Description: Recent developments in the measurement of δ34S and δ33S in sulfide minerals provide a new framework to evaluate isotopic equilibrium among sulfide minerals and a new tool to investigate mineralizing processes or sources of sulfur in ore-forming systems. Isotopic equilibrium requires that values of δ34S and δ33S are highly correlated between mineral pairs and that deviations (quantified as Δ33S) from a reference mass-dependent fractionation are the same for both minerals within experimental error. In this contribution, we apply this framework for the first time to natural samples, and evaluate isotopic equilibrium among sulfide minerals from the Archean Kidd Creek volcanogenic massive sulfide deposit in Ontario, Canada. Two of eight sulfide mineral pairs showed clear isotopic disequilibrium, in agreement with interpreted paragenetic relationships; six other pairs have isotopic compositions that are consistent with equilibrium. We discuss the implications of these results for the interpretation of mineral paragenesis and sulfur isotope geothermometry at Kidd Creek. This technique offers new possibilities for evaluating sulfur isotope systematics in Archean (〉2.45 Ga) ore deposits, in which the range of δ34S values is small but non-zero values of Δ33S are common.

Description: Hyperthermophilic iron reducers are common in hydrothermal chimneys found along the Endeavour Segment in the northeastern Pacific Ocean based on culture-dependent estimates. However, information on the availability of Fe(III) (oxyhydr) oxides within these chimneys, the types of Fe(III) (oxyhydr) oxides utilized by the organisms, rates and environmental constraints of hyperthermophilic iron reduction, and mineral end products is needed to determine their biogeochemical significance and are addressed in this study. Thin-section petrography on the interior of a hydrothermal chimney from the Dante edifice at Endeavour showed a thin coat of Fe(III) (oxyhydr) oxide associated with amorphous silica on the exposed outer surfaces of pyrrhotite, sphalerite, and chalcopyrite in pore spaces, along with anhydrite precipitation in the pores that is indicative of seawater ingress. The iron sulfide minerals were likely oxidized to Fe(III) (oxyhydr) oxide with increasing pH and Eh due to cooling and seawater exposure, providing reactants for bioreduction. Culture-dependent estimates of hyperthermophilic iron reducer abundances in this sample were 1740 and 10 cells per gram (dry weight) of material from the outer surface and the marcasite-sphalerite-rich interior, respectively. Two hyperthermophilic iron reducers, Hyperthermus sp. Ro04 and Pyrodictium sp. Su06, were isolated from other active hydrothermal chimneys on the Endeavour Segment. Strain Ro04 is a neutrophilic (pHopt 7–8) heterotroph, while strain Su06 is a mildly acidophilic (pHopt 5), hydrogenotrophic autotroph, both with optimal growth temperatures of 90–92 °C. Mössbauer spectroscopy of the iron oxides before and after growth demonstrated that both organisms form nanophase (〈12 nm) magnetite [Fe3O4] from laboratory-synthesized ferrihydrite [Fe10O14(OH)2] with no detectable mineral intermediates. They produced up to 40 mm Fe2+ in a growth-dependent manner, while all abiotic and biotic controls produced 〈3 mm Fe2+. Hyperthermophilic iron reducers may have a growth advantage over other hyperthermophiles in hydrothermal systems that are mildly acidic where mineral weathering at increased temperatures occurs.

Description: Rock and fluid samples were collected from three hydrothermal chimneys at the Endeavour Segment, Juan de Fuca Ridge to evaluate linkages among mineralogy, fluid chemistry, and microbial community composition within the chimneys. Mössbauer, midinfrared thermal emission, and visible-near infrared spectroscopies were utilized for the first time to characterize vent mineralogy, in addition to thin-section petrography, X-ray diffraction, and elemental analyses. A 282°C venting chimney from the Bastille edifice was composed primarily of sulfide minerals such as chalcopyrite, marcasite, and sphalerite. In contrast, samples from a 300°C venting chimney from the Dante edifice and a 321°C venting chimney from the Hot Harold edifice contained a high abundance of the sulfate mineral anhydrite. Geochemical modeling of mixed vent fluids suggested the oxic-anoxic transition zone was above 100°C at all three vents, and that the thermodynamic energy available for autotrophic microbial redox reactions favored aerobic sulfide and methane oxidation. As predicted, microbes within the Dante and Hot Harold chimneys were most closely related to mesophilic and thermophilic aerobes of the Betaproteobacteria and Gammaproteobacteria and sulfide-oxidizing autotrophic Epsilonproteobacteria. However, most of the microbes within the Bastille chimney were most closely related to mesophilic and thermophilic anaerobes of the Deltaproteobacteria, especially sulfate reducers, and anaerobic hyperthermophilic archaea. The predominance of anaerobes in the Bastille chimney indicated that other environmental factors promote anoxic conditions. Possibilities include the maturity or fluid flow characteristics of the chimney, abiotic Fe2+ and S2− oxidation in the vent fluids, or O2 depletion by aerobic respiration on the chimney outer wall.

