Experimental metasomatic incorporation of sulfur into fluorapatite as a 
function of coupled substitutions involving sodium, silicon, iron, and cerium

Harlov, D. E.; Casaus, Justin; Konecke, Brian A.; Simon, Adam C.

doi:10.1016/j.gca.2025.01.024

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Experimental metasomatic incorporation of sulfur into fluorapatite as a function of coupled substitutions involving sodium, silicon, iron, and cerium

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Harlov, D. E.
3.1 Inorganic and Isotope Geochemistry, 3.0 Geochemistry, Departments, GFZ Publication Database, Deutsches GeoForschungsZentrum;

Casaus, Justin
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Konecke, Brian A.
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Simon, Adam C.
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Harlov, D. E., Casaus, J., Konecke, B. A., Simon, A. C. (2025): Experimental metasomatic incorporation of sulfur into fluorapatite as a function of coupled substitutions involving sodium, silicon, iron, and cerium. - Geochimica et Cosmochimica Acta, 393, 268-289.
https://doi.org/10.1016/j.gca.2025.01.024

Cite as: https://gfzpublic.gfz-potsdam.de/pubman/item/item_5030205

Abstract

Here, we report results from hydrothermal alteration and crystallization experiments at 800 °C and 1 GPa that constrain the partitioning of S, Fe, Sr, and Ce (as a proxy for the REE) between fluorapatite and hydrothermal fluids of variable compositions. The data from these experiments demonstrate that S can be incorporated in apatite by the two known coupled substitutions S6+ + Na+ = P5+ + Ca2+ and S6+ + Si4+ = 2P5+. The data also demonstrate that the presence of Sr in hydrothermal fluids promotes the incorporation of Na and S in apatite via the coupled substitution S6+ + Na+ = P5+ + Sr2+. Our data also reveal a previously unknown intrinsic relationship between Fe and S, and Ce and S in metasomatized fluorapatite that can be explained by coupled substitutions Ca2+ + P5+ = Fe3+ + S4+ and Ca2+ + P5+ = Ce3+ + S4+, respectively. The concentrations of Cl, OH, and S in run-product apatite are positively correlated with each other, which indicates that the presence of Cl and OH can play a determinative role in the incorporation of S in apatite. Overall, the data from these metasomatism experiments involving S and apatite demonstrate that incorporation of sulfate and sulfite into apatite during metasomatism depends on the abundance of charge-balancing cations in the fluid.