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1.
During and after the application of currently used pesticides (CUPs) a significant fraction of applied pesticides can be lost to the air. A confirmatory and rapid procedure has been developed for the determination of four fungicides (carbendazim, thiabendazol, imazalil and bitertanol), three insecticides (imidacloprid, methidathion and pyriproxyfen), one helicide (methiocarb) and one acaricide (hexythiazox) in fine airborne particulate matter (PM 2.5) at trace level. The proposed method includes extraction of PM 2.5-bound pesticides by pressurized liquid extraction (PLE) followed by a direct injection into LC-MS/MS. The main parameters affecting the performance of the electrospray ionization source and PLE parameters were optimised using statistical design of experiments (DoE). The matrix effect was also evaluated. Recoveries ranged from 86 to 106% and the limit of quantification (LoQ) was 6.5 pg m(-3) for eight out of nine pesticides, when air volumes of 760 m(3) were collected. The method was applied to 60 samples collected from four stations of the monitoring network of the Regional Valencia Government (Spain) during August-October 2007. The measured concentrations ranged from not detected to 1,371 pg m(-3).  相似文献   

2.
A sensitive and confirmatory analytical method has been developed for the determination of 12 ionic per- and polyfluorinated alkyl substances (PFAS) in fine airborne particulate matter (PM2.5) at trace levels. The proposed method includes extraction of PM2.5-bound PFAS by microwave-assisted extraction (MAE) followed by centrifugation and injection into the liquid chromatograph coupled to a triple quadrupole tandem mass spectrometry system (LC-MS/MS). The main parameters affecting the performance of MAE were optimised using statistical design of experiments (DoE). Recoveries ranged from 83 to 120% and the method quantification limit (MQL) was 1.4 pg m(-3), when air volumes of 720 m(3) were sampled. This method was successfully applied to 41 samples collected from five stations of the monitoring network of the Valencian Regional Government (Spain) during April-July 2010. Eight out of 12 PFCs investigated were quantified in at least one sample (PFBA, PFPeA, PFHxS, 6:2 FTS, PFOA, PFNA, PFOS and PFDA). The measured concentrations ranged from 1.4 to 34.3 pg m(-3).  相似文献   

3.
A solid-phase extraction (SPE) procedure with the use of superparamagnetic Fe(3)O(4) nanoparticles as extracting agent was developed for HPLC-ESI-MS/MS analysis. Four most heavily used triazine pesticides (herbicides) were taken as the test compounds. The NPs showed an excellent capability to retain the compounds tested, and a quantitative extraction was achieved within 10min under the testing conditions, i.e. 100 microL NP solution was added to 400 mL sample in a beaker with stirring. After extraction, the superparamagnetic NPs were easily collected by using an external magnet. Very importantly, analytes retained on the Fe(3)O(4) NPs could be quantitatively recovered by dissolving the NPs with an HCl solution, allowing subsequent HPLC-ESI-MS/MS quantification. A capillary HPLC-ESI-MS/MS method with the present NP-based SPE procedure was developed for the determination of triazines including atrazine, prometryn, terbutryn, and propazine. Atrazine-d(5) was used as internal standard. The method had an LOD of 10 pg/mL atrazine, and a linear calibration curve over a range from 30 pg to 50.0 ng/mL. Simultaneous determination of the four triazine pesticides in water samples taken from local lakes was demonstrated.  相似文献   

