Oxidative removal of bisphenol A by manganese dioxide: efficacy, products, and pathways.

Bisphenol A (BPA) is a ubiquitous environmental contaminant with endocrine disruption potential. In this study, exploiting the outstanding oxidative capacity of manganese dioxide (delta-MnO2), we explored forthe firsttime the efficacy and mechanisms of BPA removal by MnO2. In aqueous solutions, MnO2 demonstrated an extremely efficient capacity to remove BPA. Nearly all BPA (>99%) was eliminated in 6 min in a pH 4.5 solution initially containing 800 microM MnO2 and 4.4 microM BPA. While humic acid showed negligible inhibition on BPA removal, coexisting metal ions such as Mn2+, Ca2+, Mg2+, and Fe3+ displayed suppressive effects and the inhibitive capacityfollowed the order Mn2+ > Ca2+ > Mg2+ approximately Fe3+. A total of 11 products or intermediates were indentified and a detailed reaction scheme was suggested. The products could be ascribed to a suite of reactions of radical coupling, fragmentation, substitution, and elimination, triggered by the BPA radical formed through electron transfers to MnO2. The exceptional efficiency of MnO2 in removing BPA represents a potential use of MnO2 to treat waters containing phenolic compounds and also suggests a potentially important role of oxide-facilitated abiotic transformations in BPA attenuation in natural soil and sediment environments.

Comparison of five methods for measuring sediment toxicity of hydrophobic contaminants.

Sediment toxicity from hydrophobic organic compounds (HOCs) is complicated by chemical partitioning among multiple phases and sediment-specific bioavailability. In this study, we used three hydrophobic pyrethroid insecticides as test compounds and derived 10-d median lethal concentrations (LC50s) for Chironomus tentans in three different sediments. The LC50s were expressed using HOC concentrations on a bulk sediment basis (C(S)), organic carbon (OC)-normalized sediment basis (C(S-OC)), porewater basis (C(PW)), dissolved organic carbon (DOC)-normalized porewater basis (C(PW-DOC)), and freely dissolved porewater basis (C(free)). The bulk phase C(S) and C(PW) yielded highly variable LC50s across sediment types, whereas the use of normalized concentrations C(S-OC) and C(PW-DOC) generally reduced variability due to sediment type but not that due to aging. In contrast, LC50s based on C(free) were essentially independent of sediment conditions. The sediment pore water samples contained approximately 20-90 mg L(-1) DOC, and the C(free) expressed as a percentage of the total bulk pore water concentration ranged from 9 to 28% for fenpropathrin (mean = 19%), 8 to 18% for bifenthrin (mean = 13%), and 3 to 8% for cyfluthrin (mean = 6%) across the different sediments. These results indicate thatthe use of C(free) reduces uncertainties caused by sediment variables such as OC properties and aging effects.