替代模板印迹-高效液相色谱测定空气PM2.5中的羰基化合物
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摘要
以替代模板法制备了分子印迹固相萃取柱(MISPE),该柱能够有效去除空气PM2.5样品分析过程中过量的衍生剂2,4-二硝基苯肼(2,4-DNPH),并能够大幅度浓缩样品溶液,提高羰基化合物的富集效率和监测灵敏度,缩短采样时间。与高效液相色谱联用,实现了对空气PM2.5中的羰基化合物的快速检测。本研究解决了传统固相萃取材料选择性低,不能去除2,4-DNPH干扰的瓶颈问题。本方法用于研究广州市大学城早春季节雾霾天和非霾天羰基化合物水平及其来源,结果发现无论是灰霾天气还是正常天气,14种目标羰基化合物均被检出。研究发现,在污染物排放和天气因素的影响下,灰霾天气羰基化合物总量增高,尤其是异戊醛增长迅速,并且与丙醛浓度变化呈现高度正相关。通过相关性分析,证明除了光化学反应等自然因素,人类活动对广州羰基化合物水平的干扰严重,应引起重视。
The determination of ambient carbonyls by the derivative method inevitably leads to the introduction of extra 2,4-dinitrophenylhydrazine(2,4-DNPH) into the sample solution. Traditional solid phase extraction(SPE) materials cannot remove this interference. To address this issue, a selective molecularly imprinted solid phase extraction(MISPE) column was prepared. With 2,4-dinitroaniline(2,4-DNAN) as the dummy template, MISPE could eliminate the excessive derivative agent(2,4-DNPH) in the air samples. Consequently, the sample could be concentrated effectively while the sensitivity increased greatly. By coupling MISPE and high performance liquid chromatography(HPLC), the developed method was used to study the concentration and source of 14 carbonyls of PM2.5 during spring in Guangzhou Higher Education Mega Center. Results showed that the total concentration of carbonyls increased with the level of air pollution. Particularly, the content of isovaleraldehyde increased sharply to account for 21% of the 14 total carbonyls in the haze days. Moreover, a high positive correlation between isovaleraldehyde and propionaldehyde was found either in normal days or haze days. From the correlation analysis, it was shown that anthropogenic emissions together with photochemical reaction had contributed to the abnormally high levels of carbonyls in ambient PM2.5 in the haze days. This aspect should be further investigated.
The determination of ambient carbonyls by the derivative method inevitably leads to the introduction of extra 2,4-dinitrophenylhydrazine(2,4-DNPH) into the sample solution. Traditional solid phase extraction(SPE) materials cannot remove this interference. To address this issue, a selective molecularly imprinted solid phase extraction(MISPE) column was prepared. With 2,4-dinitroaniline(2,4-DNAN) as the dummy template, MISPE could eliminate the excessive derivative agent(2,4-DNPH) in the air samples. Consequently, the sample could be concentrated effectively while the sensitivity increased greatly. By coupling MISPE and high performance liquid chromatography(HPLC), the developed method was used to study the concentration and source of 14 carbonyls of PM2.5 during spring in Guangzhou Higher Education Mega Center. Results showed that the total concentration of carbonyls increased with the level of air pollution. Particularly, the content of isovaleraldehyde increased sharply to account for 21% of the 14 total carbonyls in the haze days. Moreover, a high positive correlation between isovaleraldehyde and propionaldehyde was found either in normal days or haze days. From the correlation analysis, it was shown that anthropogenic emissions together with photochemical reaction had contributed to the abnormally high levels of carbonyls in ambient PM2.5 in the haze days. This aspect should be further investigated.
引文
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[6] Zhang Y,Zhao D,Wang B,et al.Instrum Sci Technol,2015,43(3):344
[7] Li Y,Sun H,Lai J,et al.Microchim Acta,2018,185(2):122
[8] Wang L J,Cao X M,Sun X L,et al.Chinese Journal of Chromatography,2016,34(3):240 王丽君,曹旭敏,孙晓亮,等.色谱,2016,34(3):240
[9] Liu J,Lu W H,Cui R,et al.Chinese Journal of Chromatography,2018,36(1):30 刘洁,鹿文慧,崔荣,等.色谱,2018,36(1):30
[10] Sun H,Lai J P,Fung Y S.J Chromatogr A,2014,1358(2):303
[11] Tian D T.Molecularly Imprinted Polymer Functional Material.Beijing:Science Press,2017 田大听.分子印迹聚合物功能材料.北京:科学出版社,2017
[12] Karim K,Breton F,Rouillon R,et al.Adv Drug Deliver Rev,2005,57 (12):1795
[13] Jiang C H,Wang Y J,Zheng X,et al.Research of Environmental Sciences,2016,29(9):1272 蒋朝晖,王玉娇,郑玄,等.环境科学研究,2016,29(9):1272
[14] Lü H X,Cai Q Y.Ecology and Environmental Sciences,2009,18(4):1533 吕辉雄,蔡全英.生态环境学报,2009,18(4):1533
[15] Andraca-Ayala G,Ruiz-Suarez L G.Atmosfera,2005,18(3):189
[16] Ochsenkhn K M,Lyberopoulou T,Koumarianou G,et al.Microchim Acta,2007,160(4):485
[17] Bao L F,Matsumoto M,Kubota T,et al.Atmos Environ,2012,47:546
[18] Organization W T.WHO Guidelines For Indoor Air Quality-Selected Pollutants.Geneva Switzerland:WHO Regional Office for Europe,2010
[19] Ho S S H,Ip H S S,Ho K F,et al.J Air Waste Manage,2013,63(7):864