Kalliopi Florou, Agata Błaziak, Spiro Jorga, Petro Uruci, Christina N. Vasilakopoulou, Rafał Szmigielski and Spyros N. Pandis*,
{"title":"对苯二甲酸气溶胶的性质和大气氧化作用","authors":"Kalliopi Florou, Agata Błaziak, Spiro Jorga, Petro Uruci, Christina N. Vasilakopoulou, Rafał Szmigielski and Spyros N. Pandis*, ","doi":"10.1021/acsearthspacechem.4c0020110.1021/acsearthspacechem.4c00201","DOIUrl":null,"url":null,"abstract":"<p >Terebic acid (C<sub>7</sub>H<sub>10</sub>O<sub>4</sub>) is a biogenic secondary organic aerosol constituent, produced by the oxidation of first- and second-generation products of monoterpenes such as α<i>-</i>pinene, β-pinene, and Δ<sup>3</sup>-carene. It is a processed derivative of terpenylic acid and has been identified in aerosol samples from terrestrial and forest environments. The physicochemical properties of pure terebic acid aerosol were characterized using two different atmospheric simulation chambers and a suite of online particle and gas-phase instrumentation. Its mass spectrum, obtained by a high-resolution time-of-flight mass spectrometer, had characteristic peaks at mass-to-charge (<i>m</i>/<i>z</i>) ratios 81, 96, 100, 115, and 143, mainly related to oxygenated fragment ions. The density of terebic acid aerosol was 1.33 ± 0.20 g cm<sup>–3</sup>, and its vaporization enthalpy was 85 kJ mol<sup>–1</sup>. The estimated saturation concentration at 298 K of 2.6 ± 1.2 μg m<sup>–3</sup> places terebic acid in the semivolatile organic compound category. Oxidation of terebic acid aerosol by hydroxyl (OH) radicals resulted in a substantial reduction in organic aerosol (OA) mass concentration (up to 80%), with no significant alteration in the OA spectrum or aerosol O:C ratio, indicating negligible production of secondary OA. Gas-phase analysis detected the production of smaller compounds, such as acetone. The terebic acid oxidation products were mostly in the gas phase as fragmentation appears to dominate its reaction with OH radicals. The gas-phase reaction rate constant with OH was estimated to be 3 × 10<sup>–12</sup> cm<sup>3</sup> molecule<sup>–1</sup> s<sup>–1</sup>.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 10","pages":"2090–2100 2090–2100"},"PeriodicalIF":2.9000,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00201","citationCount":"0","resultStr":"{\"title\":\"Properties and Atmospheric Oxidation of Terebic Acid Aerosol\",\"authors\":\"Kalliopi Florou, Agata Błaziak, Spiro Jorga, Petro Uruci, Christina N. Vasilakopoulou, Rafał Szmigielski and Spyros N. Pandis*, \",\"doi\":\"10.1021/acsearthspacechem.4c0020110.1021/acsearthspacechem.4c00201\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Terebic acid (C<sub>7</sub>H<sub>10</sub>O<sub>4</sub>) is a biogenic secondary organic aerosol constituent, produced by the oxidation of first- and second-generation products of monoterpenes such as α<i>-</i>pinene, β-pinene, and Δ<sup>3</sup>-carene. It is a processed derivative of terpenylic acid and has been identified in aerosol samples from terrestrial and forest environments. The physicochemical properties of pure terebic acid aerosol were characterized using two different atmospheric simulation chambers and a suite of online particle and gas-phase instrumentation. Its mass spectrum, obtained by a high-resolution time-of-flight mass spectrometer, had characteristic peaks at mass-to-charge (<i>m</i>/<i>z</i>) ratios 81, 96, 100, 115, and 143, mainly related to oxygenated fragment ions. The density of terebic acid aerosol was 1.33 ± 0.20 g cm<sup>–3</sup>, and its vaporization enthalpy was 85 kJ mol<sup>–1</sup>. The estimated saturation concentration at 298 K of 2.6 ± 1.2 μg m<sup>–3</sup> places terebic acid in the semivolatile organic compound category. Oxidation of terebic acid aerosol by hydroxyl (OH) radicals resulted in a substantial reduction in organic aerosol (OA) mass concentration (up to 80%), with no significant alteration in the OA spectrum or aerosol O:C ratio, indicating negligible production of secondary OA. Gas-phase analysis detected the production of smaller compounds, such as acetone. The terebic acid oxidation products were mostly in the gas phase as fragmentation appears to dominate its reaction with OH radicals. The gas-phase reaction rate constant with OH was estimated to be 3 × 10<sup>–12</sup> cm<sup>3</sup> molecule<sup>–1</sup> s<sup>–1</sup>.