HS-SPME-GC/MS同时测定污废水中多种VOCs异味物质
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摘要
采用顶空固相微萃取与气相色谱质谱联用技术(HS-SPME-GC/MS),建立了快速定量分析污废水中多种挥发性有机异味物质(VOCs)的方法.VOCs异味污染物主要为含氧有机物(OVOCs)、硫醚类(VSCs)和苯系物(BTEX)等三大类.针对不同异味物质的物化性质,实验优化了HS-SPME条件,如萃取纤维涂层、萃取温度、萃取时间、盐析效应及解析时间等.研究结果表明,DVB/CAR/PDMS (50/30μm)萃取头针对三类物质的选择性最高.同时综合各类异味物质的性质,优化顶空固相微萃取实验条件为:在水样中加入20%(W/V)的NaCl,65℃孵化条件下萃取30 min,解析180 s.所建方法的多种VOCs在其各自线性范围内线性良好,R~2均大于0.98,相对标准偏差为9.8%—15.5%,检出限为4—55 ng·L~(-1),加标回收率为79.1%—108.6%.对不同污废水进行了检测,实验结果证明,此方法可满足不同污废水中多种痕量VOCs异味物质的同时检测.
A rapid and quantitative method based on headspace-solid phase micro-extraction(HS-SPME) with gas chromatography-mass spectrometry(GC-MS) was used to analyze the volatile organic odorous substances(VOCs)produced in sewage wastewater. The studied VOCs, which mainly include OVOCs, VSCs and BTEX, are major odorous pollutants. According to the properties of different odorous substances, the conditions of the HS-SPME, such as extraction fiber coating, extraction temperature, extraction time, salting out effect and resolution time, were optimized experimentally.The results show that DVB/CAR/PDMS(50/30 μm) has the highest extraction selectivity for the VOCs.The optimal condition was obtained as follows: 20%(W/V) NaCl was added to the water sample, and the VOCs were extracted under incubation conditions at 65 ℃ for 30 min,and then analyzed for 180 s.The VOCs were found to be linear in the validated range with correction coefficients(R~2) better than 0.98.The detection limits of the method were all less than 4—55 ng·L~(-1), while the relative standard deviations(RSD) were in a range of 9.8%—15.5%, the average recovery rate was 79.1%—108.6%. This method was used to detect different sewage wastewaters. The experimental results show that the method can simultaneously identify multiple trace odor substances in different sewage wastewaters.
A rapid and quantitative method based on headspace-solid phase micro-extraction(HS-SPME) with gas chromatography-mass spectrometry(GC-MS) was used to analyze the volatile organic odorous substances(VOCs)produced in sewage wastewater. The studied VOCs, which mainly include OVOCs, VSCs and BTEX, are major odorous pollutants. According to the properties of different odorous substances, the conditions of the HS-SPME, such as extraction fiber coating, extraction temperature, extraction time, salting out effect and resolution time, were optimized experimentally.The results show that DVB/CAR/PDMS(50/30 μm) has the highest extraction selectivity for the VOCs.The optimal condition was obtained as follows: 20%(W/V) NaCl was added to the water sample, and the VOCs were extracted under incubation conditions at 65 ℃ for 30 min,and then analyzed for 180 s.The VOCs were found to be linear in the validated range with correction coefficients(R~2) better than 0.98.The detection limits of the method were all less than 4—55 ng·L~(-1), while the relative standard deviations(RSD) were in a range of 9.8%—15.5%, the average recovery rate was 79.1%—108.6%. This method was used to detect different sewage wastewaters. The experimental results show that the method can simultaneously identify multiple trace odor substances in different sewage wastewaters.
引文
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[16]SAWOSZCZUK T,SYGU?A-CHOLEWIN'SKA J,DEL HOYO-MELéNDEZ J M.The detection of active moulds on historical silk by the means of the headspace-solid phase micro-extraction-gas chromatography-mass spectrometry method[J].Textile Research Journal,2017,88(9):1013-25.
[17]张怀敏,段国锋,陈嘉,等.基于SPME-GC-MS和HS-GC-MS分析变质醋中挥发性成分[J].中国调味品,2017,42(1):31-36.ZHANG H,DUAN G,CHEN J,et al.Analysis of Volatile Components in metamorphic vinegar based on SPME-GC-MS and HS-GC-MS[J].Chinese Condiment,2017,42(1):31-36(in Chinese).
[18]刘斐,段凤魁,李海蓉,等.固相微萃取-气相色谱串联质谱法检测北京大气细颗粒物中的多环芳烃[J].分析化学,2015,43(4):540-546.LIU F,DUAN F,LI H,et al.Determination of polycyclic aromatic hydrocarbons in Beijing fine particles by solid phase microextraction-gas chromatography tandem mass spectrometry[J].Chinese Journal of Analytical Chemistry,2015,43(4):540-546(in Chinese).
[19]PAPAGEORGIOU M,LAMBROPOULOU D,MORRISON C,et al.Direct solid phase microextraction combined with gas chromatographymass spectrometry for the determination of biogenic amines in wine[J].Talanta,2018,183:276-282.
[20]LUCAIRE V,SCHWARTZ J J,DELHOMME O,et al.A sensitive method using SPME pre-concentration for the quantification of aromatic amines in indoor air[J].Anal Bioanal Chem,2018,410(7):1955-1963.
[2]KOTOWSKA U,ZALIKOWSKI M,ISIDOROV V A.HS-SPME/GC-MS analysis of volatile and semi-volatile organic compounds emitted from municipal sewage sludge[J].Environ Monit Assess,2012,184(5):2893-2907.
