Sunlight irradiation triggers changes in the fouling potentials of natural dissolved organic matter

Sunlight-initiated photodegradation has a great impact on the composition and properties of natural dissolved organic matter (DOM) in aquatic environments, which potentially changes the behavior and roles of DOM in water treatment facilities. Here, we explored the effect of sunlight irradiation on membrane fouling behavior of two natural DOM (i.e., Aldrich humic acid (AHA) and Suwannee River DOM (SRNOM)), particularly in the presence of calcium ion (Ca(II)). Results showed that a long-term exposure (3 months) to sunlight during the summer led to decreases in the chromophores and molecular size of both DOM. The characterization by UV-vis spectral parameter DSlope_350-400 (the slope of the log-transformed absorbance spectra in the range of 350-400 nm) indicated that sunlight-exposed DOM had a weaker Ca(II)-binding ability than unirradiated DOM, which could be attributable to the photochemically induced loss of carboxyl and phenolic groups. Additionally, AHA was found to be more susceptible to sunlight irradiation and Ca(II) addition than SRNOM, likely due to its higher aromaticity. Crucially, dead-end ultrafiltration tests showed that sunlight exposure of both AHA and SRNOM can reduce their fouling potential in the absence of Ca(II) and the presence of low Ca(II) (0.4 mM). In contrast, the addition of higher Ca(II) concentrations (2 and 3.6 mM) led to an increase in their fouling propensities. Overall, sunlight exposure can greatly alter the fouling behavior of natural DOM. This study provides a nexus between the naturally occurring transformation of DOM and its behavior (i.e., membrane fouling) in water treatment facilities.