title: Affinity of functional groups for membrane surfaces: implications for physically irreversible fouling.
abstract: Fouling in membranes used for water treatment has been attributed to the presence of natural organic matter (NOM) in water. There have been reports recently on the contribution of hydrophilic fractions of NOM (e.g., carbohydrate-like substances) to fouling, but there is still little information about the physicochemical interactions between membranes and carbohydrate-like substances. In this study, the affinity of carbohydrate-like substances to two different microfiltration (MF) membranes was investigated by using atomic force microscopy (AFM) and functionally modified microspheres. Microspheres were attached to the tip of the cantilever in an AFM apparatus and the adhesion forces working between the microspheres and the membranes were determined. The microspheres used in this study were coated with either hydroxyl groups or carboxyl groups to be used as surrogates of carbohydrate-like substances or humic acid, respectively. Measurements of adhesion force were carried out at pH of 6.8 and the experimental results demonstrated that the adhesion force to membranes was strong in the case of hydroxyl groups but weak in the case of carboxyl groups. The strong adhesion between the hydroxyl group and the membrane surface is explained by the strong hydrogen bond generated. It was also found that the affinity of the hydroxyl group to a polyvinylidenefluoride (PVDF) membrane was much higher than that to a polyethylene (PE) membrane, possibly due to the high electronegative nature of the PVDF polymer. The time course of changes in the affinity of hydroxyl group to a membrane used in a practical condition was investigated by repeatedly carrying out AFM force measurements with PE membrane specimens sampled from a pilot plant operated at an existing water treatment plant. Microspheres exhibited strong affinity to the membrane at the initial stage of operation (within 5 days), but subsequently exponential reduction of the affinity was seen until the end of operation, as a result of fouling development. However, the magnitude of affinity of hydroxyl-modified microspheres was much higher than that of carboxyl-modified microspheres even after the significant reduction of affinity of hydroxyl-modified microspheres to the membranes was seen. The results obtained in this study partially explain why hydrophilic NOM dominated over humic substances in foulants of membranes used for water treatment in recent studies on fouling.
authors.affiliation: Division of Built Environment, Graduate School of Engineering, Hokkaido University, N13W8, Kita-ku, Sapporo 060-8628, Japan.
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Yamamura
authors.forename: Katsuki
authors.initials: K
authors.lastname: Kimura
authors.forename: Takaharu
authors.initials: T
authors.lastname: Okajima
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Tokumoto
authors.forename: Yoshimasa
authors.initials: Y
authors.lastname: Watanabe