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.     

Analysis of Herbicide Krovar I™ by Liquid Chromatography with Atmospheric Pressure Chemical Ionization Mass Spectrometry

Abstract

A simple, very efficient method is presented for routine analysis of herbicide Krovar I? (active components bromacil and diuron) in water and soil samples. Water samples were extracted by liquid–liquid extraction with dichloromethane (DCM) as extraction solvent. For soil samples two different extraction techniques were compared: microwave-assisted solvent extraction and a shaking technique using a platform shaker. Extracts were analyzed by high performance liquid chromatography using a water:methanol gradient. Liquid chromatography was coupled with atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) for quantification of bromacil and diuron. Optimization of the APCI-MS was done by using standards in the flow injection analysis mode (FIA). Method detection limit for liquid samples for bromacil is 0.04 µg L^?1 and for diuron 0.03 µg L^?1. Method detection limit for soil samples is 0.01 µg g^?1 dry weight for both compounds. Results of analysis of field samples of water and soil are also presented.     

Evaluation of phenanthrene toxicity on earthworm (Eisenia fetida): An ecotoxicoproteomics approach

The goal of this study was to identify promising new biomarkers of phenanthrene by identifying differentially expressed proteins in Eisenia fetida after exposure to phenanthrene. Extracts of earthworm epithelium collected at days 2, 7, 14, and 28 after phenanthrene exposure were analyzed by two dimensional electrophoresis (2-DE) and quantitative image analysis. Comparing the intensity of protein spots, 36 upregulated proteins and 45 downregulated proteins were found. Some of the downregulated and upregulated proteins were verified by MALDI-TOF/TOF-MS and database searching. Downregulated proteins in response to phenanthrene exposure were involved in glycolysis, energy metabolism, chaperones, proteolysis, protein folding and electron transport. In contrast, oxidation reduction, oxygen transport, defense systems response to pollutant, protein biosynthesis and fatty acid biosynthesis were upregulated in phenanthrene-treated E. fetida. In addition, ATP synthase b subunit, lysenin-related protein 2, lombricine kinase, glyceraldehyde 3-phosphate dehydrogenase, actinbinding protein, and extracellular globin-4 seem to be potential biomarkers since these biomarker were able to low levels (2.5 mg kg⁻¹) of phenanthrene. Our study provides a functional profile of the phenanthrene-responsive proteins in earthworms. The variable levels and trends in these spots could play a potential role as novel biomarkers for monitoring the levels of phenanthrene contamination in soil ecosystems.     

GC/MS法测定生物样品中多溴联苯醚类化合物

本研究建立了多溴联苯醚（PBDEs）生物样品分析方法,获得了优化的前处理条件、气相色谱和质谱检测条件.对定性定量方法及实验条件必须满足的要求进行了评价.通过质量控制（quality control, QC）对整个方法进行了验证.结果证明,本研究所建立的分析方法满足生物样品PBDEs测定的要求,回收率在50.5%～112.3%之间,回收率相对标准偏差在5.3%～9.9%之间,方法检测限在7.1～161.8 pg/g之间.在建立的方法基础上,测定了部分养殖和野生鱼类样品,测得的野生鳜鱼和鲫鱼以及2个养殖鲈鱼样品的结果分别为1.53、1.11、5.31和6.15 ng/g(干重),其中主要的同族体为BDE47.     

STAC有机膨润土的表征及其处理垃圾渗滤液的研究

文章以钙基蒙脱石为原料,经钠化后与十八烷基三甲基氯化铵(又称1831,简称STAC)进行离子交换反应,合成有机膨润土,通过XRD、IR 、SEM等测试仪,对有机膨润土的结构进行了分析,同时利用改性后的STAC有机膨润土对某垃圾填埋场中的渗滤液进行处理,用GC/MS对处理前后垃圾渗滤液中主要有机组分进行了分析,结果表明,...     

戊唑醇残留分析方法实验室内质量控制研究

文章确立了小麦、香蕉中戊唑醇残留检测方法,小麦样品加水10 mL用丙酮为萃取溶剂,石油醚液液分配,中性氧化铝柱层析净化,用气相色谱(GC-NPD)检测。香蕉样品加水5 mL用丙酮为萃取溶剂,石油醚液液分配,浓缩后用气相色谱(GC-NPD)检测。分别设置不同时间批次,同一批次间的平行样及实验室内人员分析,分别从方法灵敏度、方法准确度、方法精密度及其质量控制图、标准工作液的稳定性来探讨该方法的可靠性,结果表明该方法可以作为香蕉和小麦种戊唑醇残留检测的标准分析方法。     

用GC/MS分析火灾后苯板产生固体废物中的有机物

采用GC/MS方法对某苯板厂火灾后产生的固体废弃物进行检测分析.结果表明,在苯板火灾后产生的固体废弃物中检测出61种化合物,其中被美国EPA列入优先污染物的苯系物、萘和蒽等占总有机物12.2％.     

北京大气中CFC-11的浓度观测与变化趋势

近几年大气中CFC的浓度在人类活动的影响下发生了迅速变化,考虑到CFC浓度变化对平流层臭氧和全球变暖的影响,采用两步深冷冻浓缩自动进样系统,配以气相色谱/质谱联机对北京大气中的CFC-11进行了连续观测.结果表明,1999～2003年CFC-11的浓度季节变化均呈单峰形态,峰值出现在7～8月,月平均浓度最高值为1149.5±531.9×10^-12(体积分数);谷值出现在春季的3～5月份,月平均浓度最低值为487.5±131.5×10^-12(体积分数);北京大气中CF-11年平均浓度在观测时间段内呈先上升后下降的趋势,其中1995～1998年增长较快,平均增长率为17.9%,1999年后呈缓慢下降趋势,平均下降率为10.7%,平均浓度是Mauna Loa全球基准观测站观测到大气本底CFC-11浓度的3～5倍.     

北京大气中BTEX的观测分析与研究

采用二步深冷浓缩与气相色谱/质谱联机对北京大气中的苯类物质(BTEX) 进行了长期连续观测.最近4年观测数据表明:日变化有双峰和3峰变化,冬、春季呈现与交通高峰期吻合的双峰变化,即上午08:00至10:00和下午17:00前后各出现一个高值;秋季日变化中,夜间22:00出现第3峰值;夏季日变化呈3峰型,最大峰值在正午前后.2000～2002年BTEX月平均总浓度为(44.1±24.5) nmol/mol(碳单位),季变化峰值出现在夏季.年际变化趋势中,北京大气BTEX的总平均浓度从 1999 年到2002年大幅度下降.     

β-蒎烯的液相臭氧化反应研究

研究β－蒎烯的液相臭氧化反应,利用ＧＣ／ＭＳ联用系统监测,分析了反应的全过程,确定臭氧化反应的主要产物是不蒎酮,产率为４６％,在Ｏ３存在下稳定,无次级反应,根据液相反应的分析结果,对气相反应的可能机理进行了讨论。