High resolution in situ microsensor measurements of oxygen and temperature at a vesicomyid clam colony in the Japan Deep Sea Trench

Oxygen penetration depth and temperature at the rim of the clam colony was measured with a small deep-sea microprofiler module (Treude et al., 2009), carrying 3 oxygen Clark-type microelectrodes (Revsbech et al., 1980) and one temperature sensor (Pt100, UST Umweltsensorentechnik GmbH, Germany). High-resolution microprofiles across the sediment-water interface were measured with a vertical resolution of 100 µm on a total length of 15 cm. Oxygen electrodes had a linear response to the oxygen concentration in seawater and were calibrated in situ using constant readings in the bottom water (oxygen concentration determined by Winkler titration) and the anoxic parts of the sediment.

Ex situ sulphate reduction rates of sediment at the rim of a vesicomyd clam colony in the Japan Deep Sea Trench (dive 957)

Sediment samples were collected from the rim of a large vesicomyid clam colony in the Japan Deep Sea Trench. Immediately after sample recovery onboard, the sediment core was sub-sampled for ex situ rate measurements. Sulfate reduction were measured ex situ by the whole core injection method with three replicates. We incubated the samples at in situ temperature (1.5°C) for 48 hours with carrier-free 35SO4 (dissolved in water, 50 kBq). Sediment was fixed 20 ml ZnAc solution (20%, w/v) for AOM or SR. Turnover rates were measured as previously described (Kallmeyer et al., 2004).

Mineralogy of cold seep sediment inhabited by vesicomyid clams in the Japan Deep Sea Trench

Sediment sampling was performed at the center of the clam colony. Immediately after sample recovery onboard, the sediment core was sub-sampled and preserved for later analyses. Pyrite and carbonate content of the sediment was measured by X-ray refraction analysis as previously described (Ertefai et al., 2010).

(Table 1) U and Th isotope analyses of pyrite and anhydrite of ODP Site 158-957

Hydrothermal circulation at oceanic spreading ridges causes sea water to penetrate to depths of 2 to 3 km in the oceanic crust where it is heated to ~400 °C before venting at spectacular 'black smokers'. These hydrothermal systems exert a strong influence on ocean chemistry (Edmond et al., 1979, doi:10.1016/0012-821X(79)90061-X), yet their structure, longevity and magnitude remain largely unresolved (Elderfield and Schultz., 1996, doi:10.1146/annurev.earth.24.1.191). The active Transatlantic Geotraverse (TAG) deposit, at 26° N on the Mid-Atlantic Ridge, is one of the largest, oldest and most intensively studied of the massive sulphide mounds that accumulate beneath black-smoker fields. Here we report ages of sulphides and anhydrites from the recently drilled (Humphris et al., 1995, doi:10.1038/377713a0) TAG substrate structures -determined from 234U-230Th systematics analysed by thermal ionization mass spectrometry. The new precise ages combined with existing data (Lalou et al., 1993, doi:10.1029/92JB01898; 1998, doi:10.2973/odp.proc.sr.158.214.1998) show that the oldest material (11,000 to 37,000 years old) forms a layer across the centre of the deposit with younger material (2,300-7,800 years old) both above and below. This stratigraphy confirms that much of the sulphide and anhydrite are precipitated within the mound by mixing of entrained sea water with hydrothermal fluid (James and Elderfield, 1996, doi:10.1130/0091-7613(1996)024<1147:COOFFA>2.3.CO;2). The age distribution is consistent with episodic activity of the hydrothermal system recurring at intervals of up to 2,000 years.

Isotopic and chemical compositions of rocks and minerals from the TAG hydrothermal mound, ODP Site 957

