Evaluation of reaction between SO2 and CH2OO in MCM mechanism against smog chamber data from ethylene ozonolysis
Hailiang Zhang A B , Long Jia
A B * and Yongfu Xu A B
A
B
Abstract
The process of ethylene ozonolysis is an essential source of CH2OO radicals, and the latter is an important oxidant for the atmospheric pollutant SO2. The accuracy of a widely used atmospheric chemistry model (Master Chemical Mechanism, MCM) in quantifying SO2 oxidation has not been evaluated. In this study, this accuracy was evaluated, and optimal parameters underpinned by data from smog chamber experiments.
The oxidation of SO2 by CH2OO radicals in the ethylene-O3 system is one of the important pathways of sulfate aerosol formation, but the accuracy of Master Chemical Mechanism (MCM) simulation for this reaction was not evaluated, although the MCM has been widely used in previous studies.
The oxidation of SO2 in the ethylene-O3 system was performed in detail under different conditions, which were used to evaluate the accuracy of MCM simulation for the reactions in this study.
The experimental conditions of low RH and high initial SO2 concentration favour the SO2 oxidation in the ethylene ozonolysis, and the yield of CH2OO in the ethylene ozonolysis without irradiations was determined to be 0.43. The n-hexane (C6H14) oxidation intermediates can promote the SO2 oxidation rate by generating sulfur-containing organics in the aerosol water. The original MCM simulated SO2 consumption after 4-h reaction was more than 70% smaller than the measured results. By adjusting the yield of CH2OO and updating the reaction rate constants of CH2OO-related reactions (e.g. with SO2, H2O and organic acid), the difference between experiments and simulations decreased from 70% to 6.6%.
The promotion effects of n-hexane on the oxidation of SO2 suggest that alkanes may be the precursors of sulfur-containing organics in the atmospheric environment. This study further confirms the effect of CH2OO on the oxidation of SO2 in the atmospheric environment and provides information on the performance of MCM simulation.
Keywords: Criegee intermediates, ethylene, MCM, ozone, smog chamber, sulfate, sulfur-containing organics, sulfur dioxide.
References
Assaf E, Sheps L, Whalley L, Heard D, Tomas A, Schoemaecker C, Fittschen C (2017) The reaction between CH3O2 and OH radicals: product yields and atmospheric implications. Environmental Science & Technology 51(4), 2170-2177.
| Crossref | Google Scholar | PubMed |
Berndt T, Jokinen T, Sipilä M, Mauldin RL, Herrmann H, Stratmann F, Junninen H, Kulmala M (2014a) H2SO4 formation from the gas-phase reaction of stabilized Criegee Intermediates with SO2: influence of water vapour content and temperature. Atmospheric Environment 89, 603-612.
| Crossref | Google Scholar |
Berndt T, Voigtlander J, Stratmann F, Junninen H, Mauldin 3rd RL, Sipila M, Kulmala M, Herrmann H (2014b) Competing atmospheric reactions of CH2OO with SO2 and water vapour. Physical Chemistry Chemical Physics 16(36), 19130-19136.
| Crossref | Google Scholar |
Berndt T, Kaethner R, Voigtländer J, Stratmann F, Pfeifle M, Reichle P, Sipilä M, Kulmala M, Olzmann M (2015) Kinetics of the unimolecular reaction of CH2OO and the bimolecular reactions with the water monomer, acetaldehyde and acetone under atmospheric conditions. Physical Chemistry Chemical Physics 17(30), 19862-19873.
| Crossref | Google Scholar | PubMed |
Boy M, Mogensen D, Smolander S, Zhou L, Nieminen T, Paasonen P, Plass-Dülmer C, Sipilä M, Petäjä T, Mauldin L, Berresheim H, Kulmala M (2013) Oxidation of SO2 by stabilized Criegee intermediate (sCI) radicals as a crucial source for atmospheric sulfuric acid concentrations. Atmospheric Chemistry and Physics 13(7), 3865-3879.
| Crossref | Google Scholar |
Chhantyal-Pun R, Davey A, Shallcross DE, Percival CJ, Orr-Ewing AJ (2015) A kinetic study of the CH2OO Criegee intermediate self-reaction, reaction with SO2 and unimolecular reaction using cavity ring-down spectroscopy. Physical Chemistry Chemical Physics 17(5), 3617-3626.
| Crossref | Google Scholar | PubMed |
Cox RA, Ammann M, Crowley JN, Herrmann H, Jenkin ME, McNeill VF, Mellouki A, Troe J, Wallington TJ (2020) Evaluated kinetic and photochemical data for atmospheric chemistry: volume VII – Criegee intermediates. Atmospheric Chemistry and Physics 20(21), 13497-13519.
