Abstract
Acetaldehyde is one of the important VOC species of O3 precursors in the atmospheric environment. The influences of relative humidity (RH) and initial VOC/NOx ratio (RCN) on the formation of O3 are studied in smog chamber experiments, and the MCM v3.3.1 mechanism of acetaldehyde is modified based on the experimental results. In low-RH conditions (RH = 11.6%±1.1%), the O3 concentration at 6 h increases first and then decreases with the increase of RCN, and the RCN at the inflection point of O3 concentrations is 3.2. In high-RH experiments (RH = 78.8%±1.0%), variation of the O3 concentration at 6 h with RCN is similar to that in low-RH experiments, but the RCN at the inflection point is 2.8. RH has no significant effect on the O3 concentrations under low RCN (< 3), whereas it has a negative effect under high RCN (> 3). Compared with the experimental results, original MCM v3.3.1 greatly underestimates the O3 concentrations. Addition of both the photolysis process of peroxyacetyl nitrate and the photolysis process of HNO3 on the reactor surface into the original MCM can reduce the difference between the simulated O3 concentrations and the experimental results at 6 h from 24%−35% and 17%−49% to 6%−26% and 10%−42% under low- and high-RH conditions, respectively. The maximum incremental reactivity (MIR) of acetaldehyde simulated with the modified MCM is 4.0 ppb ppb−1 without considering the effect of other VOCs.
摘 要
乙醛是大气环境中重要的含氧的挥发性有机物(VOC),是臭氧生成的重要前体物。目前已有研究表明,在部分城市地区乙醛对臭氧污染的贡献已经高于其他OVOC。然而,目前关于乙醛光化学反应的烟雾箱实验研究较少,仅有的实验研究主要关注在低相对湿度(RH)条件下不同光照强度对乙醛光化学反应臭氧生成的影响,而关于RH和反应前体物浓度比值的影响规律目前仍未见报道。此外,目前广泛应用的近显式化学反应机制MCM(Master Chemical Mechanism)对乙醛光化学反应的模拟准确性仍然有待评估,并且由于乙醛同样是其他VOC物种光化学反应的中间产物,因此MCM机理对乙醛光化学反应模拟的准确性显得尤为重要。本研究结合烟雾箱实验和数值模拟方法对乙醛光化学反应过程进行了详细研究。烟雾箱实验表明,反应初始VOC/NOx比值对乙醛光化学反应中臭氧生成浓度具有显著影响,反应第6 小时生成臭氧浓度在低RH(RH = 11.6%±1.1%)和高RH(RH = 78.8%±1.0%)条件下均随着初始VOC/NOx比值的增大呈现先增大后减小的变化趋势。在初始VOC/NOx比值小于3条件下,RH对实验中O3生成浓度没有显著影响,而在初始VOC/NOx比值大于3条件下,高RH对实验中O3生成浓度具有不利影响。与烟雾箱实验结果相比,MCM机理在低和高RH条件下对第6 小时臭氧生成浓度分别低估了24%-35%和17%-49%。在MCM 机理中增加气相过氧乙酰基硝酸酯光解过程,同时在烟雾箱辅助反应中增加反应器表面的HNO3光解过程后,MCM机理模拟第6 小时臭氧生成浓度与实验测量结果之间差异分别降低到了6%-26%(低RH)和10%-42%(高RH)。在不考虑其他VOC物种的影响条件下,采用改进后的MCM机理模拟乙醛最大臭氧生成潜势为4.0 ppb ppb-1。
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References
Baergen, A. M., and D. J. Donaldson, 2013: Photochemical renoxification of nitric acid on real urban grime. Environmental Science & Technology, 47(2), 815–820, https://doi.org/10.1021/es3037862.
Cao, Y. F., X. Qiao, P. K. Hopke, Q. Ying, Y. Y. Zhang, Y. Y. Zeng, Y. P. Yuan, and Y. Tang, 2020: Ozone pollution in the west China rain zone and its adjacent regions, southwestern China: Concentrations, ecological risk, and sources. Chemosphere, 256, 127008, https://doi.org/10.1016/j.chemosphere.2020.127008.
Carter, W. P. L., 2010: Development of the SAPRC-07 chemical mechanism. Atmos. Environ., 44(40), 5324–5335, https://doi.org/10.1016/j.atmosenv.2010.01.026.
Carter, W. P. L., and G. Heo, 2013: Development of revised SAPRC aromatics mechanisms. Atmos. Environ., 77, 404–414, https://doi.org/10.1016/j.atmosenv.2013.05.021.
