气相色谱法分析尿液样品中阿特拉津及其代谢物

建立尿液样品中阿特拉津(ATZ)及其代谢物脱乙基阿特拉津(DEA)、脱异丙基阿特拉津(DIA)、脱乙基脱异丙基阿特拉津(DEDIA)的气相色谱分析方法。样品通过乙酸乙酯萃取,硫酸钠干燥,弗罗里硅土净化,浓缩后用气相色谱ECD检测器分析。对方法中pH值等条件进行了优化,获得了较好的回收率。方法的检出限为DEDIA:2.5ng/mL,DEA、DIA、ATZ:均为5ng/mL。利用本方法对阿特拉津生产工人的实际尿液样品进行了分析。     

土壤中残留的阿特拉津及其代谢产物的高效液相色谱和气-质谱联用分析

用一种简便、快速的前处理和高效液相色谱法（HPLC）对土壤样品中残留的阿特拉津及其主要代谢产物脱乙基阿特拉津、脱异丙基阿特拉津和2-羟基阿特拉津进行定量分析,样品添加回收率因土壤种类和化合物而异：78～121%（阿特拉津、脱乙基阿特拉津、脱异丙基阿特拉津）和40～75%（2-羚基阿特拉津）,最小检测浓度为0.005mg/kg;应用气-质联用法（GC/MS）对前三种化合物和脱乙基-脱异丙基阿特拉津进行了定性分析,谱库检索匹配程度达到90%以上。     

土壤中残留的阿特拉津及其代谢产物的高效液相色谱和气－质谱联用分析

用一种简便、快速的前处理和高效液相色谱法（ＨＰＬＣ）对土壤样品中残留的阿特拉津及其主要代谢产物脱乙基阿特拉津、脱异丙基阿特拉津和２－羟基阿特拉津进行定量分析，样品添加回收率因土壤种类和化合物而异：７８～１２１％（阿特拉津、脱乙基阿特拉津、脱异丙基阿特拉津）和４０～７５％（２－羟基阿特拉津），最小格测浓度为０．００５ｍｇ／ｋｇ；应用气－质联用法（ＧＣ／ＭＳ）对前三种化合物和脱乙基－脱异丙基阿特拉津进行了定性分析，谱库检索匹配程度达到９０％以上。     

功能化聚丙烯腈纳米纤维膜同时高效萃取莠去津及其毒性代谢物

研制了一种新型固相萃取(SPE)介质,用于同时高效萃取莠去津(ATZ)及其两种毒性代谢产物脱乙基莠去津(DEA)和脱异丙基莠去津(DIA),为全面客观地评价ATZ的水污染状况提供基础.以聚丙烯腈纳米纤维(PAN NFs)膜为基底膜,制备了3种功能化的NFs膜.吸附容量和吸附效率实验结果表明,羧基修饰的PAN NFs(COOH-PAN NFs)膜对3种目标物的静态和动态吸附容量分别为2.00和0.19 mg/g,动态吸附流出率低于30.0％,显著优于其它3种NFs膜,且对极性较大的目标物保留最强,表明其为同时高效吸附ATZ、 DIA和DEA的优势SPE介质,且主要通过羧基基团与目标物之间形成的氢键进行目标物吸附.采用基于COOH-PAN NFs膜的SPE,结合高效液相色谱-二极管阵列检测器(HPLC-DAD),建立了同时检测水样中ATZ、 DIA和DEA的方法,方法回收率为81.4％～120.3％, DIA检出限(LOD, S/N=3)为0.12 ng/mL,DEA和ATZ的检出限为0.09 ng/mL,可应用于实际水样监测.     

固液萃取-高效液相色谱-串联质谱法同时测定土壤中阿特拉津及其降解产物

建立了高效液相色谱-串联质谱法(HPLC-MS/MS)同时检测土壤中阿特拉津及其降解产物残留的分析方法。样品以甲醇-水(4∶1,V/V)作为提取溶剂,使用涡旋振荡提取,采用HPLC-MS/MS法进行测定,外标法定量。在0.01、0.2和5.0mg/kg三个添加浓度水平下,阿特拉津及其降解产物的平均回收率在73.7%~104.7%之间,相对标准偏差为0.4%~5.1%;阿特拉津,羟基阿特拉津在土壤样品中的方法检出限均0.045μg/kg,而脱乙基阿特拉津、脱乙基脱异丙基阿特拉津及脱异丙基阿特拉津在土壤样品中的方法检出限则分别为0.090、0.45和0.90μg/kg。本方法的灵敏度较高,且简便、快速,能较好的解决目标物极性差别大及样品基质对检测结果的干扰等问题,可以满足土壤中阿特拉津及其降解产物残留检测的需要。     

