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Partitioning studies of polychlorinated biphenyls between aqueous solution and soil and sediment systems of Umngeni river, KwaZulu-Natal, South Africa.

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The significance of soil and sediment physicochemical properties and the environmental parameters such as pH, temperature, ionic strength, humic acid (HA) and time on the partitioning action of eight selected polychlorinated biphenyl (PCB) congeners were critically evaluated in this study to better understand the mobility, transportation, fate and distribution of hydrophobic organic pollutants in environmental media. Natural soil samples used in this study were collected along uMngeni River of KwaZulu-Natal province of South Africa. The mineral properties of soil samples were determined using the Walkley Black method, barium chloride compulsive exchange method and Brunauer-Emmet-Teller (BET) adsorption-desorption isotherm. All these were employed to observe the surface characteristics of the modeled individual soil particle sizes. Scanning electron microscopy (SEM) equipped with energy disperse X-ray (EDX) and Fourier transform infrared spectroscopy (FTIR) were used for the internal morphology and qualitative elemental analysis, as well as identification of possible functional groups in soil samples and commercial HA. Batch adsorption experiments were used for sorption studies. The results revealed that the amount of PCBs sorbed by soil was found to increase with an increase in contact time reaching equilibrium within 8 h. Among the soil chemical properties, soil organic matter was observed to correlate positively and play a more significant role in the sorption of PCBs. Soil samples with highest BET surface areas were related to the soil particle grain size. The sorption of PCBs onto soil was also found to decrease with an increase in the aqueous HA concentrations, and a change in the aqueous concentration of ionic strength was found to be less significant. Other important factors found to be more significant in the sorption were the degree of chlorination as well as stereochemistry of PCB congeners. The more hydrophobic and non-ortho (planar) congeners were found to contribute more significantly to sorption relative to the less hydrophobic and more ortho-substituted (nonplanar) congeners. Moreover, a decrease in the ratio of Si: (Al + Fe) was found to contribute positively to the sorption of PCBs. The kinetic studies on the partitioning of PCBs onto the soils was found to fit best with pseudo-second order, suggesting that the partitioning process of the selected PCBs between aqueous solution and active components in soil, involved more than onestep. Logarithmic values of organic carbon normalized sorption coefficient (log Koc) of the selected PCBs were found to decrease with an increase in the solution pH. The partitioning of PCBs onto the soils was also said to be temperature driven, where low aqueous temperatures encouraged morepartitioning of hydrophobic PCBs onto the soil. The Gibbs free energy (ΔG°) was found to be negative. Therefore, the thermodynamic studies showed that the PCB interaction with soil particle sizes was a spontaneous process. The role of initial PCB concentration on the partitioning was found to be L-type. This indicated that an increase in PCB concentration in the aqueous phase made it more difficult for PCB molecules to find a vacant site available for sorption onto the soil SOM.


Doctoral Degree. University of KwaZulu-Natal, Durban.