Carter, W. P. L., D. M. Luo, I. L. Malkina, and J. A. Pirece, 1993: An experimental and modeling study of the photochemical ozone reactivity of acetone. Final report to chemical manufacturers association contract No. KET-ACE-CRC-2.0, 43 pp.
Carter, W. P. L., J. A. Pierce, D. M. Luo, and I. L. Malkina, 1995: Environmental chamber study of maximum incremental reactivities of volatile organic compounds. Atmos. Environ., 29(18), 2499–2511, https://doi.org/10.1016/1352-2310(95)00149-S.
Chen, L. H., and Coauthors, 2020: The effects of humidity and ammonia on the chemical composition of secondary aerosols from toluene/NOx photo-oxidation. Science of The Total Environment, 728, 138671, https://doi.org/10.1016/j.scitotenv.2020.138671.
Chi, X. Y., and Coauthors, 2018: Observations of ozone vertical profiles and corresponding precursors in the low troposphere in Beijing, China. Atmospheric Research, 213, 224–235, https://doi.org/10.1016/j.atmosres.2018.06.012.
da Silva, D. B. N., E. M. Martins, and S. M. Corrêa, 2016: Role of carbonyls and aromatics in the formation of tropospheric ozone in Rio de Janeiro, Brazil. Environmental Monitoring and Assessment, 188(5), 289, https://doi.org/10.1007/s10661-016-5278-3.
Derwent, R. G., M. E. Jenkin, S. M. Saunders, and M. J. Pilling, 1998: Photochemical ozone creation potentials for organic compounds in northwest Europe calculated with a master chemical mechanism. Atmos. Environ., 32(14-15), 2429–2441, https://doi.org/10.1016/S1352-2310(98)00053-3.
Derwent, R. G., M. E. Jenkin, N. R. Passant, and M. J. Pilling, 2007: Photochemical ozone creation potentials (POCPs) for different emission sources of organic compounds under European conditions estimated with a Master Chemical Mechanism. Atmos. Environ., 41(12), 2570–2579, https://doi.org/10.1016/j.atmosenv.2006.11.019.
Dominutti, P., T. Nogueira, A. Fornaro, and A. Borbon, 2020: One decade of VOCs measurements in Sao Paulo megacity: Composition, variability, and emission evaluation in a biofuel usage context. Science of The Total Environment, 738, 139790, https://doi.org/10.1016/j.scitotenv.2020.139790.
Dong, D., M. Shao, Y. Li, S. H. Lu, Y. J. Wang, Z. Ji, and D. G. Tang, 2014: Carbonyl emissions from heavy-duty diesel vehicle exhaust in China and the contribution to ozone formation potential. Journal of Environmental Sciences, 26(1), 122–128, https://doi.org/10.1016/S1001-0742(13)60387-3.
Dong, Y. M., J. Li, J. P. Guo, Z. J. Jiang, Y. Q. Chu, L. Chang, Y. Yang, and H. Liao, 2020: The impact of synoptic patterns on summertime ozone pollution in the North China Plain. Science of The Total Environment, 735, 139559, https://doi.org/10.1016/j.scitotenv.2020.139559.
Flowers, B. A., J. F. Stanton, and W. R. Simpson, 2007: Wavelength dependence of nitrate radical quantum yield from peroxyacetyl nitrate photolysis: Experimental and theoretical studies. The Journal of Physical Chemistry A, 111(45), 11 602–11 607, https://doi.org/10.1021/jp0749118.
Gu, Y. Y., and Coauthors, 2019: Emission characteristics of 99 NMVOCs in different seasonal days and the relationship with air quality parameters in Beijing, China. Ecotoxicology and Environmental Safety, 169, 797–806 https://doi.org/10.1016/j.ecoenv.2018.11.091.
Guérette, E. A., and Coauthors, 2020: Evaluation of regional air quality models over Sydney, Australia: Part 2, Comparison of PM2.5 and ozone. Atmosphere, 11(3), 233, https://doi.org/10.3390/atmos11030233.
Guo, S. J., X. L. He, M. Chen, J. H. Tan, and Y. H. Wang, 2014: Photochemical production of atmospheric carbonyls in a rural area in southern China. Archives of Environmental Contamination and Toxicology, 66(4), 594–605, https://doi.org/10.1007/s00244-014-0013-y.
Hu, G. S., Y. F. Xu, and L. Jia, 2011: Effects of relative humidity on the characterization of a photochemical smog chamber. Journal of Environmental Sciences, 23(12), 2013–2018, https://doi.org/10.1016/S1001-0742(10)60665-1.
