Characterizing oxygenated volatile organic compounds and their sources in rural atmospheres in China
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摘要
Oxygenated volatile organic compounds(OVOCs) are important precursors and products of atmospheric secondary pollution. The sources of OVOCs, however, are still quite uncertain,especially in the atmosphere with much pollution in China. To study the sources of OVOCs in rural atmospheres, a proton transfer reaction mass spectrometry(PTR-MS) was deployed at a northern rural site(WD) and a southern rural site(YMK) in China during the summer of 2014 and 2016, respectively. The continuous observation showed that the mean concentration of TVOCs(totally 17 VOCs) measured at WD(52.4 ppbv) was far higher than that at YMK(11.1 ppbv), and the OVOCs were the most abundant at both the two sites. The diurnal variations showed that local sources of OVOCs were still prominent at WD, while regional transport influenced YMK much. The photochemical age-based parameterization method was then used to quantitatively apportion the sources of ambient OVOCs. The anthropogenic primary sources at WD and YMK contributed less(2%–16%) to each OVOC species. At both the sites, the atmospheric background had a dominant contribution(～ 50%) to acetone and formic acid, while the anthropogenic secondary formation was the main source(～ 40%) of methanol and MEK. For acetaldehyde and acetic acid, the biogenic sources were their largest source(～ 40%) at WD, while the background(39%) and anthropogenic secondary formation(42%) were their largest sources at YMK, respectively. This study reveals the complexity of sources of OVOCs in China, which urgently needs explored further.
Oxygenated volatile organic compounds(OVOCs) are important precursors and products of atmospheric secondary pollution. The sources of OVOCs, however, are still quite uncertain,especially in the atmosphere with much pollution in China. To study the sources of OVOCs in rural atmospheres, a proton transfer reaction mass spectrometry(PTR-MS) was deployed at a northern rural site(WD) and a southern rural site(YMK) in China during the summer of 2014 and 2016, respectively. The continuous observation showed that the mean concentration of TVOCs(totally 17 VOCs) measured at WD(52.4 ppbv) was far higher than that at YMK(11.1 ppbv), and the OVOCs were the most abundant at both the two sites. The diurnal variations showed that local sources of OVOCs were still prominent at WD, while regional transport influenced YMK much. The photochemical age-based parameterization method was then used to quantitatively apportion the sources of ambient OVOCs. The anthropogenic primary sources at WD and YMK contributed less(2%–16%) to each OVOC species. At both the sites, the atmospheric background had a dominant contribution(～ 50%) to acetone and formic acid, while the anthropogenic secondary formation was the main source(～ 40%) of methanol and MEK. For acetaldehyde and acetic acid, the biogenic sources were their largest source(～ 40%) at WD, while the background(39%) and anthropogenic secondary formation(42%) were their largest sources at YMK, respectively. This study reveals the complexity of sources of OVOCs in China, which urgently needs explored further.
Oxygenated volatile organic compounds(OVOCs) are important precursors and products of atmospheric secondary pollution. The sources of OVOCs, however, are still quite uncertain,especially in the atmosphere with much pollution in China. To study the sources of OVOCs in rural atmospheres, a proton transfer reaction mass spectrometry(PTR-MS) was deployed at a northern rural site(WD) and a southern rural site(YMK) in China during the summer of 2014 and 2016, respectively. The continuous observation showed that the mean concentration of TVOCs(totally 17 VOCs) measured at WD(52.4 ppbv) was far higher than that at YMK(11.1 ppbv), and the OVOCs were the most abundant at both the two sites. The diurnal variations showed that local sources of OVOCs were still prominent at WD, while regional transport influenced YMK much. The photochemical age-based parameterization method was then used to quantitatively apportion the sources of ambient OVOCs. The anthropogenic primary sources at WD and YMK contributed less(2%–16%) to each OVOC species. At both the sites, the atmospheric background had a dominant contribution(～ 50%) to acetone and formic acid, while the anthropogenic secondary formation was the main source(～ 40%) of methanol and MEK. For acetaldehyde and acetic acid, the biogenic sources were their largest source(～ 40%) at WD, while the background(39%) and anthropogenic secondary formation(42%) were their largest sources at YMK, respectively. This study reveals the complexity of sources of OVOCs in China, which urgently needs explored further.
