Geochemistry of Loihi Seamount hydrothermal deposits

High-resolution bathymetric surveys, bottom photography and sample analyses show that Loihi Seamount at the southernmost extent of the Hawaiian ëhotspotí is an active, young submarine volcano that is probably the site of an emerging Hawaiian island. Hydrothermal deposits sampled from the active summit rift system were probably formed by precipitation from cooling vent fluids or during cooling and oxidation of high-temperature polymetallic sulphide assemblages. No exotic benthic fauna were found to be associated with the presently active hydrothermal vents mapped.

Geochemistry of Lau Backarc Basin sediments

Major and minor (Mn, Sr, Ba, V, Cr, Ni, Co, Zn, Cu, Zr, Y, Sc) elements and mineralogic compositions were determined on bulk sediments collected during Ocean Drilling Program Leg 135. Three classes of sediment samples from holes drilled in the Lau Basin are discriminated by mineralogy and major element data. Samples labeled Class 1 are significantly enriched in biogenic calcite and occur predominantly in the northern part of the basin (Sites 834-835), whereas those of Class 3 are mostly enriched in volcanogenic material and are predominant in the central part of the basin (Sites 836-839). The minor element composition records the effects of the hydrothermal activity on the sediments. In the northern area of the basin (Sites 834-835), sedimentation is characterized by higher accumulation rates of the carbonate and hydrothermal fractions. These sediments are probably reworked predominantly, transported in the water column, and then settled locally. Thus, ponded sediments are probably responsible to this high accumulation rates. Diagenetic processes altered the volcanic material to a grade corresponding to the stability of phillipsite. In the central area of the basin (Sites 836-839), sedimentation is characterized by the action of bottom currents preferentially reworking the carbonate and hydrothermal fractions. Volcanogenic accumulation rates are greater at these sites than in the northern Lau Basin. Alteration of volcanic material is more important deeper in the holes and records authigenesis of clay rich in Fe-Mg, most likely smectite. Locally, clay minerals have apparently incorporated Cr and other ore-forming elements.

Organic geochemistry of sediments of the Gulf of California

The effects of intrusive thermal stress have been studied on a number of Pleistocene sediment samples obtained from Leg 64 of the DSDP-IPOD program in the Gulf of California. Samples were selected from Sites 477, 478 and 481 where the organic matter was subjected to thermal stress from sill intrusions. For comparison purposes, samples from Sites 474 and 479 were selected as representative of unaltered material. The GC and GC-MS data show that lipids of the thermally unaltered samples were derived from microbial and terrestrial higher-plant detritus. Samples from sill proximities were found to contain thermally-derived distillates and those adjacent to sills contained essentially no lipids. Curie point pyrolysis combined with GC and GC-MS was used to show that kerogens from the unaltered samples reflected their predominantly autochthonous microbial origin. Pyrograms of the altered kerogens were much less complex than the unaltered samples, reflecting the thermal effects. The kerogens adjacent to the sills produce little or no pyrolysis products since these intrusions into unconsolidated, wet sediments resulted in in situ pyrolysis of the organic matter. Examination of the kerogens by ESR showed that spin density and line width pass through a maximum during the course of alteration but ESR g-values show no correlation with maturity. Stable carbon isotope (d13C) values of kerogens decrease by 1-1.5 per mil near the sills at Sites 477 and 481 and the atomic N/C decreases slightly with proximity to a smaller sill at Site 478. Differences in maturation behavior between Site 477 and 481 and Site 478 are attributed to dissimilarities in thermal stress and to chemical and isotopic heterogeneity of Guaymas Basin protokerogen.

Analysis and compound of carbon sequestration and serpentinization from the Iberian Margin and the Northern Apennine

