Li Linjie, Thomsen Ditte, Wu Cheng, Priestley Michael, Iversen Emil Mark, Tygesen Sko Nager Jane, Luo Yuanyuan, Ehn Mikael, Roldin Pontus, Pedersen Henrik B, Bilde Merete, Glasius Marianne, Hallquist Mattias
Department of Chemistry and Molecular Biology, University of Gothenburg, Gothenburg 41296, Sweden.
Department of Chemistry, Aarhus University, Aarhus 8000, Denmark.
J Phys Chem A. 2024 Feb 8;128(5):918-928. doi: 10.1021/acs.jpca.3c07316. Epub 2024 Jan 31.
Formation of oxidized products from Δ-carene (CH) ozonolysis and their gas-to-particle partitioning at three temperatures (0, 10, and 20 °C) under dry conditions (<2% RH) and also at 10 °C under humid (78% RH) conditions were studied using a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) combined with a filter inlet for gases and aerosols (FIGAERO). The Δ-carene ozonolysis products detected by the FIGAERO-ToF-CIMS were dominated by semivolatile organic compounds (SVOCs). The main effect of increasing temperature or RH on the product distribution was an increase in fragmentation of monomer compounds (from C to C compounds), potentially via alkoxy scission losing a C group. The equilibrium partitioning coefficient estimated according to equilibrium partitioning theory shows that the measured SVOC products distribute more into the SOA phase as the temperature decreases from 20 to 10 and 0 °C and for most products as the RH increases from <2 to 78%. The temperature dependency of the saturation vapor pressure (above an assumed liquid state), derived from the partitioning method, also allows for a direct way to obtain enthalpy of vaporization for the detected species without accessibility of authentic standards of the pure substances. This method can provide physical properties, beneficial for, e.g., atmospheric modeling, of complex multifunctional oxidation products.
研究了在干燥条件(相对湿度<2%)下三种温度(0、10和20°C)以及在潮湿(相对湿度78%)条件下10°C时,Δ-蒈烯(CH)臭氧分解形成氧化产物及其气粒分配情况,采用飞行时间化学电离质谱仪(ToF-CIMS)结合气溶胶质滤器入口(FIGAERO)进行研究。FIGAERO-ToF-CIMS检测到的Δ-蒈烯臭氧分解产物以半挥发性有机化合物(SVOCs)为主。温度或相对湿度升高对产物分布的主要影响是单体化合物(从C到C化合物)的碎片化增加,可能是通过烷氧基断裂失去一个C基团。根据平衡分配理论估算的平衡分配系数表明,随着温度从20°C降至10°C和0°C,以及对于大多数产物随着相对湿度从<2%升至78%,所测SVOC产物更多地分配到二次有机气溶胶(SOA)相中。从分配方法得出的饱和蒸气压(假设为液态以上)的温度依赖性,也提供了一种直接方法,在无法获取纯物质真实标准品的情况下,获得所检测物种的汽化焓。该方法可为复杂多功能氧化产物提供物理性质,例如有利于大气建模。