Roles of phytoplankton- and macrophyte-derived dissolved organic matter in sulfamethazine adsorption on goethite

Phytoplankton-derived dissolved organic matter (PDOM) and macrophyte-derived dissolved organic matter (MDOM) exist ubiquitously in eutrophic freshwater lakes. To understand the heterogeneous roles of individual fluorescent DOM components in the adsorption of antibiotics onto sediment minerals, the adsorptive fractionation of DOM on goethite (α–FeOOH) and its interaction with sulfamethazine (SMT) were investigated using fluorescence excitation-emission matrix combined with parallel factor analysis (EEM–PARAFAC). The affinity sequence for goethite of the 4 fluorescent PARAFAC components followed the order of: tryptophan- > tyrosine- > long emission wavelength (LEW) humic- > and short emission wavelength (SEW) humic-like component. This sequence indicated the preferential adsorption of protein-like substances. Meanwhile, tyrosine-like components can strongly form complexes with SMT with a large binding constant, followed by tryptophan- and SEW humic-like components. However, LEW humic-like component did not effectively react with SMT. The main mechanism of fluorescence quenching between DOM and SMT was static quenching. The result indicated that protein-like substances in DOM were favorable to SMT adsorption by acting as a bridge to form complexes with both goethite surface and SMT molecules, whereas humic-like substances played secondary roles in the DOM–goethite–SMT ternary system. Due to its higher content of protein-like substances, PDOM improved the SMT adsorption on goethite more than MDOM. Therefore, the abundant DOM released from phytoplankton and macrophytes affected the transport of antibiotics to sediments and might eventually change their bioavailability and toxicity to organisms.