Impact of low-molecular weight organic acids on selenite immobilization by goethite: Understanding a competitive-synergistic coupling effect and speciation transformation

Abstract

The interactions between low-molecular weight organic acids (LMWOAs) and selenium (Se) on mineral/water interfaces affect the release, immobilization and bioavailability of Se in nature. Herein, the effects of three environmentally relevant LMWOAs (i.e., oxalic (Oxa), succinic (Suc) and citric (Cit) acids) on Se(IV) adsorption to goethite under oxic conditions were investigated using batch experiments, speciation fractionation, and ATR-FTIR and XPS analyses. The LMWOAs exhibited a competitive-synergistic coupling effect on Se(IV) adsorption to goethite, which inhibited the adsorption rate of Se(IV) by 14.1, 13.3 and 8.0 times. However, immobilization of Se(IV) was simultaneously enhanced by 39.1%, 34.6% and 14.1% in the following order Oxa > Suc > Cit. The results obtained by fractionation of the adsorbed Se(IV) revealed that the enhancement was due to surface binding as well as speciation transformation from ligand-exchangeable Se(IV) into residual fractions, which increased by approximately 18% in the presence of the LMWOAs. The dissolution of goethite significantly improved due to the LMWOAs and decreased to different degrees as the concentration of Se(IV) increased. The monodentate mononuclear complexes (58.2%) and Lewis base sites bonded Se (41.8%) were the predominant surface species of Se(IV) in goethite-Se(IV) system. The ATR-FTIR and high-resolution XPS analyses demonstrated that the formation of ≡FeO(SeO)O-CO surface complexes (22.8–27.0%) occurred in the presence of LMWOAs, which could be closely correlated with the interface-mediated reduction of Se(IV). In addition, the predominant mechanism for the formation of residual Se is LMWOA specific, in which ferric selenite-like precipitation was dominant for Suc (10.6%) and Cit (11.6%) and reduction was dominant for Oxa (17.5%). Overall, LMWOAs play an important role in Se(IV) immobilization and speciation transformation and may facilitate understanding the Se bioavailability in rhizosphere soils under oxic conditions.