Fluid circulation in peridotite-hosted hydrothermal systems influences the incorporation of carbon into the oceanic crust and its long-term storage. At low to moderate temperatures, serpentinization of peridotite produces alkaline fluids that are rich in CH4 and H2. Upon mixing with seawater, these fluids precipitate carbonate, forming an extensive network of calcite veins in the basement rocks, while H2 and CH4 serve as an energy source for microorganisms. Here, we analyzed the carbon geochemistry of two ancient peridotite-hosted hydrothermal systems: 1) ophiolites cropping out in the Northern Apennines, and 2) calcite-veined serpentinites from the Iberian Margin (Ocean Drilling Program (ODP) Legs 149 and 173), and compare them to active peridotite-hosted hydrothermal systems such as the Lost City hydrothermal field (LCHF) on the Atlantis Massif near the Mid-Atlantic Ridge (MAR). Our results show that large amounts of carbonate are formed during serpentinization of mantle rocks exposed on the seafloor (up to 9.6 wt.% C in ophicalcites) and that carbon incorporation decreases with depth. In the Northern Apennine serpentinites, serpentinization temperatures decrease from 240 °C to < 150 °C, while carbonates are formed at temperatures decreasing from ~ 150 °C to < 50 °C. At the Iberian Margin both carbonate formation and serpentinization temperatures are lower than in the Northern Apennines with serpentinization starting at ~ 150 °C, followed by clay alteration at < 100 °C and carbonate formation at < 19-44 °C. Comparison with various active peridotite-hosted hydrothermal systems on the MAR shows that the serpentinites from the Northern Apennines record a thermal evolution similar to that of the basement of the LCHF and that tectonic activity on the Jurassic seafloor, comparable to the present-day processes leading to oceanic core complexes, probably led to formation of fractures and faults, which promoted fluid circulation to greater depth and cooling of the mantle rocks. Thus, our study provides further evidence that the Northern Apennine serpentinites host a paleo-stockwork of a hydrothermal system similar to the basement of the LCHF. Furthermore, we argue that the extent of carbonate uptake is mainly controlled by the presence of fluid pathways. Low serpentinization temperatures promote microbial activity, which leads to enhanced biomass formation and the storage of organic carbon. Organic carbon becomes dominant with increasing depth and is the principal carbon phase at more than 50-100 m depth of the serpentinite basement at the Iberian Margin. We estimate that annually 1.1 to 2.7 × 1012 g C is stored within peridotites exposed to seawater, of which 30-40% is fixed within the uppermost 20-50 m mainly as carbonate. Additionally, we conclude that alteration of oceanic lithosphere is an important factor in the long-term global carbon cycle, having the potential to store carbon for millions of years.

Composition and alteration of volcanic rocks of ODP Hole 119-738C

During ODP Leg 119 one basement hole was drilled at Site 738, on the Southern Kerguelen Plateau. The 38.2 m of basement rocks drilled comprises three basaltic aa-lava flows with basal and top breccias, overlain by Turanian marine carbonates. Site 738 basalts probably erupted near a fracture zone, and were emplaced during the plateau-forming stage of Kerguelen Plateau evolution under quiet, subaerial to shallow water conditions. The basalts are T-MORB, chemically resembling Mesozoic continental flood basalts of the southern hemisphere. Two slightly different magma batches are distinguished by Fe, Ti, Al, Zr, and REE concentrations. Prior to eruption, the magmas had undergone significant olivine and some clinopyroxene fractionation. Incompatible and immobile trace element concentrations and ratios point to a veined upper mantle source, where a refractory mineral assemblage retains Nb, Ta, and the HREE. The basaltic melts derived from this regionally veined, enriched upper mantle have high LREE, and especially Ba and Th concentrations and bear the DUPAL isotopic signature gained from deep- seated, recycled, old oceanic(?) crust. A saponite-celadonite secondary mineral assemblage confines the alteration temperature to <170°C. Alteration is accompanied by net gains of H2O, CO2, K2O, and Rb, higher oxidation, minor Na2O, SiO2 gains, and losses of V and CaO. Released Ca, together with Ca from seawater, precipitated as calcite in veins and vesicles, plumbed the circulation system and terminated the rock/open seawater interaction.

(Table 1) Turbidity, temperature, and salinity in the hydrothermal plume and background waters above the northern part of the Mohn's Ridge at Station AMK36-3573-5

In July 1995 geological and biological studies in the axial zone of the northern part of the Mohn's Ridge (72°20'N) were carried out during Cruise 36 of R/V Akademik Mstislav Keldysh. Slopes of the neovolcanic zone, as well as a caldera on its crest were investigated with use of deep-sea manned submersibles Mir, geological and biological samples were also collected. Use of the Rosette sounding complex provided recognition of several major hydrothermal plumes. Bottom sediments of the marginal depression are enriched in metals characteristic for hydrothermal metalliferous sediments. Thus, a new unknown hydrothermal field was found.

