Guo Hongyu, Weber Rodney J, Nenes Athanasios
School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA, 30332, USA.
School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA, 30332, USA.
Sci Rep. 2017 Sep 21;7(1):12109. doi: 10.1038/s41598-017-11704-0.
High levels of ammonia (NH) have been suggested to elevate ambient particle pH levels to near neutral acidity (pH = 7), a condition that promotes rapid SO oxidation by NO to form aerosol sulfate concentration consistent with "London fog" levels. This postulation is tested using aerosol data from representative sites around the world to conduct a thorough thermodynamic analysis of aerosol pH and its sensitivity to NH levels. We find that particle pH, regardless of ammonia levels, is always acidic even for the unusually high NH levels found in Beijing (pH = 4.5) and Xi'an (pH = 5), locations where sulfate production from NO is proposed. Therefore, major sulfate oxidation through a NO-mediated pathway is not likely in China, or any other region of the world (e.g., US, Mediterranean) where the aerosol is consistently more acidic. The limited alkalinity from the carbonate buffer in dust and seasalt can provide the only likely set of conditions where NO-mediated oxidation of SO outcompetes with other well-established pathways. The mildly acidic levels associated with excessive amounts of ammonia can promote high rates of SO oxidation through transition metal chemistry, this may be an alternative important aerosol chemical contributor to the extreme pollution events.
高水平的氨(NH)被认为会使环境颗粒物的pH值升高至接近中性酸度(pH = 7),这种条件会促进NO将SO快速氧化,从而形成与“伦敦烟雾”水平一致的气溶胶硫酸盐浓度。利用来自世界各地代表性站点的气溶胶数据对这一假设进行了检验,以对气溶胶pH值及其对NH水平的敏感性进行全面的热力学分析。我们发现,无论氨水平如何,颗粒物pH值始终呈酸性,即使在北京(pH = 4.5)和西安(pH = 5)发现的异常高的NH水平下也是如此,这两个地方都被认为存在由NO产生硫酸盐的情况。因此,在中国或世界其他任何气溶胶始终酸性更强的地区(如美国、地中海地区),通过NO介导的途径进行的主要硫酸盐氧化不太可能发生。尘埃和海盐中碳酸盐缓冲液的有限碱度可能是唯一可能使NO介导的SO氧化胜过其他既定途径的条件。与过量氨相关的微酸性水平可通过过渡金属化学促进SO的高速氧化,这可能是极端污染事件中气溶胶化学的另一个重要贡献因素。