XANES spectroscopy proofs pH‐dependent P sorption partitioning to Fe oxyhydroxides versus montmorillonite in acidic soils

Abstract Background Fe and Al oxyhydroxides are well‐known phosphorus (P)‐retaining minerals in soils. Little information is available regarding the relevance of clay minerals for the sorption of P in mixed oxyhydroxide–clay mineral systems and pH effects on P sorption partitioning. Aims and Methods We wanted to investigate pH effects on P sorption partitioning between Fe oxyhydroxides and high‐activity clay minerals in mixed‐mineral systems. We quantified the relative contribution of ferrihydrite or goethite versus Al‐saturated montmorillonite (Al‐MT) to the retention of orthophosphate (oPO 4 ) and inositol hexakisphosphate (IHP) at different pH values (3–6). We combined the analysis of P solution concentration changes with the quantification of P bound to Fe(III) versus Al in the Fe oxyhydroxide/Al‐MT mixtures by X‐ray absorption near‐edge structure (XANES) spectroscopy. Results Orthophosphate was preferentially retained by ferrihydrite, compared to Al‐MT at pH 3–6. The opposite was observed for goethite at low P solution concentrations. The contribution of Al‐MT versus Fe oxyhydroxides to oPO 4 retention increased with pH. This is attributed to a speciation change of clay‐adsorbed Al from monomeric Al 3+ to polynuclear Al hydroxy species. IHP was predominantly retained by Al‐MT rather than ferrihydrite at pH 3–6, probably by the formation of adsorbed and surface‐precipitated Al phytate complexes. Conclusions Synchrotron‐based XANES spectroscopy allows for quantifying P adsorbed to co‐existing pedogenic Fe(III) oxyhydroxides versus Al‐MT in mixed‐mineral systems. Soil P retention partitioning to these minerals depends on (1) dominating P form (oPO 4 , IHP), (2) relative abundance of high‐activity clay minerals, short‐range ordered and crystalline Fe oxyhydroxides, and (3) solution pH.