单颗粒气溶胶质谱仪串联热稀释器在线测量单个气溶胶颗粒的挥发性

戴守辉等
摘要颗粒挥发性可以影响颗粒在大气中的寿命,对大气颗粒物中二次气溶胶的形成机制研究有一定的参考价值。以往研究测量颗粒挥发性采用的是热熔蚀器,其活性炭吸附器一旦老化后,在较高温度下可能会释放出活性炭,造成测量失真。本研究针对热熔蚀器的上述缺点,以稀释器替代活性炭吸附器部分,与单颗粒气溶胶质谱仪(SPAMS)连接,建立了一种在线分析单个气溶胶颗粒挥发性的测量方法。气溶胶颗粒分别通过两个通道进入SPAMS分析颗粒信息。通道1,气溶胶颗粒由管路进入加热器,被加热至不同的温度,颗粒挥发产生的气体和挥发后的颗粒内核进入稀释器部分,利用干净干燥冷的稀释气对加热挥发后的气体和颗粒进行稀释,使颗粒温度降低并短时间内不与气体发生冷凝,最后进入SPAMS进行检测。通道2为单独硅胶管,其长度与通道1相同,气溶胶颗粒通过通道2直接进入SPAMS检测。通过对比通道1和通道2获得的颗粒信息(粒径、数目和质谱信息等),得到气溶胶颗粒在不同温度下的挥发性。实验室用标准物质进行评估测试,结果表明,采用稀释器可以避免活性炭吸附器使用时间变长而失效,防止挥发性物质冷凝回到颗粒中。应用本方法初步测定了广州市春季气溶胶的挥发性,表明春季气溶胶多为高度挥发性和中度挥发性物质。
1引言
大气气溶胶颗粒对空气质量、区域和全球气候变化,以及人类健康都有重要影响\[1~3\]。挥发性是气溶胶颗粒的一个重要特性,它主要由颗粒内部物质的化学性质决定。当气溶胶被加热或被干净的空气稀释时会挥发,比如柴油动力车排放的有机化合物在低温或高浓度的情况下会优先以凝聚相存在于颗粒中,但是当排放物被稀释或加热时,这些物质则会从颗粒相中挥发出来\[4\]。颗粒挥发性会通过二次反应和干湿沉降的去除而直接影响其化学组分在大气中的寿命\[5\];Pratt等通过表征加热前后老化颗粒的化学特征,发现很多230 ℃加热后的颗粒和新鲜汽车尾气、生物质燃烧、海盐以及粉尘颗粒有相似的化学特征,表明颗粒挥发性的研究可以将高度老化的颗粒追溯至它们的初始来源\[6\],为颗粒物源解析提供参考。
颗粒挥发性可以在一定程度上反映颗粒的老化过程,对大气颗粒物中二次气溶胶的形成机制研究有一定的参考价值\[7\]。最早气溶胶挥发性的测量和分析,被称作热分馏\[8\],主要是利用颗粒中不同物质在一定温度下会快速挥发,而该特征温度与这些物质的蒸气压、沸点和蒸发焓等有密切相关\[9,10\]。挥发性的测量目前普遍采用金属加热管与活性炭吸附器串联使用,合称热熔蚀器(Thermodenuder, TD)\[11\],如图1所示,其原理是:气溶胶颗粒首先进入加热管,在不同的设定温度下,易挥发的物质从颗粒相中逃逸出来,之后进入活性炭吸附器。活性炭吸附器的作用是吸附挥发出来的气相物质,防止这部分物质在冷凝后重新和颗粒相结合。热熔蚀器通常与一些化学分析类仪器,如气溶胶质谱仪(AMS)、扫描电迁移颗粒分析仪(SMPS)、气溶胶飞行时间质谱仪(ATOFMS)等联用,可在线分析挥发性组分的化学组成及挥发后颗粒的粒径等信息 \[7,12,13\]。活性炭吸附器的另外一个作用就是使加热后的颗粒冷却,以便仪器检测。
使用热熔蚀器的缺点是一旦活性炭吸附器的吸附能力失效后,挥发物就会重新回到颗粒物中或形成新的可冷凝态\[9,14\],影响颗粒挥发性的测量。此外,活性炭吸附器可能会由于气体温度过高造成活性碳的释放,造成测量失真。本研究针对目前热熔蚀器的这些缺点,采用稀释器替代活性炭吸附器部分,与国产单颗粒气溶胶质谱仪(SPAMS)连接,建立一种在线分析气溶胶颗粒挥发性的测量方法,并对该方法进行了实验室评估和实际大气的应用。本研究可为二次气溶胶的研究提供一定的参考价值。
2LI Lei, TAN GuoBin, ZHANG Li, FU Zhong, NIAN HuiQing, HUANG ZhengXu, ZHOU Zhen, LI Mei. Chinese J. Anal. Chem., 2013, 41(12): 1831-1836
李 磊, 谭国斌, 张 莉, 傅 忠, 粘慧青, 黄正旭, 周 振, 李 梅. 分析化学, 2013, 41(12): 1831-1836
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11Huffman J A, Ziemann P J, Jayne J T, Worsnop D R, Jimenez J L. Aerosol Sci. Technol., 2008, 42(5), 395-407
12Hara K, Osada K, NishitaHara C, Yabuki M, Hayashi M, Yamanouchi T, Wada M, Shiobara M. Atmos. Chem. Phys., 2011, 11(18): 9803-9812
