微酸性电解水对溶液体系中毒死蜱的降解机制及途径分析研究

以有机磷农药毒死蜱标准品溶液体系为研究对象,通过测定微酸性电解水的反应时间和有效氯浓度对毒死蜱降解效果的影响,进而在微酸性电解水对毒死蜱降解的敏感性以及毒死蜱的降解产物等方面进行研究。采用气相色谱-质谱联用法（gas chromatography-mass spectrometry,GC-MS）检测到毒死蜱的直接降解产物氯吡硫磷一氧,在此基础上对毒死蜱在微酸性电解水主要活性成分次氯酸和羟自由基作用下的降解途径进行了分析。结果表明：有效氯浓度大于5 mg/L时,反应时间30 s内,微酸性电解水对毒死蜱的降解率达到99.96%;毒死蜱降解成氯吡硫磷一氧可能是HOCl和·OH共同参与的结果。     

强酸性电解水降解对硫磷动力学模型及降解产物

为探明强酸性电解水(Strong acidic electrolyzed water,AcEW)对对硫磷的降解规律,在模拟水环境内进行了降解实验。结果显示,随着反应时间的延长或AcEW的有效氯质量浓度(ACC)的增加,对硫磷的降解效率将增加。AcEW对对硫磷的降解反应符合化学一级反应动力学及二级动力学模型。对硫磷在AcEW(pH3.0、有效氯浓度2 mg/L)中的一级反应动力学方程为ln([parathion]t/[parathion]0)=-0.0099t。通过GC-MS(气相色谱-质谱联用仪)分析,对硫磷被AcEW降解后的产物为对氧磷和4-硝基苯酚。在AcEW中,对硫磷可能的降解途径为对硫磷-对氧磷-4-硝基苯酚-小分子有机物-无机物。     

微酸性电解水对韭菜中乐果和毒死蜱去除效果的研究

通过对韭菜分别进行乐果与毒死蜱两种典型有机磷类农药的模拟污染,采用气相色谱仪检测微酸性电解水对韭菜中有机磷农药残留的去除效果,探讨了微酸性电解水中的有效氯浓度、温度与处理时间对韭菜中两种农药去除率的影响。结果表明,微酸性电解水对有机磷农药残留的消除效果优于同一有效氯浓度的NaClO溶液。随着有效氯浓度的升高,乐果和毒死蜱的去除率先增大后降低。其中,处理时间在5~30 min内,对去除效果无显著影响;当微酸性电解水的处理温度在20~50℃时,其对韭菜中两种有机磷农药的去除率影响不显著。     

酸性电解水对苹果表面毒死蜱降解效果及降解途径分析

目的:通过研究不同条件下的酸性电解水对苹果表面毒死蜱的降解效果以及分析毒死蜱的降解途径,为苹果生产加工行业提供理论支持。方法:使用毒死蜱模拟污染苹果表面,在不同有效氯浓度（10、50、100 mg/L）和pH（pH为2.80和5.80）的酸性电解水条件下,采取浸泡处理或振荡清洗苹果的清洗方法,用气相色谱和气质联用方法测定毒死蜱残留和降解产物。结果:通过强酸性电解水降解苹果表面的毒死蜱实验,发现其降解效率与反应时间、有效氯浓度有直接关系,随着反应时间的延长或有效氯浓度的增加,降解效率也增加。当有效氯浓度达到50 mg/L时,浸泡15 min会降解55%以上的毒死蜱残留,并且与对照组自来水浸泡有极显著差异（P<0.01）。当有效氯浓度为100 mg/L时对毒死蜱的降解率超过了70%。在相同条件下强酸性电解水与微酸性电解水在降解毒死蜱的效果上无显著差异（P>0.05）,并且浸泡处理和振荡处理对实验结果没有显著影响（P>0.05）。酸性电解水处理对苹果主要品质指标没有显著影响（P>0.05）。经GC-MS分析,毒死蜱被强酸性电解水降解后,在降解产物中发现毒死蜱氧化物（CPO）和3, 5, 6-三氯吡啶-2-醇（TCP）。其可能的降解途径为毒死蜱→CPO→TCP→小分子有机物→无机物。结论:该研究结果对苹果加工产业在消除农药残留方面提供一种新方法。     

