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.

Free and dissolved gases in the area of the Calypso hydrothermal vent, Bay of Plenty, New Zealand

Gas composition and hydrochemistry of bottom waters of the Bay of Plenty in the hydrothermally active zone of the Pacific island arc are investigated. Methane content in underwater vents is an order of magnitude greater than that in volcanic exhalations on the land. Salinity, pH, total content of CO2, its partial pressure, and silica content also differ. Correlations between gas parameters, hydrochemical parameters, and biological and microbiological parameters are identified.

Alkali contents, Sr isotope and U-Th-Pb data for ocean crust vein minerals from DSDP Holes 27-261, 61-462A, and 72-516F

Cation exchange experiments (ammonium acetate and cation resin) on celadonite-smectite vein minerals from three DSDP holes demonstrate selective removal of common Sr relative to Rb and radiogenic Sr. This technique increases the Rb/Sr ratio by factors of 2.3 to 22 without significantly altering the age of the minerals, allowing easier and more precise dating of such vein minerals. The ages determined by this technique (Site 261 - 121.4+/-1.6 m.y.; Site 462A - 105.1+/-2.8 m.y.; Site 516F - 69.9+/-2.4 m.y.) are 34, 54 and 18 m.y. younger, respectively, than the age of crust formation at the site; in the case of site 462A, the young age is clearly related to off-ridge emplacement of a massive sill/flow complex. At the other sites, either the hydrothermal circulation systems persisted longer than for normal crust (10-15 m.y.), or were reactivated by off-ridge igneous activity. Celadonites show U and Pb contents and Pb isotopic compositions little changed from their basalt precursors, while Th contents are significantly lower. Celadonites thus have unusually high alkali/U,Th ratios and low Th/U ratios. If this celadonite alteration signature is significantly imprinted on oceanic crust as a whole, it will lead to very distinctive Pb isotope signatures for any hot spot magmas which contain a component of aged subducted recycled oceanic crust. Initial Sr isotope ratios of ocean crust vein minerals (smectite, celadonite, zeolite, calcite) are intermediate between primary basalt values and contemporary sea water values and indicate formation under seawaterdominated systems with effective water/rock ratios of 20-200.