基质固相分散和GC-NCI-MS法分析果汁中拟除虫菊酯农药残留量

建立了基质固相分散法（MSPD）和气相色谱-负化学离子源-质谱法（GC—NCI—MS）应用于果汁中10种拟除虫菊酯农药残留量的快速分析方法，并对这些农药NCI—MS的阴离子结构与断裂机理进行初步探讨。采用以中性氧化铝为吸附刺、Florisil硅藻土为净化剂和乙酸乙酯为洗脱剂的MSPD样品前处理方法，以PCB103为内标物和GC—NCI—MS的选择离子监测方式（SIM）进行定性与定量分析。当样品的加标浓度水平为50、250μg／kg时，平均加标回收率为86．7％～114．8％，相对标准偏差为1.9％～14．1％；除氯菊酯农药的方法检出限（MDL）为14.7μg／kg外，其余农药的MDL大都小于1．0μg／kg；线性范围为10～500μg／kg，相关系数都大于0.997，在所分析的大部分果汁中至少分析出两种以上的拟除虫菊酯农药残留。     

调味品中氯丙醇的GC/ECD和GC/MS/MS衍生化检测方法研究及应用

报道了调味品中氯丙醇的衍生化气相色谱(GC／ECD)和衍生化气相色谱双串联质谱法(GC／MS／MS)测定。GC／ECD测定酱油中3—氯—1，2—丙二醇(3—MCPD)的检出限达到0．01mg／kg，回收率为91％～104％，变异系数为2．27％～7．96％；GC／MS／MS同时测定酱油中1，3—二氯—2—丙醇、2，3—二氯—1—丙醇和3—氯—1，2—丙二醇，1，3—二氯—2—丙醇、2，3—二氯—1—丙醇的检出限为0．02mg／kg，3—氯—1，2—丙二醇的检出限为0．01mg／kg，回收率在92％～106％，变异系数为3．51％～13．33％。     

SDE-GC-ECD分析水体中有机氯农药

运用单滴溶剂萃取-气相色谱-微池电子捕获检测器(SDE—GC—μECD)联用技术对水体中有机氯农药进行了分析，优化了影响单滴溶剂萃取的多种因素。该方法除了对P，P′-DDD的线性范围在0．4～4ng／mL之间外，其余的七种目标物(α-666，β-666，γ-666，δ-666，P，P′-DDE，0，P′-DDT，P，P′-DDT)线性范围均在0．04～4．0ng／mL之间，相关系数为0．9976～0．9999，回收率范围为83．3％～96．1％，相对标准偏差为2．1％～7．8％。与传统的液液萃取相比，单滴溶剂萃取不仅准确度、精密度相当，而且还具有省时、省溶剂的优点。     

流动注射分光光度法测定工业废水中的钼

将流动注射分析技术与硫氰酸盐分光光度法相结合,建立了测定工业废水中钼的快速分析方法。在采样频率为80样／h时,检出限为0．08mg／L,线性范围为0—10mg／L。应用该方法测定工业废水样中的钼含量,相对标准偏差不大于1．3％（n=5）,加标回收率为96．6％～98．1％,测定结果与采用国家标准方法测定结果基本一致。     

固相微萃取-气相色谱-电子捕获快速富集检测海水中的有机氯农药

建立了固相微萃取(SPME)技术结合气相色谱-电子捕获(GC—ECD)检测方法,对大连近海养殖区内海水中的痕量12种有机氯农药进行检测,以便对该水域中海产品的食品安全性进行评估。该法具有较好的线性(相关系数为0．98～0．99),检出限达0．2～7ng／L,定量下限为0．66～23ng／L,重复测定的相对标准偏差小于10％(n=3),回收率为68％～133％。对影响SPME的参数和海水中存在的基质干扰进行探讨。     

凝胶渗透色谱-气相色谱-质谱测定玉米中3种农药的残留

建立以凝胶渗透色谱（GPC）和气相色谱-质谱（GC／MS）联用技术测定玉米中三唑酮、三唑醇-a，三唑醇-b残留量的方法。目标农药经乙腈提取，共提物中的油脂经液／液分配、GPC加以去除，叶黄素通过固相萃取（SPE）净化。目标农药采用GC／MS／SIM方式进行定性、定量分析。3种农药（0．05、0．5、2μs／s）的回收率在90％-110％；相对标准偏差（RSD）〈10％。     

