Early release of H₂O during subduction of carbonated ultramafic lithologies

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Eberhard, Lisa ; Plümper, Oliver ; Frost, Daniel J.:
Early release of H₂O during subduction of carbonated ultramafic lithologies.
In: Contributions to Mineralogy and Petrology. Bd. 178 (2023) Heft 3 . - 17.
ISSN 1432-0967
DOI: https://doi.org/10.1007/s00410-023-01997-y

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Abstract

To investigate the effect of carbon-bearing phases on the release of fluids in subducted serpentinites, we performed high-pressure multi-anvil experiments on representative ophicarbonate assemblages over a pressure range from 2.5 GPa to 5 GPa and from 450 °C to 900 °C, across the antigorite-out reaction. Parallel experiments were performed on carbonate-free serpentinites. In all experiments, we monitored and/or controlled the oxygen fugacity. The addition of 20 wt. % CaCO3 to a serpentinite assemblage at 2.5 GPa is found to decrease the onset of the serpentine dehydration by over 100 °C, in comparison to carbonate-free assemblages. Similarly, the final disappearance of serpentine is also affected by the presence of CaCO3. For a bulk CaCO3 content of 20 wt. %, this causes a decrease in maximum stability of antigorite by 50 °C. For a bulk CaCO3 content exceeding 25 wt. %, this difference can be as high as 100 °C in warm and 150 °C in cold subduction zones, causing antigorite to be completely dehydrated at 500 °C. This results from the reaction of CaCO3 with serpentine to form clinopyroxene and Mg-rich carbonates. This reaction, however, causes no discernible decrease in the proportion of carbonate, indicating that the amount of released carbon is insignificant. Whilst CaCO3, therefore, influences serpentine stability, there is no significant effect of hydrous phases on the carbonate stability. On the other hand, a MgCO3-bearing system shows no significant effects on the serpentinite stability field. Further experiments and oxygen fugacity calculations indicate that graphite is not stable in typical magnetite-bearing serpentinites. The reduction of carbonates to graphite would require oxygen fugacities that are 1–2 log units below those of magnetite-bearing serpentinites. This confirms earlier studies and indicates that reduction of carbonates can only occur through the infiltration of external H2-rich fluids.