Determination the Residues of Cyflumetofen and Its Metabolite in Plant Origin Food by Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry
摘 要
建立了超高效液相色谱-串联质谱法(UHPLC-MS/MS)测定水果、蔬菜、茶叶等植物源性食品中丁氟螨酯及其代谢物邻三氟甲基苯甲酸含量的方法。在样品4 g (茶叶1 g)中加入90%(体积分数)乙腈溶液10 mL、1 mol·L-1盐酸溶液1.0 mL、无水硫酸钠3 g和氯化钠2 g,振荡提取2 min后,离心,取上层乙腈相注入石墨化碳黑固相萃取小柱中净化,再用6 mL体积比为2:3的丙酮-甲醇的混合液洗脱,收集流出液和洗脱液,于40℃氮吹至近干,加入2 mL 40%(体积分数)乙腈溶液,过滤,取滤液进行UHPLC-MS/MS测定。以Waters ACQUITY UPLC BEH C18柱为固定相,以不同体积比的乙腈-含0.2%(体积分数)甲酸的5 mmol·L-1乙酸铵溶液的混合液为流动相对其进行梯度洗脱。质谱分析采用电喷雾正、负离子源(ESI+、ESI-)和多反应监测(MRM)模式,以基质匹配的混合标准溶液系列绘制工作曲线。结果显示:在大豆、茄子、甘蓝、西红柿、苹果、绿茶中,丁氟螨酯和邻三氟甲基苯甲酸的质量浓度在10~500 μg·L-1内与其对应的峰面积呈线性关系,丁氟螨酯和邻三氟甲基苯甲酸的检出限(3S/N)为0.1~2.9 μg·kg-1;按标准加入法对上述阴性样品进行加标回收试验,丁氟螨酯及邻三氟甲基苯甲酸的回收率为78.2%~93.0%,测定值的相对标准偏差(RSD,n=10)为2.8%~14%,再现性RSD (n=5)不大于15%。
Abstract
A method for determination of cyflumetofen and its metabolite o-trifluoromethyl benzoic acid in plant origin food (such as fruit, vegetable, tea) by UHPLC-MS/MS was established. 4 g of sample (1 g of tea sample) was extracted by oscillation in a mixture of 10 mL of 90% (φ) acetonitrile solution, 1.0 mL of 1 mol·L-1 hydrochloric acid solution, 3 g of anhydrous sodium sulfate and 2 g of sodium chloride for 2 min. After centrifuging, the upper acetonitrile phase was injected into graphitized carbon black solid phase extraction small column for purification, and 6 mL of a mixture of acetone and methanol at volume ratio of 2:3 was used for elution. The effluent and eluent were collected and blown to nearly dry by nitrogen, and 2 mL of 40% (φ) acetonitrile solution was added. After filtering, the filtrate was introduced into UHPLC-MS/MS for determination. Waters ACQUITY UPLC BEH C18 column was used as stationary phase, and a mixture of acetonitrile and 5 mmol·L-1 ammonium acetate solution containing 0.2% (φ) formic acid with different volume ratios was used as the mobile phase for gradient elution. ESI+, ESI- and MRM mode were adopted in MS/MS analysis. The working curves were drawn with the matrix matching of mixed standard solution series. It was showed that linear relationships between mass concentrations of cyflumetofen and o-trifluoromethyl benzoic acid and their peak areas were kept in the range of 10-500 μg·L-1 for sample of soybean, eggplant, cabbage, tomato, apple and green tea, with detection limits (3S/N) in the range of 0.1-2.9 μg·kg-1. Recovery test was made on above negative samples by standard addition method, giving results of cyflumetofen and o-trifluoromethyl benzoic acid in the range of 78.2%-93.0%. RSDs (n=10) of the determined values were ranged from 2.8% to 14%, and RSDs of reproducibility (n=5) were less than 15%.
中图分类号 O657.63 DOI 10.11973/lhjy-hx202201005
所属栏目 工作简报
基金项目
收稿日期 2020/6/19
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备注路蕴,讲师,研究方向为食品工程和食品分析
引用该论文: LU Yun,CAO Chunmei,WANG Anning,ZOU Xiaochuan. Determination the Residues of Cyflumetofen and Its Metabolite in Plant Origin Food by Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry[J]. Physical Testing and Chemical Analysis part B:Chemical Analysis, 2022, 58(1): 25~31
路蕴,曹春梅,王安宁,邹晓川. 超高效液相色谱-串联质谱法测定植物源性食品中丁氟螨酯及其代谢物的残留量[J]. 理化检验-化学分册, 2022, 58(1): 25~31
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参考文献
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【2】TONG Y L, XUE J, WU X B. Multi-residue pesticide determination in flos chrysanthemi by mixed mode SPE purification with GC-MS/MS analysis[J]. Analytical Letters, 2013,46(4):615-629.
【3】DENG F, XIONG B L, CHEN B S, et al. Microbial degradation of endosulfan in contaminated soil with the elution of surfactants[J]. Environmental Science and Pollution Research, 2016,23(13):13268-13275.