| Crossref | Google Scholar |
Daële V, Poulet G (1996) Kinetics and products of the reactions of CH3O2 with Cl and ClO. Journal de Chimie Physique 93(6), 1081-1099.
| Crossref | Google Scholar |
Davis DD, Prusazcyk J, Dwyer M, Kim P (1974) Stop-flow time-of-flight mass spectrometry kinetics study. Reaction of ozone with nitrogen dioxide and sulfur dioxide. The Journal of Physical Chemistry 78(18), 1775-1779.
| Crossref | Google Scholar |
Ge SS, Xu YF, Jia L (2017) Secondary organic aerosol formation from ethylene ozonolysis in the presence of sodium chloride. Journal of Aerosol Science 106, 120-131.
| Crossref | Google Scholar |
Guo YS, Yan C, Li C, Ma W, Feng ZM, Zhou Y, Lin ZH, Dada L, Stolzenburg D, Yin RJ, Kontkanen J, Daellenbach KR, Kangasluoma J, Yao L, Chu BW, Wang YH, Cai RL, Bianchi F, Liu YC, Kulmala M (2021) Formation of nighttime sulfuric acid from the ozonolysis of alkenes in Beijing. Atmospheric Chemistry and Physics 21(7), 5499-5511.
| Crossref | Google Scholar |
Howes NUM, Mir ZS, Blitz MA, Hardman S, Lewis TR, Stone D, Seakins PW (2018) Kinetic studies of C1 and C2 Criegee intermediates with SO2 using laser flash photolysis coupled with photoionization mass spectrometry and time resolved UV absorption spectroscopy. Physical Chemistry Chemical Physics 20(34), 22218-22227.
| Crossref | Google Scholar | PubMed |
Huang HL, Chao W, Lin JJ (2015) Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO2. Proceedings of the National Academy of Sciences 112(35), 10857-10862.
| Crossref | Google Scholar | PubMed |
Jenkin ME, Young JC, Rickard AR (2015) The MCM v3.3.1 degradation scheme for isoprene. Atmospheric Chemistry and Physics 15(20), 11433-11459.
| Crossref | Google Scholar |
Jia L, Xu YF (2016) Ozone and secondary organic aerosol formation from Ethylene-NOx-NaCl irradiations under different relative humidity conditions. Journal of Atmospheric Chemistry 73(1), 81-100.
| Crossref | Google Scholar |
Jia L, Xu YF (2018) Different roles of water in secondary organic aerosol formation from toluene and isoprene. Atmospheric Chemistry and Physics. 18, 8137-8154.
| Crossref | Google Scholar |
Jia L, Xu Y (2020) The role of functional groups in the understanding of secondary organic aerosol formation mechanism from α-pinene. The Science of the total environment 738, 139831.
| Crossref | Google Scholar | PubMed |
Jia L, Xu YF (2021) A core-shell box model for simulating viscosity dependent secondary organic aerosol (CSVA) and its application. Science of the Total Environment 789, 147954.
| Crossref | Google Scholar | PubMed |
Jia L, Xu YF, Duan MZ (2023) Explosive formation of secondary organic aerosol due to aerosol-fog interactions. Science of the Total Environment 866, 161338.
| Crossref | Google Scholar | PubMed |
Jr-Min Lin J, Chao W (2017) Structure-dependent reactivity of Criegee intermediates studied with spectroscopic methods. Chemical Society Reviews 46(24), 7483-7497.
| Crossref | Google Scholar | PubMed |
Khan MAH, Percival CJ, Caravan RL, Taatjes CA, Shallcross DE (2018) Criegee intermediates and their impacts on the troposphere. Environmental Science: Processes & Impacts 20(3), 437-453.
| Crossref | Google Scholar | PubMed |
Kim S, Guenther A, Lefer B, Flynn J, Griffin R, Rutter AP, Gong LW, Cevik BK (2015) Potential role of stabilized criegee radicals in sulfuric acid production in a high biogenic VOC environment. Environmental Science & Technology 49(6), 3383-3391.
| Crossref | Google Scholar | PubMed |
Kukui A, Chartier M, Wang J, Chen H, Dusanter S, Sauvage S, Michoud V, Locoge N, Gros V, Bourrianne T, Sellegri K, Pichon J-M (2021) Role of Criegee intermediates in the formation of sulfuric acid at a Mediterranean (Cape Corsica) site under influence of biogenic emissions. Atmospheric Chemistry and Physics 21(17), 13333-13351.