气相色谱法测定蔬菜中有机磷农药的残留量

采用DB-1型毛细管柱及氮磷检测器，建立了同时测定蔬菜中有机磷农药甲胺磷、氧化乐果、甲拌磷、甲基对硫磷残留量的气相色谱法，测定4种有机磷农药残留量的线性范围均为0．02-4．00mg／L，相关系数为0．9955～0.9980，检出限为0.0012～0．0020mg／L，加标回收率为89．3％-92．2％，相对标准偏差为2．2％～3．2％。     

气相色谱-质谱法快速筛选测定浓缩苹果汁中105种农药残留量

采用硅藻土柱层析法对样品中的农药进行提取及净化后，用气相色谱—质谱法在选择离子监测模式下进行快速测定，以保留时间和特征离子定性定量；采用此方法测定了包括有机氯农药、有机磷农药、氨基甲酸酯农药、拟除虫菊酯农药、三嗪类农药在内的105种农药，大多数农药的线性范围为0.05～10mg／kg，相关系数大于0.99；90％以上农药在0．2mg／kg添加水平的平均回收率在70％～110％的范围内。     

大体积进样气相色谱法测定空气中的痕量苯

采用气袋采样,以大体积进样气相色谱法测定空气中的痕量苯。气袋采集的样品在8h内稳定。苯含量在0．01～0．2μL／L内与对应的色谱峰面积线性相关,线性方程为A=118．45X 0．073,相关系数为0．9994。6次测定结果的相对标准偏差为2．21％,空气中苯的检出限为0．03mg／m^3。     

含硫蔬菜中50种农药多残留的气相色谱-串联质谱检测技术研究

建立了气相色谱-串联质谱（GC—MS／MS）同时检测蔬菜中50种（38种有机磷、7种有机氮和5种拟除虫菊酯类）农药的多残留分析方法。采用凝胶渗透色谱（GPC）净化技术,用确定的二级质谱分析参数,以不同的电离方式（电子轰击电离EI或化学电离CI）一次分析所有的目标化合物。依次对农药标准品、空白洋葱样品进行GC—MS／MS分析,添加2个不同浓度水平的标准品进行方法的确证。大部分农药的回收率在60％～120％,RSD的范围为1．4％～16．9％,检出限为0．2～10μg/kg,满足农药多残留的分析要求。     

Rapid simultaneous determination of multiple pesticide residues in traditional Chinese medicines using programmed temperature vaporizer injection-fast gas chromatography coupled with mass spectrometry

A fast gas chromatography coupled with mass spectrometry (GC-MS) using large volume injection with programmed temperature vaporizer in solvent vent mode (PTV-LVI-SV) was developed for the trace determination of multiple pesticide residues in traditional Chinese medicines (TCMs). Experimental conditions of PTV-LVI-SV injection were optimized by central composite design. The optimized result was that initial temperature was held at 40°C for 39 s, vent flow rate was set at 45 mL/min and vent pressure was held at 0 psi for 36 s, injection volume was 10 μL. Furthermore, the quick and effective QuEChERS (quick, easy, cheap, effective, rugged and safe) method was performed to extract and purify pesticide residues in TCMs. The prepared samples were analyzed with GC-MS in the selected ion monitoring mode (SIM). The lowest LOD was 4 μg/kg for some pesticides. The recoveries were checked by spiking samples with pesticides at 25, 50 and 250 μg/kg. The average recoveries of most pesticides were from 80 to 118%. The result indicated that QuEChERS and PTV-LVI-SV GC-MS method was a rapid and sensitive analysis technique for the determination of multiple pesticide residues in TCMs.     

气相色谱串联质谱法测定蔬菜中甲拌磷和克百威及其代谢物的残留量

建立气相色谱–三重四级杆串联质谱法(GC–MS/MS)测定蔬菜中甲拌磷及其代谢产物甲拌磷砜、甲拌磷亚砜,克百威及其代谢产物3-羟基克百威。蔬菜样品经乙腈提取、Qu ECh ERS法净化,GC–MS/MS采用选择反应监测模式(SRM)采集数据后进行分析。5种化合物的含量在检测范围内与色谱峰面积均呈良好的线性,相关系数r2为0.998 0~0.999 6。在0.02,0.05 mg/kg的添加水平下,平均回收率在73.6%~118.2%范围内,测定结果的相对标准偏差小于8.5%(n=6),方法定量限为5~10μg/kg。该方法可用于蔬菜中甲拌磷和克百威及其代谢物的常规检测。     

