螺旋膜固相萃取便携式SPI-TOF MS检测空气中苯系物
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摘要
室内装修造成的苯系物污染严重影响居民的生命健康。本研究设计了一种新型螺旋管状膜固相萃取进样装置,并与便携式单光子电离-飞行时间质谱仪(SPI-TOF MS)联用,用于空气中痕量苯系物的现场快速检测。螺旋的结构设计可以有效地增加管状膜的长度,在14min内即可完成苯、甲苯和二甲苯的检测,灵敏度分别提高了32.1、71.8和129.9倍,线性相关系数(R~2)均大于0.990 0,定量限(LOQ)分别低于33.3、67.8和93.6μg/m~3,能够满足国家规定的室内空气苯、甲苯和二甲苯的排放限值。重复测试8次,三者的相对标准偏差(RSD)分别为3%、1.7%和2.4%。该便携式质谱仪体积仅为(29×40×31)cm~3,质量为27kg,有望用于室内空气低浓度苯系物的现场多点快速检测。
Benzene series emitted from indoor decorating materials seriously affect people's health.In this study,an innovative helical membrane solid-phase extractioninlet was designed and coupled to a portable single photon ionization-time of flight mass spectrometry(SPI-TOF MS)for in situ and rapid detection of trace benzene series in air.A hollow fiber membrane(HFM)was applied to adsorb the benzene series,and the membrane material was polydimethylsiloxane(PDMS).In the membrane extraction device,the length of the HFM was prominently increased with the helical structural design of the HFM.The installation length of the HFM was as long as 150 cm,but the volume of the membrane extraction device was only(3.14×484×92)mm~3.The problem with traditional membrane inlet that had a small membrane area was solved.The operating parameters of the membrane extraction device were optimized,which mainly targeted for the sampling flow rate,desorption temperature and enrichment time.As a result,the optimal sampling flow rate was found to be 600 mL/min,the optimal desorption temperature was 180 ℃ and the enrichment time was selected as 5 min.Under the optimal conditions,compared with the direct capillary sampling,the detection sensitivity of the benzene,toluene and xylene were enhanced 32.1,71.8 and 129.9 folds within14 min analytical period,respectively.The concentration range of 69.6-3 482.1,82.1-4 107.1 and 94.6-4 732.1μg/m3 of the benzene,toluene and xylene standard gas were tested for quantitative analysis.As a result,the linear correlation coefficient(R2)of the three target compounds were all greater than 0.990 0.Based on the standard curves and the signal-to-noise(S/N)ratios,the limits of quantitation(LOQs,S/N=10)of the benzene,toluene and xylene were calculated as 33.3,67.8 and 93.6μg/m~3,respectively,which were much lower than the legal limit of BTX in room air.In addition,3 482.1,4 107.1 and 4 732.1μg/m~3 standard samples for benzene,toluene and xylene were tested by this system for 8 cycles while the thermal desorption processes of each cycle were tracked.The relative standard deviation(RSDs)of eight individual analytical periods for the BTX were 3%,1.7%and 2.4%,respectively,showed good repeatability.Finally,the whole system was used for analyzing laboratory air,and characteristic peaks of toluene,xylene,acetone,butanone and ethyl tert butyl ether(ETBE),et al were recognized in the mass spectrum.Based on the standard curves,the concentration of the toluene and xylene were calculated as 73.6 and 100.5μg/m~3.The size of the portable SPI-TOF MS was only(29×40×31)cm~3 with a weight of 27 kg,which was prospectively applied for in situ and multipoint rapid detection of trace benzene series in indoor air.
