王 東，閆思月，賈春虹，趙爾成

(北京市農(nóng)林科學(xué)院 植物保護(hù)環(huán)境保護(hù)研究院，北京 100097)

研究簡(jiǎn)報(bào)

王 東，閆思月，賈春虹，趙爾成*

(北京市農(nóng)林科學(xué)院 植物保護(hù)環(huán)境保護(hù)研究院，北京 100097)

1 實(shí)驗(yàn)部分

1.1 儀器與試劑

超高效液相色譜-串聯(lián)質(zhì)譜聯(lián)用儀，包括Waters ACQUTIY超高效液相色譜系統(tǒng)和Waters XEVO TQD三重四極桿質(zhì)譜儀(美國(guó)Waters公司)，Vortex QL-901 渦旋儀(海門(mén)市其林貝爾儀器制造有限公司)，高速多功能粉碎機(jī)(上海菲力博實(shí)業(yè)公司)，TDZ5-WS臺(tái)式低速離心機(jī)、H1650-W臺(tái)式高速離心機(jī)(長(zhǎng)沙湘儀離心機(jī)儀器有限公司)，50 mL聚四氟乙烯離心管，0.22 μm有機(jī)微孔濾膜。

1.2 實(shí)驗(yàn)方法

1.2.2 樣品前處理 準(zhǔn)確稱(chēng)取5 g粉碎玉米樣品(10 g土壤樣品)至50 mL離心管，依次加入5 mL超純水(土壤樣品需3 mL超純水)，10 mL 1%甲酸-乙腈(土壤樣品需20 mL 1%甲酸-乙腈)，渦旋3 min，使提取溶劑與樣品充分接觸進(jìn)行提取。加入3 g氯化鈉至樣品溶液中，渦旋1 min使其充分溶解，在4 000 r/min轉(zhuǎn)速下離心5 min，使提取溶劑與樣品溶液完全分離。取1.5 mL上層溶液至2 mL離心管(含150 mg 無(wú)水硫酸鎂+25 mg PSA+25 mg C18+25 mg PC)中(土壤樣品需含150 mg無(wú)水硫酸鎂+50 mg PSA+50 mg C18的2 mL離心管)，渦旋1 min凈化，以12 000 r/min轉(zhuǎn)速離心3 min，取上清液過(guò)0.22 μm濾膜進(jìn)入進(jìn)樣瓶，待測(cè)。

1.2.3 色譜條件 色譜柱：Waters Acquity UPLC BEH Shield RP 18(50 mm×2.1 mm，1.7 μm)；柱溫40 ℃；流動(dòng)相：溶劑A為0.5 mmol/L乙酸銨溶液，溶劑B為乙腈；梯度洗脫程序：0～1.0 min，90%～20%A ；1.0～3.0 min，20%～5%A；3.0～3.1 min，5%～90%A，3.1～5.0 min，90%A。流速：0.3 mL/min；進(jìn)樣體積：5 μL。

1.2.4 質(zhì)譜條件 電噴霧負(fù)離子采集模式(ESI-)，多反應(yīng)監(jiān)測(cè)模式(MRM)。 毛細(xì)管電壓：3.2 kV；離子源溫度：150 ℃；去溶劑氣(N2)溫度：350 ℃，去溶劑氣流速：500 L/h，錐孔氣流速(N2)：50 L/h；碰撞氣：氬氣。數(shù)據(jù)處理軟件：MassLynx V 4.1。其它質(zhì)譜參數(shù)見(jiàn)表1。

表1 噻酮磺隆、異唑草酮及其代謝物的質(zhì)譜檢測(cè)參數(shù)Table 1 MS /MS parameters of thiencarbazone-methyl，isoxaflutole and its metabolites

*quantitative ion

2 結(jié)果與討論

2.1 液相色譜條件優(yōu)化

2.2 提取溶劑的選擇

圖1 玉米樣品中吸附劑的影響Fig.1 Influence of adsorbent in the corn sampleA.50 mg PSA；B.50 mg PSA+50 mg PC；C.50 mg PSA+50 mg C18 ；D.25 mg PSA+25 mg C18+25 mg PC；E.50 mg PSA+50 mg C18+50 mg PC

