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.

Zircon U-Pb and Hf-O analysis of porphyries from the Duolong porphyry Cu-Au deposit in the Bangongco copper belt, central Tibet

The Duolong porphyry Cu-Au deposit (5.4 Mt at 0.72% Cu, 41 t at 0.23 g/t Au), which is related to the granodiorite porphyry and the quartz-diorite porphyry from the Bangongco copper belt in central Tibet, formed in a continental arc setting. Here, we present the zircon U-Pb ages, geochemical whole-rock, Sr-Nd whole-rock and zircon in-situ Hf-O isotopic data for the Duolong porphyries. Secondary ion mass spectrometry (SIMS) zircon U-Pb analyses for six samples yielded consistent ages of ~118 Ma, indicating a Cretaceous formation age. The Duolong porphyries (SiO2 of 58.81-68.81 wt.%, K2O of 2.90-5.17 wt.%) belong to the high-K calc-alkaline series. They show light rare earth element (LREE)-enriched distribution patterns with (La/Yb)N = 6.1-11.7, enrichment in large ion lithophile elements (e.g., Cs, Rb, and Ba) and depletion of high field strength elements (e.g., Nb), with negative Ti anomalies. All zircons from the Duolong porphyries share relatively similar Hf-O isotopic compositions (d18O=5.88-7.27 per mil; eHf(t)=3.6-7.3), indicating that they crystallized from a series of cogenetic melts with various degrees of fractional crystallization. This, along with the general absence of older inherited zircons, rules out significant crustal contamination during zircon growth. The zircons are mostly enriched in d18O relative to mantle values, indicating the involvement of an 18O-enriched crustal source in the generation of the Duolong porphyries. Together with the presence of syn-mineralization basaltic andesite, the mixing between silicic melts derived from the lower crust and evolved H2O-rich mafic melts derived from the metsomatizied mantle wedge, followed by subsequent fractional crystallization (FC) and minor crustal contamination in the shallow crust, could well explain the petrogenesis of the Duolong porphyries. Significantly, the hybrid melts possibly inherited the arc magma characteristics of abundant F, Cl, Cu, and Au elements and high oxidation state, which contributed to the formation of the Duolong porphyry Cu-Au deposit.

Hydrocarbons in hydrothermal sulfides from the Rainbow Hydrothermal Field

The Rainbow Hydrothermal Field (36°N, Mid-Atlantic Ridge) is one of three presently known fields related to serpentinization of ultramafic rocks accompanied by formation of hydrogen- and methane rich solutions. Gas chromatographic and molecular gas chromatographic - mass spectrometric investigations of sulfide ores and sediments from this field confirmed predominantly biological nature of bitumoids related to high-temperature transformation of biomass of the hydrothermal biological community. At the same time ores of the Rainbow field contain significant amounts of compounds that are not directly related to biogenic synthesis. This fact suggests possibility of abiogenic synthesis of methane and even complex hydrocarbons during serpentinization of ultramafic rocks.

Chemistry of hydrothermal clasy and sulfides of ODP Site 106-649

Several meters of unconsolidated hydrothermal sediment were recovered from the Snake Pit hydrothermal field during ODP Leg 106. Polymetallic sulfides comprise most of the sediment with minor fragments of massive sulfide, organic debris, clay minerals, and fresh glass shards. Trace element and Sr-isotope contents of hydrothermal clays and sulfides from Holes 649B and 649G indicate that these minerals precipitated from a mixed hydrothermal fluid-seawater solution. Evaluation of the REE mineral data and the Snake Pit hydrothermal fluids shows that the REE distribution coefficients between the hydrothermal fluids and clay-sulfide mixes range from 100-500. This indicates that hydrothermal fluids originating in the root-zone of the Snake Pit hydrothermal system may be modified by the precipitation of hydrothermal minerals, either in the shallow subsurface or within chimney structures. Contrasting REE profiles of clay-sulfide aggregates and massive sulfides from Holes 649B and 649G may be accounted for by spatial and/or temporal variations in redox conditions in the plumbing system.

Chemical and mineral compositions of bottom sediments and ferromanganese crusts and nodules near Iceland

Results of study of bottom sediments near Iceland and on the Jan Mayen Island are reported. It was found that in recent sediments chemical elements are mainly associated with pyro- and volcanoclastics. In some areas adjusted to deep-seated faults ancient iron-manganese crusts and sediments occur. They are rich in Ni, Co, V, Cu, Mo, Cd and other elements associated with endogenic matter.

