Probing the Mechanism of Selective Phosphate Adsorption from Wastewater Using Aqueous and Synchrotron X-ray
Neha Sharma1,2, Edward Apraku3, Hannah E Holmes1
1Department of Chemical Engineering, Stanford University, Stanford, California 94305, United States.
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Ion exchange shows promise for recovering phosphate from wastewater as value-added products but requires high phosphate selectivity to compete with conventional treatment. Hybrid anion exchange (HAIX) resins, which contain nonselective basic functional groups and selective iron oxide nanoparticles (FeOnp), can remove phosphate from wastewater. However, knowledge gaps remain regarding the mechanisms of phosphate selectivity and influence of competing ions, hindering efforts to model adsorption dynamics and design adsorption processes for varying wastewaters. To address these gaps, we integrated aqueous-phase adsorption analysis with solid-phase, synchrotron-based X-ray characterization; this integration facilitated elucidation of the distribution and speciation of iron, phosphate, and competing anions on HAIX resins. We compared a quaternary ammonium-functionalized HAIX resin (strong base anion exchange, SBA) to a tertiary amine version (weak base anion exchange, WBA) to determine the role of functional groups. X-ray radiography revealed differences in FeOnp speciation (goethite vs ferrihydrite) and distribution (peripheral vs homogeneous) between the resins, resulting in varied phosphate affinity and intraparticle diffusion resistance. Using micro-X-ray fluorescence (μ-XRF) and micro-X-ray absorption near-edge structure (μ-XANES) spectroscopy, we identified differences in where and how phosphate binds across resin types and wastewaters. Across wastewater compositions, FeOnp sites in WBA contribute more to phosphate adsorption than in SBA, possibly due to variations in Fe distribution and speciation. Phosphate adsorption densities calculated from quantitative μ-XRF maps matched those from aqueous analysis, demonstrating the effectiveness of this integrated approach. Overall, results demonstrate the use of synchrotron-based X-ray characterization for investigating adsorption mechanisms and advance HAIX as a phosphate recovery technology from wastewaters.