Benzene series emitted from indoor decorating materials seriously affect people's health.In this study,an innovative helical membrane solid-phase extractioninlet was designed and coupled to a portable single photon ionization-time of flight mass spectrometry(SPI-TOF MS)for in situ and rapid detection of trace benzene series in air.A hollow fiber membrane(HFM)was applied to adsorb the benzene series,and the membrane material was polydimethylsiloxane(PDMS).In the membrane extraction device,the length of the HFM was prominently increased with the helical structural design of the HFM.The installation length of the HFM was as long as 150 cm,but the volume of the membrane extraction device was only(3.14×484×92)mm~3.The problem with traditional membrane inlet that had a small membrane area was solved.The operating parameters of the membrane extraction device were optimized,which mainly targeted for the sampling flow rate,desorption temperature and enrichment time.As a result,the optimal sampling flow rate was found to be 600 mL/min,the optimal desorption temperature was 180 ℃ and the enrichment time was selected as 5 min.Under the optimal conditions,compared with the direct capillary sampling,the detection sensitivity of the benzene,toluene and xylene were enhanced 32.1,71.8 and 129.9 folds within14 min analytical period,respectively.The concentration range of 69.6-3 482.1,82.1-4 107.1 and 94.6-4 732.1μg/m3 of the benzene,toluene and xylene standard gas were tested for quantitative analysis.As a result,the linear correlation coefficient(R2)of the three target compounds were all greater than 0.990 0.Based on the standard curves and the signal-to-noise(S/N)ratios,the limits of quantitation(LOQs,S/N=10)of the benzene,toluene and xylene were calculated as 33.3,67.8 and 93.6μg/m~3,respectively,which were much lower than the legal limit of BTX in room air.In addition,3 482.1,4 107.1 and 4 732.1μg/m~3 standard samples for benzene,toluene and xylene were tested by this system for 8 cycles while the thermal desorption processes of each cycle were tracked.The relative standard deviation(RSDs)of eight individual analytical periods for the BTX were 3%,1.7%and 2.4%,respectively,showed good repeatability.Finally,the whole system was used for analyzing laboratory air,and characteristic peaks of toluene,xylene,acetone,butanone and ethyl tert butyl ether(ETBE),et al were recognized in the mass spectrum.Based on the standard curves,the concentration of the toluene and xylene were calculated as 73.6 and 100.5μg/m~3.The size of the portable SPI-TOF MS was only(29×40×31)cm~3 with a weight of 27 kg,which was prospectively applied for in situ and multipoint rapid detection of trace benzene series in indoor air.
引文
[1]吴鹏章,张逸,牟玉静,等.光离子色谱在室内空气苯分析中的应用[J].环境化学,2004,23(1):21-25.WU Pengzhang,ZHANG Yi,MOU Yujing,et al.The application of GC-PID to benzene analysis in indoor air[J].Environmental Chemistry,2004,23(1):21-25(in Chinese).
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[7]谭国斌,麦泽彬,喻佳俊,等.便携式飞行时间质谱仪在汽车尾气在线检测中的应用[J].质谱学报,2016,37(3):193-200.TAN Guobin,MAI Zebin,YU Jiajun,et al.Application of portable time-of-flight mass spectrometer in the online detection of vehicle exhaust[J].Journal of Chinese Mass Spectrometry Society,2016,37(3):193-200(in Chinese).
[8]CHEN P,HOU K Y,HUA L,et al.Quasitrapping chemical ionization source based on a commercial VUV lamp for time-of-flight mass spectrometry[J].Analytical Chemistry,2014,86(3):1 332-1 336.
[9]HUA L,WU Q H,HOU K Y,et al.Single photon ionization and chemical ionization combined ion source based on a vacuum ultraviolet lamp for orthogonal acceleration time-of-flight mass spectrometry[J].Analytical Chemistry,2011,83(13):5 309-5 316.
[10]JIANG J C,WANG Y,HOU K Y,et al.Photoionization-generated dibromomethane cation chemical ionization source for time-of-flight mass spectrometry and its application on sensitive detection of volatile sulfur compounds[J].Analytical Chemistry,2016,88(10):5 028-5 032.
[11]张琳,李翠萍,曹丙庆,等.现场检测质谱膜进样技术研究进展[J].分析仪器,2010,(4):1-6.ZHANG Lin,LI Cuiping,CAO Bingqing,et al.Progress of membrane introduction techniques for field detection mass spectrometry[J].Analytical Instrumentation,2010,(4):1-6(in Chinese).
[12]KETOLA R A,KOTIAHO T,CISPER M E,et al.Environmental applications of membrane introduction mass spectrometry[J].Journal of Mass Spectrometry,2002,37(5):457-476.
[13]BELL R J,SHORT R T,van AMEROM F H,et al.Calibration of an in situ membrane inlet mass spectrometer for measurements of dissolved gases and volatile organics in seawater[J].Environmental Science&Technology,2007,41(23):8 123-8 128.
