Abstract
In this work, isotopic effects of carbonyls were evaluated during the simulation sampling of gaseous carbonyls by using a carbon isotope method developed, and then variation characteristics of carbon isotopic compositions were investigated for three dominant carbonyls including formaldehyde, acetaldehyde and acetone in the roadside air of Nanning for the first time. A small difference in δ13C values (0.04 to 0.50 ‰) were observed between the calculated and measured values of carbonyl-derivatives, indicating that the effect on carbon isotopic fractionation could hardly occurred in the simulation sampling of gaseous carbonyls. The roadside air measurements showed that \({\delta }^{13}\)C values of formaldehyde, acetaldehyde and acetone were –36.02 ‰ to –31.18 ‰, –35.35 ‰ to –32.01 ‰ and –30.45 ‰ to –29.09 ‰, respectively. Further correlation of the measured \({\delta }^{13}\)C values was good for formaldehyde, acetaldehyde and acetone (R2 = 0.6275–0.7755), indicating that their similar sources could be the direct vehicular emission or indirect productions from precursors such as hydrocarbons. Particularly, formaldehyde, acetaldehyde and acetone in the roadside air were all enriched in the early afternoon by round 0.5–6 ‰ in 13C compared to other sampling durations, which was likely due to the contributions from the positive photo-oxidation productions of hydrocarbons. Finally, it was found that all measured \({\delta }^{13}\)C values (–36.5 ‰ to –29.0 ‰) agreed with the forecasted \({\delta }^{13}\)C range (–43.0 ‰ to –26.0 ‰) according to the 13C mass balance of carbonyls and their precursors such as hydrocarbons, indirectly confirming such positive productions in the roadside air.
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References
Adam, T.W., Astorga, C., Clairotte, M., Duane, M., Elsasser, M., Krasenbrink, A., Larsen, B.R., Manfredi, U., Martini, G., Montero, L., Sklorz, M., Zimmermann, R., Perujo, A.: Chemical analysis and ozone formation potential of exhaust from dual-fuel (liquefied petroleum gas/gasoline) light duty vehicles. Atmos. Environ. 45, 2842–2848 (2011). https://doi.org/10.1016/j.atmosenv.2011.03.002
Atkinson, R.: Atmospheric chemistry of VOCs and NOx. Atmos. Environ. 34, 2063–2101 (2000). https://doi.org/10.1016/S1352-2310(99)00460-4
Cheng, Y., Lee, S., Huang, Y., Ho, K., Ho, S., Yau, P., Louie, P., Zhang, R.: Diurnal and seasonal trends of carbonyl compounds in roadside, urban, and suburban environment of Hong Kong. Atmos. Environ. 89, 43–51 (2014). https://doi.org/10.1016/j.atmosenv.2014.02.014
Duan, J., Guo, S., Tan, J., Wang, S., Chai, F.: Characteristics of atmospheric carbonyls during haze days in Beijing, China. Atmos. Res. 114, 17–27 (2012). https://doi.org/10.1016/j.atmosres.2012.05.010
Guo, S., Wen, S., Wang, X., Sheng, G., Fu, J., Jia, W., Yu, Y., Lü, H.: Carbon isotope analysis of acetaldehyde and acetone by cysteamine derivatization. Rapid Commun. Mass Spectrom. 21, 1809–1812 (2007). https://doi.org/10.1002/rcm.3015
Guo, S., Wen, S., Zu, G., Wang, X., Sheng, G., and Fu, J.: “Determination of the carbon isotope composition of atmospheric acetone.” [in Chinese.] Chinese Analytical Chemistry. 36 (1): 19–23 (2008).
