Impact of seawater sulfate concentration on sulfur concentration and isotopic composition in calcite of two cultured benthic foraminifera

Abstract

Marine sediments can be used to reconstruct the evolution of seawater [SO42-] and δ34S over time, two key parameters that contribute to refine our understanding of the sulfur cycle and thus of Earth's redox state. δ34S evolution can be measured from carbonates, barites and sulfate evaporites. [SO42-] variations can be reconstructed using fluid inclusions in halites, a method that only allows a low-resolution record. Reconstruction of the past sulfur cycle could be improved if carbonates allowed the tracking of both seawater δ34S and [SO42-] variations in a sole, continuous sedimentary repository. However, most primary carbonates formed in the ocean are biogenic, and organisms tend to overprint the geochemical signatures of their carbonates through a combination of processes often collectively referred to as vital effects. Hence, calibrations are needed to allow seawater δ34S and [SO42-] reconstructions based on biogenic carbonates. Because foraminifera are important marine calcifiers, we opted to focus on calcite synthesized by individuals of rosalinid benthic foraminifera cultured in the laboratory under controlled conditions, with varying seawater [SO42-] (ranging from 0 to 180 mM). Our experimental design allowed us to obtain foraminiferal asexual reproduction over several generations. We measured bulk carbonate-associated sulfate (CAS) content and sulfur isotopic composition (δ34SCAS) on samples of tens to hundreds of specimens from a selection of culture media, where [SO42-] varied from 5 to 60 mM. Increasing or decreasing [SO42-] with respect to modern-day seawater concentration (28 mM) impacted foraminiferal population size dynamics and the total amount of bioprecipitated carbonate. Foraminiferal CAS concentration increased proportionally with [SO42-] concentration from 5 mM up to 28 mM and then showed a plateau from 28 to 60 mM. The existence of a threshold at 28 mM is interpreted as the result of a control on the precipitation fluid chemistry that foraminifera exert on the carbonate precipitation loci. However, at high seawater sulfate concentrations (> 40 mM) the formation of sulfate complexes with other cations may partially contribute to the non-linearity of the CAS concentration in foraminiferal tests at high increases in [SO42-]. Yet, despite the significant effect of seawater [SO42-] on foraminiferal reproduction and on CAS incorporation, the isotopic fractionation between CAS and seawater remains stable through varying seawater [SO42-]. Altogether, these results illustrate that CAS in biogenic calcite could constitute a good proxy for both seawater [SO42-] and δ34S and suggests that sulfate likely plays a role in foraminiferal biomineralization and biological activity.