Multiresidue determination of pesticides in agricultural products by gas chromatography/mass spectrometry with large volume injection

A method is described for the rapid determination of pesticide residues in agricultural products. Pesticides were extracted from samples with acetonitrile. To remove pigments and fatty acids, an aliquot of the extract was cleaned up by a minicolumn that was packed both with graphitized carbon black and primary secondary amine. Analysis was performed by gas chromatography/ mass spectrometry with programmable temperature vaporizer-based large volume injection using a liner packed with phenylmethylsilicone chemically bonded silica. The method was evaluated for 114 pesticides by spiking into tomato, spinach, Japanese pear, grape, and brown rice at various concentrations of each pesticide (0.02-0.4 microg/g). The method, which gave good recovery (>60%) for 108 pesticides, is characterized by high cleanup efficiency and short cleanup time, and is useful as a rapid screening analysis.     

Determination of organophosphorus pesticides by gas chromatography with mass spectrometry using a large‐volume injection technique after magnetic extraction

A fast and efficient method was developed for the extraction and determination of organophosphorus pesticides in water samples. Organophosphorus pesticides were extracted by solid‐phase extraction using magnetic multi‐walled carbon nanotubes and determined by gas chromatography with ion‐trap mass spectrometry. Parameters affecting the extraction were investigated. Under optimum conditions of the method, 10 mg magnetic multi‐walled carbon nanotubes were added into 10 mL sample. After 2 min, adsorbent particles settled at the bottom of test tube with a magnet. After removing aqueous supernatant, the analytes were desorbed with acetonitrile. Then, 70 μL of acetonitrile phase was injected into the gas chromatography and mass spectrometry system that had an ion‐trap analyzer. To achieve high sensitivity, the large‐volume‐injection technique was used with a programmed temperature vaporization inlet, and the ion‐trap mass spectrometer was operated in single ion storage mode. Under the best conditions, the enrichment factors and extraction recoveries were in the range of 113–124 and 74–103%, respectively. The limits of detection were between 3 and 15 ng/L, and the relative standard deviations were < 10%. This method was successfully used for the determination of organophosphorus pesticides in dam water, lagoon water, and river water samples with good reproducibility and recovery.     

气相色谱-质谱法分析蜂蜜中的多种农药残留

开展了蜂蜜中23种农药残留的气相色谱-电子轰击离子源质谱(GC-EI/MS)分析方法的研究,并对其中3种农药的EI/MS碎片离子的断裂机理与结构进行了初步解析。探讨了蜂蜜试样前处理条件的优化与选择。将蜂蜜试样用乙酸乙酯提取剂超声提取、Florisil硅藻土色谱柱净化和正己烷-乙酸乙酯(体积比为7∶3)混合洗脱剂洗脱后,以PCB103为内标物,采用选择离子监测(SIM)方式下的GC-EI/MS分析。当试样的加标浓度为50,100和200 μg/kg时,加标回收率为82%～120%,相对标准偏差小于11.0%。23种农药的检测限都小于10.0 μg/kg,线性范围为10～500 μg/kg,相关系数都大于0.995。此分析方法已成功地应用于蜂蜜中23种痕量农药残留的分析。     

分散固相萃取-在线凝胶色谱-气相色谱-质谱联用法快速检测紫菜中的农药多残留

建立了紫菜中农药多残留的在线凝胶色谱-气相色谱-质谱联用（GPC-GC/MS）检测方法。以有机氯、有机磷、三嗪类和菊酯类的19种农药为目标物,对比了丙酮、丙酮/二氯甲烷（1:1,v/v）和乙腈3种有机溶剂的提取效果,通过石墨化炭黑粉（GCB）和N-丙基乙二胺粉（PSA）分散固相萃取净化和GPC在线净化,气相色谱-质谱联用法分析,外标法定量。结果表明,此方法实现了在线净化与分析检测的自动化,缩短了分析时间。分析物在10~1000 μg/L范围内线性关系良好,相关系数r>0.995;采取GPC大体积进样和气相色谱进样口的程序升温方式提高了检测灵敏度,检出限为0.005~0.03 mg/kg。方法的平均添加回收率在70%~120%之间,相对标准偏差（RSD）均小于15%。该方法简单、快速、具有良好的回收率和重复性,适用于紫菜样品中农药多残留的快速灵敏检测。     

Simultaneous multidetermination of residues of pesticides and polycyclic aromatic hydrocarbons in olive and olive-pomace oils by gas chromatography/tandem mass spectrometry