【4】XIONG B L, ZHOU A H, ZHENG G C, et al. Photocatalytic degradation of endosulfan in contaminated soil with the elution of surfactants[J]. Journal of Soils and Sediments, 2015,15(9):1909-1918.
【5】LEE K M, PARK S Y, LEE K, et al. Pesticide metabolite and oxidative stress in male farmers exposed to pesticide[J]. Annals of Occupational and Environmental Medicine, 2017,29:5-12.
【6】MELGAREJO M, MENDIOLA J, KOCH H M, et al. Associations between urinary organophosphate pesticide metabolite levels and reproductive parameters in men from an infertility clinic[J]. Environmental Research, 2015,137:292-298.
【7】LIU H, YAO G, LIU X, et al. Approach for pesticide residue analysis for metabolite prothioconazole-desthio in animal origin food[J]. Journal of Agricultural and Food Chemistry, 2017,65(11):2481-2487.
【8】HERNÁNDEZ F, SANCHO J V, IBÁÑEZ M, et al. Investigation of pesticide metabolites in food and water by LC-TOF-MS[J]. TrAC Trends in Analytical Chemistry, 2008,27(10):862-872.
【9】HAYASHI N, SASAMA Y, TAKAHASHI N, et al. Cyflumetofen, a novel acaricide-its mode of action and selectivity[J]. Pest Management Science, 2013,69(9):1080-1084.
【10】YOSHIDA T, IKEMI N, TAKEUCHI Y, et al. A repeated dose 90-day oral toxicity study of cyflumetofen, a novel acaricide, in rats[J]. The Journal of Toxicological Sciences, 2012,37(1):91-104.
【11】MARCIC D. Acaricides in modern management of plant-feeding mites[J]. Journal of Pest Science, 2012,85(4):395-408.
【12】国家质量监督检验检疫总局食品安全局,中国检验检疫科学研究院.日本厚生劳动省食品中农用化学品残留检测方法(增补本2)[M].北京:中国标准出版社, 2009.
【13】SONG L, HAN Y T, YANG J, et al. Rapid single-step cleanup method for analyzing 47 pesticide residues in pepper, chili peppers and its sauce product by high performance liquid and gas chromatography-tandem mass spectrometry[J]. Food Chemistry, 2019,279:237-245.
【14】HUANG Z Q, ZHANG Y, WANG L B, et al. Simultaneous determination of 103 pesticide residues in tea samples by LC-MS/MS[J]. Journal of Separation Science, 2009,32(9):1294-1301.
【15】HAMAMOTO K, IWATSUKI K, AKAMA R, et al. Rapid multiresidue determination of pesticides in livestock muscle and liver tissue via modified QuEChERS sample preparation and LC-MS/MS[J]. Food Additives & Contaminants:Part A, 2017,34(7):1162-1171.
【16】BOTERO-COY A M, MARÍN J M, IBÁÑEZ M, et al. Multi-residue determination of pesticides in tropical fruits using liquid chromatography/tandem mass spectrometry[J]. Analytical and Bioanalytical Chemistry, 2012,402(7):2287-2300.
【17】ZHANG X N, SONG Y, JIA Q, et al. Simultaneous determination of 58 pesticides and relevant metabolites in eggs with a multi-functional filter by ultra-high performance liquid chromatography-tandem mass spectrometry[J]. Journal of Chromatography A, 2019,1593:81-90.
【18】OLIVEIRA F A D S, PEREIRA E N C, GOBBI J M, et al. Multiresidue method for detection of pesticides in beef meat using liquid chromatography coupled to mass spectrometry detection (LC-MS) after QuEChERS extraction[J]. Food Additives & Contaminants:Part A, 2018,35(1):94-109.
【19】SONG S L, MA X D, LI C J. Multi-residue determination method of pesticides in leek by gel permeation chromatography and solid phase extraction followed by gas chromatography with mass spectrometric detector[J]. Food Control, 2007,18(5):448-453.
【20】LI M M, LIU X G, DONG F S, et al. Simultaneous determination of cyflumetofen and its main metabolite residues in samples of plant and animal origin using multi-walled carbon nanotubes in dispersive solid-phase extraction and ultra-high performance liquid chromatography-tandem mass spectrometry[J]. Journal of Chromatography A, 2013,1300:95-103.
【21】LI M M, LIU X G, DONG F S, et al. Determination of cyflumetofen residue in water, soil, and fruits by modified quick, easy, cheap, effective, rugged, and safe method coupled to gas chromatography/tandem mass spectrometry[J]. Journal of Separation Science, 2012,35(20):2743-2749.
【22】HU T, PENG T, LI X J, et al. Simultaneous determination of thirty non-steroidal anti-inflammatory drug residues in swine muscle by ultra-high-performance liquid chromatography with tandem mass spectrometry[J]. Journal of Chromatography A, 2012,1219:104-113.
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