引文
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Atkinson,R.,Arey,J.,2003.Atomospheric degradation of volatile organic compounds.Chew.Rev.103,4605-4638.
Bai,Y.,Bai,Z.P.,Li,W.,2016.Characteristics and sources analysis of atmospheric volatile organic compounds in the Tibetan Plateau.Acta.Sci.Circum.36,2180-2186.
Barletta,B.,Meinardi,S.,Simpson,I.J.,Zou,S.C.,Rowland,F.S.,Blake,D.R.,2008.Ambient mixing ratios of nonmethane hydrocarbons(NMHCs)in two major urban centers of the Pearl River Delta(PRD)region:Guangzhou and Dongguan.Atmos.Environ.42,4393-4408.
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Chang,C.C.,Chen,T.Y.,Lin,C.Y.,Yuan,C.S.,Liu,S.C.,2005.Effects of reactive hydrocarbons on ozone formation in southern Taiwan.Atmos.Environ.39,2867-2878.
Chen,W.T.,Shao,M.,Lu,S.H.,Wang,M.,Zeng,L.M.,Yuan,B.,et al.,2014.Understanding primary and secondary sources of ambient carbonyl compounds in Beijing using the PMF model.Atmos.Chem.Phys.14(6),3047-3062.
de Gouw,J.A.,Warneke,C.,2007.Measurement of volatile organic compounds in the Earth's atmosphere using proton-transferreaction mass spectrometry.Mass Spectrom.Rev.26,223-257.
Derwent,R.G.,Jenkin,M.E.,Saunders,S.M.,Pilling,M.J.,Simmonds,P.G.,Passant,N.R.,et al.,2003.Photochemical ozone formation in northwest Europe and its control.Atoms.Environ.37,1983-1991.
Duan,J.C.,Guo,S.,Tan,J.H.,Wang,S.L.,Chai,F.H.,2012.Characteristics of atmospheric carbonyls during haze days in Beijing,China.Atmos.Res.114-115,17-27.
Finlayson-Pitts,B.J.,Pitts,J.N.,1997.Tropospheric air pollution:ozone,airborne toxics,polycyclic aromatic hydrocarbons,and particles.Science 276,1045-1052.
Jordan,C.,Fitz,E.,Hagan,T.,Sive,B.,Frinak,E.,Haase,K.,et al.,2009.Long-term study of VOCs measured with PTR-MS at a rural site in New Hampshire with urban influences.Atmos.Chem.Phys.9,4677-4697.
Kanaya,Y.,Cao,R.,Akimoto,H.,Fukuda,M.,Komazaki,Y.,Yokouchi,Y.,et al.,2007.Urban photochemistry in central Tokyo:1.Observed and modeled OH and HO2radical concentrations during the winter and summer of 2004.J.Geophys.Res.-Atmos.112,D21312.
Kansal,A.,2009.Sources and reactivity of NMHCs and VOCs in the atmosphere:a review.J.Hazard.Mater.166,17-26.
Legreida,G.,Loovb,J.B.,Staehelinb,J.,Hueglina,C.,Hilla,M.,Buchmanna,B.,et al.,2007.Oxygenated volatile organic compounds(OVOCs)at an urban background site in Z?urich(Europe):seasonal variation and source allocation.Atmos.Environ.41,8409-8423.
Lin,Y.C.,Schwab,J.J.,Demerjian,K.L.,Bae,M.S.,Chen,W.N.,Sun,Y.,et al.,2012.Summertime formaldehyde observations in New York City:ambient levels,sources and its contribution to HOxradicals.J.Geophys.Res.-Atmos 117,D08305.
Lindinger,W.,Hansel,A.,Jordan,A.,1998.On-line monitoring of volatile organic compounds at pptv levels by means of protontransfer-reaction mass spectrometry(PTR-MS)-Medical applications,food control and environmental research.Int.J.Mass Spectrom.173,191-241.
Liu,X.W.(Ed.),2010.Research of the Regional Characteristics of Gaseous Pollutants and Atmospheric Transport in Beijing and its Surrounding Areas.Chinese Academy of Meteorological Sciences,Beijing,China Master Thesis.
