环境空气中醛酮类化合物检测方法优化与初步应用
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摘要
环境空气中的醛酮类化合物是当今大气环境科学领域的研究热点.醛酮类化合物因反应活性较高、性质不稳定,导致检测较为困难.为准确测定环境空气中的醛酮类化合物,针对环境空气中质量浓度较高或活性较强的18种醛酮类化合物的采样和分析方法进行研究,并采用优化的方法于2018年5月对北京市典型城区环境空气中的醛酮类化合物进行了检测.结果表明:①与手动采样器同时同地点采样数据相比,自行制作的醛酮类化合物自动采样器能够实现连续采样,数据基本一致(R2为0. 999 7),其采样流速最大不超过0. 8 L/min;醛酮类化合物采样管中杂质含量最高的乙醛为0. 01μg/管,小于我国HJ 683—2014《环境空气醛、酮类化合物的测定高效液相色谱法》标准限值(0. 10μg/管).②采用所确定的二醛类化合物衍生化方法与质谱扫描条件可以成功检测乙二醛和甲基乙二醛两种二醛类化合物,建立了18种醛酮类化合物的标准曲线且标准曲线相关系数R2均大于0. 995 0.③采用该优化方法得到北京市典型城区环境空气中18种醛酮类化合物质量浓度的日变化范围为17. 73～88. 42μg/m3.
The ambient carbonyl compounds have become one of the research hotspots in atmospheric environment. Carbonyl compounds are difficult to detect because of their relatively higher reactivity and chemical instability. In order to detect ambient carbonyl and dicarbonyl compounds accurately,the sampling and analysis methods of 18 kinds of carbonyl and dicarbonyl compounds with relatively higher concentration or higher reactivity in ambient air were investigated and the optimized methods were applied to study the pollution characteristics of ambient carbonyl compounds in the typical urban area in Beijing in May 2018. The results showed that:(1) The automated multi-port sampler can collect sample continuously,under the same sampling conditions compared with the single-port sampler,the collected data had no obvious difference(R2= 0. 9997),and the maximum sampling flow rate was set to be 0. 8 L/min. The highest impurity content in the sampling tube was 0. 01 μg for one DNPH-cartridge,which was less than the standard limit of 0. 10 μg for one DNPH-cartridge(HJ 683-2014 Ambient Air-Determination of Aldehyde and Ketone Compounds-High Performance Liquid Chromatography).(2) Two dicarbonyl compounds which are glyoxal and methyl glyoxal could be successfully detected by adopting the determined derivatization method of dicarbonyl compounds and the corresponding mass spectrometry scanning conditions; The standard curves of 18 kinds of carbonyl compounds were established and the correlation coefficients R2 of the standard curves were higher than 0. 9950.(3) The mass concentrations of 18 carbonyl compounds in the ambient of the typical area in Beijing in this study period were 17. 73-88. 42 μg/m3.
The ambient carbonyl compounds have become one of the research hotspots in atmospheric environment. Carbonyl compounds are difficult to detect because of their relatively higher reactivity and chemical instability. In order to detect ambient carbonyl and dicarbonyl compounds accurately,the sampling and analysis methods of 18 kinds of carbonyl and dicarbonyl compounds with relatively higher concentration or higher reactivity in ambient air were investigated and the optimized methods were applied to study the pollution characteristics of ambient carbonyl compounds in the typical urban area in Beijing in May 2018. The results showed that:(1) The automated multi-port sampler can collect sample continuously,under the same sampling conditions compared with the single-port sampler,the collected data had no obvious difference(R2= 0. 9997),and the maximum sampling flow rate was set to be 0. 8 L/min. The highest impurity content in the sampling tube was 0. 01 μg for one DNPH-cartridge,which was less than the standard limit of 0. 10 μg for one DNPH-cartridge(HJ 683-2014 Ambient Air-Determination of Aldehyde and Ketone Compounds-High Performance Liquid Chromatography).(2) Two dicarbonyl compounds which are glyoxal and methyl glyoxal could be successfully detected by adopting the determined derivatization method of dicarbonyl compounds and the corresponding mass spectrometry scanning conditions; The standard curves of 18 kinds of carbonyl compounds were established and the correlation coefficients R2 of the standard curves were higher than 0. 9950.(3) The mass concentrations of 18 carbonyl compounds in the ambient of the typical area in Beijing in this study period were 17. 73-88. 42 μg/m3.
