PNNL

Abstract

Iron (III) oxides are ubiquitous in near-surface soils and sediments and interact strongly with dissolved phosphates via sorption, co-precipitation, mineral transformation and redox-cycling reactions. Iron oxide phases are thus, an important reservoir for dissolved phosphate, and phosphate bound to iron oxides should reflect dissolved sources as well as carry a history of the biogeochemical cycling of phosphorus (P). It has recently been demonstrated that dissolved inorganic phosphate (DIP) in rivers, lakes, estuaries and the open ocean can be used to distinguish different P sources and biological reaction pathways in the ratio of 18O/16O (?18OP) in PO43-. Here we present results of experimental studies aimed at determining whether non-biological interactions between dissolved inorganic phosphate and solid iron-oxides involve fractionation of oxygen isotopes in PO4. Determination of such fractionations is critical to any interpretation of ?18OP values of modern (e.g. hydrothermal iron oxide deposits, marine sediments, soils, groundwater systems) to ancient and extraterrestrial samples (e.g., BIF’s, Martian soils). Batch sorption experiments were performed using varied concentrations of synthetic ferrihydrite and isotopically- labeled dissolved ortho-phosphate at temperatures ranging from 4 to 95 oC. Mineral transformations and morphological changes were determined by X-Ray, Mössbauer spectroscopy and SEM image analyses. Our results reveal that isotopic fractionation between sorbed and aqueous phosphate occurs during the early phase of sorption with isotopically light phosphate preferentially incorporated into sorbed/solid phases. This fractionation showed negligible temperature-dependence and gradually decreased as a result of O-isotopic exchange between sorbed and aqueous phase phosphate, to become insignificant at greater than ~100 hours of reaction. In high-temperature experiments, this exchange was very rapid resulting in negligible fractionation between sorbed and aqueous-phase phosphate at much shorter reaction times. Mineral transformation resulted in initial preferential desorption/loss of light phosphate (P16O4) to solution. However, the continual exchange between sorbed and aqueous PO4, concomitant with this mineralogical transformation resulted again in negligible fractionation between aqueous and sorbed PO4 at long reaction times (> 2000 hrs). This finding is consistent with results obtained from natural ocean samples. This finding is important to the interpretation of PO4 O-isotope values in natural systems where iron-oxides are present and to studies of the biogeochemical cycling of P and PO4 biomarkers.