Tang X, Madronich S, Wallington T, Calamari D
Peking University, Center of Environmental Sciences, Beijing, China.
J Photochem Photobiol B. 1998 Oct;46(1-3):83-95. doi: 10.1016/s1011-1344(98)00187-0.
Reductions in stratospheric ozone (O3) cause increased penetration of ultraviolet-B (UV-B) radiation to the troposphere, and therefore increases in the chemical activity in the lower atmosphere (the troposphere). Tropospheric ozone levels are sensitive to local concentrations of nitrogen oxides (NOx) and hydrocarbons. Model studies suggest that additional UV-B radiation reduces tropospheric ozone in clean environments (low NOx), and increases tropospheric ozone in polluted areas (high NOx). Assuming other factors remain constant, additional UV-B will increase the rate at which primary pollutants are removed from the troposphere. Increased UV-B is expected to increase the concentration of hydroxyl radicals (OH) and result in faster removal of pollutants such as carbon monoxide (CO), methane (CH4), non-methane hydrocarbons (NMHCs), sulfur and nitrogen oxides, hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). Concentrations of peroxy radicals (both inorganic and organic) are expected to increase, leading to higher atmospheric levels of hydrogen peroxide (H2O2) and organic peroxides. The effects of UV-B increases on tropospheric O3, OH, methane, CO, and possibly other tropospheric constituents, while not negligible, will be difficult to detect because the concentrations of these species are also influenced by many other variable factors (e.g., emissions). Trifluoroacetic acid (TFA, CF3COOH) is produced in the atmosphere by the degradation of HCFC-123 (CF3CHCl2), HCFC-124 (CF3CHFCl), and HFC-134a (CF3CH2F), which are used as substitutes for ozone-depleting substances. The atmospheric oxidation mechanisms of these replacement compounds are well established. Reported measurements of TFA in rain, rivers, lakes, and oceans show it to be a ubiquitous component of the hydrosphere, present at levels much higher than can be explained by reported sources. The levels of TFA produced by the atmospheric degradation of HFCs and HCFCs emitted up to the year 2020 are estimated to be orders of magnitude below those of concern, and to make only a minor contribution to the current environmental burden of TFA. No significant effects on humans or the environment have been identified from TFA produced by atmospheric degradation of HCFCs and HFCs. Numerous standard short-term studies have shown that TFA has, at most, moderate toxicity.
平流层臭氧(O₃)的减少导致紫外线B(UV - B)辐射对对流层的穿透增加,进而导致低层大气(对流层)中化学活性增强。对流层臭氧水平对氮氧化物(NOₓ)和碳氢化合物的局部浓度敏感。模型研究表明,额外的UV - B辐射会降低清洁环境(低NOₓ)中的对流层臭氧,并增加污染地区(高NOₓ)的对流层臭氧。假设其他因素保持不变,额外的UV - B将提高对流层中主要污染物的去除速率。预计增加的UV - B会提高羟基自由基(OH)的浓度,并加快一氧化碳(CO)、甲烷(CH₄)、非甲烷碳氢化合物(NMHCs)、硫和氮氧化物、氢氯氟烃(HCFCs)以及氢氟碳化合物(HFCs)等污染物的去除速度。过氧自由基(包括无机和有机)的浓度预计会增加,导致大气中过氧化氢(H₂O₂)和有机过氧化物水平升高。UV - B增加对对流层O₃、OH、甲烷、CO以及可能的其他对流层成分的影响虽然不可忽视,但由于这些物质的浓度还受到许多其他可变因素(如排放)的影响,因此难以检测到。三氟乙酸(TFA,CF₃COOH)是由作为消耗臭氧层物质替代品的HCFC - 123(CF₃CHCl₂)、HCFC - 124(CF₃CHFCl)和HFC - 134a(CF₃CH₂F)在大气中降解产生的。这些替代化合物的大气氧化机制已得到充分证实。在雨水、河流、湖泊和海洋中对TFA的测量报告显示,它是水圈中普遍存在的成分,其含量远高于报告来源所能解释的水平。截至2020年排放的HFCs和HCFCs在大气中降解产生的TFA水平估计比所关注的水平低几个数量级,并且对当前TFA的环境负担贡献很小。尚未发现由HCFCs和HFCs在大气中降解产生的TFA对人类或环境有显著影响。大量标准短期研究表明,TFA至多具有中等毒性。