法操作简便?快捷和准确, 满足在核桃实际样品中戊唑醇?肟菌酯及其代谢物肟菌酸的残留检测要求?     

梨黑星病菌被哈茨木霉感染后抗氧化系统的变化

测定被哈茨木霉感染后梨黑星病菌抗氧化系统变化的结果表明,被哈茨木霉感染后梨黑星病菌过氧化氢酶、过氧化物酶和超氧化物歧化酶的活性逐渐下降;丙二醛含量和超氧阴离子产生速率上升;还原型谷胱甘肽和抗坏血酸含量降低。初步明确,梨黑星病菌被哈茨木霉感染后,活性氧清除系统等被破坏,膜脂过氧化作用加强,是最终导致菌体受害的原因之一。