同时测定蔬菜中15种有机磷农药的残留方法

了解当前本市农产品市场中关于蔬菜中有机磷农药残留的相关状况,制定相关对策,建立一种适用于多种有机磷农药快速检测的气相色谱方法。根据农药的相关性质,该气相色谱法可同时检测15种有机磷农药,其中包括:敌百虫、敌敌畏、甲胺磷、乙酰甲胺磷、灭线磷、甲拌磷、氧乐果、特丁硫磷、乐果、甲基对硫磷、马拉硫磷、杀螟硫磷、对硫磷、倍硫磷、水胺硫磷。通过对不同型号色谱柱的选择、柱温箱升温程序的控制,实现对15种常见有机磷农药的快速、便捷、准确度好的定性和定量的分析。     

酸性电解水去除葡萄表皮上赭曲霉毒素A的影响因素及机理研究

本研究采用实验室自制的电解水,以赭曲霉毒素A(OTA)标准溶液和模拟污染OTA的葡萄样品为研究对象,考察电解水对葡萄表皮上OTA的去除作用和酸性电解水的理化指标对去除OTA的影响,并初步探讨了电解水去除OTA的机理和可能的反应产物。结果表明:电解水中的酸性电解水可以去除葡萄表面污染的OTA,其中微酸性电解水的去除率最高,达到90%。酸性电解水的p H值和有效氯浓度(ACC)对去除OTA有显著的影响,p H值范围在5.0左右且ACC水平越高的微酸性电解水对OTA的去除率越高。此外,微酸性电解水中以HCl O形式存在的有效氯对去除OTA起重要作用。OTA经过微酸性电解水处理后生成三个主要产物,其分子式推测为C9H11Cl O3、C6H6Cl O3和C5H3Cl2NO3。该研究结果可为控制葡萄等食品原料中的OTA污染提供新的途径和方法。     

气相色谱法测定蔬菜中8种有机磷农药的残留量

目的采用气相色谱法同时测定蔬菜中甲胺磷、氧化乐果、乐果、甲基对硫磷、毒死蜱、对硫磷、水胺硫磷和三唑磷8种有机磷农药的残留量。方法样品经乙腈提取后,经Agilent DB-17色谱柱分离,采用火焰光度检测器检测,以外标法定量。结果毒死蜱和乐果在0.25~5μg/m L,其他6种有机磷在0.025~0.5μg/m L浓度范围内具有良好的线性关系,检出限为0.006~0.023μg/m L;8种有机磷农药的回收率为97.6%~104.8%,相对标准偏差为0.98%~1.67%。结论该方法精确可靠,重复性、稳定性和分离效果好,可用于测定蔬菜中有机磷农药的残留量。     

不同干燥方式对菊花中6种有机磷农药 残留量的影响

目的研究不同干燥方法对菊花中氧乐果、敌敌畏、甲基对硫磷、甲拌磷、内吸磷、对硫磷6种有机磷农药残留量的影响。方法将污染农药的鲜菊花分别进行蒸3 min阴干、50℃烘干、阴干和晾干处理,采用乙腈提取有机磷农药并经Carb/PSA双层固相萃取柱净化,通过气相色谱仪(配FPD检测器)测定有机磷农药残留量。结果 6种有机磷农药在0.01~0.08μg/m L浓度范围内线性良好,相关系数r0.997,回收率在78.5%~94.3%之间,相对标准偏差RSD为1.7%~5.9%,检出限为0.53~1.16μg/kg。3种干燥的菊花中均未检测到6种有机磷农药。结论蒸3 min阴干、50℃烘干和阴干3种干燥方法均显著降低菊花有机磷农药残留量。     

低温等离子体耦合微酸性电解水对三文鱼的保鲜作用

采用单因素和Box-Behnken响应面试验优化低温等离子耦合微酸性电解水对三文鱼杀菌的工艺条件,通过菌落总数、pH值、挥发性盐基氮（TVB-N）、硫代巴比妥酸反应产物（TBARS）值、羰基含量和色差等指标比较等离子体活化水、微酸性电解水及低温等离子体耦合微酸性电解水对三文鱼4℃贮藏的保鲜效果。结果显示,当低温等离子体活化时间5 min,功率320 W,浸泡时间20 min,有效氯质量浓度50 mg/mL,料液比1∶6时杀菌效果最优,均可延长三文鱼贮藏期,而低温等离子体耦合微酸性电解水更有利于缓解脂肪和蛋白氧化。本研究为水产品保鲜提供了新思路。     

