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异氰酸(HNCO)及其在大气中的命运:综述。

Isocyanic acid (HNCO) and its fate in the atmosphere: a review.

机构信息

Department of Chemistry, University of Toronto, 80 St George Street, Toronto, Ontario M5S 3H6, Canada.

出版信息

Environ Sci Process Impacts. 2019 May 22;21(5):793-808. doi: 10.1039/c9em00003h.

Abstract

Isocyanic acid (HNCO) has recently been identified in ambient air at potentially concerning concentrations for human health. Since its first atmospheric detection, significant progress has been made in understanding its sources and sinks. The chemistry of HNCO is governed by its partitioning between the gas and liquid phases, its weak acidity, its high solubility at pH above 5, and its electrophilic chemical behaviour. The online measurement of HNCO in ambient air is possible due to recent advances in mass spectrometry techniques, including chemical ionization mass spectrometry for the detection of weak acids. To date, HNCO has been measured in North America, Europe and South Asia as well as outdoors and indoors, with mixing ratios up to 10s of ppbv. The sources of HNCO include: (1) fossil fuel combustion such as coal, gasoline and diesel, (2) biomass burning such as wildfires and crop residue burning, (3) secondary photochemical production from amines and amides, (4) cigarette smoke, and (5) combustion of materials in the built environment. Then, three losses processes can occur: (1) gas phase photochemistry, (2) heterogenous uptake and hydrolysis, and (3) dry deposition. HNCO lifetimes with respect to photolysis and OH radical oxidation are on the order of months to decades. Consequently, the removal of HNCO from the atmosphere is thought to occur predominantly by dry deposition and by heterogeneous uptake followed by hydrolysis to NH3 and CO2. A back of the envelope calculation reveals that HNCO is an insignificant global source of NH3, contributing only around 1%, but could be important for local environments. Furthermore, HNCO can react due to its electrophilic behaviour with various nucleophilic functionalities, including those present in the human body through a reaction called protein carbamoylation. This protein modification can lead to toxicity, and thus exposure to high concentrations of HNCO can lead to cardiovascular and respiratory diseases, as well as cataracts. In this critical review, we outline our current understanding of the atmospheric fate of HNCO and its potential impacts on outdoor and indoor air quality. We also call attention to the need for toxicology studies linking HNCO exposure to health effects.

摘要

异氰酸(HNCO)最近在大气中被检测到,其浓度可能对人类健康造成严重影响。自首次在大气中检测到以来,人们在了解其来源和汇方面取得了重大进展。HNCO 的化学性质受其在气液两相之间的分配、弱酸性、在 pH 值高于 5 时的高溶解度以及亲电化学行为的影响。由于质谱技术的最新进展,包括用于检测弱酸的化学电离质谱,使得在线测量大气中的 HNCO 成为可能。迄今为止,已经在北美、欧洲和南亚以及户外和室内测量到 HNCO,混合比高达 10s 的 ppbv。HNCO 的来源包括:(1)化石燃料燃烧,如煤、汽油和柴油;(2)生物质燃烧,如野火和农作物残茬燃烧;(3)胺和酰胺的二次光化学产生;(4)香烟烟雾;(5)建筑环境中材料的燃烧。然后,有三种损失过程可以发生:(1)气相光化学;(2)多相吸收和水解;(3)干沉降。HNCO 相对于光解和 OH 自由基氧化的寿命为数月至数十年。因此,HNCO 从大气中的去除被认为主要通过干沉降和多相吸收随后水解为 NH3 和 CO2 来实现。根据经验计算,HNCO 是全球 NH3 的一个不重要的来源,仅贡献约 1%,但对局部环境可能很重要。此外,由于其亲电行为,HNCO 可以与各种亲核官能团反应,包括人体中存在的那些,通过一种称为蛋白质氨甲酰化的反应。这种蛋白质修饰会导致毒性,因此暴露于高浓度的 HNCO 会导致心血管和呼吸道疾病以及白内障。在这篇评论中,我们概述了我们对 HNCO 在大气中的命运及其对户外和室内空气质量的潜在影响的理解。我们还呼吁注意需要进行毒理学研究,将 HNCO 暴露与健康影响联系起来。

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