Abstract
The adsorption of organic matter and phosphate on minerals is a common natural process that has an important impact on the migration and burial of carbon and phosphorus. Previous studies have focused mainly on the influence of organic matter on the adsorption of phosphate. Yet, the influence of phosphate on the adsorption of different pools of organic matter is not well understood. This study evaluates changes in different organic matter pools during their adsorption to minerals in the presence of phosphate. Firstly, the adsorption behaviors of natural organic matter (i.e., humic acid) and phosphate on goethite were evaluated separately. Secondly, humic acid and phosphate were added to goethite at different orders to elucidate the effect of phosphate on the fractionation of humic acid components adsorbed to goethite. The results showed that when phosphate and humic acid were added simultaneously, goethite was preferentially combined with phosphate. In the absence of phosphate, SUVA254 of the humic acid solution decreased and E2/E3 of the solution increased during the adsorption. Among the six EEM-PARAFAC (excitation-emission matrix fluorescence coupled with parallel factor analysis) components of the humic acid, C1, C2, and C4 (terrestrial humus-like substances) decreased significantly and exhibited strong adsorption, C3 (microbial fulvic-like substance) showed weak adsorption, whereas C5 (photodegradation products) and C6 (tyrosine-like component) did not show evident adsorption. In the presence of phosphate, phosphate inhibited, and replaced the adsorbed C1, C2, and C4, but promoted the adsorption of C5, which increased the aromaticity and the molecular weight of the humic acid solution. Our results reveal that phosphate influences the fractionation of humic acid components adsorbed onto goethite, suggesting that phosphate can alter the chemical composition of natural organic matter interacting with minerals and thus impact the burial and fractionation of natural organic matter at the mineral-water interface.
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