高效液相色谱法测定环境空气醛酮类化合物

司利国; 邢冠华; 王超; 谭丽; 陈烨; 于建钊; 刘方; 袁懋

doi:10.7524/j.issn.0254-6108.2019021202

环境化学

高效液相色谱法测定环境空气醛酮类化合物

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司利国, 邢冠华, 王超, 谭丽, 陈烨, 于建钊, 刘方, 袁懋. 高效液相色谱法测定环境空气醛酮类化合物[J]. 环境化学, 2019, (10): 2222-2228. doi: 10.7524/j.issn.0254-6108.2019021202

引用本文:

SI Liguo, XING Guanhua, WANG Chao, TAN Li, CHEN Ye, YU Jianzhao, LIU Fang, YUAN Mao. Determination of aldehydes and ketones in ambient air using adsorbent cartridge followed by high performance liquid chromatography[J]. Environmental Chemistry, 2019, (10): 2222-2228. doi: 10.7524/j.issn.0254-6108.2019021202

Citation:

SI Liguo, XING Guanhua, WANG Chao, TAN Li, CHEN Ye, YU Jianzhao, LIU Fang, YUAN Mao. Determination of aldehydes and ketones in ambient air using adsorbent cartridge followed by high performance liquid chromatography[J]. Environmental Chemistry, 2019, (10): 2222-2228. doi: 10.7524/j.issn.0254-6108.2019021202

高效液相色谱法测定环境空气醛酮类化合物

1. 银川市环境监测站, 银川, 750001;
2. 中国环境监测总站, 北京, 100012

通讯作者: 邢冠华, E-mail: xinggh@cnemc.cn ;

基金项目:
国家重点研发计划（2017YFC0212700）资助.

Determination of aldehydes and ketones in ambient air using adsorbent cartridge followed by high performance liquid chromatography

1. Yinchuan Environmental Monitoring Centre, Yinchuan, 750001, China;
2. China National Environmental Monitoring Centre, Beijing, 100012, China

Corresponding author: XING Guanhua, xinggh@cnemc.cn ;

Fund Project: Supported by National Key R&D Program of China (2017YFC0212700).

摘要: 使用涂渍2，4-二硝基苯肼（DNPH）硅胶填充管采集环境空气中醛酮类化合物，通过高效液相色谱法检测其衍生物是一种非常经典的测定醛酮类化合物方法.然而，在此方法的广泛应用过程中，其在定性定量中的诸多问题如吸附管空白值的影响、不饱和醛酮进一步聚合的影响等却常常被忽视.本文主要研究了不同DNPH吸附柱中醛酮化合物的本底值对准确定量的影响，以及选择合适的采样体积减小采样管本底值对定量的影响；重点探讨了丙烯醛和丁烯醛两类不饱和醛的腙类衍生物在DNPH管中的稳定性，以及其腙类衍生物与DNPH进一步生成聚合物对定量的影响.通过对其衍生物在不同吸附管中聚合反应动力学试验，发现使用盐酸催化的吸附管中聚合反应要比使用磷酸催化慢得多.最后确定选择使用盐酸作为催化剂的吸附管，采样后及时解吸，采样至解吸完成时间控制在6 h以内，可有效降低聚合产物对丙烯醛和丁烯醛准确定量的影响.
- 高效液相色谱 /
- 环境空气 /
- 醛酮类化合物
Abstract: The classical method for the determination of carbonyls (aldehydes and ketones) in ambient air was conducted by using 2,4-dinitrophenylhydrazine (DNPH)-coated sorbent cartridge to collect samples. The samples were then analyzed by high performance liquid chromatography. Although this method has been used widely, there are still some drawbacks, eg, the interferences of the background levels of DNPH-cartridges, and the by-products from further reaction on carbonyl-DNP-hydrazone of unsaturated carbonyls with DNPH. This study intends to examine the background levels of three DNPH-cartridges and find an approach to avoid these effects on accurate quantification. The stability of hydrazone derivatives of unsaturated aldehydes, such as acrolein-DNP-hydrazone and crotonaldehyde-DNP-hydrazone, in DNPH-coated cartridge, as well as the effects of their polymerization by-products from the further reaction of hydrazone with DNPH on the quantification. The polymerization of the derivatives in three types of DNPH-coated cartridges purchased from different manufactures was also investigated. It was found that polymerization reaction catalyzed by hydrochloric acid in cartridges was slower than that catalyzed by phosphoric acid. The influence of polymerization products on the accurate quantitation could be reduced, when a hydrochloric acidified DNPH- coated cartridge was used and the sample collection and desorption was conducted within 6 h.
- high performance liquid chromatography (HPLC) /
- ambient air /
- carbonyls

