Formation and ripening of alginate-like exopolymer gel layers during and after membrane filtration

The properties of biofilm EPS are determined by the multiple interactions between its constituents and the surrounding environment. Because of the high complexity of biofilm EPS, its constituents' characterisation is still far from thorough, and identification of these interactions cannot be done yet. Therefore, we use gels of bacterial alginate-like exopolysaccharides (ALEs) as a model component for biofilm EPS in this work. These gels have been examined for their cohesive properties as a function of CaCl₂ and KCl concentration. Hereto, ALE gel layers were formed on membranes by dead-end filtration of ALE solutions. Accumulation of the cations Ca²⁺ and K⁺ in the gels could be well predicted from a Donnan equilibrium model based on the fixed negative charges in the ALE. This suggests that there is no specific binding of Ca²⁺ to the ALE and that on the time scale of the experiments, the Ca²⁺ ions can distribute freely over the gel and the surrounding solution. The concentration of fixed negative charges in the ALE was estimated around 1 mmol/g VSS (volatile suspended solids, organic mass) from the Donnan equilibrium. Moreover, an accumulation of H⁺ was predicted. Gels with more CaCl₂ in the supernatant were more compact and bore a higher osmotic pressure than those with less CaCl₂, revealing the role of Ca²⁺ ions in the network crosslinking. It is hypothesised that this mechanism later transitions into a rearrangement of the ALE molecules, which eventually leads to a fibrous network structure with large voids.