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Observation of isoprene hydroxynitrates in the southeastern United States and implications for the fate of NO_x

机译:美国东南部异戊二烯羟基硝酸盐的观察及其对NO_x命运的影响

摘要

Isoprene hydroxynitrates (IN) are tracers of the photochemical oxidation of isoprene in high NO_x environments. Production and loss of IN have a significant influence on the NO_x cycle and tropospheric O_3 chemistry. To better understand IN chemistry, a series of photochemical reaction chamber experiments was conducted to determine the IN yield from isoprene photooxidation at high NO concentrations (> 100 ppt). By combining experimental data and calculated isomer distributions, a total IN yield of 9(+4/−3) % was derived. The result was applied in a zero-dimensional model to simulate production and loss of ambient IN observed in a temperate forest atmosphere, during the Southern Oxidant and Aerosol Study (SOAS) field campaign, from 27 May to 11 July 2013. The 9 % yield was consistent with the observed IN/(MVK+MACR) ratios observed during SOAS. By comparing field observations with model simulations, we identified NO as the limiting factor for ambient IN production during SOAS, but vertical mixing at dawn might also contribute (~ 27 %) to IN dynamics. A close examination of isoprene's oxidation products indicates that its oxidation transitioned from a high-NO dominant chemical regime in the morning into a low-NO dominant regime in the afternoon. A significant amount of IN produced in the morning high NO regime could be oxidized in the low NO regime, and a possible reaction scheme was proposed.
机译:异戊二烯羟基硝酸盐(IN)是高NO_x环境中异戊二烯光化学氧化的示踪剂。 IN的产生和损失对NO_x循环和对流层O_3化学性质有重大影响。为了更好地理解IN化学,进行了一系列光化学反应室实验,以确定高NO浓度(> 100 ppt)下异戊二烯光氧化的IN收率。通过结合实验数据和计算出的异构体分布,得出的总IN收率为9(+ 4 / -3)%。将该结果应用于零维度模型中,以模拟在2013年5月27日至7月11日进行的南部氧化剂和气溶胶研究(SOAS)野外活动期间,在温带森林大气中观察到的环境IN的产生和损失。9%的产率与在SOAS期间观察到的IN /(MVK + MACR)比一致。通过将现场观察与模型模拟进行比较,我们确定NO是SOAS期间环境IN产生的限制因素,但黎明时的垂直混合也可能对IN动态产生影响(〜27%)。仔细检查异戊二烯的氧化产物表明,其氧化从早晨的高NO占主导地位的化学状态过渡到下午的NO占优势的低化学状态。在早晨的高NO条件下产生的大量IN可以在低NO条件下被氧化,并提出了可能的反应方案。

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