</p>\",\"PeriodicalId\":15,\"journal\":{\"name\":\"ACS Earth and Space Chemistry\",\"volume\":\"8 10\",\"pages\":\"2090–2100 2090–2100\"},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2024-09-21\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00201\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Earth and Space Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acsearthspacechem.4c00201\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Earth and Space Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsearthspacechem.4c00201","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
摘要
萜烯酸(C7H10O4)是一种生物次生有机气溶胶成分,由α-蒎烯、β-蒎烯和Δ3-蒈烯等单萜烯的第一代和第二代产物氧化产生。它是萜烯酸的加工衍生物,已在陆地和森林环境的气溶胶样本中发现。利用两种不同的大气模拟室和一套在线粒子和气相仪器对纯萜烯酸气溶胶的物理化学特性进行了鉴定。通过高分辨率飞行时间质谱仪获得的气溶胶质谱在质量电荷比(m/z)为 81、96、100、115 和 143 的位置出现了特征峰,主要与含氧碎片离子有关。苧麻酸气溶胶的密度为 1.33 ± 0.20 g cm-3,气化焓为 85 kJ mol-1。298 K 时的饱和浓度估计为 2.6 ± 1.2 μg m-3,因此苧烯酸属于半挥发性有机化合物。羟基(OH)自由基对苧烯酸气溶胶的氧化作用导致有机气溶胶(OA)质量浓度大幅降低(高达 80%),而 OA 光谱或气溶胶 O:C 比率没有发生显著变化,这表明二次 OA 的产生可以忽略不计。气相分析检测到产生了较小的化合物,如丙酮。苧烯酸的氧化产物大多在气相中,因为其与羟基自由基的反应似乎以碎片化为主。与 OH 的气相反应速率常数估计为 3 × 10-12 cm3 molecule-1 s-1。
Properties and Atmospheric Oxidation of Terebic Acid Aerosol
Terebic acid (C7H10O4) is a biogenic secondary organic aerosol constituent, produced by the oxidation of first- and second-generation products of monoterpenes such as α-pinene, β-pinene, and Δ3-carene. It is a processed derivative of terpenylic acid and has been identified in aerosol samples from terrestrial and forest environments. The physicochemical properties of pure terebic acid aerosol were characterized using two different atmospheric simulation chambers and a suite of online particle and gas-phase instrumentation. Its mass spectrum, obtained by a high-resolution time-of-flight mass spectrometer, had characteristic peaks at mass-to-charge (m/z) ratios 81, 96, 100, 115, and 143, mainly related to oxygenated fragment ions. The density of terebic acid aerosol was 1.33 ± 0.20 g cm–3, and its vaporization enthalpy was 85 kJ mol–1. The estimated saturation concentration at 298 K of 2.6 ± 1.2 μg m–3 places terebic acid in the semivolatile organic compound category. Oxidation of terebic acid aerosol by hydroxyl (OH) radicals resulted in a substantial reduction in organic aerosol (OA) mass concentration (up to 80%), with no significant alteration in the OA spectrum or aerosol O:C ratio, indicating negligible production of secondary OA. Gas-phase analysis detected the production of smaller compounds, such as acetone. The terebic acid oxidation products were mostly in the gas phase as fragmentation appears to dominate its reaction with OH radicals. The gas-phase reaction rate constant with OH was estimated to be 3 × 10–12 cm3 molecule–1 s–1.
期刊介绍:
The scope of ACS Earth and Space Chemistry includes the application of analytical, experimental and theoretical chemistry to investigate research questions relevant to the Earth and Space. The journal encompasses the highly interdisciplinary nature of research in this area, while emphasizing chemistry and chemical research tools as the unifying theme. The journal publishes broadly in the domains of high- and low-temperature geochemistry, atmospheric chemistry, marine chemistry, planetary chemistry, astrochemistry, and analytical geochemistry. ACS Earth and Space Chemistry publishes Articles, Letters, Reviews, and Features to provide flexible formats to readily communicate all aspects of research in these fields.