Effects of UV/Fe(II)/sulfite pre-treatment on NOM-enhanced Ca2+ scaling during nanofiltration treatment: Fouling mitigation, mechanisms, and correlation analysis of membrane resistance

Abstract

This study was aimed to evaluate the effects of a pre-treatment involving sulfite (S(IV)) synergistically activated by ultraviolet (UV)/Fe(II) on natural organic matter (NOM)-enhanced Ca²⁺ scaling during nanofiltration treatment. Based on the variations in the physicochemical properties and correlation analyses of irreversible resistance, the intrinsic fouling mechanisms were revealed from two aspects: bulk crystallization (interaction between NOM and inorganic ions) and surface crystallization (morphology of surface crystallization and a change in the Ca²⁺ concentration in the scaling layer). Furthermore, the degradation contribution rates of different free radicals during the UV/Fe(II)/S(IV) (UFS) treatment process were evaluated. During the reactions in the UFS, three free radicals (SO·-4, OH^·- and e- aq) were generated, and in-situ Fe(III) was formed in-situ. The carboxyl groups of the NOM were attacked by the free radicals, resulting in decreased of carboxyl concentration and density. In addition, the bond between Ca²⁺ and NOM weakened, and hydrophobic (HPO) substances were mineralized. However, the Fe(III) formed in-situ was active and electropositive, competing with Ca²⁺ for the complexation active sites on the NOM. The synergy effect of bulk crystallization and surface crystallization led to a significant decrease in the particle size of feed solution. The crystal size and roughness of membrane surface also decreased, which was conducive to reducing the membrane irreversible resistance. Correlation analysis revealed that the HPO ratio, carboxyl density and particle size (> 100 nm) ratio were effective characterization parameters for predicting irreversible resistance. This study not only provides guidance for alleviating membrane fouling caused by NOM-enhanced Ca²⁺ scaling during the nanofiltration process, but also presents the rationality of irreversible resistance during nanofiltration process and various indicators with strong linear correlation.

Keywords: Correlation analysis; Fouling mitigation; NOM-enhanced Ca(2+) scaling; Nanofiltration; UV/Fe(II) activated S(IV).