4.
A confirmatory and rapid procedure has been developed for the determination of 30 currently used pesticides (CUP) in fine airborne particulate matter (PM 2.5) at trace level. The proposed method includes extraction of PM 2.5-bound pesticides by microwave-assisted extraction (MAE) followed by a direct injection into LC–MS/MS. The main parameters affecting the MAE extraction (time, temperature and volume of solvent) were optimised using statistical design of experiments (DoE). The matrix effect was also evaluated. Recoveries ranged from 72 to 109% and the limit of quantification (LoQ) was 32.5 pg m−3 for chlorpyrifos, 13.5 pg m−3 for fenhexamid, imazalil and prochloraz, and 6.5 pg m−3 for the rest of pesticides, when air volumes of 760 m3 were collected. The method was applied to 54 samples collected from three stations of the atmospheric monitoring network of the Regional Valencia Government (Spain) during April–July 2009. Nineteen out of 30 pesticides investigated were found in at least one sample: omethoate, carbendazim, acetamiprid, thiabendazole, malathion, flusilazole, metalaxyl, azoxystrobin, iprovalicarb, myclobutanil, tebuconazole, triflumizole, cyprodinil, tebufenpyrad, buprofezin, pyriproxyfen, hexythiazox, flufenoxuron and fenazaquin. The measured concentrations ranged from 6.5 to 1208 pg m−3. To our knowledge, 11 of the pesticides detected have been reported for the first time in ambient air.  相似文献   

5.
朱永哲  冯雅男  金正汉 《色谱》2013,31(9):850-861
建立了超高效液相色谱-串联质谱法(UPLC-MS/MS),可于10 min内快速测定土壤中的239种农药残留。土壤样品经AOAC (Association of Official Analytical Chemists) QuEChERS方法处理,用乙腈萃取;无水硫酸镁、乙酸钠固液分离后,过0.2 μm滤膜;在UPLC-MS/MS正、负离子同步扫描多反应监测模式下进行分析。239种农药中,线性相关系数(r2)大于0.99的有236个,占总数的99%。在40 μg/kg添加水平下所有被检测农药的回收率均在50%~150%之间,且相对标准偏差(RSD)均小于20%;其中有209种农药的回收率达到70%~120%,有161种的RSD小于10%。方法的检出限(LOD)范围为0.69~29.04 μg/kg。土壤中多种农药残留的同时检测要求时间短、准确度和精密度高,本方法符合这些检测要求,适用于土壤中农药残留的检测。  相似文献   

6.
A simple, rapid and sensitive method for the determination of five estrogens, estrone, 17beta-estradiol, estriol, ethynyl estradiol, and diethylstilbestrol, was developed using a fully automated method consisting of in-tube solid-phase microextraction (SPME) coupled with liquid chromatography-tandem mass spectrometry (LC/MS/MS). These estrogens were separated within 8 min by HPLC using an XDB-C8 column and 0.01% ammonia/acetonitrile (60/40, v/v) at a flow rate of 0.2 mL/min. Electrospray ionization conditions in the negative ion mode were optimized for MS/MS detection of the estrogens. The optimum in-tube SPME conditions were 20 draw/eject cycles of 40 microL of sample using a Supel-Q PLOT capillary column as an extraction device. The extracted compounds were easily desorbed from the capillary by passage of the mobile phase, and no carryover was observed. Using the in-tube SPME LC/MS/MS method, good linearity of the calibration curve (r > or = 0.9996) was obtained in the concentration range from 10 to 200 pg/mL for all compounds examined. The limits of detection (S/N= 3) of the five estrogens examined ranged from 2.7 to 11.7 pg/mL. The in-tube SPME method showed 34-90-fold higher sensitivity than the direct injection method (5 microL injection). This method was applied successfully to the analysis of environmental water samples without any other pretreatment and interference peaks. Several surface water and wastewater samples were collected from the area around Asahi River, and estriol was detected at 35.7 pg/mL in the effluent of a sewage treatment plant. The recoveries of estrogens spiked into river waters were above 86%, except for estriol, and the relative standard deviations were below 0.9-8.8%.  相似文献   

