Application of quantum chemical descriptors into quantitative structure-property relationship models for prediction of the photolysis half-life of PCBs in water

Quantitative structure-property relationship(QSPR)models were developed for prediction of photolysis half-life(t_(1/2))of polychlorinated biphenyls(PCBs)in water under ultraviolet(UV)radiation.Quantum chemical descriptors computed by the PM3 Hamiltonian software were used as independent variables.The cross-validated Q^(2)_(cum)value for the optimal QSPR model is 0.966,indicating good prediction capability for lg t_(1/2)values of PCBs in water.The QSPR results show that the largest negative atomic charge on a carbon atom(Q-C)and the standard heat of formation(ΔH_(f))have a dominant effect on t_(1/2)values of PCBs.Higher Q_(C)^(-)values or lowerΔHf values of the PCBs leads to higher lg t_(1/2)values.In addition,the lg t_(1/2)values of PCBs increase with the increase in the energy of the highest occupied molecular orbital values.Increasing the largest positive atomic charge on a chlorine atom and the most positive net atomic charge on a hydrogen atom in PCBs leads to the decrease of lg t_(1/2)values.

Sequence of the main geochemical controls on the Cu and Zn fractions in the Yangtze River estuarine sediments

Metal speciation can provide sufficient infor- mation for environmental and geochemical researches. In this study, based on the speciation determination of Cu and Zn in the Yangtze Estuary sediments, roles of eight geochemical controls （i.e., total organic carbon （TOC）, clay, Fe/Mn in five chemical fractions and salinity） are fully investigated and sequenced with correlation analysis （CA） and principal components analysis （PCA）. Results show that TOC, clay and Fe/Mn oxides are key geochemical factors affecting the chemical speciation distributions of Cu and Zn in sediments, while the role of salinity appears to be more indirect effect. The influencing sequence generally follows the order： TOC 〉 clay 〉 Mn oxides 〉 Fe oxides 〉 salinity. Among the different fractions of Fe/Mn oxides, residual and total Fe content, and exchangeable and carbonate Mn exert the greatest influences, while exchangeable Fe and residual Mn show the poorest influences.

Multiphase redistribution differences of polycyclic aromatic hydrocarbons （PAHs） between two successive sediment suspensions

Successive sediment suspensions often happen in estuary, yet little research has probed into the difference in the release behaviors of organic compounds among different suspensions. This study took polycyclic aromatic hydrocarbons （PAHs） as typical organic contaminants and investigated the release behaviors between two successive suspensions with a particle entrainment simulator （PES）. Results showed that successive sediment suspensions lowered the concentration of dissolved PAHs in the overlying water via facilitating the re-adsorption of dissolved PAHs onto the suspended particles. Fast-release and slow-release periods of PAHs were successively observed in the both suspensions. The concentration changes of dissolved PAHs in the second suspension were generally similar with but hysteretic to those in the first suspension. More vigorous desorption and re-absorp- tion of PAHs were induced in the second suspension. Successive sediment suspensions obviously decreased the concentrations of mineral composition and organic matters in the overlying water, which significantly affects multi- phase distribution of PAHs.