固相微萃取/气相色谱/质谱法测定水中12种氯苯类化合物
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摘要
建立了顶空固相微萃取/气相色谱/质谱法同时测定地表水和生活饮用水中12种氯苯类化合物的新方法。对比了不同类型萃取头的萃取效果,优化了萃取时间和温度等萃取条件。最佳试验条件为10 mL样品中加入1. 5 g氯化钠,采用65μm PDMS/DVB萃取头,在50℃下萃取25 min,并于250℃下进样口解吸5 min。该方法氯苯线性范围为0. 01～2μg/L,相关系数(r)为0. 998 5,其余氯苯类化合物线性范围均可达0. 01～10μg/L,相关系数(r)均不小于0. 999 0,检出限均为0. 002 5μg/L。纯水高、低两个浓度的加标回收率为92. 2%～106%,相对标准偏差为2. 6%～7. 6%;实际水样高、低两个浓度的加标回收率为89. 6%～110%,相对标准偏差为3. 2%～8. 7%。该方法具有操作简单、灵敏度高、线性范围宽等特点,可以满足水质检测的要求。
A new method for simultaneous determination of twelve chlorobenzenes in the surface water and drinking water by headspace solid-phase microextraction/gas chromatography/mass spectrometry was established. The extraction effects of different types of extraction fibers were compared,and the extraction conditions such as extraction time and temperature were optimized. The optimal test conditions were obtained as follows: 10 mL water sample containing 1. 5 g sodium chloride,usage of 65μm PDMS/DVB fiber,25 minutes extraction under 50 ℃,and desorption for 5 min at 250 ℃. The results indicated that the proposed method allowed the measurement of chlorobenzene over the range of 0. 01-2 μg/L with a correlation coefficient of 0. 998 5,the other chlorobenzene compounds could reach the range of 0. 01-10 μg/L,the correlation coefficients were not less than 0. 999 0 and all detection limits were 0. 002 5 μg/L. The recoveries of pure water with high and low concentrations were 92. 2% to 106%,with the relative standard deviation from 2. 6%-7. 6%; Recoveries of the actual water samples with high and low concentrations were 89. 6%-110%,with the the relative standard deviation (RSD)of 3. 2%-8. 7%. This method had the advantages such as simple operation,high sensitivity and wide linear range. It could meet the monitoring requirements of water quality detection.
A new method for simultaneous determination of twelve chlorobenzenes in the surface water and drinking water by headspace solid-phase microextraction/gas chromatography/mass spectrometry was established. The extraction effects of different types of extraction fibers were compared,and the extraction conditions such as extraction time and temperature were optimized. The optimal test conditions were obtained as follows: 10 mL water sample containing 1. 5 g sodium chloride,usage of 65μm PDMS/DVB fiber,25 minutes extraction under 50 ℃,and desorption for 5 min at 250 ℃. The results indicated that the proposed method allowed the measurement of chlorobenzene over the range of 0. 01-2 μg/L with a correlation coefficient of 0. 998 5,the other chlorobenzene compounds could reach the range of 0. 01-10 μg/L,the correlation coefficients were not less than 0. 999 0 and all detection limits were 0. 002 5 μg/L. The recoveries of pure water with high and low concentrations were 92. 2% to 106%,with the relative standard deviation from 2. 6%-7. 6%; Recoveries of the actual water samples with high and low concentrations were 89. 6%-110%,with the the relative standard deviation (RSD)of 3. 2%-8. 7%. This method had the advantages such as simple operation,high sensitivity and wide linear range. It could meet the monitoring requirements of water quality detection.
引文
[1]杨丽莉,母应锋,姚诚,等.毛细管气相色谱法测定水中氯苯类化合物[J].环境监测管理与技术,2007,19(2):34-35,38.Yang Lili,Mu Yingfeng,Yao Cheng,et al.Determination of chlorobenzenes in water by gas chromatography[J].The Administration and Technique of Environmental Monitoring,2007,19(2):34-35,38(in Chinese).
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[8]陆文娟.吹扫捕集-气相色谱质谱联用法测定地表水中6种氯苯类化合物[J].化学分析计量,2015,24(6):59-62.Lu Wenjuan.Determination of 6 kinds of chlorobenzenes compounds in surface water by purge and trap gas chromatography-mass spectrometry[J].Chemical Analysis and Meterage,2015,24(6):59-62(in Chinese).
[9]刘琳娟,吴鹏,於香湘,等.磁性分散固相萃取-气相色谱法测定水中氯苯类化合物[J].环境监测管理与技术,2014,26(4):42-44.Liu Linjuan,Wu Peng,Yu Xiangxiang,et al.Magnetic dispersive solid-phase extraction technique for the determination of chlorobenzenes in environmental water samples[J].The Administration and Technique of Environmental Monitoring,2014,26(4):42-44(in Chinese).
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[11]GB 5750.8-2006,生活饮用水标准检验方法有机物指标[S].北京:中国标准出版社,2006.GB 5750.8-2006,Standard Examination Methods for Drinking Water-Organic Parameters[S].Beijing:Standards Press of China,2006(in Chinese).
[12]HJ 621-2011,水质氯苯类化合物的测定气相色谱法[S].北京:中国环境科学出版社,2011.HJ 621-2011,Water Quality-Determination of Chlorobenzenes-Gas Chromatography[S].Beijing:China Environmental Science Press,2011(in Chinese).
[13]赖永忠.顶空固相微萃取-气相色谱-质谱法测定饮用水源水中1,3,5-三氯苯[J].理化检验:化学分册,2012,48:550-551,555.Lai Yongzhong.GC-MS determination of 1,3,5-trichlorobenzene in drinking source water with sample treatment by head-space solid phase micro-extraction[J].PTCA(Part B:Chem Anal),2012,48:550-551,555(in Chinese).
