Effect of Manganese Oxide Aging and Structure Transformation on the Kinetics of Thiol Oxidation.

The kinetics and mechanism of thiol oxidation by Mn oxides undergoing dynamic structural transformation under environmentally relevant conditions remain poorly understood. In this study, thiol/disulfide pair concentrations were simultaneously determined in situ using voltammetric microelectrodes during the interaction of four common thiols (cysteine, homocysteine, cysteamine, and glutathione) with fresh and aged δ-MnO2 at pH 7.0. The reaction kinetics was first order with respect to thiol and zero order with respect to Mn oxides. A transient intermediate sulfur surface species observed during the reaction provides evidence for a mechanism involving two successive one-electron transfer steps. The reaction kinetics of fresh and aged δ-MnO2 was investigated with cysteine and compared to that of manganite, a Mn(III) oxyhydroxide phase. The reactivity of aged δ-MnO2 decreased as a result of structural transformation to cryptomelane but remained higher than that of manganite, suggesting the potential roles of transient Mn(III) surface intermediate in promoting the reduction of Mn(IV) in δ-MnO2 and cryptomelane (compared to Mn(III) in manganite). This study demonstrates the importance of correlating Mn oxide mineral structure and redox reactivity and extends the potential for thiols commonly found in sedimentary environments to be utilized as electron shuttles during dissimilatory Mn reduction.

Ferric ion mediated photodecomposition of aqueous perfluorooctane sulfonate (PFOS) under UV irradiation and its mechanism.

Perfluorooctane sulfonate (PFOS) recently has received much attention due to its global distribution, environmental persistence and bioaccumulation. The methods for PFOS decomposition are very limited due to its inertness. In this report we first found the photodecomposition of PFOS under UV was greatly accelerated by addition of ferric ions. In the presence of ferric ion (100 µM), PFOS (20 µM) decreased to below the detection limit within 48 h, with the rate constant of 1.67 d(-1), which was 50 times higher than that by direct photolysis (0.033 d(-1)). Besides fluoride and sulfate ions, C2-C8 perfluorocarboxylic acids (PFCAs) were identified as the main intermediates. It was found that addition of PFOS into the FeCl3 aqueous solution led to reduction of UV absorption, and the presence of ferric ion reduced the response of PFOS as analyzed by UPLC-MS/MS, which indicated that PFOS formed a complex with ferric ion. The ESR detection indicated that the electronic state of Fe(3+)-PFOS complex changed during reaction. And the role of oxygen and hydroxyl radical on the defluorination of PFOS was investigated. Accordingly the mechanism for PFOS photodecomposition in the presence of ferric ion was proposed.

Evaluation of phenanthrene toxicity on earthworm (Eisenia fetida): an ecotoxicoproteomics approach.

The goal of this study was to identify promising new biomarkers of phenanthrene by identifying differentially expressed proteins in Eisenia fetida after exposure to phenanthrene. Extracts of earthworm epithelium collected at days 2, 7, 14, and 28 after phenanthrene exposure were analyzed by two dimensional electrophoresis (2-DE) and quantitative image analysis. Comparing the intensity of protein spots, 36 upregulated proteins and 45 downregulated proteins were found. Some of the downregulated and upregulated proteins were verified by MALDI-TOF/TOF-MS and database searching. Downregulated proteins in response to phenanthrene exposure were involved in glycolysis, energy metabolism, chaperones, proteolysis, protein folding and electron transport. In contrast, oxidation reduction, oxygen transport, defense systems response to pollutant, protein biosynthesis and fatty acid biosynthesis were upregulated in phenanthrene-treated E. fetida. In addition, ATP synthase b subunit, lysenin-related protein 2, lombricine kinase, glyceraldehyde 3-phosphate dehydrogenase, actinbinding protein, and extracellular globin-4 seem to be potential biomarkers since these biomarker were able to low levels (2.5 mg kg(-1)) of phenanthrene. Our study provides a functional profile of the phenanthrene-responsive proteins in earthworms. The variable levels and trends in these spots could play a potential role as novel biomarkers for monitoring the levels of phenanthrene contamination in soil ecosystems.

Biomarker responses of earthworms (Eisenia fetida) exposured to phenanthrene and pyrene both singly and combined in microcosms.

Microcosm studies were undertaken to relate biomarker responses to the toxicities in soil ecosystems contaminated by phenanthrene (Phe) and pyrene (Pyr), both singly and combined. Growth inhibition, enzyme activity, MDA content, sperm count, neutral-red retention time (NRRT) and annetocin and TCTP gene transcriptions were determined in earthworm Eisenia fetida exposed to Phe and Pyr, both singly and combined pollution in microcosm. Exposure to 0.5 and 2.5 mg kg(-1) Phe or 50 and 100 mg kg(-1) Pyr alone significantly decreased E. fetida growth, NRRT and sperm count. Two-way ANOVA analysis shows that the combination of these two compounds decreased growth, SOD activities, NRRT and sperm count synergistically, but increased the CAT activities and MDA content. The highest suppression rate of growth was 48.12%, the lowest levels of SOD activities and NRRT were 51.66% and 45.57% of the control, respectively. The highest increase in CAT activities and MDA content were 120.05% and 121.03% greater than that of the control when exposed to 0.5 (Phe)+100 (Pyr) mg kg(-1) soils. A clear dose-related response with exposure concentration was established for the NRRT. Real-time PCR shows that Phe and Pyr increased the expression levels of annetocin and TCTP gene synergistically. These results demonstrate that earthworms were under physiological stress at field dose of 0.5 (Phe)+100 (Pyr) mg kg(-1) soils. Phe and Pyr synergistically decreased sperm count and NRRT, but antagonistically caused changes in antioxidant enzyme activities to disrupt the detoxification functions and inhibit earthworm growth.