引文
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[14] ATKINSON R,AREY J.Atmospheric degradation of volatile organic compounds[J].Chemical Reviews,2003,103(12):4605-4638.
[15]环境保护部.HJ 683—2014环境空气醛、酮类化合物的测定高效液相色谱法[S].北京:中国环境科学出版社,2014.
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[18] YUAN Bin,KOSS A R,WARNEKE C,et al. Proton-transferreaction mass spectrometry:applications in atmospheric sciences[J].Chemical Reviews,2017,117(21):13187-13229.
[19] CUI Long,ZHANG Zhou,HUANG Yu,et al.Measuring OVOCs and VOCs by PTR-MS in an urban roadside microenvironment of Hong Kong:relative humidity and temperature dependence,and field intercomparisons[J].Atmospheric Measurement Techniques,2016,9(12):5763-5779.
[20] JENKIN M E,YOUNG J C,RICKARD A R. The MCM v3. 3. 1degradation scheme for isoprene[J]. Atmospheric Chemistry Physics,2015,15(20):11433-11459.
[21] KOMENDA M,SCHAUB A,KOPPMANN R. Description and characterization of an on-line system for long-term measurements of isoprene,methyl vinyl ketone,and methacrolein in ambient air[J].Journal of Chromatography A,2003,995(1/2):185-201.
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[23] FU T M,JACOB D J,WITTROCK F,et al. Global budgets of atmospheric glyoxal and methylglyoxal,and implications for formation of secondary organic aerosols[J]. Journal of Geophysical Research:Atmospheres,2008.doi:10.1029/2007JD009505.
[24]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与来源分析[J].生态环境学报,2010,19(6):1387-1391.HU Ping,WEN Sheng,WEI Shilong,et al. Character of carbonyl compounds and their source in Guangzhou Wanqingsha atmosphere[J]. Ecology and Environmental Sciences,2010,19(6):1387-1391.
[25]彭华.城市大气环境中醛酮类化合物污染状况及变化规律[J].环境监测管理与技术,2011,23(1):39-41.PENG Hua.Research on aldehydes and ketones pollutants in urban air[J]. The Administration and Technique of Environmental Monitoring,2011,23(1):39-41.
[26]张丽.高效液相色谱法分析空气污染物中的醛和酮[J].环境科技,2011,24(2):60-62.ZHANG Li.Determination of aldehydes and ketones in air pollutants by HPLC[J]. Environmental Science and Technology(China),2011,24(2):60-62.
[27]朱鸭梅,崔群,王海燕.高效液相色谱法测定乙醛溶液中的乙二醛和乙醛酸[J].色谱,2010,28(1):59-63.ZHU Yamei,CUI Qun,WANG Haiyan,Determination of glyoxal and glyoxalic acid in aldehyde solution by high performance liquid chromatography[J]. Chinese Journal of Chromatography,2010,28(1):59-63.
[28]中华全国合作供销总社.GH/T 1109—2015蜂蜜中丙酮醛含量的测定高效液相色谱法[S].北京:中华全国合作供销总社,2015.
[29]牟翠翠,冯艳丽,翟金清,等. 2,4-二硝基苯肼衍生-高效液相色谱测定大气细粒子中二羰基类化合物[J].分析化学,2010,38(11):1573-1577.MU Cuicui,FENG Yanli,ZHAI Jinqing,et al. Determination of dicarbonyl compounds in ambient fine particles by high performance liquid chromatography after 2, 4-dinitrophenylhydrazine derivatization[J]. Chinese Journal of Analytical Chemistry,2010,38(11):1573-1577.
[30] SMIRNOV R S,SMOLENKOV A D,BOLOTNIK T A,et al.Precolumn derivatization with glyoxal as a new approach to the highly sensitive HPLC-UV determination of unsymmetrical dimethylhydrazine[J]. Journal of Analytical Chemistry,2013,68(9):837-844.
[31]国家质量监督检验检疫总局.GH/T 4946—2008气相色谱法术语[S].北京:中国标准出版社,2008.
[32] ZHANG Hao,LI Hong,ZHANG Qingzhu,et al.Atmospheric volatile organic compounds in a typical urban area of Beijing:pollution characterization,health risk assessment and source apportionment[J].Atmosphere,2017,8(3):1-29.