[14]黄卫,万群,符哲,等.SPME-GC同时测定地表水环境质量标准特定项目中硝基苯类和氯苯类化合物[J].中国环境监测,2011,27(3):14-16.Huang Wei,Wan Qun,Fu Zhe,et al.Simultaneously determination of nitrobenzene and chlorobenzenes compounds in specific project of surface water environmental quality standard by SPME-GC[J].Environmental Monitoring in China,2011,27(3):14-16(in Chinese).
[2]戴之希,田立勋,王国栋,等.超声辅助分散液液微萃取-气相色谱检测污泥中氯苯[J].中国环境科学,2015,35(2):471-477.Dai Zhixi,Tian Lixun,Wang Guodong,et al.Optimized ultrasonic assisted extraction dispersive liquid-liquid microextraction coupled with gas chromatographyelectron capture detector for extraction and determination of chlorobenzenes in sludge[J].China Environmental Science,2015,35(2):471-477(in Chinese).
[3]Meharg A A,Wright J,Osborn D.Chlorobenzenes in rivers draining industrial catchments[J].Sci Total Environ,2000,251/252:243-253.
[4]胡红美,郭远明,李铁军,等.静态顶空-气相色谱法测定养殖用水中11种氯苯类化合物[J].理化检验:化学分册,2015,51:25-30.Hu Hongmei,Guo Yuanming,Li Tiejun,et al.GCdetermination of 11 chlorobenzenes in aquaculture water with static headspace[J].PTCA(Part B:Chem Anal),2015,51:25-30(in Chinese).
[5]裴永强,樊占春,赵静,等.顶空固相微萃取-气相色谱法测定水中氯苯类化合物[J].环境监测管理与技术,2014,26(6):39-41,45.Pei Yongqiang,Fan Zhanchun,Zhao Jing,et al.Determination of chlorobenzenes in water by method of head space solid phase micro extraction and gas chromatography[J].The Administration and Technique of Environmental Monitoring,2014,26(6):39-41,45(in Chinese).
[6]张琦,董慧茹.固相萃取-高效液相色谱法同时测定水中的对二氯苯与六氯苯[J].分析试验室,2009,28(1):88-91.Zhang Qi,Dong Huiru.Simultaneous determination of paradichlorobenzene and hexachlorbenzen in water by solid-phase extraction and high performance liquid chromatography[J].Chinese Journal of Analysis Laboratory,2009,28(1):88-91(in Chinese).
[7]田艳,黄宁,梁柳玲,等.吹扫捕集-气相色谱质谱法测定地表水中12种氯苯类有机物[J].中国环境监测,2014,30(3):111-114.Tian Yan,Huang Ning,Liang Liuling,et al.The determination of twelve chlorobenzenes in surface water by purge and trap-GC/MS analysis[J].Environmental Monitoring in China,2014,30(3):111-114(in Chinese).
[8]陆文娟.吹扫捕集-气相色谱质谱联用法测定地表水中6种氯苯类化合物[J].化学分析计量,2015,24(6):59-62.Lu Wenjuan.Determination of 6 kinds of chlorobenzenes compounds in surface water by purge and trap gas chromatography-mass spectrometry[J].Chemical Analysis and Meterage,2015,24(6):59-62(in Chinese).
[9]刘琳娟,吴鹏,於香湘,等.磁性分散固相萃取-气相色谱法测定水中氯苯类化合物[J].环境监测管理与技术,2014,26(4):42-44.Liu Linjuan,Wu Peng,Yu Xiangxiang,et al.Magnetic dispersive solid-phase extraction technique for the determination of chlorobenzenes in environmental water samples[J].The Administration and Technique of Environmental Monitoring,2014,26(4):42-44(in Chinese).
[10]缪建军,张宝,张颖,等.液液小体积萃取GC-MS方法快速测定地表水中的氯苯类化合物[J].中国环境监测,2010,26(1):12-15.Miao Jianjun,Zhang Bao,Zhang Ying,et al.Rapid determination of chlorobenzenes in surface water by liquid-liquid small volume extraction combined with gas chromatography-mass spectrometry[J].Environmental Monitoring in China,2010,26(1):12-15(in Chinese).
[11]GB 5750.8-2006,生活饮用水标准检验方法有机物指标[S].北京:中国标准出版社,2006.GB 5750.8-2006,Standard Examination Methods for Drinking Water-Organic Parameters[S].Beijing:Standards Press of China,2006(in Chinese).
[12]HJ 621-2011,水质氯苯类化合物的测定气相色谱法[S].北京:中国环境科学出版社,2011.HJ 621-2011,Water Quality-Determination of Chlorobenzenes-Gas Chromatography[S].Beijing:China Environmental Science Press,2011(in Chinese).
[13]赖永忠.顶空固相微萃取-气相色谱-质谱法测定饮用水源水中1,3,5-三氯苯[J].理化检验:化学分册,2012,48:550-551,555.Lai Yongzhong.GC-MS determination of 1,3,5-trichlorobenzene in drinking source water with sample treatment by head-space solid phase micro-extraction[J].PTCA(Part B:Chem Anal),2012,48:550-551,555(in Chinese).
[14]黄卫,万群,符哲,等.SPME-GC同时测定地表水环境质量标准特定项目中硝基苯类和氯苯类化合物[J].中国环境监测,2011,27(3):14-16.Huang Wei,Wan Qun,Fu Zhe,et al.Simultaneously determination of nitrobenzene and chlorobenzenes compounds in specific project of surface water environmental quality standard by SPME-GC[J].Environmental Monitoring in China,2011,27(3):14-16(in Chinese).