Online measurements of typical ambient oxygenated volatile organic compounds (OVOCs) and other non-methane hydrocarbons (NMHCs) were conducted in different seasons (dry and wet seasons) of 2017 in Shenzhen University Town utilized a proton transfer reaction mass spectrometer (PTR-MS). We explored their composition characteristics and diurnal variations, and then quantified different sources of typical OVOCs based on the photochemical age-based parameterization method. Results showed that the mean concentrations of methanol were the highest both in dry and wet seasons (up to 10×10-9~12×10-9) among the measured OVOC species, followed by acetic acid, acetone and acetaldehyde (approximately 2×10-9~5×10-9), while those of formic acid and methyl ethyl ketone (MEK) were always the lowest (approximately 1×10-9~2×10-9). The peak concentrations of measured OVOCs in wet seasons were found significantly earlier than that in dry seasons, and the diurnal variation in the concentration of acetaldehyde was quite similar to that of ozone (O3), suggesting that the elevated concentration throughout the daytime may originated from secondary oxidation. While the peak concentrations of methanol and MEK were found much earlier than that of O3, indicating that they may have prominent contributions from primary emission. According to the OVOCs source apportionments, anthropogenic primary sources played the key roles for methanol, acetaldehyde, acetone and MEK in dry seasons, while formic acid and acetic acid were dominated by anthropogenic secondary sources. Besides, biogenic sources were the dominant source of acetaldehyde, acetone, MEK, formic acid and acetic acid in wet seasons.
Atkinson R. Atmospheric chemistry of VOCs and NOx[J]. AtmosphereEnvironment, 2000,34:2063-2101.
[2]
Derwent R G, Jenkin M E, Saunders S M, et al. Photochemical ozone formation in northwest Europe and its control[J]. Atmosphere Environment, 2003,37:1983-1991.
[3]
Seinfeld J H, Pandis S N. Atmospheric Chemistry and Physics:from Air Pollution to Climate Change[M]. New York:Wiley, 2006:1326.
[4]
Shao M, Wang B, Lu S H, et al. Effects of Beijing Olympics control measures on reducing reactive hydrocarbon species[J]. Environmental Science & Technology, 2011,45:514-519.
[5]
Finlayson-Pitts B J, Pitts J N. Tropospheric air pollution:Ozone, airborne toxics, polycyclic aromatic hydrocarbons, and particles[J]. Science, 1997,276:1045-1052.
[6]
Bashkin V N. Environmental Chemistry:Asian Lessons[M]. Netherlands:Kluwer Academic Pub, 2009:47-76.
[7]
Wang G, Cheng S Y, Wei W, et al. Characteristics and source apportionment of VOCs in the suburban area of Beijing, China[J]. Atmospheric Pollution Research, 2016,7:711-724.
[8]
Liu Y, Yuan B, Li X, et al. Impact of pollution controls in Beijing on atmospheric oxygenated volatile organic compounds (OVOCs) during the 2008 Olympic Games:observation and modeling implications[J]. Atmospheric Chemistry and Physics, 2015,15:3045-3062.
Louie P K K, Ho J W K, Tsang R C W, et al. VOCs and OVOCs distribution and control policy implications in Pearl River Delta region, China[J]. Atmosphere Environment, 2013,76(S1):125-135.
Cai C, Ceng F, Tie X, et al. Characteristics and source apportionment of VOCs measured in Shanghai, China[J]. Atmosphere Environment, 2010,44(38):5005-5014.
Sin D W M, Wong Y C, Louie, P K K. Trend of ambient carbonyl compounds in the urban environment of Hong Kong[J]. AtmosphereEnvironment, 2001,35:5961-5969.
de Gouw J A, Warneke C. Measurement of volatile organic compounds in the Earth's atmosphere using proton-transfer-reaction mass spectrometry[J]. Mass Spectrometry Reviews, 2007,26:223-257.
[26]
Carter W. Development of ozone reactivity scales for Volatile Organic Compounds[J]. Journal of the Air & Waste Management Association, 1994,44:881-899.
