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由半挥发性异戊二烯环氧二醇异构化产物氧化形成的二次有机气溶胶的化学成分。

Chemical Composition of Secondary Organic Aerosol Formed from the Oxidation of Semivolatile Isoprene Epoxydiol Isomerization Products.

作者信息

Frauenheim Molly, Offenberg John, Zhang Zhenfa, Surratt Jason D, Gold Avram

机构信息

Department of Environmental Sciences and Engineering, Gillings School of Global Public Health, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States.

Atmospheric Chemistry and Aerosols Branch, Atmospheric and Environmental Systems Modeling Division, Center for Environmental Measurement and Modeling, Office of Research and Development, United States Environmental Protection Agency, Research Triangle Park, North Carolina 27711, United States.

出版信息

Environ Sci Technol. 2024 Dec 24;58(51):22571-22582. doi: 10.1021/acs.est.4c06850. Epub 2024 Dec 12.

Abstract

3-Methylenebutane-1,2,4-triol and 3-methyltetrahydrofuran-2,4-diols, previously designated "C-alkene triols", were recently confirmed as in-particle isomerization products of isoprene-derived β-IEPOX isomers that are formed upon acid-driven uptake and partition back into the gas phase. In chamber experiments, we have systematically explored their gas phase oxidation by hydroxyl radical (OH) as a potential source of secondary organic aerosol (SOA). OH-initiated oxidation of both compounds in the presence of ammonium bisulfate aerosol resulted in substantial aerosol volume growth. Compositions of low-volatility products in both the gas and particulate phases were established by high-resolution mass spectrometry measurements. Under conditions mimicking the Southeast USA (50% relative humidity, bulk seed aerosol pH 1.4), we estimate the SOA yield from OH-initiated oxidation of 3-methylenebutane-1,2,4-triol to be 93.1%, equating to 1.95 ± 0.81 Tg C Yr, and from 3-methyltetrahydrofuran-2,4-diol oxidation to be 26.7%, equating to 1.76 ± 1.26 Tg C Yr. Previously unreported isoprene-derived oxidation products, 2,3-dihydroxy-2-(hydroxymethyl)propanal, 1,3,4-trihydroxybutan-2-one, and four organosulfates have been confirmed in ambient SOA, and aid in understanding isoprene oxidation pathways in HO dominated environments as NO levels continue to decline in the US. This work underlines the need for inclusion of partitioning of in-particle formed semivolatile products and their atmospheric oxidation pathways in atmospheric models.

摘要

3-亚甲基丁烷-1,2,4-三醇和3-甲基四氢呋喃-2,4-二醇,之前被称为“C-烯烃三醇”,最近被确认为异戊二烯衍生的β-环氧乙二醛异构体的颗粒内异构化产物,这些产物是在酸驱动的摄取过程中形成,并重新分配回到气相中。在腔室实验中,我们系统地研究了它们被羟基自由基(OH)气相氧化的过程,将其作为二次有机气溶胶(SOA)的潜在来源。在硫酸氢铵气溶胶存在的情况下,OH引发的这两种化合物的氧化导致气溶胶体积大幅增长。通过高分辨率质谱测量确定了气相和颗粒相中低挥发性产物的组成。在美国东南部的模拟条件下(相对湿度50%,整体种子气溶胶pH值1.4),我们估计OH引发的3-亚甲基丁烷-1,2,4-三醇氧化产生的SOA产率为93.1%,相当于1.95±0.81 Tg C/年,3-甲基四氢呋喃-2,4-二醇氧化产生的SOA产率为26.7%,相当于1.76±1.26 Tg C/年。在环境SOA中已确认了之前未报道的异戊二烯衍生的氧化产物,即2,3-二羟基-2-(羟甲基)丙醛、1,3,4-三羟基丁-2-酮和四种有机硫酸盐,这有助于理解在美国NO水平持续下降的以HO为主导的环境中的异戊二烯氧化途径。这项工作强调了在大气模型中纳入颗粒内形成的半挥发性产物的分配及其大气氧化途径的必要性。

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