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Abstract: Barite is commonly found in suspended matter in ocean waters and in marine sediments. The calculation of the barite saturation index of the world’s ocean waters has shown that the vast majority of the oceans are undersaturated with respect to pure barium sulfate, equilibrium being reached at a few locations like the Southern Ocean surface waters, deep waters of the Bay of Bengal or intermediate waters of the Pacific [Monnin, C., Jeandel, C., Cattaldo, T., Dehairs, F., 1999. The marine barite saturation state of the world’s oceans. Mar. Chem. 65 (3-4), 253–261.]. It is thus paradoxical to commonly find barite in a globally undersaturated ocean. Strontium is the most common impurity in natural barite. It is often suggested that the Ba content of ocean waters is controlled by equilibrium with Sr-substituted barite, and not with pure BaSO4. In order to address this problem, we have used the GEOSECS data (49 stations, 1404 data points) to calculate the saturation index of substituted barite in the world’s ocean using Lippmann’s description of thermodynamic equilibrium between a solid solution and an aqueous solution for the (Ba,Sr)SO4 system. Recent studies indicate that the (Ba,Sr)SO4 solid solution is most likely regular and continuous. The calculated saturation indices of the regular solid solution (with the interaction parameter A 0 equal to 1.6) are closer to those of pure barite than those calculated for the ideal solid solution. Conclusions previously reached for the pure barite case are not changed: the saturation state of ocean waters with respect to a regular solid solution is very close to that of pure barite. Sr-substitution for Ba in barium sulfate does not bring barite at equilibrium. When equilibrium is reached, the degree of Sr substitution of Ba amounts to only a few mole percent of Sr. Equilibrium values of the Sr content of the solid solutions in the intermediate (0.2–0.8) range are found for ocean surface waters where the Ba/Sr ratio is low, but as these waters are undersaturated, such solids are not stable in the water column. This provides another reason for the bimodal distribution of (Ba,Sr)SO4 solid solutions in nature, on top of that induced by the large ratio of the end member solubility products. Equilibrium is found for cold waters (i.e. for temperatures below 5°C) having a Ba content greater than about 70nmol/kg. The distribution coefficient of Sr in barite can be calculated from the Ba and Sr concentrations of these samples and from the equilibrium Sr mole fraction of the solid solution obtained from Lippmann’s diagram. It was found independent of pressure and it varies only slightly with the temperature of the sample. For the regular solid solution (with A 0 =1.6), it is:This expression (which has been established for temperatures below 5°C) can be used to directly calculate the composition of solid solutions at equilibrium with a given seawater sample, or conversely to know the Ba content of seawater at equilibrium with a given (Ba,Sr)SO4 solid solution. [Copyright &y& Elsevier]

Secondary ion mass spectrometry (SIMS) is often used to determine the sulfur contents and isotope ratios of metallic alloys in meteorites or high‐pressure experimental samples. However, SIMS analyses involve calibration and the determination of instrumental mass fractionation in reference materials with a matrix composition similar to that of the unknown samples. To provide metallic reference materials adapted to S measurements via SIMS, we synthesised a series of twenty‐eight alloys comprising four FeNi(±Si) compositions (Fe95Ni5, Fe90Ni10, Fe80Ni20, and Fe80Ni15Si5) with S contents varying from 100 μg g−1 to 4 g/100g using the “melt spinning” method, which guarantees that the metal alloys are rapidly quenched at ~ 106 K s−1. Sulfur contents were determined at the Service d'Analyse des Roches et Minéraux at the CRPG and absolute δ34S values were determined by multi‐collector ICP‐MS (MC‐ICP‐MS, ThermoScientific Neptune) and isotope ratio mass spectrometry (Thermoscientific Delta V). A δ34S value of 16.01 ± 0.31‰ was consistently obtained using the MC‐ICP‐MS, which was indistinguishable of the δ34S value of the FeS starting material (15.95 ± 0.08‰). It suggests that S did not undergo isotopic fractionation during the melting process. Of fifteen samples containing ≤ 5000 μg g−1 S, SIMS measurements with 15‐μm‐diameter spots were repeatable to within 10% relative (1 standard deviation, 1s) for S contents and 2‰ for δ34S values. However, samples containing > 5000 μg g−1 S showed FeNi–FeS immiscibility, leading to minor dispersion of the S mass fractions and δ34S values. No matrix effect was observed for Fe‐Ni, Si, or S contents in terms of the calibration curves and instrumental mass fractionation. We ultimately recommend eight samples as reliable reference materials for S isotopic measurements by SIMS, which we can share worldwide with other laboratories. [ABSTRACT FROM AUTHOR]