Theoretical study of chlordecone and surface groups interaction in an activated carbon model under acidic and neutral conditions.

Activated carbons (ACs) are widely used in the purification of drinking water without almost any knowledge about the adsorption mechanisms of the persistent organic pollutants. Chlordecone (CLD, Kepone) is an organochlorinated synthetic compound that has been used mainly as agricultural insecticide. CLD has been identified and listed as a persistent organic pollutant by the Stockholm Convention. The selection of the best suited AC for this type of contaminants is mainly an empirical and costly process. A theoretical study of the influence of AC surface groups (SGs) on CLD adsorption is done in order to help understanding the process. This may provide a first selection criteria for the preparation of AC with suitable surface properties. A model of AC consisting of a seven membered ring graphene sheet (coronene) with a functional group on the edge was used to evaluate the influence of the SGs over the adsorption. Multiple Minima Hypersurface methodology (MMH) coupled with PM7 semiempirical Hamiltonian was employed in order to study the interactions of the chlordecone with SGs (hydroxyl and carboxyl) at acidic and neutral pH and different hydration conditions. Selected structures were re-optimized using CAM-B3LYP to achieve a well-defined electron density to characterize the interactions by the Quantum Theory of Atoms in Molecules approach. The deprotonated form of surface carboxyl and hydroxyl groups of AC models show the strongest interactions, suggesting a chemical adsorption. An increase in carboxylic SGs content is proposed to enhance CLD adsorption onto AC at neutral pH conditions.

Theoretical study of γ-hexachlorocyclohexane and ß-hexachlorocyclohexane isomers interaction with surface groups of activated carbon model.

Activated carbon (AC) is employed in drinking water purification without almost any knowledge about the adsorption mechanism of persistent organic pollutants (POPs) onto it. Hexachlorocyclohexane (HCH) is an organochlorinated contaminant present in water and soils of banana crops production zones of the Caribbean. The most relevant isomers of HCH are γ-HCH and ß-HCH, both with great environmental persistence. A theoretical study of the influence of AC surface groups (SGs) on HCH adsorption is done in order to help to understand the process and may lead to improve the AC selection process. A simplified AC model consisting of naphthalene with a functional group was used to assess the influence of SGs over the adsorption process. The Multiple Minima Hypersurface (MMH) methodology was employed to study γ-HCH and ß-HCH interactions with different AC SGs (hydroxyl and carboxyl) under different hydration and pH conditions. The results obtained showed that association of HCH with SGs preferentially occurs between the axial protons of HCH and SG's oxygen atom, and the most favorable interactions occurring with charged SGs. An increase in carboxylic SGs content is proposed to enhance HCH adsorption onto AC under neutral pH conditions. Finally, this work presents an inexpensive computer aided methodology for preselecting activated carbon SGs content for the removal of a given compound.