Mineralogy and chemistry of basalts and secondary minerals from DSDP Site 417, Atlantic Ocean

Basalts from DSDP Site 417 (109 Ma) exhibit the effects of several stages of alteration reflecting the evolution of seawater-derived solution compositions and control by the structure and permeability of the crust. Characteristic secondary mineral assemblages occur in often superimposed alteration zones within individual basalt fragments. By combining bulk rock and single phase chemical analyses with detailed mineralogic and petrographic studies, chemical changes have been determined for most of the alteration stages identified in the basalts. 1) Minor amounts of saponite, chlorite, and pyrite formed locally in coarse grained portions of massive units, possibly at high temperatures during initial cooling of the basalts. No chemical changes could be determined for this stage. 2) Possible mixing of cooled hydrothermal fluids with seawater resulted in the formation of celadonite-nontronite and Fe-hydroxide-rich black halos around cracks and pillow rims. Gains of K, Rb, H20, increase of Fe 3 +/FeT and possibly some losses of Ca and Mg occurred during this stage. 3a) Extensive circulation of oxygenated seawater resulted in the formation of various smectites, K-feldspar, and Fe-hydroxides in brown and light grey alteration zones around formerly exposed surfaces. K, Rb, H20, and occasionally P were added to the rocks, Fe3+/FeT increased, and Ca, Mg, Si and occasionally Al and Na were lost. 3 b) Anoxic alteration occurred during reaction of basalt with seawater at low water-rock ratios, or with seawater that had previously reacted with basalt. Saponite-rich dark grey alteration zones formed which exhibit very little chemical change: generally only slight increases in Fe 3 +/FeT and H20 occurred. 4) Zeolites and calcite formed from seawater-derived fluids modified by previous reactions with basalt. Chemical changes involved increases of Ca, Na, H20 , and CO2 in the rocks. 5) A late stage of anoxic conditions resulted in the formation of minor amounts of Mn-calcites and secondary sulfides in previously oxidized rocks. No chemical changes were determined for this stage. Recognition of such alteration sequences is important in understanding the evolution of submarine hydrothermal systems and in interpreting chemical exchange due to seawater-basalt reactions.

Lead and strontium isotopic composition of some metalliferous and pelagic sediments and basalts at DSDP Leg 70 Holes

In recent years, metalliferous sediments have been discovered overlying newly generated oceanic crust in the East Pacific, North Atlantic, Indian Ocean, Red Sea, Gulf of Aden, and elsewhere (e.g., Boström, 1973; Lalou et al., 1977; Bischoff, 1969; Boström and Fisher, 1971; Cann et al., 1977, respectively). Such material has also been recovered by drilling from sediments lying upon older oceanic crust (Boström et al., 1972, 1976; Horowitz and Cronan, 1976). Hydrothermal circulation of seawater at a spreading ridge results in the leaching of Fe, Mn, and possibly other elements from the basaltic volcanic layer and their transport and discharge into ocean bottom waters, whereupon fine-grained Fe-Mn-rich precipitates form and settle into the ambient sediment (cf. Corliss, 1971; Dasch et al., 1971; Spooner and Fyfe, 1973; Bischoff and Dickson, 1975; Heath and Dymond, 1977; Corliss et al., 1979, Edmond et al., 1979). Mn-rich crusts have also been recovered from active ridges and are inferred to have formed in the vicinity of hydrothermal discharge areas (Scott et al., 1974; Moore and Vogt, 1976; Corliss et al., 1978; Hoffert et al., 1978). The source of the trace elements in the metalliferous deposits is generally not clear. They may be derived from seawater by adsorption onto the precipitates or crusts, or from hydrothermal solutions which have leached them from the basalts. Pb, however, can be used as a geochemical tracer because of the known isotopic compositional differences between oceanic basalts and seawater. Isotopic investigations of Pb in ferruginous sediments from the East Pacific have shown that it has been derived partly or mostly from a basaltic source (Bender et al., 1971; Dasch et al., 1971; Dymond et al., 1973). In the present study, Pb isotopic analyses have been made of a suite of metalliferous sediments (nontronite, Mn-oxide crust, Mn-Fe-oxide mud), pelagic sediments, and basalts from the Galapagos mounds area. The main purposes of the Pb study were to determine the source or sources of Pb in the metalliferous sediments, and whether or not stratigraphic variations exist in the isòtopic composition of Pb in the sediments.