Guo, S., Wen, S., Wang, X., Sheng, G., Fu, J., Hu, P., Yu, Y.: Carbon isotope analysis for source identification of atmospheric formaldehyde and acetaldehyde in Dinghushan Biosphere Reserve in South China. Atmos. Environ. 43, 3489–3495 (2009). https://doi.org/10.1016/j.atmosenv.2009.04.041
Guo, S., Chen, M., Wen, S., Sheng, G., Fu, J.: Measuring δ13C values of atmospheric acetaldehyde via sodium bisulfite adsorption and cysteamine derivatization. Isot. Environ. Health Stud. 48(4), 473–482 (2012). https://doi.org/10.1080/10256016.2012.702113
Guo, S., Chen, M.: 13C isotope evidence for photochemical production of atmospheric formaldehyde, acetaldehyde and acetone pollutants in Guangzhou. Environ. Chem. Lett. 11, 77–82 (2013). https://doi.org/10.1007/s10311-012-0382-2
Guo, S., He, X., Chen, M., Tan, J., Wang, Y.: Photochemical production of atmospheric carbonyls in a rural area in southern China. Arch. Environ. Contam. Toxicol. 66, 594–605 (2014). https://doi.org/10.1007/s00244-014-0013-y
Guo, S., Chen, M.: Pollution characteristics of atmospheric carbonyls during one haze event in Nanning, south China. Aerosol and Air Quality Research. 16, 1143–1151 (2016). https://doi.org/10.4209/aaqr.2015.01.0047
Guo, S., Chen, M., Tan, J.: Seasonal and diurnal characteristics of atmospheric carbonyls in Nanning, China. Atmos. Res. 169, 46–53 (2016). https://doi.org/10.1016/j.atmosres.2015.09.028
Hu, P., Wen, S., Liu, Y., Bi, X., Chan, L.Y., Feng, J., Wang, X., Sheng, G., Fu, J.: Carbon isotopic characterization of formaldehyde emitted by vehicles in Guangzhou, China. Atmos. Environ. 86, 148–154 (2014). https://doi.org/10.1016/j.atmosenv.2013.12.014
Iannone, R., Koppmann, R., Rudolph, J.: 12C/13C kinetic isotope effects of the gas-phase reactions of isoprene, methacrolein, and methyl vinyl ketone with OH radicals. Atmos. Environ. 43, 3103–3110 (2009). https://doi.org/10.1016/j.atmosenv.2009.03.006
Johnson, B.J., Dawson, G.A.: Collection of formaldehyde from clean air for carbon isotopic analysis. Environ. Sci. Technol. 24(6), 898–902 (1990). https://doi.org/10.1021/es00076a018
Kourtchev, I., Bejan, I., Sodeau, J.R., Wenger, J.C.: Gas phase reaction of OH radicals with (E)-β-farnesene at 296 ± 2 K: rate coefficient and carbonyl products. Atmos. Environ. 46, 338–345 (2012). https://doi.org/10.1016/j.atmosenv.2011.09.061
Lim, M.C.H., Ayoko, G.A., Morawska, L., Ristovski, Z.D., Jayaratn, e E.R., and Kokot, S.: A comparative study of the elemental composition of the exhaust emissions of cars powered by liquefied petroleum gas and unleaded petrol. Atmos. Environ. 40, 3111–3122 (2006). https://doi.org/10.1016/j.atmosenv.2006.01.007
Liu, Y., Bi, X., Chan, L.Y., Wen, S., Wang, X., Sheng, G., Fu, J.: Characteristics, loss and gain of atmospheric carbonyl compounds in winters of 2008–2010 in Pearl River Delta region, China. J. Atmos. Chem. 70, 53–67 (2013). https://doi.org/10.1007/s10874-013-9250-0
Reda, A.A., Schnelle-Kreis, J., Orasche, J., Abbaszade, G., Lintelmann, J., Arteaga-Salas, J.M., Stengel, B., Rabe, R., Harndorf, H., Sippula, O., Streibel, T., Zimmermann, R.: Gas phase carbonyl compounds in ship emissions: differences between diesel fuel and heavy fuel oil operation. Atmos. Environ. 112, 370–380 (2015). https://doi.org/10.1016/j.atmosenv.2015.03.057
