Influence of organic carbon fractions of freshwater biofilms on the sorption for phenanthrene and ofloxacin: The important role of aliphatic carbons

Sorption to biofilms is thought to be a crucial process controlling the fate of trace organic contaminants in aquatic systems. The organic composition of biofilms is regarded as the determining factor in the sorption mechanism of biofilm organic carbon fractions; however, its role is not well known. Here, the sorption of phenanthrene and ofloxacin was modeled with classic and emerging organic contaminants, respectively, by comparatively investigating nine type of freshwater biofilms cultured in a river, lake, and reservoir in spring, summer, and autumn. The chemical features of the nine biofilms were analyzed using elemental analysis, infrared spectroscopy, X-ray photoelectron spectroscopy, and carbon-13 nuclear magnetic resonance. Results showed that the freshwater biofilms were aliphatic-rich natural amorphous solid substances with O-containing functional groups, and their surface polarity was significantly lower than their bulk polarity. All the isotherms of phenanthrene and ofloxacin sorption by the biofilms were linear. The organic carbon-normalized partition coefficient values for phenanthrene and ofloxacin on the nine biofilms ranged from 91.9 to 364.2 L g−1 and 3.2 to 43.2 L g−1, respectively. The van der Waals interaction between a majority of aliphatic carbon (73.4%–83.9%) in biofilms and the two sorbates was much stronger than π-π interactions between a minority of aromatic carbon (12.7%–21.7%) and sorbates. The surface polarity of the biofilms regulated polar interactions including the hydrogen bonding and electron donor–acceptor interactions. Both the aliphatic carbon and surface polarity in the biofilms enhanced the sorption of phenanthrene and ofloxacin. The sorption characteristics and mechanisms of polycyclic aromatic hydrocarbons and antibiotics on biofilms shown in our present and previous studies are different from those of other ubiquitous natural solid materials such as soils and sediments. This study provides insight into the importance of aliphatic carbon fractions of freshwater biofilms for the sorption of classic and emerging organic contaminants.