Sulfur concentrations and isotopic composition of serpentinized oceanic peridotites

The mineralogy, contents, and isotopic compositions of sulfur in oceanic serpentinites reflect variations in temperatures and fluid fluxes. Serpentinization of <1 Ma peridotites at Hess Deep occurred at high temperatures (200°-400°C) and low water/rock ratios. Oxidation of ferrous iron to magnetite maintained low fO2 and produced a reduced, low-sulfur assemblage including NiFe alloy. Small amounts of sulfate reduction by thermophilic microbes occurred as the system cooled, producing low-delta34S sulfide (1.5? to -23.7?). In contrast, serpentinization of Iberian Margin peridotites occurred at low temperatures(~20°-200°C) and high water/rock ratios. Complete serpentinization and consumption of ferrous iron allowed evolution to higher fO2. Microbial reduction of seawater sulfate resulted in addition of low-delta34S sulfide (~15 to ~43?) and formation of higher-sulfur assemblages that include valleriite and pyrite. The high SO4/total S ratio of Hess Deep serpentinites (0.89) results in an increase of total sulfur and high delta34S of total sulfur (mean ~8?). In contrast, Iberian Margin serpentinites gained large amounts of 34S-poor sulfide (mean total S = 3800 ppm), and the high sulfide/total S ratio (0.61) results in a net decrease in delta34S of total sulfur (mean ~ -5?). Thus serpentinization is a net sink for seawater sulfur, but the amount fixed and its isotopic composition vary significantly. Serpentinization may result in uptake of 0.4-14 * 10**12 g S/yr from the oceans, comparable to isotopic exchange in mafic rocks of seafloor hydrothermal systems and approaching global fluxes of riverine sulfate input and sedimentary sulfide output.

Geochemistry, isotopes, trace elements and fluid inclusion geothermometry at DSDP Hole 83-504B

Stockwork-like metal sulfide mineralizations were found at 910-928 m below seafloor (BSF) in the pillow/dike transition zone of Hole 504B. This is the same interval where most physical properties of the 5.9-m.y.-old crust of the Costa Rica Rift change from those characteristic of Layer 2B to those of Layer 2C. The pillow lavas, breccias, and veins of the stockwork-like zone were studied by transmitted and reflected light microscopy, X-ray diffraction, and electron microprobe analysis. Bulk rock oxygen isotopic analyses as well as isolated mineral oxygen and sulfur isotopic analyses and fluid inclusion measurements were carried out. A complex alteration history was reconstructed that includes three generations of fissures, each followed by precipitation of characteristic hydrothermal mineral parageneses: (1) Minor and local deposition of quartz occurred on fissure walls; adjacent wall rocks were silicified, followed by formation of chlorite and minor pyrite I in the veins, whereas albite, sphene, chlorite and chlorite-expandable clay mixtures, actinolite, and pyrite replaced igneous phases in the host rocks. The hydrothermal fluids responsible for this first stage were probably partially reacted seawater, and their temperatures were at least 200-250° C. (2) Fissures filled during the first stage were reopened and new cracks formed. They were filled with quartz, minor chlorite and chlorite-expandable clay mixtures, traces of epidote, common pyrite, sphalerite, chalcopyrite, and minor galena. During the second stage, hydrothermal fluids were relatively evolved metal- and Si-rich solutions whose temperatures ranged from 230 to 340° C. The fluctuating chemical composition and temperature of the solutions produced a complex depositional sequence of sulfides in the veins: chalcopyrite I, ± Fe-rich sphalerite, chalcopyrite II ("disease"), Fe-poor sphalerite, chalcopyrite III, galena, and pyrite II. (3) During the last stage, zeolites and Mg-poor calcite filled up the remaining spaces and newly formed cracks and replaced the host rock plagioclase. Analcite and stilbite were first to form in veins, possibly at temperatures below 200°C; analcite and earlier quartz were replaced by laumontite at 250°C, whereas calcite formation temperature ranged from 135 to 220°C. The last stage hydrothermal fluids were depleted in Mg and enriched in Ca and 18O compared to seawater and contained a mantle carbon component. This complex alteration history paralleling a complex mineral paragenesis can be interpreted as the result of a relatively long-term evolution of a hydrothermal system with superimposed shorter term fluctuations in solution temperature and composition. Hydrothermal activity probably began close to the axis of the Costa Rica Rift with the overall cooling of the system and multiple fracturing stages due to movement of the crust away from the axis and/or cooling of a magmatic heat source.