A multiresidue method for determining major pesticides and polycyclic aromatic hydrocarbons (PAHs) in olive oils in a single injection by use of gas chromatography/tandem mass spectrometry (GC-MS/MS) is proposed. Samples are previously extracted with an acetonitrile/n-hexane mixture and cleaned up by gel permeation chromatography. Electron ionization and chemical ionization allow pesticides and PAHs to be determined in a single analysis. The precision obtained was quite satisfactory (relative standard deviations ranged from 3 to 7.8%), and so were recoveries (84-110%). The linear relation was observed from 1 to 500 microg/kg for pesticides and 0.3 to 200 microg/kg for PAHs; also, the determination coefficient, R(2), was better than 0.995 in all instances. The proposed method was applied to the routine analysis of PAH and pesticide residues in virgin and refined olive oil and olive-pomace oil samples.     

直接进样–超高效液相色谱串联质谱法同时测定水源水中9种农药

建立直接进样–超高效液相色谱三重四级杆质谱联用(UPLC–MS–MS)快速测定水源水中9种痕量农药残留的方法。水样无需富集,经超高效液相色谱分离,串联三重四级杆质谱检测,在7.5 min内完成9种目标化合物的分析。9种农药的检出限(S/N≥3)在0.01~1.4μg/L之间,在各自的考察浓度范围内线性关系良好(r≥0.995)。在1.0~80μg/L添加水平内,实际样品的平均加标回收率为66.2%~114.0%,测定结果的相对标准偏差为2.3%~20.4%(n=6)。该法操作简便,重现性好,可用于饮用水源水中农药残留的快速测定。     

Large volume injection of water in gas chromatography–mass spectrometry using the Through Oven Transfer Adsorption Desorption interface: Application to multiresidue analysis of pesticides

In the present work, the potential of the Through Oven Transfer Adsorption Desorption (TOTAD) interface for the large volume injection (LVI) of aqueous samples in gas chromatography (GC) using a mass spectrometry (MS) detector is demonstrated. To this end, a new method for the determination of pesticides in water is presented, being the first developed method in which injection of large amounts of polar solvents using the TOTAD interface and an MS detector are combined, is applied to the determination of pesticides in water. Water samples, as large as 5 ml, were directly injected into a capillary GC. No sample pre-treatment step other than simple filtration was needed. The TOTAD interface allows the introduction of several millilitres of water, while maintaining good chromatographic characteristics. The water is almost entirely eliminated, so that LVI of aqueous samples and an MS detector can be used without problems. Organophosphorus, organochlorine, and triazine pesticides were determined in one run. Calibration curves were linear in the range tested and the sensitivity achieved injecting 5 ml of water sample was sufficient for most of the target pesticides but not for all of them. Sensitivity of the analysis can be improved by increasing the sample volume. No variability was observed in the retention times and relative standard deviations from absolute peak areas were good, considering that they corresponded to the overall analysis. The method was applied to the analysis of pesticide residues in real water samples.     

Development of a procedure for the multiresidue analysis of pesticides in vineyard soils and its application to real samples

A procedure for multiresidue analysis was developed for the extraction and determination of 17 pesticides, including herbicides, fungicides, and insecticides, as well as certain degradation products, in vineyard soils from La Rioja region (Spain). Different solvents and mixtures were tested in spiked pesticide‐free soils, and pesticides were comparatively evaluated by gas chromatography with mass spectrometry and liquid chromatography with mass spectrometry. Recoveries >70%, with relative standard deviations <9%, were obtained when a mixture of methanol/acetone or a mixture of methanol/CaCl₂ 0.01 M for the most polar compounds was selected as the extraction solvent. Method validation was accomplished with acceptable linearity (r² ≥ 0.987) within the concentration range of 0.005–1 μg/mL corresponding to 1.667–333.4 μg/kg and 0.835–167.1 μg/kg for liquid chromatography with mass spectrometry and gas chromatography with mass spectrometry, respectively, and detection limits <0.4 μg/kg for the compounds were studied. The extraction method was applied to 17 real vineyard soil samples, and terbuthylazine and its metabolite desethylterbuthylazine were the most ubiquitous compounds, as they were detected in the 100% of the soils analyzed. The presence of fungicides was also high, and the presence of insecticides was lower than other pesticides. The results confirm the usefulness of the optimized procedure for monitoring residues in vineyard soils.