Janik, R., M. Kubov, and B. Schieber, 2020: The ground-level ozone concentration in beech (Fagus sylvatica L.) forests in the West Carpathian Mountains. Environmental Monitoring and Assessment, 192(4), 233, https://doi.org/10.1007/s10661-020-8176-7.
Jenkin, M. E., S. M. Saunders, and M. J. Pilling, 1997: The tropospheric degradation of volatile organic compounds: A protocol for mechanism development. Atmos. Environ., 31(1), 81–104, https://doi.org/10.1016/S1352-2310(96)00105-7.
Jenkin, M. E., S. M. Saunders, V. Wagner, and M. J. Pilling, 2003: Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part B): Tropospheric degradation of aromatic volatile organic compounds. Atmospheric Chemistry and Physics, 3, 181–193, https://doi.org/10.5194/acp-3-181-2003.
Jenkin, M. E., J. C. Young, and A. R. Rickard, 2015: The MCM v3.3.1 degradation scheme for isoprene. Atmospheric Chemistry and Physics, 15(20), 11 433–11 459, https://doi.org/10.5194/acp-15-11433-2015.
Jia, L., 2007: A study of the kinetics of alkene ozonolysis and ozone formation reactivity of isopentane. M.S. thesis, Beijing Normal University. (in Chinese with English abstract)
Jia, L., and Y. F. Xu, 2016: Ozone and secondary organic aerosol formation from Ethylene-NOx-NaCl irradiations under different relative humidity conditions. Journal of Atmospheric Chemistry volume, 73(1), 81–100, https://doi.org/10.1007/s10874-015-9317-1.
Jia, L., and Y. F. Xu, 2018: Different roles of water in secondary organic aerosol formation from toluene and isoprene. Atmospheric Chemistry and Physics, 18(11), 8137–8154, https://doi.org/10.5194/acp-18-8137-2018.
Jia, L., Y. F. Xu, M. F. Ge, L. Du, and G. S. Zhuang, 2009: Smog chamber studies of ozone formation potentials for isopentane. Chinese Science Bulletin, 54(24), 4624–4632, https://doi.org/10.1007/s11434-009-0482-y.
Jia, L., Y. F. Xu, and Y. Z. Shi, 2011: Characterization of photochemical smog chamber and initial experiments. Environmental Science, 32 351–361. (in Chinese with English abstract)
Kalabokas, P., and Coauthors, 2020: A study of the influence of tropospheric subsidence on spring and summer surface ozone concentrations at the JRC Ispra station in northern Italy. Atmospheric Chemistry and Physics, 20(4), 1861–1885, https://doi.org/10.5194/acp-20-1861-2020.
Kinose, Y., Y. Fukamachi, S. Okabe, H. Hiroshima, M. Watanabe, and T. Izuta, 2020: Toward an impact assessment of ozone on plant carbon fixation using a processbased plant growth model: A case study of Fagus crenata grown under different soil nutrient levels. Science of The Total Environment, 716, 137008, https://doi.org/10.1016/j.scitotenv.2020.137008.
Li, Q. Q., and Coauthors, 2020: An investigation into the role of VOCs in SOA and ozone production in Beijing, China. Science of The Total Environment, 720, 137536, https://doi.org/10.1016/j.scitotenv.2020.137536.
Liang, T. T., J. P. Niu, S. Y. Zhang, Q. Q. Song, and J. Zhou, 2020: Effects of high-temperature heat wave and ozone on hypertensive rats. International Journal of Biometeorology, 64(7), 1039–1050, https://doi.org/10.1007/s00484-019-01788-w.
Libuda, H. G., and F. Zabel, 1995: Uv absorption cross sections of acetyl peroxynitrate and trifluoroacetyl peroxynitrate at 298 K. Berichte der Bunsengesellschaft für physikalische Chemie, 99(10), 1205–1213, https://doi.org/10.1002/bbpc.199500061.
Luo, H., L. Jia, Q. Wan, T. C. An, and Y. J. Wang, 2019: Role of liquid water in the formation of O3 and SOA particles from 1:2,3-trimethylbenzene. Atmos. Environ., 217, 116955, https://doi.org/10.1016/j.atmosenv.2019.116955.
Luo, H., G. Y. Li, J. Y. Chen, Y. J. Wang, and T. C. An, 2020: Reactor characterization and primary application of a state of art dual-reactor chamber in the investigation of atmospheric photochemical processes. Journal of Environmental Sciences, 98, 161–168, https://doi.org/10.1016/j.jes.2020.05.021.
Ma, X. Y., H. L. Jia, T. Sha, J. L. An, and R. Tian, 2019: Spatial and seasonal characteristics of particulate matter and gaseous pollution in China: Implications for control policy. Environmental Pollution, 248, 421–428, https://doi.org/10.1016/j.envpol.2019.02.038.