Composition and age of ores and bottom sediments accumulated within and near the Rainbow hydrothermal field

Results of direct geological and geochemical observations of the modern Rainbow hydrothermal field (Mid-Atlantic Ridge, 36°14'N; 33°54'W) carried out from the deep-sea manned Mir submersibles during Cruises 41 and 42 of the R/V Akademik Mstislav Keldysh in 1998-1999 and data of laboratory studies of collected samples are under consideration in the paper. The field lacks neovolcanic rocks and the axial part of the rift is filled in with a serpentinite protrusion. In this field there occur metalliferous sediments, as well as active and relict sulfide edifices composed of sulfide minerals; pyrrhotite, chalcopyrite, isocubanite, sphalerite, marcasite, pyrite, bornite, chalcosine, digenite, magnetite, anhydrite, rare troilite, wurtzite, millerite, and pentlandite have been determined. Sulfide ores are characterized by concentric-zoned textures. During in situ measurements during 35 minutes temperature of hydrothermal fluids was varying within a range from 250 to 350°C. Calculated chemical and isotopic composition of hydrothermal fluid shows elevated concentrations of Cl, Ni, Co, CH4, and H2. Values of d34S of H2S range from +2.4 to +3.1 per mil, of d13C of CH4 from -15.2 to -11.2 per mil, and d13C of CO2 from +1.0 to -4.0 per mil. Fluid inclusions are homogenized at temperatures from 140 to 360°C, whereas salinity of the fluid varies from 4.2 to 8.5 wt %. d34S values of sulfides range from +1.3 to +12.5 per mil. 3He/4He ratio in mineral-forming fluid contained in the fluid inclusions from sulfides of the Rainbow field varies from 0.00000374 to 0.0000101. It is shown that hydrothermal activity in the area continues approximately during 100 ka. It is assumed that the fluid and sulfide edifices contain components from the upper mantle. A hypothesis of phase separation of a supercritical fluid that results in formation of brines is proposed. Hydrothermal activity is related to the tectonic, not volcanic, phase of the Mid-Atlantic Ridge evolution.

Geochemistry on Yangla copper deposit, China

The Yangla copper deposit, situated in the middle section of Jinshajiang tectonic belt between Zhongza-Zhongdian block and Changdu-Simao block, is a representative and giant copper deposit that has been discovered in Jinshajiang-Lancangjiang-Nujiang region in recent years. There are coupled relationship between Yangla granodiorite and copper mineralization in the Yangla copper deposit. Five molybdenite samples yielded a well-constrained 187Re-187Os isochron age of 233.3±3 Ma, the metallogenesis is therefore slightly younger than the crystallization age of the granodiorite. S, Pb isotopic compositions of the Yangla copper deposit indicate that the ore-forming materials were derived from the mixture of upper crust and mantle, also with the magmatic contributions. In the late Early Permian, the Jinshajiang Oceanic plate was subducted to the west, resulting in the formation of a series of gently dipping thrust faults in the Jinshajiang tectonic belt, meanwhile, accompanied magmatic activities. In the early Late Triassic, which was a time of transition from collision-related compression to extension in the Jinshajiang tectonic belt, the thrust faults were tensional; it would have been a favorable environment for forming ore fluids. The ascending magma provided a channel for the ore-forming fluid from the mantle wedge. After the magma arrived at the base of the early-stage Yangla granodiorite, the platy granodiorite at the base of the body would have shielded the late-stage magma from the fluid. The magma would have cooled slowly, and some of the ore-forming fluid in the magma would have entered the gently dipping thrust faults near the Yangla granodiorite, resulting in mineralization.

Chemical composition and fluxes of deep sea suspended matter within and over the 9°50'N hydrothermal field, EPR

Results of geochemical studies of suspended matter from the water mass over the hydrothermal field at 9°50'N on the East Pacific Rise are reported. The suspended matter was sampled in background waters, in the buoyant plume, and in the near-bottom waters. Contents of Si, Al, P, Corg, Fe, Mn, Cu, Zn, Ni, Co, As, Cr, Cd, Pb, Ag, and Hg were determined. No definite correlations were found between the elements in the background waters. Many of the chemical elements correlated with Fe and associated with its oxyhydroxides in the buoyant plume. In the near-bottom waters trace elements are associated with Fe, Zn, and Cu (probably, with their sulfides formed during mixing of hydrothermal fluids with seawater). Chemical composition of sediment matter precipitated in a sediment trap was similar to the near-bottom suspended matter.

