Reactivity between PbSO4 and CaCO3 particles relevant to the modification of mineral particles and chemical forms of Pb in particles sampled at two remote sites during an Asian dust event

During the transboundary transport of anthropogenic heavy metals by mineral particles providing reaction sites, the divalent metal salt PbSO₄ can be converted to PbCO₃ in the presence of water. We carried out laboratory experiments to study the transformation process under various conditions by incorporating test particles comprising CaCO₃ of a particulate mineral component, PbSO₄, and NaCl. After the immersion of PbSO₄ particles in contact with CaCO₃ particles in a water droplet, the conversion of PbSO₄ into PbCO₃ was confirmed by the change in morphology of the original particles to stick or needle form; the percentages of the chemical forms relative to the total Pb were determined by X-ray absorption near edge structure (XANES) analysis. Approximately 60–80% of PbSO₄ was converted to PbCO₃ after 24 h. A small amount of stick particles was detected when NaCl particles attached to PbSO₄/CaCO₃ particles were exposed to air with a relative humidity (RH) of 80–90% for 24 h. XANES measurements of the samples revealed that the molar percentage of PbCO₃ relative to the total Pb content was 4%.Field experiments were also conducted to determine the chemical forms of the Pb particles during the Kosa (Asian dust storm) event. Samples were collected from two remote sites in Japan and Korea. The mass size distribution of Pb aerosols collected in Japan was bimodal with two peaks in the coarse mode; the enrichment factor of Pb suggested that its source was anthropogenic. Pb L3 edge XANES measurements of both samples indicated that they had similar shapes. These measurements also indicated that the major Pb components for the samples collected in Japan were PbO, PbSO₄ PbCl₂, and PbCO₃, with molar percentages of 44%, 30%, 21%, and 5%, respectively. No significant differences were found between the component ratios of the samples collected in Japan and Korea, suggesting that definite transformation did not occur during the transport of the Kosa particles from Korea to Japan. On the basis of these observations, we postulate that the transformation process either occurred mainly before the particles arrived at Korea or did not take place after the particles left continental Asia.     

Compilation and application of a primary PM2.5 emissions inventory with high sectoral resolution in Japan

To elucidate the macro-structure of the PM_2.5 emissions generated by Japan's economic activities, this paper presents an emission inventory of primary particles of PM_2.5 with high sectoral resolution based on the Japanese Input–Output Tables, comprising some 400 sectors. These primary PM_2.5 emissions were estimated by multiplying the estimated energy consumption associated with each fuel type by a PM₁₀ emission factor incorporating the technological level of dust collection in each sector and the mass ratio of PM_2.5 to PM₁₀. Non-energy emissions from agricultural open burning were also determined. Total PM_2.5 emissions in 2000 were 252 kt, 49% of which were due to mobile emission sources. Changes in total PM_2.5 emissions between 1990 and 2000 were also calculated. This showed that a substantial increase in energy sector emissions due to rising coal consumption was offset by a sharp decline in emissions from road vehicles and shipping vessels, resulting in an overall decrease in total emissions. In addition, the emissions induced by economic demand in each sector were quantified by means of input–output analysis, which revealed that demand for construction, foods and communications and services constituted the principal causes of real domestic emissions. An assessment of sectoral contributions to PM_2.5 emissions that takes into account the effects of human exposure, expressed as external costs, suggests that the contribution of transportation is greater than indicated on the grounds of direct emissions alone.     

Analysis for Chemical Characterization of Atmospheric Aerosols Application of X-ray Microprobe System and Double Thin Film Method

The X-ray microprobe system was applied to ultra trace characterization of single Kosa aerosols and non-Kosa aerosols simultaneously collected at Yasaka, Japan and TaeAnn, Korea. We demonstrated remarkable mass increase of heavy metals as well as soil components in individual particles during the Kosa event compared with the non-Kosa period at Yasaka. Backward trajectory analysis suggested that the Kosa samples were in the mixing state of mineral components and anthropogenic heavy elements. Double thin film method was applied to investigate the seasonal change of the mixing states of single sea-salt aerosols associated with chlorine loss due to the heterogeneous reactions between sea-salt particles and acidic gases. It was revealed that the percentages of both chloride-nitrate mixed particles and sulfate-nitrate ones were larger in wintertime than those in summertime and fraction of chloride-nitrate mixed particles increased with an increase of particle size. Comparison between the size-segregated bulk analysis and the single particle analysis demonstrated that remarkable chloride depletion occurred in coarse particles sampled on May in the former analysis, while chloride depletion in coarse particles was not marked in the latter analysis. The discrepancy attributes to the difference of the sampling time between both analyses because significant change of air mass route occurred during the bulk sampling after completion of the single particle sampling.     

pH buffering additives mitigate the inhibition of thermophilic dry methane fermentation

Journal of Material Cycles and Waste Management - This study describes the process of mitigation of fermentation inhibition using additives through a pH-buffering effect on thermophilic dry methane...