[1]	World Health Organization (WHO),. Acrolein. Environmental Health Criteria 127[M].Geneva:World Health Organization, 1992.
[2]	U.S.EPA. Health and Environmental Effects Profile for Formaldehyde:EPA/600/x-85/362[R]. Cincinnati:Environmental Criteria and Assessment Office, Office of Health and Environmental Assessment, Office of Research and Development, 1988.
[3]	CHRISTENSEN C S, SKOV H, NIELSEN T, et al. Temporal variation of carbonyl compound concentrations at a semi-rural site in Denmark[J]. Atmospheric Environment, 2000, 34(2):287-296.
[4]	NORDMAN H, KESKINEN H, TUPPURAINEN M. Formaldehyde asthma-rare or overlooked[J]. Journal of Allergy and Clinical Immunology, 1985, 75(1):91-99.
[5]	KERNS W D, PAVKOA K L, DONOFRIO D J, et al. Carcinogenicity of formaldehyde in rats and mice after long-term inhalation exposure[J]. Cancer Res, 1983, 43(9):4382-4392.
[6]	FENG Z H, HU W W, HU Y, et al. Acrolein is a major cigarette-related lung cancer agent preferential binding at p53 mutational hotspots and inhibi-tion of DNA repair[J]. Proceedings of the National Academy of Sciences of the United States of America, 2006, 103:15404-15409.
[7]	国家环保总局.空气和废气监测和分析方法[M].北京:环境科学出版社, 2003. State Environmental Protection Administration. Monitoring and Analytical Methods of Air and Exhaust Gas[M]. Beijing:Environmental Science Press, 2003(in Chinese).
[8]	杜世娟,陈志凌,李月琪,等.GC-FID-MS法手工监测环境空气中117种VOCs污染物[C]. 2018全国VOCs监测与治理高峰论坛论文集, 2018. DU S J,CHEN Z L,LI Y Q, et al. Manual monitoring method of 117 kinds of VOCs by GC-FID-MS[C]. 2018 National VOCs Monitoring and Governance Summit Forum Papers Collection, 2018 (in Chinese).
[9]	刘绿叶,袁斌,金燕. 采用Carbonyl色谱柱超高效液相色谱法分析13种醛酮化合物[J]. 环境化学,2013, 32(4):715-716. LIU L Y, YUAN B, JIN Y. Analysis of 13 aldehydes and ketones by carbonyl column ultra high performance liquid chromatography[J]. Environmental Chemistry, 2013, 32(4):715-716(in Chinese).
[10]	Method for the determination of aldehydes and ketones in ambient air using high performance liquid chromatography (HPLC):Compendium Method TO-5 in Compendium of Methods for the Dete rmination of Toxic Organic Compounds in Ambient Air[S]. U.S. Environmental Protection Agency:Washington DC, 1984.
[11]	Determination of Formaldehyde in Ambient Air Using Absorbent Cartridge Followed by High Performance Liquid Chromato-graphy (HPLC)[active sampling methodology]:Compendium Method TO-11 A in Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air[S]. U.S. Environmental Protection Agency:Washington DC, 1999.
[12]	U.S.EPA. Determination of Formaldehyde in Ambient Air Using Absorbent Cartridge Followed by High Performance Liquid Chromatography (HPLC)[active sampling methodology]:Compendium Method TO-11 A in Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air[S]:Washington, DC, U.S. Environmental Protection Agency,2016.
[13]	GROSJEAN E, GROSJEAN D, FRASER M P, et al. Air quality model evaluation data for organics. 2. C1-C14 carbonyls in Los Angeles air[J]. Environmental Science and Technology, 1996, 30(9):2687-2703.
[14]	UCHIYAMA S, ANDO M, AOYAGI S. Isomerization of aldehyde-2,4-dinitrophenylhydrazone derivatives and validation of high-performance liquid chromatographic analysis[J]. Journal of Chromatography A, 2003, 996(1):95-102.
[15]	JASON S, FAN Z H. PAUL J, et al. Low acetaldehyde collection efficiencies for 24-hour sampling with 2,4-dinitrophenylhydrazine (DNPH)-coated solid sorbents[J]. Environmental Science and Technology, 2007, 41(2):580-585.
[16]	HO S S H, HO K F, LIU W D, et al. Unsuitability of using the DNPH-coated solid sorbent cartridge for determination of airborne unsaturated carbonyls[J]. Atmospheric Environment, 2011, 45(1):261-265.
[17]	霍茵,邱雄雄,詹松,等.超高效液相色谱法测定空气中13种醛酮类化合物[J], 环境化学,2013, 30(9):1823-1825. HUO Y, QIU X X, ZHAN S, et al. Determination of 13 aldehydes and ketones in air by ultra high performance liquid chromatography[J], Environmental Chemistry, 2013, 30(9):1823-1825(in Chinese).
[18]	范智超,王斐,何莹,等. 环境空气中多种羰基化合物的测定[J].环境监测与管理技术,2018,30(2):43-45. FAN Z C, WANG F, HE Y, et al. Simultaneous determination of multiple carbonyl compounds in ambient air[J]. The Administration and Technique of Environmental Monitoring, 2018, 30(2):43-45(in Chinese).
[19]	胡平,文晟,魏世龙,等.广州万顷沙大气中醛酮类化合物的污染特征于来源分析[J]. 生态环境学报,2010, 19(6):1387-1391. HU P, WEN S, WEI S L, et al. Character of carbonyl compounds and their source in Guangzhou Wanqingsha atmosphere[J]. Ecology and Environmental Sciences, 2010, 19(6):1387-1391(in Chinese).
[20]	SCHULTE L R, LINDAHL R, LEVIN J O, et al. Characterization of chemical interferences in the determination of unsaturated aldehydes using aromatic hydrazine reagents and liquid chromatography[J]. Journal of Environmental Monitoring, 2001, 3(3):306-310.

