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.     

Method of removal of volatile organic compounds by using wet scrubber coupled with photo-Fenton reaction - Preventing emission of by-products

The photo-Fenton reaction was applied as a novel method for the removal of volatile organic compounds (VOCs) in the gas phase, and its effectiveness was experimentally examined. In conventional VOCs removal methods using a photocatalyst or ozone, VOCs are oxidized in the gas phase. Therefore, incompletely oxidized intermediates, which may have adverse effects on health, are likely to contaminate the treated air. On the other hand, in the VOCs removal method developed in this study, because the VOCs are oxidized in the liquid phase by the photo-Fenton reaction, any incompletely oxidized intermediates produced are confined to the liquid phase. As a result, the contamination of the treated air by these harmful intermediates can be prevented. Using a semi-batch process, it was found that the removal efficiency for toluene in a one-pass test (residence time of 17 s) was 61%, for an inlet toluene gas concentration of 930 ppbv, an initial iron ion concentration of 20 mg L⁻¹, and an initial hydrogen peroxide concentration of 630 mg L⁻¹. The removal efficiency was almost constant as long as H₂O₂ was present in the solution. Proton transfer reaction mass spectrometry analysis confirmed the absence of any incompletely oxidized intermediates in the treated air.     

Sodic soils reclaimed with by-product from flue gas desulfurization: corn production and soil quality

Interest is growing in the use of by-product from flue gas desulfurization (FGD) to reclaim sodic soils by controlling the pH and excessive Na+. This study evaluated the effects on corn (Zea mays) production and pH and electrical conductivity (EC) of calcareous sodic soil during four times of cultivation when the by-product was applied once at the first cultivation (Study I) and the impacts on plant and soil quality at first cultivation when the by-product was applied to the soil at 23,000 kg ha-1 (Study II). In Study I, the germination rate and corn production increased by applying the by-product (0, 5,800, 11,600, and 23,100 kg ha-1), and the greatest total amounts of corn production during the four times of cultivation was when the by-product was applied at 23,100 kg ha-1. In Study II, the pH, exchangeable sodium percentage (ESP), clay dispersion and soluble Na+ in the soil decreased and soluble Mg2+ and soluble K+ in the soil increased. The soil pH was reduced from 9.0 to 7.7 by applying the by-product. However, the by-product decreased the concentrations of total N and P in corn leaves in this study. No significant difference in the concentrations of Mo, Zn, Pb, Ni, Cd, Mn, Cr, Cu, and Al in corn leaves and the soil was observed between the by-product addition and the control except for B in the soil and Fe in corn leaves. The concentration of B in the soil was reduced from 28.7 mg kg-1 to 25.4 mg kg-1 and the concentration of Fe in corn leaves increased from 17.5 mg kg-1 to 22.6 mg kg-1 by applying the by-product in our study.     

Contamination status of persistent organochlorines in human breast milk from Japan: recent levels and temporal trend

Contamination levels of persistent organochlorines (OCs) such as polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), hexachlorobenzene (HCB), and chlordane compounds (CHLs) was examined in human breast milk collected during 2001-2004 from Fukuoka prefecture in Japan. The concentrations of OCs such as dioxins and related compounds, DDTs, CHLs and HCB in human breast milk from primiparae were comparable to or slightly higher than the data obtained during 1998, indicating that the levels of these contaminants in Japanese human breast milk have not decreased since 1998 and Japanese are continuously exposed to these chemicals, presumably via fish intake. In addition, OC levels in human breast milk from primiparae were significantly higher than those from multiparae, implying elimination of OCs via lactation. Furthermore, significant positive correlations were observed between levels of OCs in human breast milk and the age of primiparae. These results indicate that the mothers with higher age may transfer higher amounts of OCs to the first infant than to the infants born afterwards through breast-feeding, and hence the first born children might be at higher risk by OCs.     