[14]LAPACK M A,TOU J C,ENKE C G.Membrane mass spectrometry for the direct trace analysis of volatile organic compounds in air and water[J].Analytical Chemistry,1990,62(13):1 265-1 271.
[15]KROGH E T,GILL C G.Membrane introduction mass spectrometry(MIMS):a versatile tool for direct,real-time chemical measurements[J].Journal of Mass Spectrometry,2014,49(12):1 205-1 213.
[16]HOU K Y,LI F L,CHEN W,et al.An insource stretched membrane inlet for on-line analysis of VOCs in water with single photon ionization TOF MS[J].Analyst,2013,138(19):5 826-5 831.
[17]侯可勇,陈新华,董璨,等.快速测量挥发性有机物的膜进样-飞行时间质谱仪的设计和应用[J].高等学校化学学报,2007,28(7):1 240-1 245.HOU Keyong,CHEN Xinhua,DONG Can,et al.Design and application of membrane inlettime-of-flight mass spectrometer for rapid analysis of volatile organic compounds[J].Chemical Journal of Chinese Universities,2007,28(7):1 240-1 245(in Chinese).
[18]崔华鹏,侯可勇,吴庆浩,等.连续测量水中挥发性有机物的膜进样-单光子电离-质谱仪的研制及其应用[J].分析化学,2010,38(5):760-764.CUI Huapeng,HOU Keyong,WU Qinghao,et al.Development and application of a membrane inlet-single photon ionization-mass spectrometer for on-line analysis volatile organic compounds in water[J].Chinese Journal of Analytical Chemistry,2010,38(5):760-764(in Chinese).
[19]RAEPPEL C,APPENZELLER B M,MILLET M.Determination of seven pyrethroids biocides and their synergist in indoor air by thermaldesorption gas chromatography/mass spectrometry after sampling on Tenax TA(R)passive tubes[J].Talanta,2015,131:309-314.
[20]GARRIDO-DELGADO R,MERCADER-TREJO F,ARCE L,et al.Enhancing sensitivity and selectivity in the determination of aldehydes in olive oil by use of a Tenax TA trap coupled to a UV-ion mobility spectrometer[J].Journal of Chromatography A,2011,1 218(42):7 543-7 549.
[21]李金旭,侯可勇,赵无垛,等.磁增强光电子电离便携式飞行时间质谱仪的研制及其在挥发性还原态硫化物测量中的应用[J].分析化学,2015,43(3):444-450.LI Jinxu,HOU Keyong,ZHAO Wuduo,et al.Magnetic field enhanced photoelectron ionization source portable TOF-MS and its application in analysis of volatile reduced sulfur compounds[J].Chinese Journal of Analytical Chemistry,2015,43(3):444-450(in Chinese).
[2]HUE J,DUPOY M,BORDY T,et al.Benzene and xylene detection by absorbance in the range of 10-100ppb application:quality of indoor air[J].Sensors and Actuators B:Chemical,2013,189(2):194-198.
[3]SINHA S N,KULKARNI P K,SHAH S H,et al.Environmental monitoring of benzene and toluene produced in indoor air due to combustion of solid biomass fuels[J].The Science of the Total Environment,2006,357(11 213):280-287.
[4]GRUENKE L D,CRAIG J C,WESTER R C,et al.Quantitative analysis of benzene by selected ion monitoring/gas chromatography/mass spectrometry[J].Journal of Analytical Toxicology,1986,10(6):225-232.
[5]CHIKAMOTO T,SAKODA K.Distribution of aromatic hydrocarbons in ambient air[J].Journal of Japan Society of Air Pollution,1977,12(7):389-401.
[6]TURNER P G,DUGDALE A,YOUNG I S,et al.Portable mass spectrometry for measurement of anaesthetic agents and methane in respiratory gases[J].The Veterinary Journal,2008,177(1):36-44.
[7]谭国斌,麦泽彬,喻佳俊,等.便携式飞行时间质谱仪在汽车尾气在线检测中的应用[J].质谱学报,2016,37(3):193-200.TAN Guobin,MAI Zebin,YU Jiajun,et al.Application of portable time-of-flight mass spectrometer in the online detection of vehicle exhaust[J].Journal of Chinese Mass Spectrometry Society,2016,37(3):193-200(in Chinese).
