School of Chemical and Biomolecular Engineering, Georgia Institute of Technology , Atlanta, Georgia 30332, United States.
School of Earth and Atmospheric Sciences, Georgia Institute of Technology , Atlanta, Georgia 30332, United States.
Environ Sci Technol. 2017 Jul 18;51(14):7831-7841. doi: 10.1021/acs.est.7b01460. Epub 2017 Jul 6.
Nitrate radical (NO) oxidation of biogenic volatile organic compounds (BVOC) is important for nighttime secondary organic aerosol (SOA) formation. SOA produced at night may evaporate the following morning due to increasing temperatures or dilution of semivolatile compounds. We isothermally dilute the oxidation products from the limonene+NO reaction at 25 °C and observe negligible evaporation of organic aerosol via dilution. The SOA yields from limonene+NO are approximately constant (∼174%) at 25 °C and range from 81 to 148% at 40 °C. Based on the difference in yields between the two temperatures, we calculated an effective enthalpy of vaporization of 117-237 kJ mol. The aerosol yields at 40 °C can be as much as 50% lower compared to 25 °C. However, when aerosol formed at 25 °C is heated to 40 °C, only about 20% of the aerosol evaporates, which could indicate a resistance to aerosol evaporation. To better understand this, we probe the possibility that SOA from limonene+NO and β-pinene+NO reactions is highly viscous. We demonstrate that particle morphology and evaporation is dependent on whether SOA from limonene is formed before or during the formation of SOA from β-pinene. This difference in particle morphology is present even at high relative humidity (∼70%).
硝自由基(NO)氧化生物源挥发性有机化合物(BVOC)对于夜间次生有机气溶胶(SOA)的形成非常重要。由于温度升高或半挥发性化合物的稀释,夜间产生的 SOA 可能会在次日清晨蒸发。我们在 25°C 下对柠檬烯+NO 反应的氧化产物进行等温稀释,发现有机气溶胶通过稀释几乎没有蒸发。在 25°C 下,柠檬烯+NO 的 SOA 产率约为 174%且保持不变,而在 40°C 下的产率范围为 81%至 148%。基于两种温度下产率的差异,我们计算出蒸发的有效焓约为 117-237 kJ/mol。与 25°C 相比,40°C 下的气溶胶产率可能低 50%。然而,当在 25°C 下形成的气溶胶加热到 40°C 时,只有约 20%的气溶胶蒸发,这可能表明气溶胶蒸发存在阻力。为了更好地理解这一点,我们探讨了柠檬烯+NO 和β-蒎烯+NO 反应生成的 SOA 具有高粘性的可能性。我们证明了来自柠檬烯的 SOA 是在形成来自β-蒎烯的 SOA 之前还是期间形成,这会影响颗粒形态和蒸发。即使在相对湿度较高(约 70%)的情况下,这种颗粒形态的差异仍然存在。