[3]GHADER M,SHOKOUFI N,ES-HAGHI A,et al.Headspace solid-phase microextraction(HS-SPME)combined with GC-MS as a process analytical technology(PAT)tool for monitoring the cultivation of C.tetani[J].J Chromatogr B Analyt Technol Biomed Life Sci,2018,1083:222-232.
[4]ALLARD S,CHARROIS J W,JOLL C A,et al.Simultaneous analysis of 10 trihalomethanes at nanogram per liter levels in water using solid-phase microextraction and gas chromatography mass-spectrometry[J].J Chromatogr A,2012,1238:15-21.
[5]YANG Y Q,YIN H X,YUAN H B,et al.Characterization of the volatile components in green tea by IRAE-HS-SPME/GC-MS combined with multivariate analysis[J].PLoS One,2018,13(3):e0193393.
[6]QIN Z,PANG X,CHEN D,et al.Evaluation of Chinese tea by the electronic nose and gas chromatography-mass spectrometry:Correlation with sensory properties and classification according to grade level[J].Food Research International,2013,53(2):864-874.
[7]LARA-GONZALO A,SANCHEZ-URIA J E,SEGOVIA-GARCIA E,et al.Critical comparison of automated purge and trap and solid-phase microextraction for routine determination of volatile organic compounds in drinking waters by GC-MS[J].Talanta,2008,74(5):1455-1462.
[8]黄旭锋,闫海阔,姚林江,等.吹扫捕集-快速气相色谱-质谱联用法测定水中54种挥发性有机物[J].环境工程学报,2015,9(4):2014-2020.HUANG X F,YAN H K,YAO L J,et al.Determination of 54 volatile organic compounds in water by purge and trap-fast gas chromatography-mass spectrometry[J].Journal of Environmental Engineering,2015,9(4):2014-2020(in Chinese).
[9]GUO Q,LI X,YU J,et al.Comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry for the screening of potent swampy/septic odor-causing compounds in two drinking water sources in China[J].Analytical Methods,2015,7(6):2458-2468.
[10]董军,武法伟,刘文,等.不同前处理方法对GC-MS法测定水中多种SVOCs效率的影响[J].环境监测管理与技术,2017,29(6):50-53.DONG J,WU F,LIU W,et al.Effects of different pretreatment methods on the determination of the efficiency of various SVOCs in water by GC-MS method[J].Environmental Monitoring Management and Technology,2017,29(6):50-53(in Chinese).
[11]KIM H,HONG Y,SANG B I,et al.Application of SPE followed by large-volume injection GC/MS for the analysis of geosmin and2-methylisoborneol in water[J].Analytical Methods,2015,7(16):6678-6685.
[12]CHEN Q,SONG J,BI J,et al.Characterization of volatile profile from ten different varieties of Chinese jujubes by HS-SPME/GC-MScoupled with E-nose[J].Food Res Int,2018,105:605-615.
[13]孙静,王锐,尹大强.顶空固相微萃取-气质联用法同时测定城市水源水中的九种嗅味物质[J].环境化学,2016,35(2):280-286.SUN J,WANG R,YIN D.Simultaneous determination of nine odorant substances in urban source water by headspace solid phase microextraction-mass spectrometry[J].Environmental Chemistry,2016,35(2):280-286(in Chinese).
[14]吴颖娟,陈飒,邓怡,等.HS-SPME/GC/MS法测定水中甲硫醚和二甲基三硫醚[J].中国给水排水,2017,24(33):124-127.WU Y,CHEN W,DENG Y,et al.Determination of methyl sulfide and dimethyl trisulfide in water by HS-SPME/GC/MS method[J].China Water and Wastewater,2017,24(33):124-127(in Chinese).
[15]TIAN T,YANG H,YANG F,et al.Optimization of fermentation conditions and comparison of flavor compounds for three fermented greengage wines[J].LWT.Food Science and Technolog,2018,89:542-550.
[16]SAWOSZCZUK T,SYGU?A-CHOLEWIN'SKA J,DEL HOYO-MELéNDEZ J M.The detection of active moulds on historical silk by the means of the headspace-solid phase micro-extraction-gas chromatography-mass spectrometry method[J].Textile Research Journal,2017,88(9):1013-25.
[17]张怀敏,段国锋,陈嘉,等.基于SPME-GC-MS和HS-GC-MS分析变质醋中挥发性成分[J].中国调味品,2017,42(1):31-36.ZHANG H,DUAN G,CHEN J,et al.Analysis of Volatile Components in metamorphic vinegar based on SPME-GC-MS and HS-GC-MS[J].Chinese Condiment,2017,42(1):31-36(in Chinese).
[18]刘斐,段凤魁,李海蓉,等.固相微萃取-气相色谱串联质谱法检测北京大气细颗粒物中的多环芳烃[J].分析化学,2015,43(4):540-546.LIU F,DUAN F,LI H,et al.Determination of polycyclic aromatic hydrocarbons in Beijing fine particles by solid phase microextraction-gas chromatography tandem mass spectrometry[J].Chinese Journal of Analytical Chemistry,2015,43(4):540-546(in Chinese).
[19]PAPAGEORGIOU M,LAMBROPOULOU D,MORRISON C,et al.Direct solid phase microextraction combined with gas chromatographymass spectrometry for the determination of biogenic amines in wine[J].Talanta,2018,183:276-282.
[20]LUCAIRE V,SCHWARTZ J J,DELHOMME O,et al.A sensitive method using SPME pre-concentration for the quantification of aromatic amines in indoor air[J].Anal Bioanal Chem,2018,410(7):1955-1963.
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