Enhanced sulfate formation by nitrogen dioxide: Implications from in situ observations at the SORPES station

Enhanced sulfate formation by nitrogen dioxide: Implications from in situ observations at the SORPES station
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二氧化氮增强硫酸盐形成:SORPES 站现场观测的影响

DOI:
10.1002/2015jd023607
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发表时间:
2015-12
期刊:
J. Geophys. Res.
影响因子:
--
通讯作者:
Congbin Fu
Congbin Fu
中科院分区:
其他
文献类型:
--
作者:
Jianning Sun;Xiuqun Yang;Markku Kulmala;Congbin Fu

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研究硫酸盐的形成过程不仅对于空气污染控制很重要,而且对于了解气候系统也很重要。尽管二次硫酸盐产生的机制已被广泛研究,但表明 NO2 在真实大气中 SO2 氧化中的重要作用的现场观测证据却很少。在这项研究中,我们报告了两个独特的案例,来自在中国东部地球系统区域过程观测站(SORPES)进行的密集活动,显示了二氧化氮和相关氮化学形成硫酸盐的明显不同的机制。第一个案例发生在矿物粉尘与人为污染物、特别是高浓度氮氧化物混合的事件中。研究表明,NO2 不仅在 SO2 的表面催化反应中发挥着重要作用,而且在粉尘诱导的 NO2 光化学非均相反应中也发挥着重要作用,这些反应产生了额外的 OH 自由基来源,以促进新颗粒的形成和生长。第二种情况是在高NH3 浓度的雾/云条件下,S(IV) 被NO2 水氧化引起的。作为副产物,形成的亚硝酸盐增强了 HONO 的形成,并进一步促进了顺风区硫酸盐的气相形成。这项研究强调了氮氧化物在增强大气氧化能力方面的作用,并表明氮氧化物的增加对东亚颗粒物污染形成和区域气候变化具有潜在的非常重要的影响。
Investigating sulfate formation processes is important not only for air pollution control but also for understanding the climate system. Although the mechanisms of secondary sulfate production have been widely studied, in situ observational evidence implicating an important role of NO2 in SO2 oxidation in the real atmosphere has been rare. In this study, we report two unique cases, from an intensive campaign conducted at the Station for Observing Regional Processes of the Earth System (SORPES) in East China, showing distinctly different mechanisms of sulfate formation by NO2 and related nitrogen chemistry. The first case occurred in an episode of mineral dust mixed with anthropogenic pollutants and especially high concentrations of NOx. It reveals that NO2 played an important role, not only in surface catalytic reactions of SO2 but also in dust‐induced photochemical heterogeneous reactions of NO2, which produced additional sources of OH radicals to promote new particle formation and growth. The second case was caused by aqueous oxidation of S(IV) by NO2 under foggy/cloudy conditions with high NH3 concentration. As a by‐product, the formed nitrite enhanced HONO formation and further promoted the gas‐phase formation of sulfate in the downwind area. This study highlights the effect of NOx in enhancing the atmospheric oxidizing capacity and indicates a potentially very important impact of increasing NOx on particulate pollution formation and regional climate change in East Asia.
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