7.
建立了一种固相萃取/高效液相色谱-串联质谱(SPE/HPLC-MS/MS)同时检测水体中24种农药的分析方法。样品用乙腈提取后,经固相萃取小柱富集净化。以乙腈-0.1%(体积分数)甲酸水溶液为流动相梯度洗脱,在电喷雾离子源正离子模式下(ESI+)采用多反应监测(MRM)模式检测。结果显示,24种农药在1~200μg/L范围内具有良好的线性关系,相关系数(r2)均不小于0.998,水样中3个添加水平(5、20、100μg/L)下的回收率为65.9%~127.8%,相对标准偏差(RSD)为0.7%~14.2%;方法检出限为0.05~0.71 ng/L。采用该方法对大连地区10个河流入海口及2个水库的水样进行了检测,12个站位的样品中共检出10种农药,质量浓度为0.2~558.3 ng/L。结果表明,所建立的SPE/HPLC-MS/MS方法高效、灵敏、可靠,可用于实际水体中多种农药的同时检测。  相似文献   

8.
A method for the determination of ultra-trace amounts of organochlorine pesticides (OCPs) in river water was developed by using stir bar sorptive extraction (SBSE) followed by thermal desorption and comprehensive two-dimensional gas chromatography coupled to high-resolution time-of-flight mass spectrometry (SBSE-TD-GC×GC-HRTOF-MS). SBSE conditions such as extraction time profiles, phase ratio (β: sample volume/polydimethylsiloxane (PDMS) volume), and modifier addition, were examined. Fifty milli-liter sample including 10% acetone was extracted for 3 h using stir bars with a length of 20 mm and coated with a 0.5 mm layer of PDMS (PDMS volume, 47 μL). The stir bar was thermally desorbed and subsequently analyzed by GC×GC-HRTOF-MS. The method showed good linearity over the concentration range from 50 to 1000 pg L(-1) or 2000 pg L(-1) for all analytes, and the correlation coefficients (r(2)) were greater than 0.9903 (except for β-HCH, r(2)=0.9870). The limit of detection (LOD) ranged from 10 to 44 pg L(-1). The method was successfully applied to the determination of 16 OCPs at pg L(-1) to ng L(-1) in river water. The results agree fairly well with the values obtained by a conventional liquid-liquid extraction (LLE)-GC-HRMS (selected ion monitoring: SIM) method using large sample volume (20 L). The method also allows screening of non-target compounds, e.g. pesticides and their degradation products, polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and pharmaceuticals and personal care products (PPCPs) and metabolites in the same river water sample, by using full spectrum acquisition with accurate mass in GC×GC.  相似文献   

9.
A low temperature microwave-assisted extraction method (MAE) is reported for the analysis of polycyclic aromatic hydrocarbons (PAHs) in airborne particulate matter (PM). The main parameters affecting the extraction efficiency (choice of extractants, microwave power, and extraction time) were investigated and optimized. The optimized procedure requires a 20 ml mixture of acetone:n-hexane (1:1) for extraction of PAHs in PM at 150 W of microwave energy (20 min extraction time). Clean-up of MAE extracts was not found to be necessary. The optimized method was validated using two different SRM (1648-urban particulate matter and 1649a, urban dust). The results obtained are in good agreement with certified values. PAHs recoveries for both reference materials were between 79 and 122% with relative standard deviation ranging from 3 to 21%. Detection limits were determined based on blank determination using two kinds of quartz filter substrates (n = 10), which ranged from 0.001 (0.03) ng m−3 (pg/μg) for B(k)Ft to 1.119 (37.3) for Naph in ng m−3 (pg/μg), respectively. The repeatability and day-to-day reproducibility obtained in this study were in the range of 4-16 and 3-25% for spiked standards and SRM 1649, respectively. The optimized and validated MAE technique was applied to the extraction of PAHs from a set of real world PM samples collected in Singapore. The sum of particulate-bound PAHs in outdoor PM ranged from 1.05 to 3.45 ng m−3 while that in indoor PM (cooking emissions) ranged from 27.6 to 75.7 ng m−3, respectively.  相似文献   