| Crossref | Google Scholar |
Li MZ, Karu E, Brenninkmeijer C, Fischer H, Lelieveld J, Williams J (2018) Tropospheric OH and stratospheric OH and Cl concentrations determined from CH4, CH3Cl, and SF6 measurements. Npj Climate and Atmospheric Science 1, 29.
| Crossref | Google Scholar |
Liu Y, Liu F, Liu S, Dai D, Dong W, Yang X (2017) A kinetic study of the CH2OO Criegee intermediate reaction with SO2, (H2O)2, CH2I2 and I atoms using OH laser induced fluorescence. Physical Chemistry Chemical Physics 19(31), 20786-20794.
| Crossref | Google Scholar | PubMed |
Liu CT, Mu YJ, Zhang CL, Liu JF, Liu PF, He XW, Li XR (2021) A comparison investigation of atmospheric NMHCs at two sampling sites of Beijing city and a rural area during summertime. Science of the Total Environment 783, 146867.
| Crossref | Google Scholar |
Mauldin 3rd RL, Berndt T, Sipilä M, Paasonen P, Petäjä T, Kim S, Kurtén T, Stratmann F, Kerminen VM, Kulmala M (2012) A new atmospherically relevant oxidant of sulphur dioxide. Nature 488(7410), 193-196.
| Crossref | Google Scholar | PubMed |
Newland MJ, Rickard AR, Alam MS, Vereecken L, Muñoz A, Ródenas M, Bloss WJ (2015) Kinetics of stabilised criegee intermediates derived from alkene ozonolysis: reactions with SO2, H2O and decomposition under boundary layer conditions. Physical Chemistry Chemical Physics 17(6), 4076-4088.
| Crossref | Google Scholar | PubMed |
Newland MJ, Nelson BS, Muñoz A, Ródenas M, Vera T, Tárrega J, Rickard AR (2020) Trends in stabilisation of Criegee intermediates from alkene ozonolysis. Physical Chemistry Chemical Physics 22(24), 13698-13706.
| Crossref | Google Scholar | PubMed |
Nguyen TB, Tyndall GS, Crounse JD, Teng AP, Bates KH, Schwantes RH, Coggon MM, Zhang L, Feiner P, Milller DO, Skog KM, Rivera-Rios JC, Dorris M, Olson KF, Koss A, Wild RJ, Brown SS, Goldstein AH, de Gouw JA, Brune WH, Keutsch FN, Seinfeld JH, Wennberg PO (2016) Atmospheric fates of Criegee intermediates in the ozonolysis of isoprene. Physical Chemistry Chemical Physics 18(15), 10241-10254.
| Crossref | Google Scholar | PubMed |
Sakamoto Y, Inomata S, Hirokawa J (2013) Oligomerization reaction of the criegee intermediate leads to secondary organic aerosol formation in ethylene ozonolysis. Journal of Physical Chemistry A 117(48), 12912-12921.
| Crossref | Google Scholar | PubMed |
Sarwar G, Fahey K, Kwok R, Gilliam RC, Roselle SJ, Mathur R, Xue J, Yu J, Carter WPL (2013) Potential impacts of two SO2 oxidation pathways on regional sulfate concentrations: aqueous-phase oxidation by NO2 and gas-phase oxidation by Stabilized Criegee Intermediates. Atmospheric Environment 68, 186-197.
| Crossref | Google Scholar |
Sipilä M, Jokinen T, Berndt T, Richters S, Makkonen R, Donahue NM, Mauldin Iii RL, Kurtén T, Paasonen P, Sarnela N, Ehn M, Junninen H, Rissanen MP, Thornton J, Stratmann F, Herrmann H, Worsnop DR, Kulmala M, Kerminen VM, Petäjä T (2014) Reactivity of stabilized Criegee intermediates (sCIs) from isoprene and monoterpene ozonolysis toward SO2 and organic acids. Atmospheric Chemistry and Physics 14(22), 12143-12153.
| Crossref | Google Scholar |
Stewart GJ, Nelson BS, Drysdale WS, Acton WJF, Vaughan AR, Hopkins JR, Dunmore RE, Hewitt CN, Nemitz E, Mullinger N, Langford B, Shivani , Reyes-Villegas E, Gadi R, Rickard AR, Lee JD, Hamilton JF (2021) Sources of non-methane hydrocarbons in surface air in Delhi, India. Faraday Discussions 226, 409-431.
| Crossref | Google Scholar | PubMed |
Vereecken L (2017) The reaction of Criegee intermediates with acids and enols. Physical Chemistry Chemical Physics 19(42), 28630-28640.
