Adsorption of natural organic matter onto carbonaceous surfaces: atomic force microscopy study

The microscopic structure of carbonaceous surfaces exposed to natural organic matter (NOM) under aqueous conditions has been explored using atomic force microscopy (AFM). Dismal Swamp Water was used as the NOM source, while highly ordered pyrolytic graphite (HOPG) served as a surrogate for the graphene sheets that characterize the surface of many carbonaceous materials in aquatic environments. Under acidic conditions, the HOPG surface was covered with a densely packed monolayer of NOM molecules. In some cases, aggregates of well-defined, individual NOM molecules were observed that exhibited a degree of registry with respect to the HOPG substrate. This suggests that adsorbate-substrate interactions play a role in moderating the structure of the adsorbate layer. As the pH increased, the concentration of adsorbed NOM decreased systematically because of increasingly repulsive interactions between adsorbates. Increasing the ionic strength produced a modest increase in the concentration of adsorbed NOM. Ca2+ ions exerted a more pronounced influence on both the surface coverage of adsorbed NOM molecules and the size of individual adsorbates because of the effects of intermolecular complexation. In contrast to the spherical structures observed by AFM under aqueous conditions, adsorbed NOM formed a mixture of "ringlike" assemblies and larger aggregates upon drying.