Surface complexation modeling of Cu(II) sorption to montmorillonite-bacteria composites

Surface complexation modeling, isothermal titration calorimetry, and batch adsorption were employed to characterize the adsorption of Cu onto montmorillonite, Pseudomonas putida X4, and their composites at mass ratios of 2:1, 6:1, and 12:1, respectively. Different enthalpy values were found for Cu adsorption to permanent (-6.43kJ/mol) and variable charge sites (8.51kJ/mol) on montmorillonite. The component additivity (CA) method was used to predict the adsorption of Cu on the composites by combining end member models for montmorillonite and P. putida. A reduced adsorption was observed at pH<5.5 due to physical blocking between montmorillonite and P. putida. By contrast, the enhanced binding at high pH levels was ascribed to the formation of bridging structures among the clay mineral-Cu-bacteria complexes. These deviations in the CA method were corrected by adding reactions of >RCOOH…XNa and >RCOOCuOHXNa. The increased adsorption of the composites confirmed the decrease of permanent negative charge sites and the formation of ternary complexes. The results help elucidate the effect of Cu adsorption onto clay minerals-bacteria composites. The newly developed "CA-site masking-bridging" model can be used to predict Cu speciation in systems in which the active interaction of bacteria and clay minerals occurs.