[27]
Barletta B, Meinardi S, Simpson I J, et al. Ambient mixing ratios of nonmethane hydrocarbons (NMHCs) in two major urban centers of the Pearl River Delta (PRD) region:Guangzhou and Dongguan[J]. AtmosphereEnvironment, 2008,42:4393-4408.
[28]
Atkinson R, Arey J. Atomospheric degradation of volatile organic compounds[J]. Chemical Reviews, 2003,103:4605-4638.
[29]
Zhang Y, Wang X, Barletta B, et al. Source attributions of hazardous aromatic hydrocarbons in urban, suburban and rural areas in the Pearl River Delta (PRD) region[J]. Journal of Hazardous Materials, 2013, 250:403-411.
[30]
Ma Y, Diao Y, Zhang B, et al. 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[J]. Atmospheric Measurement Techniques, 2016,9:6101-6116.
[31]
Lü H, Cai Q Y, Wen S, et al. Seasonal and diurnal variation of carbonyl compounds in the urban atmosphere of Guangzhou, China[J]. Science of the Total Environment, 2010,408:3523-3529.
Huang J, Feng Y L, Li J, et al. Characteristics of carbonyl compounds in ambient air of Shanghai, China[J]. Journal of Atmospheric Chemistry, 2008,61:1-20.
[34]
Stoji? A, Stoji? S S, Šoštari? A, et al. Characterization of VOC sources in an urban area based on PTR-MS measurements and receptor modeling[J]. Environmental Science and Pollution Research, 2015, 22:13137-13152.
[35]
Dai W T, Ho S S H, Ho K F, et al. Seasonal and diurnal variations of mono- and di-carbonyls in Xi'an, China[J]. Atmospheric Research, 2012,113:102-112.
[36]
Millet D B, Donahue N M, Pandis S N, et al. Atmospheric volatile organic compound measurements during the Pittsburgh Air Quality Study:Results, interpretation, and quantification of primary and secondary contributions[J]. Journal of Geophysical Research-Atmospheres, 2005,110(D07S07):1-17.
[37]
Ho K F, Lee S C, Louie P K K, et al. Seasonal variation of carbonyl compoundconcentrations inurban area of Hong Kong[J]. Atmosphere Environment, 2002,36:1259-1265.
[38]
Alex B G, Patrick R Z, Peter H. Isoprene and monoterpene emission rate variability:model evaluations and sensitivity analyses[J]. Journal of Geophysical Research-Atmospheres, 1993,98:12609-12617.
[39]
Paatero P, Tapper U. Positive matrix factorization-a nonnegative factor model with optimal utilization of error-estimates of data values[J]. Environmetrics, 1994,5:111-126.
[40]
Brocco D, Fratarcangeli R, Lepore L, et al. Determination of Aromatic Hydrocarbons in Urban Air of Roma[J]. AtmosphereEnvironment, 1997,31:557-566.
[41]
Kim JC. Factors controlling natural VOC emissions in a southeastern US pine forest[J]. AtmosphereEnvironment, 2001,35:3279-3292.
[42]
Possanzini M, Tagliacozzo G, Cecinato A. Ambient levels and sources of lower carbonyls at Montelibretti, Rome (Italy)[J]. Water Air and Soil Pollution, 2007,183:447-454.
[43]
Yuan B, Shao M, de Gouw J, et al. Volatile organic compounds (VOCs) in urban air:How chemistry affects the interpretation of positive matrix factorization (PMF) analysis[J]. Journal of Geophysical Research-Atmospheres, 2012,117(D24302):1-17.
[44]
Duan J, Guo S, Tan J, et al. Characteristics of atmospheric carbonyls during haze days in Beijing, China[J]. Atmospheric Research, 2012, 114-115:17-27.
[45]
Huang X, Yun H, Gong Z, et al. Source apportionment and secondary organic aerosol estimation of PM2.5 in an urban atmosphere in China[J]. Science China-Earth Sciences, 2014,57:1352-1362.