10.
运用气相色谱-离子阱质谱(ion trap mass spectrometry,ITMS)建立了大气中8种多溴二苯醚的二级质谱(MS/MS)检测方法。优化后的MS/MS方法对7种三溴至七溴二苯醚(BDE28、-47、-99、-100、-153、-154、-183)和十溴二苯醚(BDE209)的仪器检出限分别为0.04~0.23 pg和9.38 pg;方法检出限为6.0~27.1 pg/m3和211.6 pg/m3;6点标准曲线相关系数(r)为0.9980~0.9999。方法对8种目标物的加标回收率为79.1%~101.0%,相对标准偏差(RSD)为4.3%~14.3%(n=6)。对6份南京实际大气样品的检测结果表明:离子阱质谱的选择反应监测(selected reaction monitoring,SRM)技术能有效的降低背景干扰。优化后的MS/MS方法对目标化合物有较高的灵敏度,可应用于大气中痕量多溴二苯醚的定量检测。  相似文献   

11.
Direct thermal desorption-gas chromatography-mass spectrometry (DTD-GC-MS) is a technique that is finding application in the characterisation of the semivolatile organic carbon fraction of ambient and combustion source particulate matter (PM) collected on filters. In this study, three DTD-GC-MS methods were assessed and compared to a conventional solvent extraction method for analysis of a mixture of target analytes in solution and of diesel PM collected on quartz filters. The target analytes included n-alkanes, hopanes, steranes and polycyclic aromatic hydrocarbons. This study showed that while the three DTD-GC-MS methods were generally comparable to the solvent extraction method, (1) the choice of calibration strategy and calibration materials has a significant impact on the measured accuracy of a method; (2) very large variations were seen in all methods for the more volatile compounds such as C10 to C13 n-alkanes and naphthalene; (3) accuracy, defined as difference from the known concentration of a liquid sample, ranged from 5% to 32%; (4) precision, defined as the relative standard deviation, ranged from 4% to 16%. The average difference of DTD-GC-MS results from the solvent extraction results for the diesel PM filters ranged from 20% to 40%. This difference was driven by the large number of target analytes present at relatively low concentrations (<25 pg/mm2) and their corresponding higher variability. Differences in performance among the compound classes were noted. Minimum detection limits for the DTD-GC-MS methods were on the order of 0.1 to 1 pg/mm2 and were as good as or better than those obtained for the solvent extraction method.  相似文献   

12.
潘煜辰  伊雄海  邓晓军  赵善贞  陈舜胜  杨惠琴  韩丽  朱坚 《色谱》2012,30(11):1159-1165
建立了亚临界水萃取及气相色谱-串联质谱(GC-MS/MS)检测红茶中21种有机氯和拟除虫菊酯农药残留的方法。在萃取压力为5 MPa条件下,样品经150 ℃的亚临界水提取15 min后,将目标物转移至丙酮-正己烷(1:1, v/v)中,经ENVI-Carb固相萃取净化小柱净化,DB-5毛细管气相色谱柱分离,在多反应监测(MRM)模式下进行MS/MS检测,基质匹配溶液内标法定量。各目标物在5.0~320.0 μg/L范围内线性关系良好,相关系数均大于0.99,其定量限(信噪比(S/N)>10)为50 ng/g,检出限(S/N>3)为10 ng/g。茶叶基质中添加50、100和200 ng/g的标准品时,21种农药的回收率为70.18%~119.98%,相对标准偏差(RSD)为5.01%~11.76%。该方法的灵敏度、准确度和精密度均符合农药残留测定的技术要求,适用于红茶中有机氯和拟除虫菊酯农药残留的检测。  相似文献   

