Mechanisms of pore water organic matter adsorption to montmorillonite

The extent and mechanisms of adsorption of marine pore water organic matter to montmorillonite were studied in a series of batch and sequential adsorption experiments. Pore water natural organic matter (pNOM) and easily extracted natural organic matter (eNOM) were collected from Liberty Bay (Puget Sound, WA, USA) sediments. The pNOM and eNOM were each divided into two size fractions using a 1000 D ultrafilter. Batch adsorption isotherms were approximately linear, and the >1000 D fractions of both pNOM and eNOM had larger partition coefficients (Kd) than the <1000 D fractions. A two-component fit of the sequential adsorption data indicated that pNOM and eNOM contained a similar amount of NOM (30%) that was not surface reactive toward montmorillonite. After correcting the batch adsorption Kds for the non-reactive components, the Kds estimated by batch and sequential adsorption were identical ( 2.7 l/kg for >1000 D pNOM and eNOM, and 1.6 l/kg for <1000 D pNOM and eNOM). Mechanisms of adsorption were investigated by systematically changing conditions (pH, temperature and ionic composition) of >1000 D fractions during batch isotherm experiments. Adsorption of NOM was found to decrease with increased temperature, suggesting that hydrophobic effects were not the dominant adsorption mechanisms in this system. Ion exchange was also not an important adsorption mechanism because adsorption increased with ionic strength. The observed enhancement in adsorption with ionic strength indicated that van der Waals interactions were important in the adsorption of NOM. Ligand exchange was found to be a significant mechanism since the presence of SO42− in solution reduced the amount of NOM adsorbed. Ca2+ enhanced adsorption slightly more than Na+, suggesting that cation bridging was involved. The relative contributions of van der Waals interactions, ligand exchange and cation bridging were estimated to be approximately 60%, 35% and 5%, respectively, for adsorption of NOM in a CaCl2 solution.