A comparison between natural and anthropogenic emissions of the reduced sulfur compounds H2S, COS, and CS2 in a tropical industrialized region

Extensive ambient concentration and flux measurements have been performed in the heavily polluted region of Cubatão/Brazil. Substantial contribution of anthropogenic sources to the local reduced sulfur burden has been observed. As a result of this atmospheric sulfur burden average gas exchange between vegetated soils and the atmosphere shows net deposition. Based mainly on own field measurements a local budget for H₂S, COS, and CS₂ has been made up in order to calculate anthropogenic emissions. All major sources and sinks in the chosen atmospheric reservoir (24×20×1 km) have been taken into account. Due to the small reservoir size fluxes across its boundaries are dominant sources and sinks. The differences between outflux and influx therefore account for the unknown anthropogenic emissions which have been determined to be 80±10 (H₂S), 66±15 (COS), and 29±6 Mmol year^-1 (CS₂). Other sources and sinks like natural emissions, chemical conversion, and dry deposition turned out to be of minor importance on a local scale. In fact, inside the investigated reservoir natural emissions were below 0.5% of anthropogenic emissions. Anthropogenic emissions of H₂S, COS, and CS₂ quantified in this work have been compared with global emission estimates for these compounds made by other authors. We conclude that global anthropogenic emissions of reduced sulfur compounds especially of COS and CS₂ are currently under-estimated.     

地基消光测量确定新疆博斯腾湖地区大气气溶胶模型

为确定新疆博斯腾湖地区气溶胶主要组分,减小辐射传输计算和卫星遥感应用中由于气溶胶模型误判造成的误差,分别取大陆型、背景沙漠型、体积百分比自定义模型和两种动态气溶胶模型,用6S辐射传输算法计算出对应于太阳光度计测量时段的各波段大气气溶胶光学厚度。将模式计算值与测量值进行比较,确定测量地区的大气气溶胶模型。将该方法用于2010年在新疆博斯腾湖地区测量的太阳光度计数据,结果显示该地区在测量时段较为符合体积百分比自定义模型,沙尘性粒子体积百分比均在88%上,符合当地靠近沙尘源地和测量时段浮尘天气频发的实际情况。     

The Effect of Atmospheric Organic Compounds on the Fe-Catalyzed S(IV) Autoxidation in Aqueous Solution

Laboratory experiments were conducted with real atmospheric aerosol particles as well as with synthetic solutions under dark conditions, to simulate some of the chemical features of aerosols. In solutions obtained by the leaching of aerosols (size range >D _ae: 0.4–1.6 m) that contained sufficient amounts of transition metal ions (e.g. Fe) and organic species (e.g. oxalate), S(IV) oxidation rates were significantly lower than those expected from the Fe-catalyzed S(IV) autoxidation in Milli-Q water. The results suggest that oxalate is responsible for much of the observed inhibition. Acetate and formate also inhibit the reaction, but to a much lesser extent. Oxalate has a strong inhibiting effect on the Fe-catalyzed S(IV) autoxidation at all investigated pH values (2.8, 3.7 and 4.5). It was established that Fe(III)-oxalato complexes affect the redox cycling of Fe(II)/Fe(III) and that the observed decrease of the reaction rate is caused by the reduced amount of catalytically active Fe(III) due to the complexation with oxalate. For the system Fe-S(IV)-O₂-oxalate at initial pH 3.7 the reaction rate was calculated using exponential simplification to account for oxalate influence on the amount of free Fe(III) by the following equation:–r_S(IV) = k · [S(IV)] · [Fe(III))] · e ^-b·[Ox]