Liu,Y.,Yuan,B.,Li,X.P.,Shao,M.Z.,Lu,S.,Li,Y.,et al.,2015.Impact of pollution controls in Beijing on atmospheric oxygenated volatile organic compounds(OVOCs)during the 2008 Olympic Games:observation and modeling implications.Atmos.Chem.Phys.15,3045-3062.
Luecken,D.J.,Hutzell,W.T.,Strum,M.L.,Pouliot,G.A.,2012.Regional sources of atmospheric formaldehyde and acetaldehyde,and implications for atmospheric modeling.Atmos.Environ.47,477-490.
Ma,Y.,Diao,Y.W.,Zhang,B.J.,Wang,W.W.,Ren,X.R.,Yang,D.S.,et al.,2016.Detection of formaldehyde emissions from an industrial zone in the Yangtze River Delta region of China using a proton transfer reaction ion-drift chemical ionization mass spectrometer.Atmos.Meas.Tech.9,6101-6116.
Ministry of Ecology and Environment of the People's Repubic of China,2017.Bulletin of Ecology and Environment of the People's Repubic of China.pp.7-14.
Parrish,D.D.,Ryerson,T.B.,Mellqvist,J.,Johansson,J.,Fried,A.,Richter,D.,et al.,2012.Primary and secondary sources of formaldehyde in urban atmospheres:Houston Texas region.Atmos.Chem.Phys.12,3273-3288.
Possanzini,M.,Tagliacozzo,G.,Cecinato,A.,2007.Ambient levels and sources of lower carbonyls at Montelibretti,Rome(Italy).Water Air Soil Pollut.183,447-454.
Seinfeld,J.H.,Pandis,S.N.,2006.Atmospheric Chemistry and Physics:From Air Pollution to Climate Change.Wiley,New York.
Sin,D.W.M.,Wong,Y.C.,Louie,P.K.K.,2001.Trend of ambient carbonyl compounds in the urban environment of Hong Kong.Atmos.Environ.35,5961-5969.
Wu,Q.Z.,Wang,Z.F.,Gbaguidi,A.,Gao,C.,Li,L.N.,Wang,W.,2011.A numerical study of contributions to air pollution in Beijing during CAREBeijing-2006.Atmos.Chem.Phys.12,5997-6011.
Xue,L.K.,Wang,T.,Guo,H.,Blake,D.R.,Tang,J.,Zhang,X.C.,et al.,2013.Sources and photochemistry of volatile organic compounds in the remote atmosphere of western China:results from the Mt.Waliguan Observatory.Atmos.Chem.Phys.13,8551-8567.
Yang,L.Y.,1990.Several problems in the monitoring of atmospheric background pollution.Plateau Meteorol.9,337-346.
Yuan,B.,Shao,M.,de Gouw,J.,Parrish,D.D.,Lu,S.H.,Wang,M.,et al.,2012.Volatile organic compounds(VOCs)in urban air:How chemistry affects the interpretation of positive matrix factorization(PMF)analysis.J.Geophys.Res.-Atmos 117(D24302),1-17.
Zhang,J.K.,Wang,Y.S.,Wu,F.K.,Sun,J.,2012.Study on atmospheric VOCs in Gongga Mountain base station.Environ.Sci.33,4159-4166.
Zhang,Y.,Wang,X.,Barletta,B.,Simpson,I.J.,Blake,D.R.,Fu,X.,et al.,2013.Source attributions of hazardous aromatic hydrocarbons in urban,suburban and rural areas in the Pearl River Delta(PRD)region.J.Hazard.Mater.250,403-411.
Zhang,R.H.,Li,Q.,Zhang,R.N.,2014.Meteorological conditions for the persistent severe fog and haze event over eastern China in January 2013.Sci.China Earth Sci.57,26-35.
Zhu,B.,Han,Y.,Wang,C.,Huang,X.F.,Xia,S.Y.,Niu,Y.B.,et al.,2018.Understanding primary and secondary sources of ambient oxygenated volatile organic compounds(OVOCs)in Shenzhen utilizing photochemical age-based parameterization method.J.Environ.Sci.Available https://doi.org/10.1016/j.jes.2018.03.008 Accessed March 9,2018.
Atkinson,R.,2000.Atmospheric chemistry of VOCs and NOx.Atmos.Environ.34,2063-2101.
Atkinson,R.,Arey,J.,2003.Atomospheric degradation of volatile organic compounds.Chew.Rev.103,4605-4638.