[33]王琴,邵敏,魏强,等.北京及周边地区大气羰基化合物的时空分布特征初探[J].环境科学,2011,32(12):3522-3530.WANG Qin,SHAO Min,WEI Qiang,et al. Spatial and temporal variations of ambient carbonyl compounds in Beijing and its surrounding areas[J]. Environmental Science,2011,32(12):3522-3530.
[34]蒋朝晖,王玉娇,郑玄,等.张家界森林大气中醛酮类化合物浓度变化特征[J].环境科学研究,2016,29(9):1272-1278.JIANG Zhaohui,WANG Yujiao,ZHENG Xuan,et al. Variation characteristics of atmospheric carbonyl compounds in Zhangjiajie forest[J].Research of Environmental Sciences,2016,29(9):1272-1278.
[2] ZHANG Yujie,MU Yujing,PENG Liang,et al.Atmospheric BTEX and carbonyls during summer seasons of 2008-2010 in Beijing[J].Atmospheric Environment,2012,59(9):186-191.
[3] VOLKAMER R,SHEEHY P,MOLINA L T,et al. Oxidative capacity of the Mexico City atmosphere:part 1. a radical source perspective[J]. Atmospheric Chemistry and Physics,2010,10(14):6969-6991.
[4] HOFZUMAHAUS A,ROHRER F,LU K,et al.Amplified trace gas removal in the troposphere[J]. Science,2009,324(5935):1702-1704.
[5] SEINFELD J H,PANDIS S N.Atmospheric chemistry and physics:from air pollution to climate change[M]. 3rd ed. Hoboken,New Jersey,US:John Wiley&Sons Press,2016:48-52.
[6] KOPPMANN R. Volatile organic compounds in the atmosphere[M].Oxford,England:Blackwell Press,2007:513-514.
[7]唐孝炎,张远航,邵敏.大气环境化学[M].2版.北京:高等教育出版社,2006:115-118.
[8] YANG Xue,XUE Likun,WANG Tao,et al. Observations and explicit modeling of summertime carbonyl formation in Beijing:identification of key precursor species and their impact on atmospheric oxidation chemistry[J]. Journal of Geophysical Research:Atmospheres,2018,123:1426-1440.
[9] MONKS P S,GRANIER C,FUZZI S,et al. Atmospheric composition change-global and regional air quality[J].Atmospheric Environment,2009,43(33):5268-5350.
[10] ZHANG Renyi,WANG Gehui,GUO Song,et al.Formation of urban fine particulate matter[J]. Chemical Reviews,2015,115(10):3803-3855.
[11] HO K F,HO S S H,HUANG R J,et al.Spatiotemporal distribution of carbonyl compounds in China[J].Environmental Pollution,2015(197):316-324.
[12] LUECKEN D J,NAPELENOK S L,STRUM M,et al.Sensitivity of ambient atmospheric formaldehyde and ozone to precursor species and source types across the United States[J]. Environmental Science&Technology,2018,52(8):4668-4675.
[13] WANG Bo,LEE S C,HO K F. Characteristics of carbonyls:concentrations and source strengths for indoor and outdoor residential microenvironments in China[J]. Atmospheric Environment,2007,41(13):2851-2861.
[14] ATKINSON R,AREY J.Atmospheric degradation of volatile organic compounds[J].Chemical Reviews,2003,103(12):4605-4638.
[15]环境保护部.HJ 683—2014环境空气醛、酮类化合物的测定高效液相色谱法[S].北京:中国环境科学出版社,2014.
[16] US EPA. Compendium method TO-11A determination of formaldehyde in ambient air using adsorbent cartridge followed by high performance liquid chromatography(HPLC):active sampling methodology[S]. Cincinnati:Center for Environmental Research Information Office of Research and Development,1999.
[17]环境保护部.HJ 759—2015环境空气挥发性有机物的测定罐采样/气相色谱-质谱法[S].北京:中国环境科学出版社,2015.
[18] YUAN Bin,KOSS A R,WARNEKE C,et al. Proton-transferreaction mass spectrometry:applications in atmospheric sciences[J].Chemical Reviews,2017,117(21):13187-13229.
[19] CUI Long,ZHANG Zhou,HUANG Yu,et al.Measuring OVOCs and VOCs by PTR-MS in an urban roadside microenvironment of Hong Kong:relative humidity and temperature dependence,and field intercomparisons[J].Atmospheric Measurement Techniques,2016,9(12):5763-5779.