Saengsai, S., and W. Jinsart, 2015: Evaluation of urban ozone formation by photochemical ozone creation potential indices and generalized additive model. Proc. Int. Conf. on Biological, Civil and Environmental Engineering, Bali, Indonesia.
Seinfeld, J. H., and S. N. Pandis, 2006: Atmospheric Chemistry and Physics: From Air Pollution to Climate Change. 2nd ed. Wiley, 1149 pp.
Seltzer, K. M., D. T. Shindell, P. Kasibhatla, and C. S. Malley, 2020: Magnitude, trends, and impacts of ambient long-term ozone exposure in the United States from 2000 to 2015. Atmospheric Chemistry and Physics, 20(3), 1757–1775, https://doi.org/10.5194/acp-20-1757-2020.
Shi, Y. Z., Y. F. Xu, and L. Jia, 2012: Development and application of atmospheric chemical mechanisms. Climatic and Environmental Research, 17(1), 112–124, https://doi.org/10.3878/j.issn.1006-9585.2011.10061. (in Chinese with English abstract)
Talukdar, R. K., J. B. Burkholder, A. M. Schmoltner, J. M. Roberts, R. R. Wilson, and A. R. Ravishankara, 1995: Investigation of the loss processes for peroxyacetyl nitrate in the atmosphere: Uv photolysis and reaction with OH. J. Geophys. Res., 100(D7), 14 163–14 173, https://doi.org/10.1029/95JD00545.
Thera, B. T. P., and Coauthors, 2019: Composition and variability of gaseous organic pollution in the port megacity of Istanbul: Source attribution, emission ratios, and inventory evaluation. Atmospheric Chemistry and Physics, 19(23), 15 131–15 156, https://doi.org/10.5194/acp-19-15131-2019.
Venecek, M. A., W. P. L. Carter, and M. J. Kleeman, 2018: Updating the SAPRC Maximum Incremental Reactivity (MIR) scale for the United States from 1988 to 2010. Journal of the Air & Waste Management Association, 68(12), 1301–1316, https://doi.org/10.1080/10962247.2018.1498410.
Wang, T., L. K. Xue, P. Brimblecombe, Y. F. Lam, L. Li, and L. Zhang, 2017: Ozone pollution in China: A review of concentrations, meteorological influences, chemical precursors, and effects. Science of The Total Environment, 575, 1582–1596, https://doi.org/10.1016/j.scitotenv.2016.10.081.
Wang, W. G., K. Li, L. Zhou, M. F. Ge, S. Q. Hou, S. R. Tong, Y. J. Mu, and L. Jia, 2015: Evaluation and application of dual-reactor chamber for studying atmospheric oxidation processes and mechanisms. Acta Physico-Chimica Sinica, 31, 1251–1259, https://doi.org/10.3866/PKU.WHXB201504161.
Ye, C. X., H. L. Gao, N. Zhang, and X. L. Zhou, 2016: Photolysis of nitric acid and nitrate on natural and artificial surfaces. Environmental Science & Technology, 50(7), 3530–3536, https://doi.org/10.1021/acs.est.5b05032.
Ye, C. X., N. Zhang, H. L. Gao, and X. L. Zhou, 2019: Matrix effect on surface-catalyzed photolysis of nitric acid. Scientific Reports, 9, 4351, https://doi.org/10.1038/s41598-018-37973-x.
Zhao, T. Y., and Coauthors, 2020: Depression and anxiety with exposure to ozone and particulate matter: An epidemiological claims data analysis. International Journal of Hygiene and Environmental Health, 228, 113562, https://doi.org/10.1016/j.ijheh.2020.113562.
Zong, R. H., L. K. Xue, T. Wang, and W. X. Wang, 2018: Intercomparison of the Regional Atmospheric Chemistry Mechanism (RACM2) and Master Chemical Mechanism (MCM) on the simulation of acetaldehyde. Atmos. Environ., 186, 144–149, https://doi.org/10.1016/j.atmosenv.2018.05.013.
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This work was supported by the National Key R&D Program of China (2017YFC0210005), the National Natural Science Foundation of China (Nos. 41875163, 41875166 and 41375129).
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Zhang, H., Xu, Y., Jia, L. et al. Smog Chamber Study on the Ozone Formation Potential of Acetaldehyde. Adv. Atmos. Sci. 38, 1238–1251 (2021). https://doi.org/10.1007/s00376-021-0407-5
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DOI: https://doi.org/10.1007/s00376-021-0407-5