固相萃取-高效液相色谱/串联质谱法同时测定牛奶中阿特拉津及其两类代谢物的残留

建立了高效液相色谱质谱联用检测牛奶中阿特拉津及其两类代谢物残留的同步分析方法。样品中加入1%HCl和0.265 mol/L Na2S2O3后,由冰乙腈提取,混合型阳离子交换柱固相萃取净化,采用液相色谱-串联质谱进行测定,外标法定量。阿特拉津及其代谢物在0.4～100μg/L范围内线性良好,标准曲线相关系数R2>0.99。在1～25μg/L浓度范围内,除脱异丙基羟基阿特拉津的平均加标回收率较低约为64.2%外,其它目标物的回收率在75.0%～119.0%之间,相对标准偏差为1.5%～14.5%;脱乙基阿特拉津、羟基阿特拉津、脱乙基羟基阿特拉津的检出限为0.1μg/L;其余目标物的检出限为0.5μg/L。本方法的灵敏度较高,且简便、快速,可以较好地解决目标物极性差别大及样品基质对检测结果的干扰等问题,可以满足牛奶中阿特拉津及其两类代谢物残留检测的需要。     

气相色谱法测定水生植物中的阿特拉津残留

确立了一套检测水生植物中阿特拉津残留量的方法.样品经石油醚-二氯甲烷混合液振荡萃取,经硅镁吸附剂层析柱净化后,采用气相色谱-电子捕获检测器检测水生植物中阿特拉津的残留量.该方法在0.062～1.0mg/L范围内峰面积与阿特拉津浓度的线性关系良好(r~2=0.9993).在0.5mg/L、1.0mg/L、1.5mg/L ...     

阿特拉津及其降解产物的磺酸化聚合物柱固相萃取及高效液相色谱-质谱法测定

建立了环境水样中痕量除草剂阿特拉津(ATR)及其环境中的主要降解产物Deethylatrazine(DEA),Deisopropylatrazine(DIA),Hydroxyatrazine(HA)的Oasis MCX(磺酸化(二乙烯基苯-N-乙烯基吡咯烷酮)共聚物)小柱离线萃取,HPLC-MS选择离子检测的分析方法。对MCX(60mg,3mL)小柱的萃取条件(样品溶液的pH,上样速率,上样体积,洗脱液pH)进行了优化,得出最佳的实验条件。ATR,DEA,DIA,HA的穿透体积均大于450mL。本实验利用HPLC-APCI选择离子模式对被分析物进行检测,500mL水样的化合物检出限为0．01～0．06μg／L;回收率均大于75％,符合欧盟饮用水中单种农药浓度不应超出0．1μg／L的检测标准。该方法用于官厅水库坝后水样的分析,测出该处水样中ATR为2．04μg/L,DEA为11．4μg／L,DIA为0．75μg／L。     

固相萃取-硅烷化-气质联用分析尿中莠去津及其去烃基代谢物

建立了固相萃取-硅烷化-气质联用分析尿中除草剂莠去津(ATRZ)及其代谢物去异丙基莠去津(DIA)、去乙基莠去津(DEA)和去乙基去异丙基莠去津(DDA)的方法.尿样加入内标,碱化后用GDX501大孔树脂进行固相萃取,萃取物进行TMS衍生化,选择离子监测气质联用法分析.尿中ATRZ、DIA、DEA和DDA的提取率分别为85.3%、78.6%、80.2%和71.7%; 检出限分别为0.9、0.9、1.5和1.2 μg/L;在5～500 μg/L浓度范围内工作曲线的线性关系良好.方法可用于莠去津中毒者和职业接触者尿样的分析.     

固相萃取/气相色谱-串联质谱法测定水产品中莠去津及其代谢物残留

该文采用固相萃取（SPE）和气相色谱－串联质谱（GC－MS/MS）技术,实现了对水产品中莠去津（ATR）及其代谢物脱乙基莠去津（DEA）、脱乙基脱异丙基莠去津（DDA）和脱异丙基莠去津（DIA）的定量分析。以乙腈为提取溶剂,采用GCB/NH2固相萃取柱净化,在多反应监测模式（MRM）下对水产品中的目标物进行定量分析。结果表明,ATR、DEA、DDA和DIA在0.5～100.0 μg/L质量浓度范围内具有较好的线性关系,相关系数（r2）为0.999 1～0.999 9;检出限（LOD）为0.02～0.13 μg/kg;在10.0、20.0、50.0 μg/kg 3个加标水平下的平均回收率为83.6%～98.4%,相对标准偏差（RSD,n = 3）为3.6%～8.1%。该方法具有较好的准确度、灵敏度和精密度,适用于水产品中ATR及其代谢产物残留的检测。     

尿中莠去津去烃基代谢物的特丁二甲硅烷基衍生化/气相色谱-质谱联用分析法

建立了尿中除草剂莠去津(ATRZ)代谢物去乙基莠去津(DEA)、去异丙基莠去津(DIA)及去乙基去异丙基莠去津(DDA)的分析方法.尿样加入内标2-氨基-4-甲氧基-6-甲基-1,3,5-三氮嗪(AMMT),碱化后用高极性GDX501大孔树脂吸附、乙酸乙酯洗脱进行固相萃取,萃取物在乙腈溶剂中用N-甲基-N-特丁二甲硅烷...     

