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Constraining temporal variations in metal and sulfur sources using high-resolution mineral-scale analysis of pyrite: evidence from the Brothers volcano, Kermadec arc, New Zealand

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Abstract

Variations in trace metal contents and sulfur isotope ratios (δ34S) within pyrite, at the scale of individual mineral grains, preserves a record of temporal fluctuations in the source of metals and sulfur as well as changes in the chemical composition and temperature of hydrothermal fluid during the evolution of the Brothers volcano, Kermadec arc, New Zealand. In this study, we analyzed pyrite from drill core recovered from two geochemically distinct hydrothermal systems at the Brothers volcano, the seawater-influenced NW Caldera (Site U1530) and magmatic-volatile-dominated Upper Cone (Site U1528) during the International Ocean Discovery Program’s Expedition 376. At the NW Caldera site, from 189 m below the seafloor, a seawater-derived hydrothermal fluid forming chlorite-rich alteration overprints early pyrophyllite + illite alteration. Within ~ 30 m of the seafloor at this same site, pyrite contains zones of high As content with a variable δ34S signature that ranges from -4.5 to 3.4‰ (n = 26). Values for δ34S > 0‰ record shallow mixing of seawater with upwelling hydrothermal fluids. In deeper parts of the system, but still within the chlorite-rich alteration zone, δ34S values > 0‰ are absent, indicating that relatively more sulfur is contributed from magmatic volatile degassing and SO2 disproportionation. In the pyrophyllite-rich alteration zone, pyrite contains Co-enriched cores that correspond to sharp changes in δ34S values from -5.3‰ to 4.6‰ (n = 68). Cobalt enrichment occurs in response to the mixing of seawater-derived hydrothermal fluid with Co-rich magmatic brines. At the Upper Cone site, a relatively constant supply of a low-salinity magmatic fluid results in pyrite grains that rarely exhibit any internal zonation in trace metal content. In pyrite where zonation does exist, a correlation between Cu and Sb and uniformly low δ34S values (< 0‰) indicates a link between metal enrichment, the pulsed degassing of magmatic volatiles, and SO2 disproportionation.

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Acknowledgements

This research used samples provided by the International Ocean Discovery Program (IODP). We thank the crew and technical staff aboard the D/V JOIDES Resolution during Expedition 376: “Brothers Arc Flux”, May-July 5th, 2018. CdR acknowledges funding from the Ministry of Business, Innovation and Employment (MBIE) of the New Zealand Government by way of a GNS SSIF (Strategic Science Investment Fund) award. JWJ acknowledges the support of the Canadian Research Chair program. W Aylward is thanked for assistance whilst performing EPMA mapping. We thank V Maslennikov and an anonymous reviewer for their constructive comments and Editor-in-Chief K Kelley for the editorial handling of this manuscript.

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Authors and Affiliations

  1. Department of Geoscience, University of Nevada, Las Vegas, USA

    Andrew J. Martin

  2. Department of Earth Sciences, Memorial University of Newfoundland, St. John’s, Canada

    Andrew J. Martin, John W. Jamieson & Graham D. Layne

  3. GNS Science, 1 Fairway Drive, Lower Hutt, 5040, New Zealand

    Cornel E. J. de Ronde

  4. MAF-IIC SIMS Facility, Memorial University of Newfoundland, St. John’s, Canada

    Glenn Piercey

  5. GEOMAR, Helmholtz Centre for Ocean Research Kiel, 24148, Kiel, Germany

    Philipp A. Brandl

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  3. Cornel E. J. de Ronde
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  4. Graham D. Layne
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  5. Glenn Piercey
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Contributions

AJM was responsible for the study conception and design. Material preparation, data collection and analysis was performed by AJM, GP and WA. The manuscript was written by AJM, and all authors provided comments on previous versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to Andrew J. Martin.

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Martin, A.J., Jamieson, J.W., de Ronde, C.E.J. et al. Constraining temporal variations in metal and sulfur sources using high-resolution mineral-scale analysis of pyrite: evidence from the Brothers volcano, Kermadec arc, New Zealand. Miner Deposita 58, 1237–1262 (2023). https://doi.org/10.1007/s00126-023-01177-9

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