2.3 凈化吸附劑的選擇

本實(shí)驗(yàn)采用分散固相萃取作為凈化方法，其中吸附劑是決定凈化效果的關(guān)鍵因素，吸附劑需要滿(mǎn)足去除基質(zhì)中主要雜質(zhì)的同時(shí)，不吸附目標(biāo)分析物。通常分散固相萃取中常用的吸附劑有PSA、C18和PC等。其中，PSA主要去除脂肪酸、極性色素、糖類(lèi)物質(zhì)等極性基質(zhì)雜質(zhì)，C18和PC去除部分脂肪、脂溶性和色素等雜質(zhì)的能力較強(qiáng)。本實(shí)驗(yàn)對(duì)上述3種吸附劑進(jìn)行了考察。

2.4 基質(zhì)效應(yīng)

表2 4種分析物的線(xiàn)性范圍、線(xiàn)性方程、相關(guān)系數(shù)(r)及基質(zhì)效應(yīng)Table 2 Linear ranges，linear equations，correlation coefficients(r) and matrix effects(ME) for four analytes

2.5 方法性能評(píng)估

表3 玉米及土壤樣品中噻酮磺隆、異唑草酮及其代謝物的加標(biāo)回收率及相對(duì)標(biāo)準(zhǔn)偏差(RSD，n=5)Table 3 Spiked recoveries and RSDs(n=5) of thiencarbazone-methyl,isoxaflutole and its metabolites pesticides in corn and soil samples

2.6 與已有方法的比較

表4 本方法與玉米中噻酮磺隆或異唑草酮及其代謝物殘留檢測(cè)分析方法的比較Table 4 Comparison of this method with other methods for the determination of thiencarbazone-methyl，isoxaflutole and its metabolites in corn

2.7 實(shí)際樣品的分析

3 結(jié) 論

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Determination of Thiencarbazone-methyl，Isoxaflutole and their Metabolites Residues in Corn and Soil by Dispersive Solid-phase Extraction Combined with Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry

WANG Dong，YAN Si-yue，JIA Chun-hong，ZHAO Er-cheng*

(Institute of Plant Protection and Environment Protection，Beijing Academy of Agriculture and Forestry Science，Beijing 100097，China)

A new method was established for the determination of thiencarbazone-methyl，isoxaflutole and their metabolites RPA203328 and RPA202248 residues in corn and soil by dispersive solid-phase extraction(d-SPE) combined with ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS).The samples were extracted with acidified acetonitrile(containing 1% formic acid)，and acetonitrile phase was separated from sample solution through salting-out phenomenon with sodium chloride.The acetonitrile solution was cleaned up by dispersive solid-phase extraction.The analytes were determined by ultra performance liquid chromatography-tandem mass spectrometry.Factors affecting the extraction efficiency，such as type of extraction solvent，cleanup sorbent and instrumental condition，were investigated.The performance of this method was evaluated under the optimal conditions at the same time.The results indicated that the matrix effects of four target compounds in corn were more than 10%,and the matrix effects of the other three target compounds in soil were more than 10% except that for the RPA202248 was less than 10%.The calibration curves for all the analytes were linear in the range of 0.001-1.0 μg/mL with correlation coefficients of 0.994 5-0.999 5.The recoveries at spiked range of 0.005-0.1 mg/kg were in the range of 72.9%-116.5%，with relative standard deviations(n=5) of 0.75%-17.8%.The limits of quantitation were 0.005-0.01 mg/kg.With the advantage of quickness，high performance and environmental friendliness，the developed method is suitable for the determination of thiencarbazone-methyl，isoxaflutole and their metabolites residues in corn and soil.

dispersive solid-phase extraction(d-SPE)；ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS)；thiencarbazone-methyl；isoxaflutole；metabolites；pesticide residue；corn；soil

10.3969/j.issn.1004-4957.2017.03.010

2016-10-10；

2016-11-25

O657.63；TQ613.1

A

1004-4957(2017)03-0355-06

*通訊作者：趙爾成，博士，副研究員，研究方向：農(nóng)藥殘留分析，電話(huà)：010-51503438，E-mail：342126913@qq.com