[20] JENKIN M E,YOUNG J C,RICKARD A R. The MCM v3. 3. 1degradation scheme for isoprene[J]. Atmospheric Chemistry Physics,2015,15(20):11433-11459.
[21] KOMENDA M,SCHAUB A,KOPPMANN R. Description and characterization of an on-line system for long-term measurements of isoprene,methyl vinyl ketone,and methacrolein in ambient air[J].Journal of Chromatography A,2003,995(1/2):185-201.
[22] SURRATT J D,CHAN A W H,EDDINGSAAS N C,et al.Reactive intermediates revealed in secondary organic aerosol formation from isoprene[J]. Proceedings of the National Academy of Sciences,2010,107(15):6640-6645.
[23] FU T M,JACOB D J,WITTROCK F,et al. Global budgets of atmospheric glyoxal and methylglyoxal,and implications for formation of secondary organic aerosols[J]. Journal of Geophysical Research:Atmospheres,2008.doi:10.1029/2007JD009505.
[24]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与来源分析[J].生态环境学报,2010,19(6):1387-1391.HU Ping,WEN Sheng,WEI Shilong,et al. Character of carbonyl compounds and their source in Guangzhou Wanqingsha atmosphere[J]. Ecology and Environmental Sciences,2010,19(6):1387-1391.
[25]彭华.城市大气环境中醛酮类化合物污染状况及变化规律[J].环境监测管理与技术,2011,23(1):39-41.PENG Hua.Research on aldehydes and ketones pollutants in urban air[J]. The Administration and Technique of Environmental Monitoring,2011,23(1):39-41.
[26]张丽.高效液相色谱法分析空气污染物中的醛和酮[J].环境科技,2011,24(2):60-62.ZHANG Li.Determination of aldehydes and ketones in air pollutants by HPLC[J]. Environmental Science and Technology(China),2011,24(2):60-62.
[27]朱鸭梅,崔群,王海燕.高效液相色谱法测定乙醛溶液中的乙二醛和乙醛酸[J].色谱,2010,28(1):59-63.ZHU Yamei,CUI Qun,WANG Haiyan,Determination of glyoxal and glyoxalic acid in aldehyde solution by high performance liquid chromatography[J]. Chinese Journal of Chromatography,2010,28(1):59-63.
[28]中华全国合作供销总社.GH/T 1109—2015蜂蜜中丙酮醛含量的测定高效液相色谱法[S].北京:中华全国合作供销总社,2015.
[29]牟翠翠,冯艳丽,翟金清,等. 2,4-二硝基苯肼衍生-高效液相色谱测定大气细粒子中二羰基类化合物[J].分析化学,2010,38(11):1573-1577.MU Cuicui,FENG Yanli,ZHAI Jinqing,et al. Determination of dicarbonyl compounds in ambient fine particles by high performance liquid chromatography after 2, 4-dinitrophenylhydrazine derivatization[J]. Chinese Journal of Analytical Chemistry,2010,38(11):1573-1577.
[30] SMIRNOV R S,SMOLENKOV A D,BOLOTNIK T A,et al.Precolumn derivatization with glyoxal as a new approach to the highly sensitive HPLC-UV determination of unsymmetrical dimethylhydrazine[J]. Journal of Analytical Chemistry,2013,68(9):837-844.
[31]国家质量监督检验检疫总局.GH/T 4946—2008气相色谱法术语[S].北京:中国标准出版社,2008.
[32] ZHANG Hao,LI Hong,ZHANG Qingzhu,et al.Atmospheric volatile organic compounds in a typical urban area of Beijing:pollution characterization,health risk assessment and source apportionment[J].Atmosphere,2017,8(3):1-29.
[33]王琴,邵敏,魏强,等.北京及周边地区大气羰基化合物的时空分布特征初探[J].环境科学,2011,32(12):3522-3530.WANG Qin,SHAO Min,WEI Qiang,et al. Spatial and temporal variations of ambient carbonyl compounds in Beijing and its surrounding areas[J]. Environmental Science,2011,32(12):3522-3530.
[34]蒋朝晖,王玉娇,郑玄,等.张家界森林大气中醛酮类化合物浓度变化特征[J].环境科学研究,2016,29(9):1272-1278.JIANG Zhaohui,WANG Yujiao,ZHENG Xuan,et al. Variation characteristics of atmospheric carbonyl compounds in Zhangjiajie forest[J].Research of Environmental Sciences,2016,29(9):1272-1278.