[8]CHEN P,HOU K Y,HUA L,et al.Quasitrapping chemical ionization source based on a commercial VUV lamp for time-of-flight mass spectrometry[J].Analytical Chemistry,2014,86(3):1 332-1 336.
[9]HUA L,WU Q H,HOU K Y,et al.Single photon ionization and chemical ionization combined ion source based on a vacuum ultraviolet lamp for orthogonal acceleration time-of-flight mass spectrometry[J].Analytical Chemistry,2011,83(13):5 309-5 316.
[10]JIANG J C,WANG Y,HOU K Y,et al.Photoionization-generated dibromomethane cation chemical ionization source for time-of-flight mass spectrometry and its application on sensitive detection of volatile sulfur compounds[J].Analytical Chemistry,2016,88(10):5 028-5 032.
[11]张琳,李翠萍,曹丙庆,等.现场检测质谱膜进样技术研究进展[J].分析仪器,2010,(4):1-6.ZHANG Lin,LI Cuiping,CAO Bingqing,et al.Progress of membrane introduction techniques for field detection mass spectrometry[J].Analytical Instrumentation,2010,(4):1-6(in Chinese).
[12]KETOLA R A,KOTIAHO T,CISPER M E,et al.Environmental applications of membrane introduction mass spectrometry[J].Journal of Mass Spectrometry,2002,37(5):457-476.
[13]BELL R J,SHORT R T,van AMEROM F H,et al.Calibration of an in situ membrane inlet mass spectrometer for measurements of dissolved gases and volatile organics in seawater[J].Environmental Science&Technology,2007,41(23):8 123-8 128.
[14]LAPACK M A,TOU J C,ENKE C G.Membrane mass spectrometry for the direct trace analysis of volatile organic compounds in air and water[J].Analytical Chemistry,1990,62(13):1 265-1 271.
[15]KROGH E T,GILL C G.Membrane introduction mass spectrometry(MIMS):a versatile tool for direct,real-time chemical measurements[J].Journal of Mass Spectrometry,2014,49(12):1 205-1 213.
[16]HOU K Y,LI F L,CHEN W,et al.An insource stretched membrane inlet for on-line analysis of VOCs in water with single photon ionization TOF MS[J].Analyst,2013,138(19):5 826-5 831.
[17]侯可勇,陈新华,董璨,等.快速测量挥发性有机物的膜进样-飞行时间质谱仪的设计和应用[J].高等学校化学学报,2007,28(7):1 240-1 245.HOU Keyong,CHEN Xinhua,DONG Can,et al.Design and application of membrane inlettime-of-flight mass spectrometer for rapid analysis of volatile organic compounds[J].Chemical Journal of Chinese Universities,2007,28(7):1 240-1 245(in Chinese).
[18]崔华鹏,侯可勇,吴庆浩,等.连续测量水中挥发性有机物的膜进样-单光子电离-质谱仪的研制及其应用[J].分析化学,2010,38(5):760-764.CUI Huapeng,HOU Keyong,WU Qinghao,et al.Development and application of a membrane inlet-single photon ionization-mass spectrometer for on-line analysis volatile organic compounds in water[J].Chinese Journal of Analytical Chemistry,2010,38(5):760-764(in Chinese).
[19]RAEPPEL C,APPENZELLER B M,MILLET M.Determination of seven pyrethroids biocides and their synergist in indoor air by thermaldesorption gas chromatography/mass spectrometry after sampling on Tenax TA(R)passive tubes[J].Talanta,2015,131:309-314.
[20]GARRIDO-DELGADO R,MERCADER-TREJO F,ARCE L,et al.Enhancing sensitivity and selectivity in the determination of aldehydes in olive oil by use of a Tenax TA trap coupled to a UV-ion mobility spectrometer[J].Journal of Chromatography A,2011,1 218(42):7 543-7 549.
[21]李金旭,侯可勇,赵无垛,等.磁增强光电子电离便携式飞行时间质谱仪的研制及其在挥发性还原态硫化物测量中的应用[J].分析化学,2015,43(3):444-450.LI Jinxu,HOU Keyong,ZHAO Wuduo,et al.Magnetic field enhanced photoelectron ionization source portable TOF-MS and its application in analysis of volatile reduced sulfur compounds[J].Chinese Journal of Analytical Chemistry,2015,43(3):444-450(in Chinese).