Lead in bottom sediments, nodules, and sulfides from the Black Sea

A study of lead distribution in recent, ancient Black Sea and Neweuxinian bottom sediment shows similar vertical distributions of the element in the oxygen and hydrogen sulfide zones of the sea; i.e. hydrogen sulfide contamination does not affect lead contents in bottom sediments of the sea. Lead distribution in sediment mass of the Black Sea reflects dependence of accumulation of the element on the hydrodynamic regime of the sea and forms of its migration. It is noted that absence of lead accumulation in Black Sea nodules results from specific nodule formation and from geochemical activity of the element. A large role of diagenetic sulfide formation in lead geochemistry is shown. Degree of lead accumulation in iron sulfides depends on conditions of sedimentation and on physical and chemical parameters in the sea.

Chemical and mineral compositions of sulfide deposits from the Snake Pit hydrothermal field, Mid-Atlantic Ridge rift zone

The Snake Pit hydrothermal field is located on the top of a neovolcanic rise on the Mid-Atlantic Ridge at sea depths between 3460 and 3510 m. It was surveyed during several oceanological expeditions including DSDP Legs. Additional scientific materials were obtained in 2002 and 2003 during expedition onboard R/V Akademik Mstislav Keldysh with two Mir deep-sea manned submersibles. Three eastern hydrothermal mounds (Moose, Beehive, and Fir Tree) are located on the upper part of the eastern slope of the rise over a common fractured pedestal composed of fragments of massive sulfides. The western group of hydrothermal deposits is encountered on the western slope of the axial graben. Within this mature hydrothermal field, which was formed over the past 4000 years, we studied morphology of the hydrothermal mounds, chemistry and mineralogy of hydrothermal deposits, chemistry of sulfide minerals, and isotope composition of sulfur in them.

Platinum-group, major, and trace element abundances in ODP Leg 183 basalts

Seventeen basalts from Ocean Drilling Program (ODP) Leg 183 to the Kerguelen Plateau (KP) were analyzed for the platinum-group elements (PGEs: Ir, Ru, Rh, Pt, and Pd), and 15 were analyzed for trace elements. Relative concentrations of the PGEs ranged from ~0.1 (Ir, Ru) to ~5 (Pt) times primitive mantle. These relatively high PGE abundances and fractionated patterns are not accounted for by the presence of sulfide minerals; there are only trace sulfides present in thin-section. Sulfur saturation models applied to the KP basalts suggest that the parental magmas may have never reached sulfide saturation, despite large degrees of partial melting (~30%) and fractional crystallization (~45%). First order approximations of the fractionation required to produce the KP basalts from an ~30% partial melt of a spinel peridotite were determined using the PELE program. The model was adapted to better fit the physical and chemical observations from the KP basalts, and requires an initial crystal fractionation stage of at least 30% olivine plus Cr-spinel (49:1), followed by magma replenishment and fractional crystallization (RFC) that included clinopyroxene, plagioclase, and titanomagnetite (15:9:1). The low Pd values ([Pd/Pt]_pm < 1.7) for these samples are not predicted by currently available Kd values. These Pd values are lowest in samples with relatively higher degrees of alteration as indicated by petrographic observations. Positive anomalies are a function of the behavior of the PGEs; they can be reproduced by Cr-spinel, and titanomagnetite crystallization, followed by titanomagnetite resorption during the final stages of crystallization. Our modeling shows that it is difficult to reproduce the PGE abundances by either depleted upper or even primitive mantle sources. Crustal contamination, while indicated at certain sites by the isotopic compositions of the basalts, appears to have had a minimal affect on the PGEs. The PGE abundances measured in the Kerguelen Plateau basalts are best modeled by melting a primitive mantle source to which was added up to 1% of outer core material, followed by fractional crystallization of the melt produced. This reproduces both the abundances and patterns of the PGEs in the Kerguelen Plateau basalts. An alternative model for outer core PGE abundances requires only 0.3% of outer core material to be mixed into the primitive mantle source. While our results are clearly model dependent, they indicate that an outer core component may be present in the Kerguelen plume source.