Preservation of Hydrothermal Fluid Copper Isotope Signatures in Chalcopyrite‐Rich Chimneys: A Case Study From the PACMANUS Vent Field, Manus Basin.

Samin, Apolline; Roerdink, Desiree L.; Reeves, Eoghan P.; Scheffler, Johannes; Bach, Wolfgang; Beinlich, Andreas; Jamieson, John W.; Rouxel, Olivier

Copper isotopes (δ65Cu) in hydrothermal fluids have the potential to provide information on ore‐forming processes occurring below the seafloor, but Cu isotope data from high‐temperature fluids are scarce. Here, we examine the extent to which coexisting sulfide minerals in a hydrothermal chimney can preserve fluid Cu isotope ratios using a fluid‐solid pair of a black smoker (333°C) from the Roman Ruins vent area (PACMANUS) in the Manus Basin. Two ca. 3 cm long transects through the chalcopyrite‐rich chimney wall show an increase in δ65Cu from 0.48 to 2.28‰ from the interior to the exterior, coupled with limited variation in sulfide δ34S (1.52–4.72‰). The Cu isotopic composition of chalcopyrite from the innermost wall closely resembles the δ65Cu value of the paired hydrothermal fluid, indicating that chalcopyrite in the inner ∼5 mm of the chimney records the Cu isotope ratio of the venting fluid. Beyond this, an increase in sulfide δ65Cu toward the exterior correlates with an increase in the relative abundance of secondary Cu sulfides. The appearance of bornite coincides with the presence of small barite crystals, suggesting this represents a redox gradient between reduced hydrothermal fluids and oxidized seawater admixing inwards. Elevated δ65Cu in this zone can be explained by the precipitation of secondary Cu sulfides from 65Cu‐enriched fluids formed during oxidative chalcopyrite dissolution. Our findings indicate that interactions with oxidizing seawater shift chalcopyrite δ65Cu values over small spatial scales, and that caution must be applied if chimney sulfides are used to reconstruct δ65Cu values of high‐temperature hydrothermal fluids. Plain Language Summary: Kilometers below the surface of the ocean, hydrothermal "chimney" structures emit hot and metal‐rich fluids from the seafloor. The chemical composition of these hot fluids can tell about the reactions that occur beneath the seafloor. In this study, we test how copper‐bearing minerals in a hydrothermal chimney record and preserve the copper isotopic composition of these hot fluids. To do so, we compare copper isotope ratios in a hydrothermal fluid and its paired chimney from a seafloor hot spring near Papua New Guinea and find that these ratios are very similar for minerals only in the innermost part of the chimney. Copper isotope ratios increase as the mineralogy of copper changes toward the outside of the chimney wall. This appears to result from cold seawater that enters the chimney and modifies the chemistry and mineralogy of the minerals in the structure. The resulting changes in copper isotope ratios within small cm‐scales of the chimney wall are as large as overall ranges observed in copper isotope ratios from seafloor hot springs globally. Therefore, our findings act as a cautionary tale for the use of chimney minerals to reconstruct the copper isotopic composition of hydrothermal fluids. Key Points: Hydrothermal fluid Cu isotope ratios are preserved in chalcopyrite in the innermost part of a black smoker chimneyCu isotope ratios are altered by seawater‐driven oxidative dissolution of chalcopyrite and precipitation of bornite and chalcociteBulk chimney Cu isotope ratios cannot be used as a record of fluid Cu isotope values

PAPUA New Guinea; COPPER isotopes; CHIMNEYS; SULFIDE minerals; FLUIDS; HOT springs

Geochemistry, Geophysics, Geosystems: G3, 2024, Vol 25, Issue 2, p1

1525-2027

Academic Journal

10.1029/2023GC011349