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The association processes between engineered TiO2 nanoparticles and SuwanneeRiver humic acids are investigated by isothermal titration calorimetry and bymeasuring the exchanged heat during binding process allowing the determinationof thermodynamic (change of enthalpy, Gibbs free energy and entropy) andreaction (binding affinity constant, reaction stoichiometry) parameters. Ourresults indicate that strong TiO2-Suwannee River humic acid interactions areentropically and enthalpically favorable with exothermic binding reactions andthat the mixing order is also an important parameter. High humic acidconcentrations induce homoagglomeration ("self" assembly) and are shown tofavor an enthalpically driven association process. Light scattering techniquesare also considered to investigate the influence of TiO2 surface chargemodifications and agglomeration mechanisms. Patch and bridging mechanisms arefound to result into the formation of large agglomerates once charge inversionof TiO2-humic acid complexes is achieved. Moreover van der Waals interactionsare also found to play a significant role during interaction processes due tothe amphiphilic character of humic acids.

environmental science. nano

Isothermal titration calorimetry as a powerful tool to quantify and  better understand agglomeration mechanisms during interaction processes  between TiO2 nanoparticles and humic acids