固相萃取-高效液相色谱法测定环境水样中的三嗪类化合物

建立了固相萃取-高效液相色谱法(SPE-HPLC)测定地表水中三嗪类化合物的方法。考察了4种不同固相萃取柱对三嗪类化合物的吸附效果,最终选择ENVI-18固相萃取柱用于萃取地表水中的三嗪类化合物;系统研究了环境水样中三嗪类化合物的最佳固相萃取条件,选择洗脱溶剂为甲醇,洗脱溶剂用量5 mL,水样在萃取前不需要添加甲醇,不调节pH值。测定了方法的检测限,结果表明,扑草净、莠去津、西玛津、脱乙基莠去津、羟基化莠去津和脱异丙基莠去津的最低检测限依次为0.14 μg/L,0.12 μg/L,0.08 μg/L,0.08 μg/L,0.10 μg/L和0.18 μg/L。将该法应用于实际环境水样的分析测定,结果表明某湖水中扑草净的含量为（9.33±0.27） μg/L,某江水中莠去津和扑草净的含量分别为（5.28±0.43） μg/L和（7.12±0.54） μg/L。     

土壤中莠去津及其降解产物的提取及高效液相色谱-质谱分析

建立了高效液相色谱-质谱联用(HPLC-MS)选择离子检测(SIM)分析环境土样中的痕量莠去津及其降解产物脱乙基莠去津(deethylatrazine,DEA)、脱异丙基莠去津(deisopropylatrazine,DIA)、羟基化莠去津(HA)的方法。土样用双蒸水超声提取,然后用Waters Oasis MCX固相萃取小柱富集纯化土样提取液,测得莠去津及其降解物在不同加标浓度(4.5~120 ng/g)下的回收率为：莠去津40.4%~82.0%,DEA 60.6%~86.5%,DIA 69.2%~86     

Multiresidue analysis of atrazine, diuron and their degradation products in sewage sludge by liquid chromatography tandem mass spectrometry

A multiresidue method has been developed to analyze atrazine (ATZ), diuron (DIU), and their major degradation products, desethylatrazine (DEA), desisopropylatrazine (DIA), and dichlorophenylmethylurea in sewage sludge. Liquid chromatography coupled to electrospray tandem mass spectrometry (LC–ESI-MS–MS) allowed, in the multiple-reaction monitoring mode, the simultaneous analysis of these pesticides in only one run after their extraction with ethyl acetate–dichloromethane 90:10 (v/v) and a cleanup on a Florisil column. Stable isotopically labeled ATZ and DIU were used as internal standards to overcome matrix effects during the pesticide quantification. Using fortified samples, the method gave rise to 86–115% as mean recovery values depending on the analyte. Limits of detection (LODs) and of quantification (LOQs) ranging from 0.3 (DIA) to 1.5 (DEA) μg kg⁻¹ dw and from 0.4 (DIA) to 2.0 (DEA) μg kg⁻¹ dw, respectively, were sufficient to achieve the monitoring of these molecules in sludge from wastewater treatment plants of the Ile-de-France region.     

Pesticide levels in ground and surface waters of Primavera do Leste Region, Mato Grosso, Brazil

Residues of the herbicides simazine, metribuzin, metolachlor, trifluralin, atrazine, and two metabolites of atrazine, deisopropylatrazine (DIA) and deethylatrazine (DEA), are surveyed in the surface and groundwater of the Primavera do Leste region, Mato Grosso, Brazil during September and December 1998 and April 1999. Different water source sampling stations of groundwater (irrigation water well, drinking water well, and water hole) and surface water (dam and river) are set up based on agricultural land use. A solid-phase extraction procedure followed by gas chromatography-nitrogen-phosphorus detection is used for the determination of these compounds. All compounds are detected at least once in water samples. A temporal trend of pesticide contamination is observed, with the highest contamination frequency occurring in December during the main application season. Metribuzin shows the highest individual detection frequencies throughout the monitoring period, followed by metolachlor, simazine, and DEA. The maximum mean concentrations of pesticides in this study are in the range from 0.14 to 1.7 microg/L. We deduct that the contamination of water resources is predominantly caused by non-point pollution of pesticides used in intensive cash-crop cultures of the Cerrado area. Therefore, a continuous monitoring of pesticide concentrations in water resources of this tropical region is necessary to detect the longer term contamination trends and developing health risks.     

Determination of interfering triazine degradation products by gas chromatography-ion trap mass spectrometry

Deethylatrazine (DEA), an atrazine degradation product, has been added to the US Environmental Protection Agency's Drinking Water Contaminant Candidate List (CCL). In its gas chromatographic analysis, DEA can coelute with deisopropylatrazine (DIA), another degradation product. The present work demonstrates that the coelution of DEA and DIA can induce a significant (up to approximately 50%) positive bias in the DEA determination, when using an ion-trap mass spectrometer as the detector. The DIA determination is unaffected by the coelution within experimental error. This may be explained in terms of gas-phase ion fragment populations. A correction factor to the observed DEA concentration may be developed based on the measured DIA concentration.