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新兴研究者系列:城市道路灰尘对臭氧的吸收作用,以及农用除冰盐在吸收臭氧过程中氯元素被激活的首个证据:对高纬度城市冬季空气质量的影响。

Emerging investigator series: ozone uptake by urban road dust and first evidence for chlorine activation during ozone uptake by agro-based anti-icer: implications for wintertime air quality in high-latitude urban environments.

机构信息

Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada.

Department of Chemistry, York University, Toronto, Ontario, Canada.

出版信息

Environ Sci Process Impacts. 2022 Nov 16;24(11):2070-2084. doi: 10.1039/d1em00393c.

Abstract

High-latitude urban regions provide a unique and complex range of environmental surfaces for uptake of trace pollutant gases, including winter road maintenance materials (, gravel, rock salts, and anti-icer, a saline solution applied to roads during winter). In an effort to reduce the negative environmental and economic impacts of road salts, many municipalities have turned to agro-based anti-icing materials that are rich in organic material. To date, the reactivity of both anti-icer and saline road dust with pollutant gases remain unexplored, which limits our ability to assess the potential impacts of these materials on air quality in high-latitude regions. Here, we used a coated-wall flow tube to investigate the uptake of ozone, an important air pollutant, by road dust collected in Edmonton, Canada. At 25% relative humidity (RH) and 50 ppb ozone, for ozone uptake by this sample is (8.0 ± 0.7) × 10 under dark conditions and (2.1 ± 0.1) × 10 under illuminated conditions. These values are 2-4× higher than those previously obtained by our group for natural mineral dusts, but are not large enough for suspended road dust to influence local ozone mixing ratios. In a separate set of experiments, we also investigated the uptake of ozone by calcium chloride ( road salt) and commercial anti-icer solution. Although ozone uptake by pure calcium chloride was negligible, ozone uptake by anti-icer was significant, which implies that the reactivity of anti-icer is conferred by its organic content. Importantly, ozone uptake by anti-icer-and, to a lesser extent, road dust doped with anti-icer-leads to the release of inorganic chlorine gas, which we collected using inline reductive trapping and quantified using ion chromatography. To explain these results, we propose a novel pathway for chlorine activation: here, ozone oxidation of the anti-icer organic fraction (in this case, molasses) yields reactive OH radicals that can oxidize chloride. In summary, this study demonstrates the ability of road dust and anti-icer to influence atmospheric oxidant mixing ratios in cold-climate urban areas, and highlights previously unidentified air quality impacts of winter road maintenance decisions.

摘要

高纬度城市地区为痕量污染物气体的吸收提供了独特而复杂的环境表面,包括冬季道路养护材料(砾石、岩盐和防冻剂,即冬季施用于道路的盐水溶液)。为了减少道路盐的负面环境和经济影响,许多市政府已转向富含有机物质的基于农业的防冻材料。迄今为止,防冻剂和含盐道路灰尘与污染物气体的反应性仍未得到探索,这限制了我们评估这些材料对高纬度地区空气质量的潜在影响的能力。在这里,我们使用涂壁流动管研究了在加拿大埃德蒙顿收集的道路灰尘对臭氧(一种重要的空气污染物)的吸收。在相对湿度为 25%和 50 ppb 臭氧下,该样品在黑暗条件下的臭氧吸收速率为(8.0 ± 0.7)× 10,在光照条件下的臭氧吸收速率为(2.1 ± 0.1)× 10。这些值比我们小组以前对天然矿物质灰尘获得的值高 2-4 倍,但不足以使悬浮的道路灰尘影响当地臭氧混合比。在另一组实验中,我们还研究了氯化钙(道路盐)和商业防冻剂溶液对臭氧的吸收。虽然纯氯化钙对臭氧的吸收可以忽略不计,但防冻剂对臭氧的吸收是显著的,这意味着防冻剂的反应性是由其有机含量赋予的。重要的是,防冻剂和抗冻剂掺杂的道路灰尘对臭氧的吸收导致无机氯气的释放,我们使用在线还原捕集收集了这些氯气,并使用离子色谱进行了定量。为了解释这些结果,我们提出了一种新的氯激活途径:在这里,防冻剂有机部分(在这种情况下是糖蜜)的臭氧氧化生成可以氧化氯的反应性 OH 自由基。总之,这项研究表明道路灰尘和防冻剂有能力影响寒冷气候城市地区的大气氧化剂混合比,并突出了冬季道路养护决策对空气质量的以前未被识别的影响。

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