气相色谱-静电场轨道阱高分辨质谱法测定水中16种痕量亚硝胺
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摘要
建立了固相萃取-气相色谱-静电场轨道阱高分辨质谱检测饮用水中16种痕量亚硝胺的方法。水样经固相萃取富集、氮吹定量浓缩后,用DB-35MS色谱柱分离,高分辨质谱全扫描模式检测,内标法定量。对色谱分离条件、质谱离子源温度、色谱载气流速、进样方式以及脉冲压力等参数进行优化,得到最优条件为离子源温度280℃、载气流速2.0 mL/min、脉冲不分流且脉冲压力为200 kPa。通过四因素三水平正交实验得到最佳的固相萃取条件为Chromabond HR-P萃取柱、10 mL乙酸乙酯洗脱。结果表明,本方法对于不同亚硝胺的线性范围为0.2～500μg/L,相关系数(R~2)为0.9943～0.9997,检出限(LOD)为0.05～0.5 ng/L,定量限(LOQ)为0.1～1.0 ng/L,远低于目前各国的限量水平。4个不同水平的加标回收率为72.4%～114.8%,相对标准偏差(RSD,n=6)为0.8%～9.5%。采用本方法对北京地区的12个实际水样进行测定,有5种亚硝胺被检出,含量为0.9～20.4 ng/L。本方法灵敏度和准确度高,选择性好,适用于水中痕量亚硝胺的检测。
A method for determination of 16 kinds of N-nitrosamines in drinking water was established using solid phase extraction-gas chromatography-orbitrap mass spectrometry. The water sample was extracted by solid phase extraction,concentrated by nitrogen blowing,separated by DB-35 MS column,detected by highresolution mass spectrometry,and quantified by internal standard method. The chromatographic separation conditions,such as ion source temp,carrier gas flow,injection mode and surge pressure of the method were optimized,and the optimal conditions were obtained including 280℃ of ion source temp,2. 0 mL/min of carrier gas flow,and 200 kPa of splitless and surge pressure. Based on four-factor three-level orthogonal experiment,the solid phase extraction conditions were optimized as Chromabond HR-P and 10 mL of ethyl acetate. The results showed that the limits of detection (LOD) of the analytes were 0.05-0.50 ng/L,and the limits of quantitation (LOQ) were 0.2-2.0 ng/L,which were far lower than the literature value. The linear range was 0.2-500 μg/L with correlation coefficients (R~2) of 0.9943-0.9997. The recoveries at four different spiking concentrations ranged from 72. 4% to 114. 8%,and the relative standard deviations (RSD,n = 6)ranged from 0. 8% to 9. 5%. Finally,12 actual water samples collected in Beijing were measured. Among them,five kinds of nitrosamines within 0. 9 ng/L to 20. 4 ng/L were detected. The method exhibited high sensitivity,selectivity and accuracy,and was suitable for the determination of trace nitrosamines in water.
A method for determination of 16 kinds of N-nitrosamines in drinking water was established using solid phase extraction-gas chromatography-orbitrap mass spectrometry. The water sample was extracted by solid phase extraction,concentrated by nitrogen blowing,separated by DB-35 MS column,detected by highresolution mass spectrometry,and quantified by internal standard method. The chromatographic separation conditions,such as ion source temp,carrier gas flow,injection mode and surge pressure of the method were optimized,and the optimal conditions were obtained including 280℃ of ion source temp,2. 0 mL/min of carrier gas flow,and 200 kPa of splitless and surge pressure. Based on four-factor three-level orthogonal experiment,the solid phase extraction conditions were optimized as Chromabond HR-P and 10 mL of ethyl acetate. The results showed that the limits of detection (LOD) of the analytes were 0.05-0.50 ng/L,and the limits of quantitation (LOQ) were 0.2-2.0 ng/L,which were far lower than the literature value. The linear range was 0.2-500 μg/L with correlation coefficients (R~2) of 0.9943-0.9997. The recoveries at four different spiking concentrations ranged from 72. 4% to 114. 8%,and the relative standard deviations (RSD,n = 6)ranged from 0. 8% to 9. 5%. Finally,12 actual water samples collected in Beijing were measured. Among them,five kinds of nitrosamines within 0. 9 ng/L to 20. 4 ng/L were detected. The method exhibited high sensitivity,selectivity and accuracy,and was suitable for the determination of trace nitrosamines in water.
