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Hydrothermal activities on ultraslow-spreading ridges exhibit diverse characteristics, long histories with multiple participants, and might form large-scale, high-grade sulfide deposits. The Duanqiao hydrothermal field (DHF) is located at the segment with the thickest oceanic crust and a large axial magma chamber on the Southwest Indian Ridge, providing unique perspective of sulfide metallogenesis on ultraslow-spreading ridges. Previous studies revealed that DHF sulfide exhibits distinct features of enrichment of ore-forming elements in comparison with those of hydrothermal fields on sediment-starved mid-ocean ridges. However, the genesis and processes responsible for such differences remain poorly constrained. In this study, mineralogical, geochemical and S and Pb isotopic analyses were performed on relict sulfide mound samples to characterize DHF formation. The samples show clear concentric mineral zonation from the interior to the exterior wall. Assemblages of chalcopyrite, sphalerite, and pyrite are distributed mainly in the interior wall, whereas pyrite and marcasite are distributed mainly in the exterior wall. The low Cu content and Pb isotopic composition of the sulfide indicate that the metals are derived mainly from basement basalts. The δ34S values exhibit positive values distributed over a reasonably narrow range (2.42‰–7.97‰), which suggests approximately 62.1%–88.5% of S with basaltic origin. Compared with most hydrothermal fields along the sediment starved mid-ocean ridges, the DHF sulfide shows particularly high contents of Pb (263–2630 ppm), As (234–726 ppm), Sb (7.32–44.3 ppm), and Ag (35.2 to >100 ppm). The δ34S values exhibit an increasing tendency from the sample exterior to the interior. We propose that these features probably reflect the existence of a subsurface zone refining process. Our results provide new insight into the sulfide formation process and contribute to understanding the metallogenic mechanism of hydrothermal sulfides on ultraslow-spreading ridges.

Reaction of ultramafic rocks with seawater and subsequent serpentinization has been considered one of the most important factors controlling the formation of ultramafic-hosted seafloor massive sulfide (UM-SMS) deposits. However, the mineralization processes responsible for these deposits remain poorly understood, in particular because they are less abundant as compared with their basaltic counterparts. In this work, serpentinites with different alteration grades collected at the Tianzuo hydrothermal field (THF), Southwest Indian Ridge, were studied. Mineralogical and chemical analyses were performed in the secondary opaque minerals resulting from serpentinization to understand the role of this process during the formation of UM-SMS deposits. Our results show that these opaque minerals mainly consist of magnetite, hematite, pentlandite, and minor pyrite, suggestive of high but varying oxygen and sulfur fugacities. The hematite is characterized by an enrichment in Mg, Si, Ni, and Co as compared with magnetite. Pentlandite associated with hematite has elevated and consistent Ni contents as compared with that associated with magnetite. These results indicate that breakdown and decomposition of primary silicate and sulfide minerals during serpentinization has controlled the sources of ore-forming materials. Concentrations of Te are variable and show a positive correlation with Ni in pentlandite associated with magnetite or hematite, suggesting that gabbroic intrusions provided additional material to the hydrothermal system. Oxidation and sulfidation conditions are ideal for the formation of trisulfur ion S3− in THF, which can significantly improve the capability of hydrothermal fluids for leaching ore-forming metals from the wall rocks, promoting the formation of THF. In addition of reduced systems, hydrothermal fluids with high oxygen and sulfur fugacities triggered by extensive seawater infiltration can most likely also develop in ultramafic-hosted systems. These results suggest that the areas with well-developed fractures are promising candidates for further exploration of UM-SMS deposits along mid-oceanic ridges.

The recently explored inactive Tianzuo hydrothermal field, in the amagmatic segment of the ultraslow-spreading Southwest Indian Ridge (SWIR), is closely associated with detachment faults. In this site, sulfide minerals are hosted by serpentine-bearing ultramafic rocks and include high-temperature (isocubanite, sphalerite, and minor pyrrhotite) and low-temperature (pyrite I, marcasite, pyrite II, and covellite) phases. In this study, trace-element concentrations of isocubanite and pyrite II were used to elucidate mineralization processes in ultramafic rocks hosting sulfides. Results show that isocubanite is enriched in metals such as Cu, Co, Sn, Te, Zn, Se, Pb, Bi, Cd, Ag, In, and Mn, and pyrite II is enriched in Mo and Tl. The marked enrichment in Te, Cu, Co, and In in isocubanite (compared with Se, Zn, Ni, and Sn, respectively) is most likely due to the contribution of magmatic fluids from gabbroic intrusions beneath the hydrothermal field. The intrusion of gabbroic magmas would have enhanced serpentinization reactions and provided a relatively oxidizing environment through the dissolution of anhydrite precipitated previously in the reaction zone, within high temperature and low pH conditions. This might have facilitated the extraction of metals by initial hydrothermal fluids, leading to the general enrichment of most metals in isocubanite. Metals in pyrite II have compositions similar to those of isocubanite, except for strong depletion in magmatically derived Te, Cu, Co, and In. This means that serpentinization processes had a dominating role in pyrite II precipitation as well. The enrichment of pyrite II in Mo and Tl is also indicative of seawater contribution in its composition. The study concludes that serpentinization reactions contribute effectively both to high- and low-temperature sulfide mineralization at Tianzuo hydrothermal field, with gabbroic intrusions further promoting high-temperature sulfide mineralization, providing additional metals, fluids and heat. In contrast, low-temperature sulfide mineralization occurred during the cooling of gabbroic intrusions, with decreasing rates of serpentinization reactions and a significant influence of seawater.

Hydrothermal activity on mid-ocean ridges is an important mechanism for the delivery of Zn from the mantle to the surface environment. Zinc isotopic fractionation during hydrothermal activity is mainly controlled by the precipitation of Zn-bearing sulfide minerals, in which isotopically light Zn is preferentially retained in solid phases rather than in solution during mineral precipitation. Thus, seafloor hydrothermal activity is expected to supply isotopically heavy Zn to the ocean. Here, we studied sulfide-rich samples from the Duanqiao-1 hydrothermal field, located on the Southwest Indian Ridge. We report that, at the hand-specimen scale, late-stage conduit sulfide material has lower δ66Zn values (−0.05 ± 0.15 ‰; n = 19) than early-stage material (+0.13 ± 0.15 ‰; n = 10). These lower values correlate with enrichments in Pb, As, Cd, and Ag, and elevated δ34S values. We attribute the low δ66Zn values to the remobilization of earlier sub-seafloor Zn-rich mineralization. Based on endmember mass balance calculations, and an assumption of a fractionation factor (αZnS-Sol.) of about 0.9997 between sphalerite and its parent solution, the remobilized Zn was found consist of about 1/3 to 2/3 of the total Zn in the fluid that formed the conduit samples. Our study suggests that late-stage subsurface hydrothermal remobilization may release isotopically-light Zn to the ocean, and that this process may be common along mid-ocean ridges, thus increasing the size of the previously identified isotopically light Zn sink in the ocean.