EPS adsorption to goethite: Molecular level adsorption mechanisms using 2D correlation spectroscopy

The adsorption of extracellular polymeric substances (EPS) onto soil minerals is an important process for understanding bacterial adhesion to mineral surfaces and environmental cycling of nutrients and contaminants. To clarify the molecular level mechanisms and processes of EPS adsorption, the interaction mechanisms between EPS and goethite was explored using two-dimensional (2D) Fourier transformation infrared (FTIR) correlation spectroscopy (CoS) assisted by C 1s near edge X-ray absorption fine structure spectroscopy (NEXAFS). Results show that the amide functional groups of EPS play an important role in its adsorption on goethite, and the adsorption of EPS-proteins on goethite is a function of electrolyte concentration, with increasing adsorption at a higher electrolyte concentration. Results also show that the order in which the EPS functional groups interact and bind with goethite is dependent on electrolyte concentration, where carboxyl and phosphoryl functional groups are the first to adsorb at low electrolyte concentration, while amide groups are the first to adsorb at higher electrolyte concentration. Deconvolution and curve fitting of the amide I band at the end of the adsorption process (~300 min) shows that the secondary structure of proteins is converted from a random coil conformation to aggregated strands, α-helices and turns. This conversion leads to increased adsorption of EPS-proteins and explains the overall adsorption increase of EPS on goethite surfaces with an increasing concentration of electrolyte. Furthermore, the adsorption of the carboxyl functional groups of EPS decreases with increasing electrolyte concentration, likely due to more effective screening of the goethite surface charge with increasing concentration of electrolyte. The integrated results from ATR-FTIR and 2D-CoS allow us to construct a comprehensive overview of EPS-goethite interaction processes at the molecular level, which can be used to improve our understanding of EPS-mineral interactions in the natural environment. These results also provide fundamental information for a better understanding of bacterial biofilm formation on soil and sediment minerals, and facilitate research on the subsequent interaction of nutrients and contaminants with the reactive constituents of biofilms in natural and contaminated environments.