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首页> 外文期刊>Atmospheric Chemistry and Physics Discussions >Heterogeneous OH oxidation of isoprene-epoxydiol-derived organosulfates: kinetics, chemistry and formation of inorganic sulfate
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Heterogeneous OH oxidation of isoprene-epoxydiol-derived organosulfates: kinetics, chemistry and formation of inorganic sulfate

机译:异戊二烯 - 环氧二醇衍生的有机硫酸盐的异质oh氧化:动力学,化学和无机硫酸盐的形成

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摘要

Acid-catalyzed multiphase chemistry of epoxydiols formed from isoprene oxidation yields the most abundant organosulfates (i.e., methyltetrol sulfates) detected in atmospheric fine aerosols in the boundary layer. This potentially determines the physicochemical properties of fine aerosols in isoprene-rich regions. However, chemical stability of these organosulfates remains unclear. As a result, we investigate the heterogeneous oxidation of aerosols consisting of potassium 3-methyltetrol sulfate ester (C5H11SO7K) by gas-phase hydroxyl (OH) radicals at a relative humidity (RH) of 70.8%. Real-time molecular composition of the aerosols is obtained by using a Direct Analysis in Real Time (DART) ionization source coupled to a high-resolution mass spectrometer. Aerosol mass spectra reveal that 3-methyltetrol sulfate ester can be detected as its anionic form (C5H11SO7-) via direct ionization in the negative ionization mode. Kinetic measurements reveal that the effective heterogeneous OH rate constant is measured to be 4.74±0.2×10-13cm3molecule?1s?1 with a chemical lifetime against OH oxidation of 16.2±0.3?days, assuming an OH radical concentration of 1.5×106moleculescm?3. Comparison of this lifetime with those against other aerosol removal processes, such as dry and wet deposition, suggests that 3-methyltetrol sulfate ester is likely to be chemically stable over atmospheric timescales. Aerosol mass spectra only show an increase in the intensity of bisulfate ion (HSO4-) after oxidation, suggesting the importance of fragmentation processes. Overall, potassium 3-methyltetrol sulfate ester likely decomposes to form volatile fragmentation products and aqueous-phase sulfate radial anion (SO4?-). SO4?- subsequently undergoes intermolecular hydrogen abstraction to form HSO4-. These processes appear to explain the compositional evolution of 3-methyltetrol sulfate ester during heterogeneous OH oxidation.
机译:由异戊二烯氧化形成的环氧二醇的酸催化的多相化学产生最丰富的有机硫酸盐(即甲基四硫酸盐)在边界层中的大气细腻气溶胶中检测到。这可能决定了富含异戊二烯区域的细气溶胶的物理化学特性。然而,这些有机硫酸盐的化学稳定性仍然尚不清楚。结果,我们研究了通过70.8%的相对湿度(RH)的气相羟基(OH)自由基通过气相羟基(OH)基团组成的气溶胶的异质氧化。通过使用直接分析(DART)电离源耦合到高分辨率质谱仪来获得气溶胶的实时分子组成。气溶胶质谱表明,通过在负电离模式中通过直接电离可以通过直接电离检测3-甲基四硫酸酯酯作为其阴离子形式(C5H11SO7-)。动力学测量表明,测量有效的异构OH速率常数为4.74±0.2×10-13cm3mm3m2〜1s?1,用化学寿命为16.2±0.3?天,假设oh自由基浓度为1.5×106moleculescm?3 。将这种寿命与反对其他气溶胶去除方法(如干湿沉积)的比较表明,3-甲基四硫酸酯酯在大气压尺寸上可能在化学稳定。气溶胶质谱仅显示氧化后双硫酸酯离子(HSO4-)的强度增加,表明碎片过程的重要性。总体而言,3-甲基四硫酸氢磺酸酯可能分解以形成挥发性碎片产物和水相硫酸盐径向阴离子(SO 4→ - )。 SO4? - 随后经历分子间氢抽取以形成HSO4-。这些方法似乎在异晶oh氧化过程中解释了3-甲基四硫酸酯酯的组成演变。

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