Formation of Toxic Unsaturated Multifunctional and Organosulfur Compounds From the Photosensitized Processing of Fluorene and DMSO at the Air-Water Interface
Formation of Toxic Unsaturated Multifunctional and Organosulfur Compounds From the Photosensitized Processing of Fluorene and DMSO at the Air-Water Interface
复制标题
芴和 DMSO 在空气-水界面光敏处理形成有毒不饱和多官能团和有机硫化合物
DOI：
10.1029/2019jd031839
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发表时间：
2020
影响因子：
4.4
通讯作者：
Gligorovski Sasho
中科院分区：
文献类型：
--
作者：
Mekic Majda;Zeng Jiafa;Jiang Bin;Li Xue;Lazarou Yannis G.;Brigante Marcello;Herrmann Hartmut;Gligorovski Sasho
多环芳烃和二甲基亚砜(DMSO)在海面上普遍存在。海-气界面的光化学是挥发性有机化合物的潜在重要来源，但相关的化学过程目前还不是很清楚。当含有荧烯(FL)和二甲基亚砜(DMSO)混合物的水溶液被光化辐射照射时，水相中会出现大量不饱和的高分子化合物，气相中还会观察到各种饱和和不饱和的含氧多官能团化合物，其中大多数比FL的毒性更大。提出了一种可能的步骤序列，导致在水溶液中和在气相中观察到一些化合物。反应吉布斯能的理论计算支持由FL(3FL*)的激发三重态引发的反应途径。观察到有机硫化合物的形成发生在3FL*与DMSO反应引发的气相和水相中。由于富含多环芳烃和DMSO的海洋边界层中普遍存在多环芳烃和DMSO，上述水表面的光敏化化学对海洋边界层中二次有机气溶胶的形成有重要影响。
Polycyclic aromatic hydrocarbons and dimethyl sulfoxide (DMSO) are ubiquitous at the sea surface. Photochemistry at the air‐sea interface is a potentially important source of volatile organic compounds, but the relevant chemical processes are currently not well known. When aqueous solutions containing a mixture of fluorene (FL) and DMSO are irradiated with actinic radiation, a large suite of unsaturated high molecular weight compounds appear in the aqueous phase; a broad variety of saturated and unsaturated oxygenated multifunctional compounds are also observed in the gas phase, most of which are more toxic than FL. A possible sequence of steps leading to some of the observed compounds in aqueous solution as well as in the gas phase is proposed. The reaction pathways initiated by excited triplet state of FL (3FL*) are supported by theoretical calculations of the reaction Gibbs energies. The formation of organosulfur compounds has been observed to occur in the gas and the aqueous phases initiated by the reaction between3FL* and DMSO. The aforementioned photosensitized chemistry at the water surface can have an important impact on the formation of secondary organic aerosol in marine boundary layer as polycyclic aromatic hydrocarbons and DMSO enriched at the water surface are ubiquitous.