13Hall W A, Johnston M V. Aerosol Sci. Technol., 2012, 46(9): 983-989
14Cheng M D, Allman S E. Rev. Sci. Instrum., 2011, 82(12): 125106
15LI Mei, DONG JunGuo, HUANG ZhengXu, LI Lei, GAO Wei, NIAN HuiQing, FU Zhong, CHENG Ping, ZHOU Zhen. Chinese J. Anal. Chem., 2012, 40(6): 936-939
李 梅, 董俊国, 黄正旭, 李 磊, 高 伟, 粘慧青, 傅 忠, 程 平, 周 振. 分析化学, 2012, 40(6): 936-939
16Ishizaka Y, Adhikari M. J. Geophys. Res., 2003, 108(D4): 4138
AbstractVolatility can influence the lifetime of particles in the atmosphere, and provide useful information on the formation of secondary aerosol. The previous studies generally utilized thermodenuder (TD) to investigate the volatility behavior of particles. Using TD, semivolatile species are vaporized at different temperature, and the vaporized gas is adsorpted by activated charcoal. However, carbon might be emitted from activated charcoal under high temperature or activated charcoal ageing. In this study, a new method was developed for the measurement of particle volatility by coupling a thermodiluter system to an online single particle aerosol mass spectrometer (SPAMS). Aerosol particles were passed into two different channels, and then analyzed by SPAMS. Through Channel 1, aerosol particles were heated to different temperature by heating tube, then nonvolatile particles and volatile gas entered into the diluter. After diluting and cooling by diluent air, the nonvolatile particles were analyzed by SPAMS. Through Channel 2, aerosol particles were analyzed directly by SPAMS without the heating process. Particle volatility was obtained by comparing the information (particle size, particle number and mass spectrum) of particles through Channels 1 and 2. Laboratory tests showed that the diluter could avoid the recondensation of volatiles to the particles. This developed method was applied in the real time measurement of individual particle volatility in the spring of Guangzhou. The results showed that these particles were primarily comprised of highly volatile and moderate volatile species.