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高效液相色谱法测定环境空气醛酮类化合物

通讯作者: 邢冠华, E-mail: xinggh@cnemc.cn ;

1. 银川市环境监测站, 银川, 750001;
2. 中国环境监测总站, 北京, 100012

收稿日期: 2019-02-12

基金项目:

国家重点研发计划（2017YFC0212700）资助.

关键词:

摘要: 使用涂渍2，4-二硝基苯肼（DNPH）硅胶填充管采集环境空气中醛酮类化合物，通过高效液相色谱法检测其衍生物是一种非常经典的测定醛酮类化合物方法.然而，在此方法的广泛应用过程中，其在定性定量中的诸多问题如吸附管空白值的影响、不饱和醛酮进一步聚合的影响等却常常被忽视.本文主要研究了不同DNPH吸附柱中醛酮化合物的本底值对准确定量的影响，以及选择合适的采样体积减小采样管本底值对定量的影响；重点探讨了丙烯醛和丁烯醛两类不饱和醛的腙类衍生物在DNPH管中的稳定性，以及其腙类衍生物与DNPH进一步生成聚合物对定量的影响.通过对其衍生物在不同吸附管中聚合反应动力学试验，发现使用盐酸催化的吸附管中聚合反应要比使用磷酸催化慢得多.最后确定选择使用盐酸作为催化剂的吸附管，采样后及时解吸，采样至解吸完成时间控制在6 h以内，可有效降低聚合产物对丙烯醛和丁烯醛准确定量的影响.

English Abstract

Determination of aldehydes and ketones in ambient air using adsorbent cartridge followed by high performance liquid chromatography

Corresponding author: XING Guanhua, xinggh@cnemc.cn ;

1. Yinchuan Environmental Monitoring Centre, Yinchuan, 750001, China;
2. China National Environmental Monitoring Centre, Beijing, 100012, China

Received Date: 2019-02-12

Fund Project: Supported by National Key R&D Program of China (2017YFC0212700).

Keywords:

high performance liquid chromatography (HPLC) /
ambient air /
carbonyls

Abstract: The classical method for the determination of carbonyls (aldehydes and ketones) in ambient air was conducted by using 2,4-dinitrophenylhydrazine (DNPH)-coated sorbent cartridge to collect samples. The samples were then analyzed by high performance liquid chromatography. Although this method has been used widely, there are still some drawbacks, eg, the interferences of the background levels of DNPH-cartridges, and the by-products from further reaction on carbonyl-DNP-hydrazone of unsaturated carbonyls with DNPH. This study intends to examine the background levels of three DNPH-cartridges and find an approach to avoid these effects on accurate quantification. The stability of hydrazone derivatives of unsaturated aldehydes, such as acrolein-DNP-hydrazone and crotonaldehyde-DNP-hydrazone, in DNPH-coated cartridge, as well as the effects of their polymerization by-products from the further reaction of hydrazone with DNPH on the quantification. The polymerization of the derivatives in three types of DNPH-coated cartridges purchased from different manufactures was also investigated. It was found that polymerization reaction catalyzed by hydrochloric acid in cartridges was slower than that catalyzed by phosphoric acid. The influence of polymerization products on the accurate quantitation could be reduced, when a hydrochloric acidified DNPH- coated cartridge was used and the sample collection and desorption was conducted within 6 h.