超声波协同微酸性电解水对小龙虾净化及品质的影响

为了探究小龙虾（Procambarus clarkii）的净化工艺,采用超声波清洗协同微酸性电解水减菌技术对小龙虾进行活体净化处理。本文以小龙虾的菌落总数、芽孢总数及清洗液浊度为评价指标,以微酸性电解水的有效氯浓度、浸泡时间以及超声波功率为单因素水平,研究了微酸性电解水对小龙虾的减菌效果和超声波对小龙虾的清洗效果。结果表明:微酸性电解水的有效氯质量浓度越高,处理时间越长减菌效果越好。当微酸性电解水有效氯质量浓度60 mg/L,处理小龙虾50 min后菌落总数和芽孢总数分别下降了4.26 lg CFU/g、500 CFU/g,减菌率分别达到了99.99%、92.61%;使用超声波技术对小龙虾进行清洗处理,超声功率50 W处理50 min后小龙虾存活率为100%,清洗液浊度为181 NTU,显著优于对照组（P<0.05）。超声波技术协同微酸性电解水对小龙虾活体净化处理后,小龙虾初始菌由7.17 lg CFU/g降到3.52 lg CFU/g,净化效果显著优于车间气泡清洗工艺（P<0.05）。小龙虾净化前后的营养价值和品质无显著性差异（P>0.05）,该工艺合理有效。     

食品安全抽检环节芹菜中10种有机磷农药的残留降解规律研究

目的 研究食品安全抽检环节芹菜中10种有机磷农药的残留降解规律.方法 以芹菜为基质,选择10种有机磷农药(乐果、毒死蜱、甲基对硫磷、杀螟硫磷、甲基异柳磷、喹硫磷、水胺硫磷、杀扑磷、三唑磷、伏杀硫磷)作为研究对象,采用加标后均质的制样方法制备样品,将农药残留检测结果通过拟合一级动力学模型预测农药的降解半衰期,研究抽检样品...     

Highly sensitive and selective amperometric microbial biosensor for direct determination of p-nitrophenyl-substituted organophosphate nerve agents

We report herein a whole cell-based amperometric biosensor for highly selective, highly sensitive, direct, single-step, rapid, and cost-effective determination of organophosphate pesticides with a p-nitrophenyl substituent. The biosensor was comprised of a p-nitrophenol degrader, Pseudomonas putida JS444, genetically engineered to express organophosphorus hydrolase (OPH) on the cell surface immobilized on the carbon paste electrode. Surface-expressed OPH catalyzed hydrolysis of the p-nitrophenyl substituent organophosphorus pesticides such as paraoxon, parathion, and methyl parathion to release p-nitrophenol, which was subsequently degraded by the enzymatic machinery of P. putida JS444. The electrooxidization current of the intermediates was measured and correlated to the concentration of organophosphates. The best sensitivity and response time were obtained using a sensor constructed with 0.086 mg dry weight of cells operating at 600 mV applied potential (vs Ag/AgCl reference) in 50 mM citrate--phosphate pH 7.5 buffer with 50 microM CoCl2 at room temperature. Under optimum operating conditions the biosensor measured as low as 0.28 ppb of paraoxon, 0.26 ppb of methyl parathion, and 0.29 ppb parathion. These detection limits are comparable to cholinesterase inhibition-based biosensors. Unlike the inhibition-based format, this biosensor manifests a selective response to organophosphate pesticides with a p-nitrophenyl substituent only, has a simplified single-step protocol with short response time, and can be used for repetitive/multiple and on-line analysis. The service life of the microbial amperometric biosensor was 5 days when stored in the operating buffer at 4 degrees C. The new biosensor offers great promise for rapid environmental monitoring of OP pesticides with nitrophenyl substituent.     

