Oxygen isotope fractionation in phosphates: the role of dissolved complex anions in isotope exchange (original) (raw)

Professor Dr Jochen Hoefs on the occasion of his 75th birthday. Oxygen isotope fractionation factors for phosphates were calculated by means of the increment method. The results suggest that Ag 3 PO 4 and BiPO 4 are enriched in 18 O relative to AgPO 4 , and the three phosphates are consistently depleted in 18 O relative to Ba 3 [PO 4 ] 2 ; fluorapatite and chlorapatite exhibit a similar behaviour of oxygen isotope fractionation with consistent enrichment of 18 O relative to hydroxya-patite. The valence, radii and coordination of metal cations play a quantitative role in dictating the 18 O/ 16 O partitioning in these phosphates of different compositions. The calculated fractionation factors for the Ag 3 PO 4 –H 2 O system are in agreement with experimental determinations derived from enzyme-catalysed isotope exchange between dissolved inorganic phosphate and water at the longest reaction durations at low temperatures. This demonstrates that the precipitated Ag 3 PO 4 has completely captured the oxygen isotope fractionation in the dissolved inorganic phosphate. The calculated fractionation factors for the F/Cl-apatite–water systems are in agreement with the enzyme-catalysed experimental fractionations for the dissolved phosphate–water system at the longest reaction durations but larger than fractionations derived from bacteria-facilitated exchange and inorganic precipitation experiments as well as natural observations. For the experimental calibrations of oxygen isotope fractionation involving the precipitation of dissolved phosphate species from aqueous solutions, the fractionation between precipitate and water is primarily dictated by the isotope equilibration between the dissolved complex anions and water prior to the precipitation. Therefore, the present results provide a quantitative means to interpret the temperature dependence of oxygen isotope fractionation in inorganic and biogenic phosphates.