Development and application of LC–APCI–MS method for biomonitoring of animal and human exposure to imidacloprid

Imidacloprid (IMI) is a relatively new neuro-active neonicotinoid insecticide and nowadays one of the largest selling insecticides worldwide. In the present study a LC–APCI–MS based method was developed and validated for the quantification of imidacloprid and its main metabolite 6-chloronicotinic acid (6-CINA) in urine and hair specimens. The method was tested in biomonitoring of intentionally exposed animals and subsequently applied for biomonitoring of Cretan urban and rural population.     

FeCl3改性污泥生物炭对水中吡虫啉的吸附性能研究

以脱水污泥为原料,制备污泥生物炭（SBC）和FeCl₃改性污泥生物炭（Fe-SBC）处理低浓度吡虫啉（IMI）废水（浓度为10 mg·L^-1）,考察SBC和Fe-SBC对IMI的吸附性能及影响因素,并探究其吸附机理.采用SEM、XRD、FTIR、BET及元素分析等探得污泥生物炭FeCl₃改性成功.Fe-SBC对IMI的最大吸附量为4.915 mg·g^-1,是SBC的1.97倍,表现出更好的IMI吸附性能.pH和离子强度的变化对Fe-SBC的吸附性能影响较小,最大波动幅度分别为4.4%和7.8%.两种生物炭对IMI的吸附均符合准二级动力学模型,Freundlich模型可以更好地描述其等温吸附曲线.热力学研究表明,SBC吸附IMI是非自发吸附,而Fe-SBC是自发吸附.Fe-SBC对IMI的吸附机理包括静电作用力、氢键作用力及π-π键相互作用力.多次热解再生后的Fe-SBC对IMI的去除率仍可达93.088%.     

烯式吡虫啉(olefin IMI)光解及其光解产物研究

烟碱类杀虫剂吡虫啉(imidacloprid,IMI)在环境中可代谢为生物活性提高10倍的烯式吡虫啉(olefin IMI).研究了olefin IMI的光稳定性、光解动力学和光解代谢途径.结果表明:olefin IMI在避光条件下较为稳定,室温下放置400 d后,olefin IMI含量仅减少3%;而在室内模拟日光条件下,olefin IMI易于分解,光解反应符合一级动力学方程(r＞0.99),半衰期为4 d.olefin IMI的光解反应存在2条主要途径:一是羟基化生成4,5-二羟基化吡虫啉,该产物进一步氧化断裂药效基团硝基亚胺基生成羰基化产物;二是直接脱去硝基基团生成胍基产物.