Effect of fulvic acid on neodymium uptake by goethite

[Display omitted] ► Binary Nd-goethite systems feature a classic cation sorption edge. ► Binary FA-goethite systems: FA is strongly sorbed to goethite below the PZC. ► Ternary systems: FA significantly enhances Nd uptake below the goethite PZC. ► Ternary systems: elevated [FA] suppresses Nd uptake above the goethite PZC. ► Ternary systems: goethite dissolution dramatically increases with elevated [FA]. Experimental studies of the interaction of aqueous neodymium (Nd), Suwannee River fulvic acid (FA), and solid phase goethite were conducted. Results from blank systems (individual Nd and FA), binary systems (Nd–goethite, FA–goethite, and Nd–FA), and ternary systems (Nd–FA–goethite) at 0.1mol/kg and 25°C are reported. In the binary Nd–goethite system a classic sorption edge is observed, whereby virtually all Nd is removed from solution above the goethite point of zero charge (PZC). Similarly, the binary FA–goethite system exhibits strong FA sorption; However in this system near complete removal of FA from solution is observed below the goethite PZC. In the binary Nd–FA system, both aqueous Nd and FA feature a sharp decrease in concentration at ca. pH 9. Various experiments in the ternary system were conducted. For all concentrations, FA enhanced Nd sorption below the goethite PZC, attributed to the formation of a Type B ternary surface complex (mineral–ligand–metal ion). Notably, the 100ppm FA ternary system showed anomalously high dissolved Nd in solution above the PZC (i.e., Nd sorption suppression) and a concomitant increase in goethite dissolution (∼9ppm total Fe3+ observed above circa pH 9.5). Our results suggest that Nd–FA complexation plays a key role in Nd uptake by goethite, and that this process is largely governed by pH: Whereas at pHs below the goethite PZC, Nd–FA complexation facilitates Nd sorption, above the PZC, and particularly at elevated FA concentrations, the formation of aqueous Nd–FA complexes suppresses Nd removal. Moreover, under these conditions, goethite dissolution may also play a role in mitigating Nd uptake by goethite.