13.
搅拌棒吸附子萃取与GC-MS法测定水中20种有机氯农药   总被引:2,自引:0,他引:2  
建立了搅拌棒吸附子萃取/气相色谱-质谱法(SBSE/GC-MS)同时检测水中α-六六六、γ-六六六、β-六六六、七氯、δ-六六六、艾氏剂、环氧七氯、γ-氯丹、顺-氯丹、硫丹Ⅰ、p,p-滴滴伊、狄氏剂、异狄氏剂、p,p-滴滴滴、硫丹Ⅱ、p,p-滴滴涕、异狄氏剂醛、硫丹硫酸盐、甲氧滴滴涕、异狄氏剂酮20种有机氯农药含量的方法.样品在室温下经拌棒吸附子搅拌吸附,甲醇解吸附后,以J&W DB-35 MS(30 m×0.25 mm×0.25 μm)石英毛细管色谱柱为分析柱,气相色谱-质谱选择离子流模式检测.考察了萃取时间、氯化钠及甲醇加入量等对萃取的影响.实验结果表明:在2.5 ~20.0 μg/L 范围内,20种有机氯农药呈良好的线性关系,检出限(S/N=3)为0.008 ~0.118 μg/L,水样中分别添加2.5、20 μg/L的20种有机氯农药,回收率为 52% ~117%,相对标准偏差小于13%(n= 6).该方法操作简便、快速、灵敏度高,应用于实际样品检测,结果满意.  相似文献   

14.
A method has been developed and optimised for the determination of two natural estrogens, estrone (E1) and 17beta-estradiol (E2), and one synthetic estrogen, 17alpha-ethynylestradiol (EE2), in river sediments at the sub-ng/g level. This procedure includes microwave-assisted solvent extraction (MASE), solid-phase extraction and high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS) with electrospray ionisation. Using sediments spiked with the three estrogens at 10 ng/g wet weight, efficient extraction (>92%) of all the three analytes was achieved by MASE, and whole-procedure recoveries ranged from 82 to 98%. Optimisation of the LC separation allowed for substantial reduction of ionisation suppression in the electrospray source to a final level of <18% suppression. Time-of-flight mass spectrometry (TOF-MS) and MS/MS were compared for the analysis of sediment extracts, with the latter technique proving to be the most selective. The method detection limits achieved by LC-MS/MS were 15, 30 and 40 pg/g for E1, E2 and EE2, respectively, which were 13-fold lower than those obtained by LC-TOF-MS. Analysis of river sediments collected from the River Ouse, UK, showed the presence of the natural estrogens at sub-ng/g level. E1 levels ranged from 0.40 ng/g (dry weight) to 3.30 ng/g while E2 levels ranged from <0.03 to 1.20 ng/g and EE2 was never detected (<0.04 ng/g).  相似文献   

15.
张帆  黄志强  张莹  李忠海  王美玲 《色谱》2010,28(4):348-355
建立了食品中20种氨基甲酸酯类农药残留量的高效液相色谱-串联质谱联用(HPLC-MS/MS)测定与确证方法。20种氨基甲酸酯类农药在0.005~0.1 mg/kg范围内线性良好,相关系数为0.991 7~0.999 6;在0.005~0.025 mg/kg范围内, 20种目标物的回收率为51.2%~125.0%,相对标准偏差为1.4%~19.8%。该方法准确、灵敏、快速,可满足国际上对食品中这20种氨基甲酸酯类农药残留量的检测需要。  相似文献   

16.
A novel design for a rapid clean‐up method was developed for the analysis of pesticide residues in fruit and vegetables followed by LC–ESI‐MS/MS. The acetonitrile‐based sample extraction technique was used to obtain the extracts, and further clean‐up was carried out by applying the streamlined procedure on a multiplug filtration clean‐up column coupled with a syringe. The sorbent used for clean‐up in this research is multiwalled carbon nanotubes, which was mixed with anhydrous magnesium sulfate to remove water from the extracts. This method was validated on 40 representative pesticides and apple, cabbage, and potato sample matrices spiked at two concentration levels of 10 and 100 μg/kg. It exhibited recoveries between 71 and 117% for most pesticides with RSDs < 15%. Matrix‐matched calibrations were performed with the coefficients of determination >0.995 for most studied pesticides between concentration levels of 10–500 μg/L. The LOQs for 40 pesticides ranged from 2 to 50 μg/kg. The developed method was successfully applied to the determination of pesticide residues in market fruit and vegetable samples.  相似文献   

