Organosulfate Formation in Proxies for Aged Sea Spray Aerosol: Reactive Uptake of Isoprene Epoxydiols to Acidic Sodium Sulfate
Organosulfate Formation in Proxies for Aged Sea Spray Aerosol: Reactive Uptake of Isoprene Epoxydiols to Acidic Sodium Sulfate
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DOI：
10.1021/acsearthspacechem.2c00156
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发表时间：
2022-11
影响因子：
3.4
通讯作者：
Madeline E. Cooke;N. C. Armstrong;Ziying Lei;Yuzhi Chen;Cara M. Waters;Yue Zhang-;Nicolas A. Buchenau;Monica Q. Dibley;Isabel R Ledsky;Tessa Szalkowski;Jamy Y. Lee;K. Baumann;Zhenfa Zhang;W. Vizuete;A. Gold;J. Surratt;A. Ault
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作者：
Madeline E. Cooke;N. C. Armstrong;Ziying Lei;Yuzhi Chen;Cara M. Waters;Yue Zhang-;Nicolas A. Buchenau;Monica Q. Dibley;Isabel R Ledsky;Tessa Szalkowski;Jamy Y. Lee;K. Baumann;Zhenfa Zhang;W. Vizuete;A. Gold;J. Surratt;A. Ault
异戊二烯是全球排放量最高的生物源挥发性有机化合物（BVOC），其氧化是大气中二次有机气溶胶（SOA）的重要来源。由氧化产物异戊二烯环氧二醇（IEPOX）异构体的酸驱动反应形成的颗粒状有机硫酸盐是SOA质量的重要贡献者。大多数研究都集中在硫酸铵颗粒上有机硫酸盐的形成，通常在低pH值。然而，最近的工作表明，海喷雾气溶胶（SSA）的积累模式（约100 nm）是相当酸性（pH值约2），并经历进一步的非均相反应与H2SO 4形成Na 2SO 4。在此，我们证明，大量的SOA，包括有机硫酸盐，形成酸性硫酸钠颗粒（pH = 1.4 ± 0.1），通过受控的实验室实验。对于酸性硫酸钠和硫酸铵颗粒观察到相当的有机硫酸盐形成，即使具有钠相对于铵作为主要阳离子的酸性颗粒形成较少的SOA体积。 两者都表现出核-壳形态后，反应吸收的IEPOX，然而，有机硫酸盐被确定与拉曼显微光谱的核心和外壳的硫酸铵SOA颗粒，但只有在核心的硫酸钠SOA。在加拉帕戈斯岛的环境样本中也发现了关键的有机硫酸盐。我们的研究结果表明，异戊二烯衍生的SOA上形成的老年SSA是潜在的一个重要的，但未得到充分重视，源SOA和有机硫酸盐在海洋和沿海地区，可以修改SOA的预算。
Oxidation of isoprene, the biogenic volatile organic compound (BVOC) with the highest emissions globally, is a large source of secondary organic aerosol (SOA) in the atmosphere. Particulate organosulfates formed from acid-driven reactions of the oxidation products isoprene epoxydiol (IEPOX) isomers are important contributors to SOA mass. Most studies have focused on organosulfate formation on ammonium sulfate particles, often at low pH. However, recent work has shown that sea spray aerosol (SSA) in the accumulation mode (∼100 nm) is quite acidic (pH ∼2) and undergoes further heterogeneous reactions with H2SO4to form Na2SO4. Herein, we demonstrate that substantial SOA, including organosulfates, are formed on acidic sodium sulfate particles (pH = 1.4 ± 0.1) via controlled laboratory experiments. Comparable organosulfate formation was observed for acidic sodium and ammonium sulfate particles even though acidic particles with sodium versus ammonium as the primary cation formed less SOA volume. Both exhibited core-shell morphology after the reactive uptake of IEPOX; however, organosulfates were identified with Raman microspectroscopy in the core and shell of ammonium sulfate SOA particles, but only in the core for sodium sulfate SOA. Key organosulfates were also identified in ambient samples from the Galápagos Island. Our results suggest that isoprene-derived SOA formed on aged SSA is potentially an important, but underappreciated, source of SOA and organosulfates in marine and coastal regions that could modify SOA budgets.