Bai,Y.,Bai,Z.P.,Li,W.,2016.Characteristics and sources analysis of atmospheric volatile organic compounds in the Tibetan Plateau.Acta.Sci.Circum.36,2180-2186.
Barletta,B.,Meinardi,S.,Simpson,I.J.,Zou,S.C.,Rowland,F.S.,Blake,D.R.,2008.Ambient mixing ratios of nonmethane hydrocarbons(NMHCs)in two major urban centers of the Pearl River Delta(PRD)region:Guangzhou and Dongguan.Atmos.Environ.42,4393-4408.
Bashkin,V.N.,2009.Environmental Chemistry:Asian Lessons.Kluwer Academic Pub.,Netherlands,Netherlands.
Carter,W.,1994.Development of ozone reactivity scales for Volatile Organic Compounds.J.Air Waste Manage.Assoc.44,881-899.
Chang,C.C.,Chen,T.Y.,Lin,C.Y.,Yuan,C.S.,Liu,S.C.,2005.Effects of reactive hydrocarbons on ozone formation in southern Taiwan.Atmos.Environ.39,2867-2878.
Chen,W.T.,Shao,M.,Lu,S.H.,Wang,M.,Zeng,L.M.,Yuan,B.,et al.,2014.Understanding primary and secondary sources of ambient carbonyl compounds in Beijing using the PMF model.Atmos.Chem.Phys.14(6),3047-3062.
de Gouw,J.A.,Warneke,C.,2007.Measurement of volatile organic compounds in the Earth's atmosphere using proton-transferreaction mass spectrometry.Mass Spectrom.Rev.26,223-257.
Derwent,R.G.,Jenkin,M.E.,Saunders,S.M.,Pilling,M.J.,Simmonds,P.G.,Passant,N.R.,et al.,2003.Photochemical ozone formation in northwest Europe and its control.Atoms.Environ.37,1983-1991.
Duan,J.C.,Guo,S.,Tan,J.H.,Wang,S.L.,Chai,F.H.,2012.Characteristics of atmospheric carbonyls during haze days in Beijing,China.Atmos.Res.114-115,17-27.
Finlayson-Pitts,B.J.,Pitts,J.N.,1997.Tropospheric air pollution:ozone,airborne toxics,polycyclic aromatic hydrocarbons,and particles.Science 276,1045-1052.
Jordan,C.,Fitz,E.,Hagan,T.,Sive,B.,Frinak,E.,Haase,K.,et al.,2009.Long-term study of VOCs measured with PTR-MS at a rural site in New Hampshire with urban influences.Atmos.Chem.Phys.9,4677-4697.
Kanaya,Y.,Cao,R.,Akimoto,H.,Fukuda,M.,Komazaki,Y.,Yokouchi,Y.,et al.,2007.Urban photochemistry in central Tokyo:1.Observed and modeled OH and HO2radical concentrations during the winter and summer of 2004.J.Geophys.Res.-Atmos.112,D21312.
Kansal,A.,2009.Sources and reactivity of NMHCs and VOCs in the atmosphere:a review.J.Hazard.Mater.166,17-26.
Legreida,G.,Loovb,J.B.,Staehelinb,J.,Hueglina,C.,Hilla,M.,Buchmanna,B.,et al.,2007.Oxygenated volatile organic compounds(OVOCs)at an urban background site in Z?urich(Europe):seasonal variation and source allocation.Atmos.Environ.41,8409-8423.
Lin,Y.C.,Schwab,J.J.,Demerjian,K.L.,Bae,M.S.,Chen,W.N.,Sun,Y.,et al.,2012.Summertime formaldehyde observations in New York City:ambient levels,sources and its contribution to HOxradicals.J.Geophys.Res.-Atmos 117,D08305.
Lindinger,W.,Hansel,A.,Jordan,A.,1998.On-line monitoring of volatile organic compounds at pptv levels by means of protontransfer-reaction mass spectrometry(PTR-MS)-Medical applications,food control and environmental research.Int.J.Mass Spectrom.173,191-241.
Liu,X.W.(Ed.),2010.Research of the Regional Characteristics of Gaseous Pollutants and Atmospheric Transport in Beijing and its Surrounding Areas.Chinese Academy of Meteorological Sciences,Beijing,China Master Thesis.
