1. Constraining sulfur incorporation in calcite using inorganic precipitation experiments.
- Author
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Karancz, Szabina, Uchikawa, Joji, de Nooijer, Lennart J., Wolthers, Mariëtte, Conner, Kyle A., Hite, Corinne G., Zeebe, Richard E., Sharma, Shiv K., and Reichart, Gert-Jan
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INORGANIC chemistry , *FIELD research , *CARBON dioxide , *SULFATES , *SULFUR , *CALCITE - Abstract
The sulfur over calcium ratio (S/Ca) in foraminiferal shells was recently proposed as a new and independent proxy for reconstructing marine inorganic carbon chemistry. This new approach assumes that sulfur is incorporated into CaCO 3 predominantly in the form of sulfate (SO 4 2−) through lattice substitution for carbonate ions (CO 3 2–), and that S/Ca thus reflects seawater [CO 3 2–]. Although foraminiferal growth experiments validated this approach, field studies showed controversial results suggesting that the potential impact of [CO 3 2–] may be overwritten by one or more parameters. Hence, to better understand the inorganic processes involved, we here investigate S/Ca values in inorganically precipitated CaCO 3 (S/Ca (cc)) grown in solutions of CaCl 2 − Na 2 CO 3 − Na 2 SO 4 − B(OH) 3 − MgCl 2. Experimental results indicate the dependence of sulfate partitioning in CaCO 3 on the carbon chemistry via changing pH and suggest that faster precipitation rates increase the partition coefficient for sulfur. The S/Ca ratios of our inorganic calcite samples show positive correlation with modelled [CaSO 4 0] (aq) , but not with the concentration of free SO 4 2− ions. This challenges the traditional model for sulfate incorporation in calcite and implies that the uptake of sulfate potentially occurs via ion-ion pairs rather than being incorporated as single anions. Based on the [Ca2+] dependence via speciation, we here suggest a critical evaluation of this potential proxy. As sulfate complexation seems to control sulfate uptake in inorganic calcite, application as a proxy using foraminiferal calcite may be limited to periods for which seawater chemistry is well-constrained. As foraminiferal calcite growth is modulated by inward Ca2+ flow to the site of calcification coupled to outward H+ pumping, sulfate incorporation as CaSO 4 0 ion-pair in the foraminifer's shell also provides a mechanistic link for the observed relationship between S/Ca (cc) and [CO 3 2–]. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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