KeywordsAerosol; Single particle; Volatility; Diluter; Single particle aerosol mass spectrometer
11Huffman J A, Ziemann P J, Jayne J T, Worsnop D R, Jimenez J L. Aerosol Sci. Technol., 2008, 42(5), 395-407
12Hara K, Osada K, NishitaHara C, Yabuki M, Hayashi M, Yamanouchi T, Wada M, Shiobara M. Atmos. Chem. Phys., 2011, 11(18): 9803-9812
13Hall W A, Johnston M V. Aerosol Sci. Technol., 2012, 46(9): 983-989
14Cheng M D, Allman S E. Rev. Sci. Instrum., 2011, 82(12): 125106
15LI Mei, DONG JunGuo, HUANG ZhengXu, LI Lei, GAO Wei, NIAN HuiQing, FU Zhong, CHENG Ping, ZHOU Zhen. Chinese J. Anal. Chem., 2012, 40(6): 936-939
李 梅, 董俊国, 黄正旭, 李 磊, 高 伟, 粘慧青, 傅 忠, 程 平, 周 振. 分析化学, 2012, 40(6): 936-939
16Ishizaka Y, Adhikari M. J. Geophys. Res., 2003, 108(D4): 4138
AbstractVolatility can influence the lifetime of particles in the atmosphere, and provide useful information on the formation of secondary aerosol. The previous studies generally utilized thermodenuder (TD) to investigate the volatility behavior of particles. Using TD, semivolatile species are vaporized at different temperature, and the vaporized gas is adsorpted by activated charcoal. However, carbon might be emitted from activated charcoal under high temperature or activated charcoal ageing. In this study, a new method was developed for the measurement of particle volatility by coupling a thermodiluter system to an online single particle aerosol mass spectrometer (SPAMS). Aerosol particles were passed into two different channels, and then analyzed by SPAMS. Through Channel 1, aerosol particles were heated to different temperature by heating tube, then nonvolatile particles and volatile gas entered into the diluter. After diluting and cooling by diluent air, the nonvolatile particles were analyzed by SPAMS. Through Channel 2, aerosol particles were analyzed directly by SPAMS without the heating process. Particle volatility was obtained by comparing the information (particle size, particle number and mass spectrum) of particles through Channels 1 and 2. Laboratory tests showed that the diluter could avoid the recondensation of volatiles to the particles. This developed method was applied in the real time measurement of individual particle volatility in the spring of Guangzhou. The results showed that these particles were primarily comprised of highly volatile and moderate volatile species.
KeywordsAerosol; Single particle; Volatility; Diluter; Single particle aerosol mass spectrometer
11Huffman J A, Ziemann P J, Jayne J T, Worsnop D R, Jimenez J L. Aerosol Sci. Technol., 2008, 42(5), 395-407
12Hara K, Osada K, NishitaHara C, Yabuki M, Hayashi M, Yamanouchi T, Wada M, Shiobara M. Atmos. Chem. Phys., 2011, 11(18): 9803-9812
13Hall W A, Johnston M V. Aerosol Sci. Technol., 2012, 46(9): 983-989
14Cheng M D, Allman S E. Rev. Sci. Instrum., 2011, 82(12): 125106
15LI Mei, DONG JunGuo, HUANG ZhengXu, LI Lei, GAO Wei, NIAN HuiQing, FU Zhong, CHENG Ping, ZHOU Zhen. Chinese J. Anal. Chem., 2012, 40(6): 936-939
李 梅, 董俊国, 黄正旭, 李 磊, 高 伟, 粘慧青, 傅 忠, 程 平, 周 振. 分析化学, 2012, 40(6): 936-939
16Ishizaka Y, Adhikari M. J. Geophys. Res., 2003, 108(D4): 4138
AbstractVolatility can influence the lifetime of particles in the atmosphere, and provide useful information on the formation of secondary aerosol. The previous studies generally utilized thermodenuder (TD) to investigate the volatility behavior of particles. Using TD, semivolatile species are vaporized at different temperature, and the vaporized gas is adsorpted by activated charcoal. However, carbon might be emitted from activated charcoal under high temperature or activated charcoal ageing. In this study, a new method was developed for the measurement of particle volatility by coupling a thermodiluter system to an online single particle aerosol mass spectrometer (SPAMS). Aerosol particles were passed into two different channels, and then analyzed by SPAMS. Through Channel 1, aerosol particles were heated to different temperature by heating tube, then nonvolatile particles and volatile gas entered into the diluter. After diluting and cooling by diluent air, the nonvolatile particles were analyzed by SPAMS. Through Channel 2, aerosol particles were analyzed directly by SPAMS without the heating process. Particle volatility was obtained by comparing the information (particle size, particle number and mass spectrum) of particles through Channels 1 and 2. Laboratory tests showed that the diluter could avoid the recondensation of volatiles to the particles. This developed method was applied in the real time measurement of individual particle volatility in the spring of Guangzhou. The results showed that these particles were primarily comprised of highly volatile and moderate volatile species.
KeywordsAerosol; Single particle; Volatility; Diluter; Single particle aerosol mass spectrometer
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