Variability and reliability of POP concentrations in multiple breast milk samples collected from the same mothers

Risk assessment of infant using a realistic persistent organic pollutant (POP) exposure through breast milk is essential to devise future regulation of POPs. However, recent investigations have demonstrated that POP levels in breast milk collected from the same mother showed a wide range of variation daily and monthly. To estimate the appropriate sample size of breast milk from the same mother to obtain reliable POP concentrations, breast milk samples were collected from five mothers living in Japan from 2006 to 2012. Milk samples from each mother were collected 3 to 6 times a day through 3 to 7 days consecutively. Food samples as the duplicated method were collected from two mothers during the period of breast milk sample collection. Those were employed for POP (PCBs, DDTs, chlordanes, and HCB) analysis. PCB concentrations detected in breast milk samples showed a wide range of variation which was maximum 63 and 60% of relative standard deviation (RSD) in lipid and wet weight basis, respectively. The time course trend of those variations among the mothers did not show any typical pattern. A larger amount of PCB intake through food seemed to affect 10 h after those concentrations in breast milk in lipid weight basis. Intraclass correlation coefficient (ICC) analyses indicated that the appropriate sample size for good reproducibility of POP concentrations in breast milk required at least two samples for lipid and wet weight basis.     

Biochemical and cellular effects of electrophiles present in ambient air samples

Ambient vapor-phase samples collected in Riverside, California had shown that both redox and electrophilic activity were present, with the vapor phase containing higher levels of electrophiles than the particle phase. In this study, the biochemical effects of the vapor-phase electrophiles were examined using the purified thiol proteins, glyceraldehyde-3-phosphate dehydrogenase (GAPDH), protein tyrosine phosphatase 1B (PTP1B) and KELCH-1 like ECH-associated protein 1 (Keap1). The results demonstrated that the thiol proteins were inactivated by the vapor-phase samples through covalent modifications. Next, two cellular responses, epidermal growth factor receptor (EGFR)/mitogen-activated protein (MAP) kinase and NF-E2-related factor 2 (Nrf2), to the ambient vapor-phase samples were assessed in A549 and RAW 264.7 cell lines, respectively. The vapor-phase samples, at non-oxidative concentrations, increased phosphorylation of EGFR, which is negatively regulated by PTP1B, and its downstream MAP kinase, extracellular signal-regulated kinase (ERK)1/2. Activation of Nrf2, which requires Keap1 alkylation, and expression of its downstream proteins were also observed. The electrophilic compounds present in ambient vapor-phase were shown to modify cellular proteins through covalent modification and to activate diverse cellular responses that can lead to inflammatory and adaptive responses.     

Synergistic increase in cell lethality by dieldrin and H2O2 in rat thymocytes: Effect of dieldrin on the cells exposed to oxidative stress

Dieldrin, one of persistent pesticides, is highly resistant to biotic and abiotic degradation. It is accumulated in organisms. Recent studies suggest that dieldrin exerts a potent cytotoxic action on cells exposed to oxidative stress. In this study, the effect of dieldrin on rat thymocytes exposed to hydrogen peroxide (H₂O₂)-induced oxidative stress was examined. Dieldrin at 5 μM and H₂O₂ at 300 μM slightly increased cell lethality from a control value of 5.4 ± 0.5% (mean ± standard deviation of four experiments) to 7.8 ± 1.3% and 9.0 ± 0.3%, respectively. Simultaneous application of dieldrin and H₂O₂ significantly increased cell lethality to 46.2 ± 1.8%. The synergistic increase in cell lethality was dependent on dieldrin concentration (0.3–5 μM) but not on H₂O₂ concentration (30–300 μM). Dieldrin accelerated H₂O₂-induced cell death, which was estimated with the help of annexin V-FITC and propidium iodide. Presence of either dieldrin or H₂O₂ decreased the cellular content of nonprotein thiol and increased intracellular Zn²⁺ concentration. The combination of dieldrin and H₂O₂ further pronounced these effects. TPEN, a chelator of intracellular Zn²⁺, significantly attenuated the synergistic increase in cell lethality induced by dieldrin and H₂O₂. It is, therefore, suggested that dieldrin augments the cytotoxicity of H₂O₂ in a Zn²⁺-dependent manner.