Dithiothreitol-Measured Oxidative Potential of Reference Materials of Mineral Dust: Implications for the Toxicity of Mineral Dust Aerosols in the Atmosphere.

Oxidative stress is a mechanism that might raise the toxicity of mineral dust aerosols. We evaluated the oxidative potential (OP) of four reference materials (RMs) of mineral dusts using dithiothreitol assay. The OP of the water-soluble fraction of the dust RMs accounts for 40%-70% of the OP of the total fraction. The values of total and water-soluble OP normalized by the surface area of insoluble particles showed agreement among the different dust RMs. The surface area of insoluble dust particles was therefore inferred as an important factor affecting the OP of mineral dust. Using the relation between total OP and the surface area of insoluble particles of the dust RMs, we estimated the total OPs of fine and coarse atmospheric mineral dust aerosols assuming a typical particle size distribution of Asian dust aerosols observed in Japan. Mass-normalized total OPs were estimated at 44 and 23 pmol min-1 µg-1 for fine and coarse atmospheric mineral dust particles. They closely approximate the values observed for urban aerosols in Japan, which suggests that mineral dust plume advection can lead to a marked increase in human exposure to redox-active aerosols, even far downwind from mineral dust source regions.

Atmospheric sea-salt and halogen cycles in the Antarctic.

Atmospheric sea-salt and halogen cycles play important roles in atmospheric science and chemistry including cloud processes and oxidation capacity in the Antarctic troposphere. This paper presents a review and summarizes current knowledge related to sea-salt and halogen chemistry in the Antarctic. First, presented are the seasonal variations and size distribution of sea-salt aerosols (SSAs). Second, SSA origins and sea-salt fractionation on sea-ice and ice sheets on the Antarctic continent are presented and discussed. Third, we discuss SSA release from the cryosphere. Fourth, we present SSA dispersion in the Antarctic troposphere and transport into inland areas. Fifth, heterogeneous reactions on SSAs as a source of reactive halogen species and their relationship with atmospheric chemistry are shown and discussed. Finally, we attempt to propose an outlook for obtaining better knowledge related to sea-salt and halogen chemistry and their effects on the Antarctic and the Arctic.

Dithiothreitol-Measured Oxidative Potential of Size-Segregated Particulate Matter in Fukuoka, Japan: Effects of Asian Dust Events.

Oxidative potential is an important property of particulate matter (PM) that has been regarded as a more health-relevant metric than PM mass. We investigated the oxidative potential of size-segregated PM and effects of Asian dust events in Fukuoka, western Japan. Aerosol particles with diameters smaller and larger than 2.5 µm (fine and coarse particles, respectively) were collected continually from 16 March through 26 May 2016. The oxidative potential was analyzed using dithiothreitol (DTT) assay; chemical components of PM were also found. Air-volume normalized oxidative potential quantified by DTT assay (DTTv) was significantly higher during Asian dust events than during nondust-event days. The mean DTTv of fine and coarse particles during Asian dust events were, respectively, 1.5 and 2.7 times higher than that during nonevent days. DTTv of fine particles was highly correlated with elements dominated by anthropogenic combustion sources and with the elements emitted from multiple sources including mineral dust and combustion sources. DTTv of coarse particles strongly correlated with the mineral dust derived elements, suggesting concentration of mineral dust particles as an important controlling factor especially for the oxidative potential of the coarse particles. We estimated the contributions of water-soluble transition metals to the oxidative potential of PM. Water-soluble transition metals (mainly Cu and Mn) can explain only approximately 37% and 60% of the measured oxidative potential of fine and coarse particles, respectively, suggesting substantial contributions of aerosol components other than water-soluble transition metals such as quinones and insoluble minerals.

Important contributions of sea-salt aerosols to atmospheric bromine cycle in the Antarctic coasts.

Polar sunrise activates reactive bromine (BrOx) cycle on the Antarctic coasts. BrOx chemistry relates to depletion of O3 and Hg in polar regions. Earlier studies have indicated "blowing snow" as a source of atmospheric BrOx. However, surface O3 depletion and BrO enhancement occurs rarely under blowing snow conditions at Syowa Station, Antarctica. Therefore, trigger processes for BrOx activation other than the heterogeneous reactions on blowing snow particles must be considered. Results of this study show that enhancement of sea-salt aerosols (SSA) and heterogeneous reactions on SSA are the main key processes for atmospheric BrOx cycle activation. Blowing snow had Br- enrichment, in contrast to strong Br- depletion in SSA. In-situ aerosol measurements and satellite BrO measurements demonstrated clearly that a BrO plume appeared simultaneously in SSA enhancement near the surface. Results show that surface O3 depletion at Syowa Station occurred in aerosol enhancement because of SSA dispersion during the polar sunrise. Amounts of depleted Br- from SSA were matched well to the tropospheric vertical column density of BrO and BrOx concentrations found in earlier work. Our results indicate that SSA enhancement by strong winds engenders activation of atmospheric BrOx cycles via heterogeneous reactions on SSA.

Ambient fine and coarse particles in Japan affect nasal and bronchial epithelial cells differently and elicit varying immune response.