引文
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20 U.S.Environmental Protection Agency,Method 521,Determination of Nitrosamines in Drinking Water by Solid Phase Extraction and Capillary Column Gas Chromatography with Large Volume Injection and Chemical Ionization Tandem Mass Spectrometry(MS/MS),EPA/600/R-05/054,Cincinnati,2004
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23 JIA Li-Ming,CHEN Xin,LIN Nan,ZHAO Wei,DU Ying-Qiu.Environmental Chemistry,2016,35(6):1325-1328贾立明,陈鑫,林楠,赵伟,杜英秋.环境化学,2016,35(6):1325-1328
24 Kawata K,Ibaraki T,Tanabe A,Yagoh H,Shinoda A,Suzuki H,Yasuhara A.J.Chromatogr.A,2001,911(1):75-83
25 Hung H W,Lin T F,Chiu C H,Chang Y C,Hsieh T Y.Water Air Soil Pollut.,2010,213(1-4):459-469
2 Chen W,Li X,Huang H,Zhu X,Jiang X,Zhang Y,Cen K,Zhao L,Liu X,Qi S.Chemosphere,2017,168:1400-1410
3 Boyd J M,Hrudey S E,Li X F,Richardson S D.Tr AC-Trend.Anal.Chem.,2011,30(9):1410-1421
4 Zhao Y Y,Boyd J M,Woodbeck M,Andrews R C,Qin F,Hrudey S E,Li X F.Environ.Sci.Technol.,2008,42(13):4857-4862
5 IARC.Monographson the Evaluation of the Carcinogenic Risk of Chemicals to Humans:Volume 27 Some Aromatic Amines,Anthraquinones and Nitroso Sompounds,and Inorganic Fluorides Used in Drinking Water and Dental Preparations
6 United States Environmental Protection Agency(USEPA).Integrated Risk Information System,Office of Research and Development(ORD),National Center for Environmental Assessment,2003
7 California Department of Public Health(CDPH).NDMA and Other Nitrosamines-drinking water issues.[EB/OL].[2010-11-20].http://www.cdph.ca.gov/certlic/drinkingwater/Pages/NDMA.aspx
8 Planas C,Palacios O,Ventura F,Rivera J,Caixach J.Talanta,2008,76(4):906-913
9 Raksit A,Johri S.J.AOAC Int.,2001,84(5):1413-1419
10 Krauss M,Longrée P,Dorusch F,Ort C,Hollender J.Water Res.,2009,43(17):4381-4391
11 Grebel J E,Young C C,Suffet I H.J.Chromatogr.A,2006,1117(1):11-18
12 Kodamatani H,Yamazaki S,Saito K,Amponsaa-Karikari A,Kishikawa N,Kuroda N,Tomiyasu T,Komatsu Y.J.Chromatogr.A,2009,1216(1):92-98
13 Byun M W,Ahn H J,Kim J H,Lee J W,Yook H S,Han S B.J.Chromatogr.A,2004,1054(1):403-407
14 ZHAO Zhuang,XU Yang-Biao,LIU Xiang-Hong,SHI Xiao-Guang,LU Yi-Xiang.Chinese Journal of Chromatography,2017,35(10):1086-1093赵庄,许杨彪,刘向红,施晓光,鲁毅翔.色谱,2017,35(10):1086-1093
15 HJ 809-2016,Water Quality-Determination of Nitrosamine Compounds-Gas Chromatography.Environmental Protection Standard of the People's Republic of China水质亚硝胺类化合物的测定气相色谱法.中华人民共和国国家环境保护标准.HJ 809-2016
16 Fan C C,Lin T F.Chemosphere,2018,200:48-56
17 Fu S C,Tzing S H,Chen H C,Wang Y C,Ding W H.Anal.Bioanal.Chem.,2012,402(6):2209-2216
18 Mcdonald J A,Harden N B,Nghiem L D,Khan S J.Talanta,2012,99(18):146-154
19 Zhao Y Y,Boyd J,Hrudey S E,Li X F.Environ.Sci.Technol.,2006,40(24):7636-7641
20 U.S.Environmental Protection Agency,Method 521,Determination of Nitrosamines in Drinking Water by Solid Phase Extraction and Capillary Column Gas Chromatography with Large Volume Injection and Chemical Ionization Tandem Mass Spectrometry(MS/MS),EPA/600/R-05/054,Cincinnati,2004
21 LI Pi,BAI Hua,LI Hai-Yu,CHEN Ming,LV Qing,ZHANG Qing.Chinese Journal of Chromatography,2014,32(1):81-88李丕,白桦,李海玉,陈明,吕庆,张庆.色谱,2014,32(1):81-88
22 Pozzi R,Bocchini P,Pinelli F,Galletti G C.J.Chromatogr.A,2011,1218(14):1808-1814
23 JIA Li-Ming,CHEN Xin,LIN Nan,ZHAO Wei,DU Ying-Qiu.Environmental Chemistry,2016,35(6):1325-1328贾立明,陈鑫,林楠,赵伟,杜英秋.环境化学,2016,35(6):1325-1328
24 Kawata K,Ibaraki T,Tanabe A,Yagoh H,Shinoda A,Suzuki H,Yasuhara A.J.Chromatogr.A,2001,911(1):75-83
25 Hung H W,Lin T F,Chiu C H,Chang Y C,Hsieh T Y.Water Air Soil Pollut.,2010,213(1-4):459-469