High Gas-Phase Methanesulfonic Acid Production in the OH-Initiated Oxidation of Dimethyl Sulfide at Low Temperatures.
High Gas-Phase Methanesulfonic Acid Production in the OH-Initiated Oxidation of Dimethyl Sulfide at Low Temperatures.
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DOI：
10.1021/acs.est.2c05154
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发表时间：
2022-10-04
影响因子：
11.4
通讯作者：
Worsnop, Douglas R.
中科院分区：
文献类型：
--
作者：
Shen, Jiali;Scholz, Wiebke;He, Xu-Cheng;Zhou, Putian;Marie, Guillaume;Wang, Mingyi;Marten, Ruby;Surdu, Mihnea;Rorup, Birte;Baalbaki, Rima;Amorim, Antonio;Ataei, Farnoush;Bell, David M.;Bertozzi, Barbara;Brasseur, Zoe;Caudillo, Lucia;Chen, Dexian;Chu, Biwu;Dada, Lubna;Duplissy, Jonathan;Finkenzeller, Henning;Granzin, Manuel;Guida, Roberto;Heinritzi, Martin;Hofbauer, Victoria;Iyer, Siddharth;Kemppainen, Deniz;Kong, Weimeng;Krechmer, Jordan E.;Kuerten, Andreas;Lamkaddam, Houssni;Lee, Chuan Ping;Lopez, Brandon;Mahfouz, Naser G. A.;Manninen, Hanna E.;Massabo, Dario;Mauldin, Roy L.;Mentler, Bernhard;Mueller, Tatjana;Pfeifer, Joschka;Philippov, Maxim;Piedehierro, Ana A.;Roldin, Pontus;Schobesberger, Siegfried;Simon, Mario;Stolzenburg, Dominik;Tham, Yee Jun;Tome, Antonio;Umo, Nsikanabasi Silas;Wang, Dongyu;Wang, Yonghong;Weber, Stefan K.;Welti, Andre;de Jonge, Robin Wollesen;Wu, Yusheng;Zauner-Wieczorek, Marcel;Zust, Felix;Baltensperger, Urs;Curtius, Joachim;Flagan, Richard C.;Hansel, Armin;Moehler, Ottmar;Petaja, Tuukka;Volkamer, Rainer;Kulmala, Markku;Lehtipalo, Katrianne;Rissanen, Matti;Kirkby, Jasper;El-Haddad, Imad;Bianchi, Federico;Sipila, Mikko;Donahue, Neil M.;Worsnop, Douglas R.
关键词：
二甲基硫(DMS)通过其氧化产物(主要是甲烷磺酸和硫酸)形成的云凝结核(CCN)影响气候。尽管它们很重要，但准确预测DMS氧化过程中的MSA和H_2SO_4仍然具有挑战性。通过在欧洲核子研究中心的宇宙离开室外液滴(云)舱中进行的综合实验，我们表明，从+25℃降低到−10°C时，从OH引发的二甲基硫的氧化中气相MSA的生成增加了一个数量级，而H_2SO_4的生成受到的影响不大。这导致了气相H_2SO_4与MSA的比率(H_2SO_4/MSA)小于低温下的H_2SO_4/MSA，这与极地地区的现场观测一致。通过更新的DMS氧化机理，我们发现甲烷亚磺酸，CH3S(O)OH，MSIA，形成了大量的MSA。总体而言，我们的结果表明，MSA的产率比广泛使用的主化学机理(MCMv3.3.1)预测的高2-10倍，而NOx的影响没有温度那么显著。我们的最新机制解释了在现场观察中观察到的高MSA生成率，特别是在低温下，从而证实了MSA在自然硫循环和自然CCN形成中的更大重要性。我们的机制将改进对当前和历史上的气相H_2SO_4/MSA测量的解释。了解OH在大气中引发的DMS氧化过程对于正确描述从浮游植物DMS排放到气候影响的过程链是至关重要的。
Dimethyl sulfide (DMS) influences climate via cloud condensation nuclei (CCN) formation resulting from its oxidation products (mainly methanesulfonic acid, MSA, and sulfuric acid, H2SO4). Despite their importance, accurate prediction of MSA and H2SO4 from DMS oxidation remains challenging. With comprehensive experiments carried out in the Cosmics Leaving Outdoor Droplets (CLOUD) chamber at CERN, we show that decreasing the temperature from +25 to −10 °C enhances the gas-phase MSA production by an order of magnitude from OH-initiated DMS oxidation, while H2SO4 production is modestly affected. This leads to a gas-phase H2SO4-to-MSA ratio (H2SO4/MSA) smaller than one at low temperatures, consistent with field observations in polar regions. With an updated DMS oxidation mechanism, we find that methanesulfinic acid, CH3S(O)OH, MSIA, forms large amounts of MSA. Overall, our results reveal that MSA yields are a factor of 2–10 higher than those predicted by the widely used Master Chemical Mechanism (MCMv3.3.1), and the NOx effect is less significant than that of temperature. Our updated mechanism explains the high MSA production rates observed in field observations, especially at low temperatures, thus, substantiating the greater importance of MSA in the natural sulfur cycle and natural CCN formation. Our mechanism will improve the interpretation of present-day and historical gas-phase H2SO4/MSA measurements. Understanding the OH-initiated DMS oxidation process in the atmosphere is essential to properly describe the process chain from phytoplankton DMS emissions to climate effects.
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影响因子：
4.4
作者：
BATES, TS;CALHOUN, JA;QUINN, PK
通讯作者：
QUINN, PK
影响因子：
5.5
作者：
Canaval, Eva;Hyttinen, Noora;Hansel, Armin
通讯作者：
Hansel, Armin
影响因子：
6.3
作者：
Carslaw, K. S.;Boucher, O.;Kulmala, M.
通讯作者：
Kulmala, M.
影响因子：
4.3
作者：
Damian, V;Sandu, A;Carmichael, GR
通讯作者：
Carmichael, GR
DOI：
10.1073/pnas.1211878109
发表时间：
2012-11-13
影响因子：
11.1
作者：
Dawson, Matthew L.;Varner, Mychel E.;Finlayson-Pitts, Barbara J.
通讯作者：
Finlayson-Pitts, Barbara J.