Strontium- and oxygen-isotopic measurements of samples recovered from the Trans-Atlantic Geotraverse (TAG) hydrothermal mound during Leg 158 of the Ocean Drilling Program provide important constraints on the nature of fluid-rock interactions during basalt alteration and mineralization within an active hydrothermal deposit. Fresh Mid-Ocean Ridge Basalt (MORB), with a 87Sr/86Sr of 0.7026, from the basement beneath the TAG mound was altered at both low and high temperatures by seawater and altered at high temperature by near end-member black smoker fluids. Pillow breccias occurring beneath the margins of the mound are locally recrystallized to chlorite by interaction with large volumes of conductively heated seawater (>200°C). The development of a silicified, sulfide-mineralized stockwork within the basaltic basement follows a simple paragenetic sequence of chloritization followed by mineralization and the development of a quartz+pyrite+paragonite stockwork cut by quartz-pyrite veins. Initial alteration involved the development of chloritic alteration halos around basalt clasts by reaction with a Mg-bearing mixture of upwelling, high-temperature (>300°C), black smoker-type fluid with a minor (<10%) proportion of seawater. Continued high-temperature (>300°C) interaction between the wallrock and these Mg-bearing fluids results in the complete recrystallization of the wallrock to chlorite+quartz+pyrite. The quartz+pyrite+paragonite assemblage replaces the chloritized basalts, and developed by reaction at 250-360°C with end-member hydrothermal fluids having 87Sr/86Sr ~0.7038, similar to present-day vent fluids. The uniformity of the 87Sr/86Sr ratios of hydrothermal assemblages throughout the mound and stockwork requires that the 87Sr/86Sr ratio of end-member hydrothermal fluids has remained relatively constant for a time period longer than that required to change the interior thermal structure and plumbing network of the mound and underlying stockwork. Precipitation of anhydrite in breccias and as late-stage veins throughout most of the mound and stockwork, down to at least 125 mbsf, records extensive entrainment of seawater into the hydrothermal deposit. 87Sr/86Sr ratios indicate that most of the anhydrite formed from ~2:1 mixture of seawater and black smoker fluids (65%±15% seawater). Oxygen-isotopic compositions imply that anhydrite precipitated at temperatures between 147°C and 270°C and require that seawater was conductively heated to between 100°C and 180°C before mixing and precipitation occurred. Anhydrite from the TAG mound has a Sr-Ca partition coefficient Kd ~0.60±0.28 (2 sigma). This value is in agreement with the range of experimentally determined partition coefficients (Kd ~0.27-0.73) and is similar to those calculated for anhydrite from active black smoker chimneys from 21°N on the East Pacific Rise. The d18O (for SO4) of TAG anhydrite brackets the value of seawater sulfate oxygen (~9.5?). Dissolution of anhydrite back into the oceans during episodes of hydrothermal quiescence provides a mechanism of buffering seawater sulfate oxygen to an isotopically light composition, in addition to the precipitation and dissolution of anhydrite within the oceanic basement during hydrothermal recharge at the mid-ocean ridges.

Noble metals and associated trace elements in sulfides from the active TAG mound, ODP Site 158-957

Primary sulfides from cores of ODP Holes 158-957M, 158-957C, and 158-957H on the active TAG hydrothermal mound (Mid-Atlantic Ridge, 26°08'N) have been studied for concentrations of several chemical elements. Based on 262 microprobe analyses it has been found that the sulfides have extremely heterogeneous distribution of noble metals (Au, Ag, Pt, and Pd) and several associated elements (Hg, Co, and Se). Noble metals are arranged in the following order in terms of decreasing abundance, i.e. concentration level above detection limits (the number of analyses containing a specific element is given in parentheses): Au (65), Ag (46), Pt (21), and Pd (traces). The associated trace elements have the following series: Co (202), Hg (132), and Se (49). The main carriers of "invisible" portion of the noble metals are represented by pyrite (Au, Hg), marcasite and pyrite (Ag, Co), sphalerite and chalcopyrite (Pt, Pd), and chalcopyrite (Se). Noble metal distribution in sulfides reveals a lateral zonality: maximal concentrations and abundance of Au in chalcopyrite (or Pt and Ag in chalcopyrite and pyrite) increase from the periphery (Hole 957H) to the center (holes 957C and 957M) of the hydrothermal mound, while Au distribution in pyrite displays a reversed pattern. Co concentration increases with depth. Vertical zonality in distribution of the elements mentioned above and their response to evolution of ore genesis are under discussion in the paper.

Composition of hydrothermal massive sulfide deposits from ODP Site 158-957 and Leg 169 sites

Sulfide mineral major and trace element analyses were performed on more than 50 polished slabs representing mineralization from three seafloor hydrothermal massive sulfide deposits. Samples from the Bent Hill and ODP Mound massive sulfide deposits, both on the Juan de Fuca Ridge, can be contrasted with samples from the Trans-Atlantic Geotraverse (TAG) hydrothermal mound on the Mid-Atlantic Ridge. The massive sulfide at Bent Hill is predominantly pyrite and pyrrhotite, with increasing amounts of copper-bearing sulfide minerals at the base of the massive sulfide body and through the stockwork to an interval 200 m below seafloor that hosts high copper mineralization (Deep Copper Zone). ODP Mound contains much more abundant sphalerite and copper-bearing sulfides as compared to either Bent Hill or TAG, which are predominantly pyrite with much less abundant chalcopyrite. Copper-bearing sulfides from the Deep Copper Zone beneath Bent Hill and the lowest sampled interval of ODP Mound are petrographically and chemically similar, but distinct from copper-bearing minerals higher in either sequence.