Identification of Trace Carbofuran in Environmental Water by Liquid Chromatography-Tandem Mass Spectrometry
摘 要
采集水样后,立即按比例在每升水样中加入1.0 mol·L-1硝酸溶液5 mL,并于4℃温度下保存。取此水样9.0 mL,加入甲酸-乙腈(1+99)混合液1.0 mL,混匀,经0.2 μm滤膜过滤。滤液按工作条件在Shim-pack XR-ODS Ⅱ色谱柱上分离,以0.1%(体积分数)甲酸溶液-乙腈(3+7)混合液作流动相进行洗脱。洗脱液按选定条件泵入质谱离子源,在ESI+模式下,克百威的准分子离子为m/z 222.2[M+H]+,MS/MS裂解最强和次强碎片离子分别为m/z 123.0和m/z 165.1,两者的峰强比为Im/z 123.0:Im/z 165.1=100:20。选择离子对m/z 222.2/123.0和m/z 222.2/165.1作为定性分析离子对,并选择前者作为定量分析离子对。所提出的克百威的可能裂解途径采用Q Exactive高分辨质谱予以确认。在水样分析中,根据分析对象色谱分离的保留时间(2.67 min)和裂解后的碎片离子及其峰的强度比,与克百威标准溶液的结果比较,即可判定水样中是否存在克百威。定量分析的结果表明:克百威质量浓度在0.05~10.0 μg·L-1内与对应的峰面积呈线性关系,其检出限(3S/N)为0.01 μg·L-1。用标准加入法进行回收试验,测得回收率在88.4%~96.5%之间。精密度试验的结果表明:其日内相对标准偏差(n=6)在0.90%~5.6%之间,日间相对标准偏差(n=6)在1.8%~7.3%之间。
Abstract
To the water samples, after collection, 5 mL of 1.0 mol·L-1 HNO3 solution was added immediately for every liter of the sample, which should be then stored at 4℃. 9.0 mL of the sample was taken and mixed with 1.0 mL of a mixed solution of formic acid and acetonitrile (1+99). The solution was filtered through 0.2 μm filtering membrane, and the filtrate was passed through Shim-pack XR-ODS Ⅱ chromatographic column and eluted with the mobile phase of mixed solution of 0.1% (φ) formic acid solution and acetonitrile (3+7) to separate carbofuran (CF) from other co-existing impurities. The eluate was pumped to the ionic source of MS/MS under optimized condition, and under the mode of ESI+, the ion of quasi-molecule of CF,[M+H]+ m/z 222.2, was fragmented to 2 main fragmented ions of m/z 123.0 and m/z 165.1. Ratio of peak strengths of these 2 ions was Im/z 123.0:Im/z 165.1=100:20. In latter testings, the ion-pairs of m/z 222.2/123.0 and m/z 222.2/165.1 were used for qualitative analysis, and the former ion pair was used for quantitative analysis. The proposed pathway of fragmentation of CF was confirmed by Q Exactive HRMS. In the analysis of water samples, based on the data of retention time (2.67 min) and fragmented ions, as well as the ratio of the peak strengths, as given by the analyte, and by comparing with the data given by standard solution of CF, the presence or not of CF in the sample could be concluded. As shown by results of quantitative testing, linear relationship was obtained between values of peak area and mass concentration of CF in the range of 0.05 to 10.0 μg·L-1, with detection limit (3S/N) of 0.01 μg·L-1. Values of recovery found by standard addition method ranged from 88.4% to 96.5%, and values of inner-day RSDs (n=6) and inter-day RSDs (n=6) were in the ranges of 0.90%-5.6% and 1.8%-7.3% respectively.
中图分类号 O657.63 DOI 10.11973/lhjy-hx201809001
所属栏目 试验与研究
基金项目 国家自然科学基金项目(21677128);浙江省自然科学基金项目(LY16B050001,LY17B050001,LY18B050001);宁波市公益类重大专项(2015C110019)
收稿日期 2017/10/20
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联系人作者金米聪(jmcjc@163.com)
备注陈晓红,学士,主要从事理化检测新技术方面的研究
引用该论文: CHEN Xiaohong,LU Wei,SONG Zhijun,CAI Meiqiang,JIN Micong. Identification of Trace Carbofuran in Environmental Water by Liquid Chromatography-Tandem Mass Spectrometry[J]. Physical Testing and Chemical Analysis part B:Chemical Analysis, 2018, 54(9): 993~997
陈晓红,鲁伟,宋志军,蔡美强,金米聪. 液相色谱-串联质谱法确证分析环境水样中痕量克百威[J]. 理化检验-化学分册, 2018, 54(9): 993~997
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【2】CAPKIN E, ALTINOK I. Effects of chronic carbosulfan exposure on liver antioxidant enzyme activities in rainbow trout[J]. Environmental Toxicology and Pharmacology, 2013,36(1):80-87.
【3】MORENO-GONZALEZ D, HUERTAS-PEREZ J F, GAMIZ-GRACIA L, et al. Determination of carbamates at trace levels in water and cucumber by capillary liquid chromatography[J]. International Journal of Environment Analytical Chemistry, 2011,91(14):1329-1340.
【4】阳海,周硕林,尹明亮,等.克百威光催化降解动力学的研究[J].中国环境科学, 2013,33(1):82-87.
【5】宋禹,张昌朋,赵华,等.丁硫克百威、克百威和3-羟基克百威在小白菜、水稻和土壤中的分析检测方法[J].农药, 2014,53(10):739-741.
【6】方宗壮,谢艳丽,王萌,等.气相色谱-质谱法测定豇豆中丁硫克百威、克百威和3-羟基克百威的残留[J].保鲜与加工, 2016,16(5):94-99.
【7】于峰.农药克百威和丁硫克百威的质谱分析[J].质谱学报, 2000,21(3/4):63-64.
【8】潘波,林勇,姜蕾,等.丁硫克百威对水中食蚊鱼的毒性及其降解产物克百威的动态变化[J].农业环境科学学报, 2013,32(9):1764-1770.
【9】张明月,李建平,马永民,等.水中呋喃丹的柱前衍生-高效液相色谱测定法[J].环境与健康杂志, 2013,30(12):1106-1107.
【10】姚丽君,杨璐,代弟,等.液相色谱-串联质谱法同时检测蔬菜中百克威和3-羟基克百威残留[J].食品安全质量检测学报, 2017,8(4):1370-1375.
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