| Crossref | Google Scholar |
Vereecken L, Novelli A, Taraborrelli D (2017) Unimolecular decay strongly limits the atmospheric impact of Criegee intermediates. Physical Chemistry Chemical Physics 19, 31599-31612.
| Crossref | Google Scholar |
Vereecken L, Novelli A, Kiendler-Scharr A, Wahner A (2022) Unimolecular and water reactions of oxygenated and unsaturated Criegee intermediates under atmospheric conditions. Physical Chemistry Chemical Physics 24(11), 6428-6443.
| Crossref | Google Scholar | PubMed |
Welz O, Savee JD, Osborn DL, Vasu SS, Percival CJ, Shallcross DE, Taatjes CA (2012) Direct kinetic measurements of criegee intermediate (CH2OO) formed by reaction of CH2I with O2. Science 335(6065), 204-207.
| Crossref | Google Scholar | PubMed |
Welz O, Eskola AJ, Sheps L, Rotavera B, Savee JD, Scheer AM, Osborn DL, Lowe D, Murray Booth A, Xiao P, Anwar H Khan M, Percival CJ, Shallcross DE, Taatjes CA (2014) Rate coefficients of C1 and C2 criegee intermediate reactions with formic and acetic acid near the collision limit: Direct kinetics measurements and atmospheric implications. Angewandte Chemie International Edition 53(18), 4547-4550.
| Crossref | Google Scholar | PubMed |
Yang S, Li X, Song M, Liu Y, Yu X, Chen S, Lu S, Wang W, Yang Y, Zeng L, Zhang Y (2021) Characteristics and sources of volatile organic compounds during pollution episodes and clean periods in the Beijing–Tianjin–Hebei region. Science of the Total Environment 799, 149491.
| Crossref | Google Scholar | PubMed |
Yao D, Tang GQ, Sun J, Wang YH, Yang Y, Wang YM, Liu BX, He H, Wang YS (2022) Annual nonmethane hydrocarbon trends in Beijing from 2000 to 2019. Journal of Environmental Sciences 112, 210-217.
| Crossref | Google Scholar | PubMed |
Ye J, Abbatt JPD, Chan AWH (2018) Novel pathway of SO2 oxidation in the atmosphere: reactions with monoterpene ozonolysis intermediates and secondary organic aerosol. Atmospheric Chemistry and Physics 18(8), 5549-5565.
| Crossref | Google Scholar |
Yu SS, Jia L, Xu YF, Zhang HL, Zhang Q, Pan YP (2022) Wall losses of oxygenated volatile organic compounds from oxidation of toluene: effects of chamber volume and relative humidity. Journal of Environmental Sciences 114, 475-484.
| Crossref | Google Scholar | PubMed |
Zhang Q, Xu YF, Jia L (2019) Secondary organic aerosol formation from OH-initiated oxidation of m-xylene: effects of relative humidity on yield and chemical composition. Atmospheric Chemistry and Physics 19(23), 15007-15021.
| Crossref | Google Scholar |
Zhang L, Li H, Wu Z, Zhang W, Liu K, Cheng X, Zhang Y, Li B, Chen Y (2020) Characteristics of atmospheric volatile organic compounds in urban area of Beijing: variations, photochemical reactivity and source apportionment. Journal of Environmental Sciences 95, 190-200.
| Crossref | Google Scholar | PubMed |
Zhang H, Xu Y, Jia L, Xu M (2021a) Smog chamber study on the ozone formation potential of acetaldehyde. Advances in Atmospheric Sciences 38(7), 1238-1251.
| Crossref | Google Scholar |
Zhang HL, Xu YF, Jia L (2021b) A chamber study of catalytic oxidation of SO2 by Mn2+/Fe3+ in aerosol water. Atmospheric Environment 245, 118019.
| Crossref | Google Scholar |
Zhang H L, Xu YF, Jia L (2022) Hydroxymethanesulfonate formation as a significant pathway of transformation of SO2. Atmospheric Environment 294, 119474.
| Crossref | Google Scholar |
Zong RH, Xue LK, Wang TB, Wang WX (2018) Inter-comparison of the Regional Atmospheric Chemistry Mechanism (RACM2) and Master Chemical Mechanism (MCM) on the simulation of acetaldehyde. Atmospheric Environment 186, 144-149.
| Crossref | Google Scholar |
Zulkifli MFH, Hawari N, Latif MT, Abd Hamid HH, Mohtar AAA, Idris W, Mustaffa NIH, Juneng L (2022) Volatile organic compounds and their contribution to ground-level ozone formation in a tropical urban environment. Chemosphere 302, 134852.
| Crossref | Google Scholar |