Ambient particulate matter (PM) epidemiologically exacerbates respiratory and immune health, including allergic rhinitis (AR) and bronchial asthma (BA). Although fine and coarse particles can affect respiratory tract, the differences in their effects on the upper and lower respiratory tract and immune system, their underlying mechanism, and the components responsible for the adverse health effects have not been yet completely elucidated. In this study, ambient fine and coarse particles were collected at three different locations in Japan by cyclone technique. Both particles collected at all locations decreased the viability of nasal epithelial cells and antigen presenting cells (APCs), increased the production of IL-6, IL-8, and IL-1ß from bronchial epithelial cells and APCs, and induced expression of dendritic and epithelial cell (DEC) 205 on APCs. Differences in inflammatory responses, but not in cytotoxicity, were shown between both particles, and among three locations. Some components such as Ti, Co, Zn, Pb, As, OC (organic carbon) and EC (elemental carbon) showed significant correlations to inflammatory responses or cytotoxicity. These results suggest that ambient fine and coarse particles differently affect nasal and bronchial epithelial cells and immune response, which may depend on particles size diameter, chemical composition and source related particles types.

Interactive effects of specific fine particulate matter compositions and airborne pollen on frequency of clinic visits for pollinosis in Fukuoka, Japan.

BACKGROUND: Previous studies have revealed the interactive effects of airborne pollen and particulate matter on the daily consultations for pollinosis, but it is uncertain which compositions are responsible. This study aimed to investigate the interactive effects of specific PM2.5 compositions and airborne pollen on the daily number of clinic visits for pollinosis in Fukuoka. METHODS: We obtained daily data on pollen concentrations, PM2.5 compositions, PM2.5 mass, gaseous pollutants (SO2, NO2, CO, and O3), and weather variables monitored in Fukuoka between February and April, 2002-2012. In total, 73,995 clinic visits for pollinosis were made at 10 clinics in Fukuoka Prefecture during the study period. A time-stratified case-crossover design was applied to examine the interactive effects. The concentrations of PM2.5 and its compositions were stratified into low (<15th percentile), moderate (15th-85th percentile), and high (>85th percentile) levels, and the association between airborne pollen and daily clinic visits for pollinosis was analyzed within each level. RESULTS: We found a significant interaction between specific PM2.5 compositions and airborne pollen. Specifically, the odds ratio of daily clinic visits for pollinosis per interquartile increase in pollen concentration (39.8 grains/cm2) at the average cumulative lag of 0 and 2 days during high levels of non-sea-salt Ca2+ was 1.446 (95% CI: 1.323-1.581), compared to 1.075 (95% CI: 1.067-1.083) when only moderate levels were observed. This result remained significant when other air pollutants were incorporated into the model and was fairly persistent even when different percentile cut-off points were used. A similar interaction was found when we stratified the data according to non-sea-salt SO42- levels. This finding differed from estimates made according to PM2.5 and NO3- levels, which predicted that the effects of pollen were strongest in the lower levels. CONCLUSIONS: Associations between airborne pollen and daily clinic visits for pollinosis could be enhanced by high levels of specific PM2.5 compositions, especially non-sea-salt Ca2+.

"Sizing" Heterogeneous Chemistry in the Conversion of Gaseous Dimethyl Sulfide to Atmospheric Particles.

The oxidation of biogenic dimethyl sulfide (DMS) emissions is a global source of cloud condensation nuclei. The amounts of the nucleating H2SO4(g) species produced in such process, however, remain uncertain. Hydrophobic DMS is mostly oxidized in the gas phase into H2SO4(g) + DMSO(g) (dimethyl sulfoxide), whereas water-soluble DMSO is oxidized into H2SO4(g) in the gas phase and into SO4(2-) + MeSO3(-) (methanesulfonate) on water surfaces. R = MeSO3(-)/(non-sea-salt SO4(2-)) ratios would therefore gauge both the strength of DMS sources and the extent of DMSO heterogeneous oxidation if Rhet = MeSO3(-)/SO4(2-) for DMSO(aq) + ·OH(g) were known. Here, we report that Rhet = 2.7, a value obtained from online electrospray mass spectra of DMSO(aq) + ·OH(g) reaction products that quantifies the MeSO3(-) produced in DMSO heterogeneous oxidation on aqueous aerosols for the first time. On this basis, the inverse R dependence on particle radius in size-segregated aerosol collected over Syowa station and Southern oceans is shown to be consistent with the competition between DMSO gas-phase oxidation and its mass accommodation followed by oxidation on aqueous droplets. Geographical R variations are thus associated with variable contributions of the heterogeneous pathway to DMSO atmospheric oxidation, which increase with the specific surface area of local aerosols.

Transboundary secondary organic aerosol in western Japan indicated by the δ13C of water-soluble organic carbon and the m/z 44 signal in organic aerosol mass spectra.

The stable carbon isotope ratio (δ13C) of low-volatile water-soluble organic carbon (LV-WSOC) was measured in filter samples of total suspended particulate matter, collected every 24 h in the winter of 2010 at an urban site and two rural sites in western Japan. Concentrations of the major chemical species in fine aerosol (<1.0 µm) were also measured in real time by aerosol mass spectrometers. The oxidation state of organic aerosol was evaluated using f44; i.e., the proportion of the signal at m/z 44 (CO2+ ions from the carboxyl group) to the sum of all m/z signals in the organic mass spectra. A strong correlation between LV-WSOC and m/z 44 concentrations was observed, which suggested that LV-WSOC was likely to be associated with carboxylic acids in fine aerosol. Plots of δ13C of LV-WSOC versus f44 showed random variation at the urban site and systematic trends at the rural sites. The systematic trends qualitatively agreed with a simple binary mixture model of secondary organic aerosol with background LV-WSOC with an f44 of ∼0.08 and δ13C of -17‰ or higher. Comparison with reference values suggested that the source of background LV-WSOC was likely to be primary emissions associated with C4 plants.