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A thermodynamic investigation of barium and calcium sulfate stability in sediments at an oceanic ridge axis (Juan de Fuca, ODP legs 139 and 169)
Authors:Christophe Monnin  Sabine Balleur  Bruno Goffe
Institution:1 CNRS/Université Paul Sabatier, Laboratoire Mécanismes de Transfert en Géologie, 38 rue des Trente Six Ponts, 31400 Toulouse, France
2 CNRS/Ecole Normale Supérieure, Laboratoire de Géologie, 24 rue Lhomond, 75005 Paris, France
3 Etudes et Production Schlumberger, 1 rue Henri Bequerel, 92140 Clamart, France
Abstract:We have used a new thermodynamic model of barium and calcium sulfate solubilities in multicomponent electrolyte solutions (Monnin, 1999) to investigate the stabilities of barite and anhydrite in seawater or in marine sediment porewaters at high temperature and pressure. As a further test supplementing those previously carried out during model development, we have calculated the temperature at which standard seawater becomes saturated with respect to anhydrite. The model predicts that, upon heating at 500 bars, standard seawater becomes saturated with respect to anhydrite at 147 ± 5°C, which compares well with the literature value of 150°C (Bishoff and Seyfried, 1978). At 20 bars the calculated saturation temperature is 117 ± 3°C. This points to a non negligible pressure effect even at moderate pressures.We have calculated the barite and anhydrite saturation indices for the in situ temperatures and pressures, from the composition of porewaters collected at ODP Sites 855, 856, 857, 858, 1035 and 1036 during ODP Legs 139 and 169 (Juan de Fuca and Gorda ridges, NE Pacific). Calculated saturation indices for porewater samples collected at depths corresponding to temperatures between 70° and 110-120°C at an in situ pressure of about 260 bars yield equilibrium values for anhydrite and barite. Saturation indices of samples collected at depths where the temperature exceeds 110-120°C, however, yield values indicating supersaturation with respect to anhydrite and undersaturation with respect to barite. This result is consistent with the redissolution of anhydrite during cooling, leading to the well documented sampling artifact affecting porewater compositions in high temperature marine sediments: anhydrite dissolution increases the porewater sulfate content, which in turn induces a loss of barium from solution through barite precipitation (the common ion effect). We postulate that this redissolution occurs in sediment samples for which the in situ temperature exceeds 110-120°C: below this limit anhydrite remains at equilibrium or does not have time to significantly dissolve before porewaters are sampled.
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