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Sulfide oxidation as a process for the formation of copper-rich magmatic sulfides

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Abstract

Typical magmatic sulfides are dominated by pyrrhotite and pentlandite with minor chalcopyrite, and the bulk atomic Cu/Fe ratio of these sulfides is typically less than unity. However, there are rare magmatic sulfide occurrences that are dominated by Cu-rich sulfides (e.g., bornite, digenite, and chalcopyrite, sometimes coexisting with metallic Cu) with atomic Cu/Fe as high as 5. Typically, these types of sulfide assemblages occur in the upper parts of moderately to highly fractionated layered mafic–ultramafic intrusions, a well-known example being the Pd/Au reef in the Upper Middle Zone of the Skaergaard intrusion. Processes proposed to explain why these sulfides are so unusually rich in Cu include fractional crystallization of Fe/(Ni) monosulfide and infiltration of postmagmatic Cu-rich fluids. In this contribution, we explore and experimentally evaluate a third possibility: that Cu-rich magmatic sulfides may be the result of magmatic oxidation. FeS-dominated Ni/Cu-bearing sulfides were equilibrated at variable oxygen fugacities in both open and closed system. Our results show that the Cu/Fe ratio of the sulfide melt increases as a function of oxygen fugacity due to the preferential conversion of FeS into FeO and FeO1.5, and the resistance of Cu2S to being converted into an oxide component even at oxygen fugacities characteristic of the sulfide/sulfate transition (above FMQ + 1). This phenomenon will lead to an increase in the metal/S ratio of a sulfide liquid and will also depress its liquidus temperature. As such, any modeling of the sulfide liquid line of descent in magmatic sulfide complexes needs to address this issue.

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Acknowledgments

Financial support by the DFG to Chris Ballhaus (grant Ba 964/24-1) and Raúl Fonseca (grant Fo 698/1-1) are gratefully acknowledged. Beate Spiering is thanked for her assistance with the electron microprobe analysis of our samples. We are especially grateful to Georg Nover and Thomas Schulz for their invaluable assistance during the piston cylinder experiments and to Nils Jung for his lapidary work on our samples. We would also like to thank James Mungall and Tony Naldrett for revising an earlier version of this manuscript, which led to its vast improvement. Vera Laurenz is thanked for helpful comments and discussions. We are grateful for the detailed reviews by Emil Mackovicky and Reid Keays made on this manuscript, as well as the editorial handling by Mike Lesher.

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Authors and Affiliations

  1. Institut für Mineralogie, Universität Münster, Corrensstr. 24, 48149, Münster, Germany

    Cora C. Wohlgemuth-Ueberwasser & Jasper Berndt

  2. Steinmann-Institut für Geologie, Mineralogie, Paläontologie, Universität Bonn, Poppelsdorfer Schloss, 53115, Bonn, Germany

    Cora C. Wohlgemuth-Ueberwasser, Raúl O. C. Fonseca & Chris Ballhaus

  3. PetroTectonics Centre, Department of Geological Sciences, Stockholm University, 106 91, Stockholm, Sweden

    Cora C. Wohlgemuth-Ueberwasser

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  1. Cora C. Wohlgemuth-Ueberwasser
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  2. Raúl O. C. Fonseca
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Correspondence to Cora C. Wohlgemuth-Ueberwasser.

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Editorial handling: C.M. Lesher

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Wohlgemuth-Ueberwasser, C.C., Fonseca, R.O.C., Ballhaus, C. et al. Sulfide oxidation as a process for the formation of copper-rich magmatic sulfides. Miner Deposita 48, 115–127 (2013). https://doi.org/10.1007/s00126-012-0420-9

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