Liu,Y.,Yuan,B.,Li,X.P.,Shao,M.Z.,Lu,S.,Li,Y.,et al.,2015.Impact of pollution controls in Beijing on atmospheric oxygenated volatile organic compounds(OVOCs)during the 2008 Olympic Games:observation and modeling implications.Atmos.Chem.Phys.15,3045-3062.
Luecken,D.J.,Hutzell,W.T.,Strum,M.L.,Pouliot,G.A.,2012.Regional sources of atmospheric formaldehyde and acetaldehyde,and implications for atmospheric modeling.Atmos.Environ.47,477-490.
Ma,Y.,Diao,Y.W.,Zhang,B.J.,Wang,W.W.,Ren,X.R.,Yang,D.S.,et al.,2016.Detection of formaldehyde emissions from an industrial zone in the Yangtze River Delta region of China using a proton transfer reaction ion-drift chemical ionization mass spectrometer.Atmos.Meas.Tech.9,6101-6116.
Ministry of Ecology and Environment of the People's Repubic of China,2017.Bulletin of Ecology and Environment of the People's Repubic of China.pp.7-14.
Parrish,D.D.,Ryerson,T.B.,Mellqvist,J.,Johansson,J.,Fried,A.,Richter,D.,et al.,2012.Primary and secondary sources of formaldehyde in urban atmospheres:Houston Texas region.Atmos.Chem.Phys.12,3273-3288.
Possanzini,M.,Tagliacozzo,G.,Cecinato,A.,2007.Ambient levels and sources of lower carbonyls at Montelibretti,Rome(Italy).Water Air Soil Pollut.183,447-454.
Seinfeld,J.H.,Pandis,S.N.,2006.Atmospheric Chemistry and Physics:From Air Pollution to Climate Change.Wiley,New York.
Sin,D.W.M.,Wong,Y.C.,Louie,P.K.K.,2001.Trend of ambient carbonyl compounds in the urban environment of Hong Kong.Atmos.Environ.35,5961-5969.
Wu,Q.Z.,Wang,Z.F.,Gbaguidi,A.,Gao,C.,Li,L.N.,Wang,W.,2011.A numerical study of contributions to air pollution in Beijing during CAREBeijing-2006.Atmos.Chem.Phys.12,5997-6011.
Xue,L.K.,Wang,T.,Guo,H.,Blake,D.R.,Tang,J.,Zhang,X.C.,et al.,2013.Sources and photochemistry of volatile organic compounds in the remote atmosphere of western China:results from the Mt.Waliguan Observatory.Atmos.Chem.Phys.13,8551-8567.
Yang,L.Y.,1990.Several problems in the monitoring of atmospheric background pollution.Plateau Meteorol.9,337-346.
Yuan,B.,Shao,M.,de Gouw,J.,Parrish,D.D.,Lu,S.H.,Wang,M.,et al.,2012.Volatile organic compounds(VOCs)in urban air:How chemistry affects the interpretation of positive matrix factorization(PMF)analysis.J.Geophys.Res.-Atmos 117(D24302),1-17.
Zhang,J.K.,Wang,Y.S.,Wu,F.K.,Sun,J.,2012.Study on atmospheric VOCs in Gongga Mountain base station.Environ.Sci.33,4159-4166.
Zhang,Y.,Wang,X.,Barletta,B.,Simpson,I.J.,Blake,D.R.,Fu,X.,et al.,2013.Source attributions of hazardous aromatic hydrocarbons in urban,suburban and rural areas in the Pearl River Delta(PRD)region.J.Hazard.Mater.250,403-411.
Zhang,R.H.,Li,Q.,Zhang,R.N.,2014.Meteorological conditions for the persistent severe fog and haze event over eastern China in January 2013.Sci.China Earth Sci.57,26-35.
Zhu,B.,Han,Y.,Wang,C.,Huang,X.F.,Xia,S.Y.,Niu,Y.B.,et al.,2018.Understanding primary and secondary sources of ambient oxygenated volatile organic compounds(OVOCs)in Shenzhen utilizing photochemical age-based parameterization method.J.Environ.Sci.Available https://doi.org/10.1016/j.jes.2018.03.008 Accessed March 9,2018.