New tracer compounds for secondary organic aerosol formation from beta-caryophyllene oxidation
New tracer compounds for secondary organic aerosol formation from beta-caryophyllene oxidation
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DOI：
10.1016/j.atmosenv.2013.07.060
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发表时间：
2013-12
影响因子：
5
通讯作者：
Anna van Eijck;T. Opatz;D. Taraborrelli;R. Sander;T. Hoffmann
中科院分区：
文献类型：
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作者：
Anna van Eijck;T. Opatz;D. Taraborrelli;R. Sander;T. Hoffmann
合成了5种β-香石竹烯氧化产物（β-香石竹酸（I）、3，3-二甲基-2-（3-氧代丁基）环丁烷甲酸（β CA 198）（II）、β-降冰片烯酸（III）、β-丁香叶氨酸（IV）和2-（2-羧乙基）-3，3-二甲基环丁烷甲酸（β CA 200）（V）），并通过核磁共振谱对其结构进行了表征。在两种不同臭氧混合比下进行了β-香芹烯的反应室实验，并通过APCI-MS和HPLC-ESI-MS对颗粒相中的羧酸氧化产物进行了表征。在反应室气溶胶中发现所有五种合成的酸都是β-香紫苏烯氧化产物。反应室实验的主要氧化产物为β-14-羟基诺卡酮酸、β-诺卡酮酸（III）和β CA 198（II）。根据气室实验和大气化学箱模型CAABA/MECCA的应用，估算了酸的产物产率。最后，对2010年夏季在芬兰Hyytiälä进行的HUMPPA活动期间采集的环境气溶胶样本进行了分析，以确定羧酸β-卡丁车烯氧化产物。所有五个合成的化合物被检测到，并在环境气溶胶样品中进行定量。环境空气样本中的主要β-香芹烯羧酸氧化产物是β-降冰片烯酸（III）和β CA 198（II），浓度范围约为0.2-14 ng m− 3和0.8-6.8 ng m−3。这两种酸在环境气溶胶中的浓度通常高于β-丁香酸（IV）（在以前的研究中经常用作氧化示踪剂）的浓度，其浓度约为0.16 ng m− 3，这一事实导致得出结论，这两种酸更适合作为β-丁香烯二次有机气溶胶形成的示踪化合物。
Five products from β-caryophyllene oxidation (β-caryophyllonic acid (I), 3,3-dimethyl-2-(3-oxobutyl)cyclobutanecarboxylic acid (βCA198) (II), β-nocaryophyllonic acid (III), β-caryophyllinic acid (IV), and 2-(2-carboxyethyl)-3,3-dimethylcyclobutanecarboxylic acid (βCA200) (V)) were synthesized and their structures confirmed by nuclear magnetic resonance spectroscopy. Reaction chamber experiments with β-caryophyllene at two different ozone mixing ratios were performed and the carboxylic acid oxidation products in the particle phase were characterized by APCI–MS and HPLC–ESI–MS. All five synthesized acids were found as β-caryophyllene oxidation products in the reaction chamber aerosol. The main oxidation products of the reaction chamber experiments were β-14-hydroxynocaryophyllonic acid, β-nocaryophyllonic acid (III) and βCA198 (II). Product yields of the acids were estimated based on the chamber experiments and the application of the atmospheric chemistry box model CAABA/MECCA. Finally, ambient aerosol samples taken during the HUMPPA campaign in Hyytiälä, Finland in summer 2010 were analysed for the carboxylic acid β-caryophyllene oxidation products. All five synthesized compounds were detected and were quantified in the ambient aerosol samples. The major β-caryophyllene carboxylic acid oxidation products in the ambient air samples were β-nocaryophyllonic acid (III) and βCA198 (II) with concentrations in the range of about 0.2–14 ng m−3and 0.8–6.8 ng m−3. The fact that the concentrations of these two acids in ambient aerosol are generally higher than the concentration of β-caryophyllinic acid (IV) (often used in previous studies as oxidation tracer) with a concentration of about 0.16 ng m−3leads to the conclusion that these two acids are better suited as tracer compounds for β-caryophyllene secondary organic aerosol formation.