臭氧水降解苹果表面有机磷农药的研究

有机磷农药残留超标是制约我国浓缩苹果汁出口的一大瓶颈。文中建立了苹果表面有机磷农药降解模拟体系,比较了在不同清洗方式和起始浓度下,臭氧水对苹果中常见的甲胺磷、甲拌磷、乐果、二螓磷、马拉硫磷、毒死蜱等6种有机磷农药的降解效果。结果表明,臭氧水能有效降解苹果表面的有机磷农药残留。臭氧浓度越高,有机磷农药的降解效果越好；苹果表面有机磷农药起始浓度越低,农药残留的降解率越高。当苹果表面有机磷农药起始浓度为1～2 mg/kg 时,用浓度为14 mg/L 的臭氧水溶液动态清洗20 min,6种有机磷农药的降解效果可达35%～64%。     

A brief study on the degradation kinetics of seven organophosphorus pesticides in skimmed milk cultured with Lactobacillus spp. at 42 °C

Seven organophosphorus pesticides (OPPs) including dimethoate, fenthion, malathion, methyl parathion, monocrotophos, phorate and trichlorphon were added to skimmed milk. The milk was inoculated with one strain of Lactobacillus spp. including L. bulgaricus, L. paracasei and L. plantarum, and cultured at 42 °C for 24 h to investigate their impacts on degradation kinetics of the OPPs. The residual OPPs in the milk were extracted by an extraction solvent and quantified in a gas chromatography after purification. Degradation rate constant and half live periods of the OPPs were calculated from a first-order reaction kinetics model. The result shows that the selected Lactobacillus spp. exhibited some acceleration on OPPs degradation totally. Dimethoate and methyl parathion were more stable but malathion was the most labile. Both L. bulgaricus and L. plantarum had stronger acceleration on the degradation of the OPPs studied.     

酸性电解水对果蔬杀菌及保鲜效果的研究

本研究采用酸性电解水对新鲜菠菜、桃子及樱桃进行处理,考察了酸性电解水对上述果蔬在不同贮藏条件下保鲜效果的影响.结果表明,pH 3.04、有效氯浓度(ACC)30.2 mg/kg的强酸性电解水和pH 5.68、ACC 26.6 mg/kg的微酸性电解水浸泡处理5min均能使菠菜表面的微生物数下降2.0lg cfu/g以上...     

Photocatalytic degradation of selected s-triazine herbicides and organophosphorus insecticides over aqueous TiO2 suspensions

The photocatalytic degradation of selected s-triazine herbicides and organophosphorus insecticides was carried out in aqueous TiO2 suspensions under simulated solar light. The tested herbicides from the s-triazines group were atrazine, propazine, cyanazine, prometryne, and irgarol. The tested insecticides from the organophosphorus group were ethyl parathion, methyl parathion, ethyl bromophos, methyl bromophos, and diclofenthion. Degradation kinetics followed first-order reaction and has been monitored through gas chromatography. The degradation was fast with half-lives varying from 10.2 to 38.3 min depending on the nature and the structure of compounds. The generated transformation products (TPs) were formed via oxidation, dealkylation, and dechlorination for s-triazines and via oxidation and photohydrolysis for organophosphates. The TPs of irgarol, bromophos, and dichlofenthion were identified using solid-phase extraction (SDB-disks) and GC-MS techniques, and possible degradation routes were proposed showing similar degradation pathways as for other triazines and organophosporus pesticides. This work points out to the necessity of extended knowledge of the successive steps in a solar-assisted detoxification process.     

基于MnO2纳米片类氧化酶特性的有机磷农药荧光分析方法建立

利用MnO2纳米片类氧化酶特性并结合有机磷农药的酶抑制原理,构建一种快速、简便、高灵敏有机磷农药荧光分析方法。通过测定反应体系荧光强度前后的变化,可以检测样品中有机磷农药的含量。通过优化酶浓度、底物浓度和反应时间,发现乙酰胆碱酯酶浓度为9.375 U/L,底物浓度为10 mmol/L,反应时间为11 min时,该荧光分析方法检测性能最佳,对氧磷的动态检测范围为1.56～200 ng/mL,检出限达到0.5 ng/mL（RSN=3）,运用该方法测定标准添加的自来水、卷心菜、燕麦样品的回收率在83.4%～105.9%之间,表明该方法具有很高的灵敏度与准确性,为快速高灵敏测定有机磷农药提供一种新的可能。