Description: Volcanic arcs are the surface expression of magmatic systems that result from subduction of mostly oceanic lithosphere at convergent plate boundaries. Arcs with a submarine component include intraoceanic arcs and island arcs that span almost 22,000 km on Earth’s surface, and the vast majority of them are located in the Pacific region. Hydrothermal systems hosted by submarine arc volcanoes commonly contain a large component of magmatic fluid. This magmatic-hydrothermal signature, coupled with the shallow water depths of arc volcanoes and their high volatile contents, strongly influences the chemistry of the fluids and resulting mineralization and likely has important consequences for the biota associated with these systems. The high metal content and very acidic fluids in these hydrothermal systems are thought to be important analogs to numerous porphyry copper and epithermal gold deposits mined today on land. During International Ocean Discovery Program (IODP) Expedition 376 (5 May–5 July 2018), a series of five sites was drilled on Brothers volcano in the Kermadec arc. The expedition was designed to provide the missing link (i.e., the third dimension) in our understanding of hydrothermal activity and mineral deposit formation at submarine arc volcanoes and the relationship between the discharge of magmatic fluids and the deep biosphere. Brothers volcano hosts two active and distinct hydrothermal systems: one is seawater influenced and the other is affected by magmatic fluids (largely gases). In total, 222.4 m of volcaniclastics and lavas were recovered from the five sites drilled, which include Sites U1527 and U1530 in the Northwest (NW) Caldera seawater-influenced hydrothermal field; Sites U1528 and U1531 in the magmatic fluid-influenced hydrothermal fields of the Upper and Lower Cones, respectively; and Site U1529, located within an area of low crustal magnetization that marks the West (W) Caldera upflow zone on the caldera floor. Downhole logging and borehole fluid sampling were completed at two sites, and two tests of a prototype turbine-driven coring system (designed by the Center for Deep Earth Exploration [CDEX] at Japan Agency for Marine-Earth Science and Technology [JAMSTEC]) for drilling and coring hard rocks were conducted. Core recovered from all five sites consists of dacitic volcaniclastics and lava flows with only limited chemical variability relative to the overall range in composition of dacites in the Kermadec arc. Pervasive alteration with complex and variable mineral assemblages attest to a highly dynamic hydrothermal system. The upper parts of several drill holes at the NW Caldera hydrothermal field are characterized by secondary mineral assemblages of goethite + opal + zeolites that result from low-temperature (〈150°C) reaction of rock with seawater. At depth, NW Caldera Site U1527 exhibits a higher temperature (~250°C) secondary mineral assemblage dominated by chlorite + quartz + illite + pyrite. An older mineral assemblage dominated by diaspore + quartz + pyrophyllite + rutile at the bottom of Hole U1530A is indicative of acidic fluids with temperatures of ~230°–320°C. In contrast, the alteration assemblage at Site U1528 on the Upper Cone is dominated by illite + natroalunite + pyrophyllite + quartz + opal + pyrite, which attests to high-temperature reaction of rocks with acid-sulfate fluids derived from degassed magmatic volatiles and the disproportionation of magmatic SO2. These intensely altered rocks exhibit extreme depletion of major cation oxides, such as MgO, K2O, CaO, MnO, and Na2O. Furthermore, very acidic (as low as pH 1.8), relatively hot (≤236°C) fluids collected at 160, 279, and 313 meters below seafloor in Hole U1528D have chemical compositions indicative of magmatic gas input. In addition, preliminary fluid inclusion data provide evidence for involvement of two distinct fluids: phase-separated (modified) seawater and a ~360°C hypersaline brine, which alters the volcanic rock and potentially transports metals in the system. The material and data recovered during Expedition 376 provide new stratigraphic, lithologic, and geochemical constraints on the development and evolution of Brothers volcano and its hydrothermal systems. Insights into the consequences of the different types of fluid–rock reactions for the microbiological ecosystem elucidated by drilling at Brothers volcano await shore-based studies.