17.
The development, optimization and validation of a liquid chromatography–atmospheric pressure photoionization tandem mass spectrometric (LC–APPI/MS/MS) method for the determination of 15 azaarenes (4-azafluorene, benzo[h] and -[f]quinoline, phenanthridine, acridine, 1-azafluoranthene, 4-azapyrene, benz[a]- and -[c]acridine, -10-azabenzo[a]pyrene, 7,9- and 7,10-dimethylbenz[c]acridine, dibenz[a,j]-, -[c,h] and [a,i]acridine) in airborne particulate matter is described. Each compound was detected and quantified operating in multiple reaction monitoring mode. Extraction of azaarenes was achieved using accelerated solvent extraction (ASE) with dichlormethane/methanol (50/50, v/v). After extraction, no additional clean-up procedure like solid phase or liquid/liquid extraction was necessary. Limits of quantification (S/N × 10) ranged from 0.2 pg/μl to 1.4 pg/μl, matrix dependent recoveries were between 57% and 94%, with relative standard deviations from 8% to 17%. Applicability of the method was demonstrated analyzing 10 samples of particulate matter (PM2.5) collected in winter 2008. In all samples dimethylbenz[c]acridines as well as dibenzacridines were below the limit of quantification, concentration of the remaining analytes were in the range from 0.002 ng/m3 to 0.356 ng/m3.  相似文献   

18.
建立了浊点萃取-异辛烷反萃取-气相色谱(ECD)检测茶叶中联苯菊酯(Bifenthrin)、甲氰菊酯(Fenpropathrin)、功夫菊酯(Cyhalothrin)、氯菊酯(Permethrin)、氰戊菊酯(Fenvalerate)、溴氰菊酯(Deltamethrin)6种拟除虫菊酯农药残留的方法.对含1.2%(m/V)聚乙二醇6000(PEG6000)表面活性剂和40%(m/V)(NH4)2SO4的6种拟除虫菊酯溶液进行加热萃取,所获得的富集相用异辛烷超声反萃取,并经离心对上层异辛烷溶液进行进一步净化处理,即可获得富集倍数达75倍的6种农药.本方法的检出限(LOD)为:联苯菊酯、甲氰菊酯和功夫菊酯0.4 μg/kg;氰戊菊酯2.1 μg/kg;氯菊酯和溴氰菊酯3.0 μg/kg;用本方法测定了新鲜茶叶中6种拟除虫菊酯农药,含量分别为4.17, 4.15, 4.09, 4.01, 3.93和3.51 μg/kg.在上述茶叶样品中添加20 μg/kg 的6种农药后测定,添加回收率为72.3%~85.6%; 相对标准偏差为2.2%~5.6%.  相似文献   

19.
气相色谱-质谱法分析蜂蜜中的多种农药残留   总被引:2,自引:0,他引:2  
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。  相似文献   

20.
建立大气细颗粒物(PM2.5)中16种多环芳烃(PAHs)的快速溶剂提取-直接进样-高效液相色谱测定方法.PM2.5经玻璃纤维滤膜收集,采样后的滤膜直接用乙腈经快速溶剂萃取仪提取,以乙腈和水作为流动相,提取液通过ZORBAX Eclipse PAH液相色谱柱分离,紫外串联荧光检测器检测.16种PAHs分离效果良好,在0.025~5.000μg/mL范围内线性相关系数r≥0.9998,方法加标回收率为78.3%~113.2%,相对标准偏差为0.5%~9.5%,检出限为0.007~0.062 ng/m3.本方法操作简便、快速、准确、灵敏,适于PM2.5中16种PAHs的同时测定.  相似文献   

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