Rieley, G.: Derivatization of organic compounds prior to gas chromatographic -combustion-isotope ratio mass spectrometric analysis: identification of isotope fractionation processes. Analyst 119, 915 – 919 (1994). https://doi.org/10.1039/AN9941900915
Rottenberger, S., Kuhn, U., Wolf, A., Schebeske, G., Oliva, S.T., Tavares, T.M., Kesselmeier, J.: Formaldehyde and acetaldehyde exchange during leaf development of the Amazonian deciduous tree species Hymenaea courbaril. Atmos. Environ. 39, 2275–2279 (2005). https://doi.org/10.1016/j.atmosenv.2004.12.027
Rudolph, J., Czuba, E.: The stable carbon isotope fractionation for reactions of selected hydrocarbons with OH-radicals and its relevance for atmospheric chemistry. J. Geophys. Res. 105(D24), 29329–29346 (2000). https://doi.org/10.1029/2000JD900447
Rudolph, J., Czuba, E., Normal, A.L., Huang, L., Ernst, D.: Stable carbon isotope composition of hydrocarbons in emissions from transportation related sources and atmospheric observations in an urban atmosphere. Atmos. Environ. 36, 1173–1181 (2002). https://doi.org/10.1016/S1352-2310(01)00537-4
Tanner, R. L., Zielinska, B., Uberna, E., Harshfield, G., McNichol, A. P.: Concentrations of carbonyl compounds and the carbon isotopy of formaldehyde at a coastal site in Nova Scotia during the NARE summer intensive. J. Geophys. Res. 101 (D22), 28961–28970 (1996). https://doi.org/10.1029/95JD03574
Wen, S., Feng, Y., Yu, Y., Bi, X., Wang, X., Sheng, G., Fu, J., Peng, P.: Development of a compound-specific isotope analysis method for atmospheric formaldehyde and acetaldehyde. Environ. Sci. Technol. 39(16), 6202–6207 (2005). https://doi.org/10.1021/es049553q
von Eckstaedt, C.V., Grice, K., Ioppolo-Armanios, M., Jones, M.: δ13C and δD of volatile organic compounds in an alumina industry stack emission. Atmos. Environ. 45, 5477–5483 (2011). https://doi.org/10.1016/j.atmosenv.2011.06.064
Yamada, K., Hattori, R., Ito, Y., Shibata, H., Yoshida, N.: Carbon isotopic signatures of methanol and acetaldehyde emitted from biomass burning source. Geophys. Res. Lett. 36, L18807 (2009). https://doi.org/10.1029/2009GL038962
Ye, H.W., Epstein, S.: Hydrogen and carbon isotopes of petroleum and related organic matter. Geochim. Cosmochim. Acta 45, 753–762 (1981). https://doi.org/10.1016/0016-7037(81)90046-6
Yu, Y.X., Wen, S., Feng, Y.L., Bi, X.H., Wang, X.M., Peng, P.A., Sheng, G.Y., Fu, J.M.: Development of a compound-specific carbon isotope analysis method for atmospheric formaldehyde via NaHSO3 and cysteamine derivatization. Anal. Chem. 78, 1206–1211 (2006). https://doi.org/10.1021/ac051616f
Zhang, Y., Xue, L., Dong, C., Wang, T., Mellouki, A., Zhang, Q., Wang, W.: Gaseous carbonyls in China’s atmosphere: tempo-spatial distributions, sources, photochemical formation, and impact on air quality. Atmos. Environ. 214, 116863 (2019). https://doi.org/10.1016/j.atmosenv.2019.116863
Acknowledgements
This research is financed by funds of the Natural Scientific Foundations of Guangxi Province (No.2014GXNSFAA118301; No.2013GXNSFAA019286) and the National Natural Scientific Foundations of China (No.41373109; No.41163008). The authors acknowledge any contributions from all staff for their fine help in this work.
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Guo, S. Carbon isotopic signatures of carbonyls from roadside air observation. J Atmos Chem 78, 239–250 (2021). https://doi.org/10.1007/s10874-021-09423-y
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DOI: https://doi.org/10.1007/s10874-021-09423-y