(Appendix) Petrographic information, trace element and Sr isotope ratios of Pito Deep samples

Fluid flow through the axial hydrothermal system at fast spreading ridges is investigated using the Sr-isotopic composition of upper crustal samples recovered from a tectonic window at Pito Deep (NE Easter microplate). Samples from the sheeted dike complex collected away from macroscopic evidence of channelized fluid flow, such as faults and centimeter-scale hydrothermal veins, show a range of 87Sr/86Sr from 0.7025 to 0.7030 averaging 0.70276 relative to a protolith with 87Sr/86Sr of ~0.7024. There is no systematic variation in 87Sr/86Sr with depth in the sheeted dike complex. Comparison of these new data with the two other localities that similar data sets exist for (ODP Hole 504B and the Hess Deep tectonic window) reveals that the extent of Sr-isotope exchange is similar in all of these locations. Models that assume that fluid-rock reaction occurs during one-dimensional (recharge) flow lead to significant decreases in the predicted extent of isotopic modification of the rock with depth in the crust. These model results show systematic misfits when compared with the data that can only be avoided if the fluid flow is assumed to be focused in isolated channels with very slow fluid-rock exchange. In this scenario the fluid at the base of the crust is little modified in 87Sr/86Sr from seawater and thus unlike vent fluids. Additionally, this model predicts that some rocks should show no change from the fresh-rock 87Sr/86Sr, but this is not observed. Alternatively, models in which fluid-rock reaction occurs during upflow (discharge) as well as downflow, or in which fluids are recirculated within the hydrothermal system, can reproduce the observed lack of variation in 87Sr/86Sr with depth in the crust. Minimum time-integrated fluid fluxes, calculated from mass balance, are between 1.5 and 2.6 * 10**6 kg/m**2 for all areas studied to date. However, new evidence from both the rocks and a compilation of vent fluid compositions demonstrates that some Sr is leached from the crust. Because this leaching lowers the fluid 87Sr/86Sr without changing the rock 87Sr/86Sr, these mass balance models must underestimate the time-integrated fluid flux. Additionally, these values do not account for fluid flow that is channelized within the crust.

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.

Chemical composition of upper Cenozoic at DSDP Leg 70 Holes

The hydrothermal deposits that we analyzed from Leg 70 are composed of ferruginous green clays and fragments of manganese-hydroxide crust. Data from X-ray diffraction, IR-spectroscopy, electron diffraction, and chemical analyses indicate that the hydrothermal green clays are composed of disordered mixed-layer phases of celadonite-nontronite. Electron diffraction shows that the parameters of the unit cells and the degree of three-dimensional ordering of mixed-layer phases with 80% celadonite interlayers are very close to Fe-micas of polymorphic modification IM-celadonite. In some sections, there is a tendency for the number of celadonite layers to increase with depth. The manganese-hydroxide crust fragments are predominantly composed of todorokite (buserite). An essential feature of hydrothermal accumulation is the sharp separation of Fe and Mn. Ba/Ti and Ba/Sr ratios are typical indicators of hydrothermal deposits. Sediments composing the hydrothermal mounds were deposited from moderately heated waters, which had extracted the components from solid basalts in environments where there were considerable gradients of temperature, eH, and pH. The main masses of Fe and Mn were deposited in the late Pleistocene. Postsedimentary alteration of deposited hydrothermal sediments led to their slight recrystallization and, in the green clays, to celadonitization. Further, factor analysis (by Varentsov) of chemical components from these hydrothermal deposits revealed paragenetic assemblages. Green clays corresponding to a definite factor assemblage were formed during the main stage of hydrothermal mineral formation. Manganese hydroxide and associated components were largely accumulated during an early stage and at the end of the main stage.

Geochemistry of middle Eocene-lower Oligocene pelagic sediments of ODP Hole 105-647A

Geochemical analyses of the middle Eocene through lower Oligocene lithologic Unit IIIC (260-518 meters below seafloor [mbsf]) indicate a relatively constant geochemical composition of the detrital fraction throughout this depositional interval at Ocean Drilling Program (ODP) Site 647 in the southern Labrador Sea. The main variability occurs in redox-sensitive elements (e.g., iron, manganese, and phosphorus), which may be related to early diagenetic mobility in anaerobic pore waters during bacterial decomposition of organic matter. Initial preservation of organic matter was mediated by high sedimentation rates (36 m/m.y.). High iron (Fe) and manganese (Mn) contents are associated with carbonate concretions of siderite, manganosiderite, and rhodochrosite. These concretions probably formed in response to elevated pore-water alkalinity and total dissolved carbon dioxide (CO2) concentrations resulting from bacterial sulfate reduction, as indicated by nodule stable-isotope compositions and pore-water geochemistry. These nodules differ from those found in upper Cenozoic hemipelagic sequences in that they are not associated with methanogenesis. Phosphate minerals (carbonate-fluorapatite) precipitated in some intervals, probably as the result of desorption of phosphorus from iron and manganese during reduction. The bulk chemical composition of the sediments differs little from that of North Atlantic Quaternary abyssal red clays, but may contain a minor hydrothermal component. The silicon/ aluminum (Si/Al) ratio, however, is high and variable and probably reflects original variations in biogenic opal, much of which is now altered to smectite and/or opal CT. An increase in the sodium/potassium (Na/K) ratio in the upper Eocene corresponds to the beginning of coarsergrained feldspar flux to the site, possibly marking the onset of more vigorous deep currents. Although the Site 647 cores provide a nearly complete high-resolution, high-latitude Eocene-Oligocene record, the high sedimentation rate and somewhat unusual diagenetic conditions have led to variable alteration of benthic foraminifers and fine-fraction carbonate and have overprinted the original stable-isotope records. Planktonic foraminifers are less altered, but on the whole, there is little chance of sorting out the nature and timing of environmental change on the basis of our stable-isotope analyses.

Lithium sources in pore fluids of Peru slope

High Li concentrations, up to a maximum of 1155 µM are observed in the pore fluids of the Peru convergent margin slope sediments. At Ocean Drilling Program Sites 683 and 685 (ca. 9°S), the Li concentration depth gradients are twice as steep as at Site 682 and 688 (ca. 11°S). Within the sediments, the most important Li sources are from aluminosilicate minerals. Biogenic opal-A contains little Li and thus dilutes the Li concentration of the bulk sediments. The sediment compositions and the thermal regimes are similar at 9° and 11°S, suggesting there is an additional, non-sedimentary source for the observed high Li concentrations in the northern pore fluids. At 9°S, the 87Sr/86Sr ratios reach a maximum value of 0.709958. The observed radiogenic 87Sr/86Sr values in the pore fluids support the suggestion that the additional Li may derive from exchange reactions with underlying continental crust. The high concentrations of Li at 11°S may derive from basalt alteration at moderate to high temperatures, as suggested by the non-radiogenic 87Sr/86Sr ratios in these pore fluids, which reach a minimum value of 0.707218. Based on (1) Li concentrations in the pore fluids in slope sediments from Peru and several other margins, and (2) an approximate estimate of fluid flux from continental margins into the ocean, continental margins provide an estimated 1 to 3 * 10**10 moles Li/yr to the ocean. This source of oceanic Li, which has not been considered previously, is of the same order of magnitude as some estimates of hydrothermal and river Li fluxes and may have important consequences for the oceanic Li isotope budget. The sink is unknown for this newly discovered and possibly large Li source, but it may be more pervasive low-temperature alteration of oceanic basement than previously estimated, or burial of mineral phases, such as authigenic clay minerals, or metal oxyhydroxides which may be Li-rich.

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.

Descriptions, isotopes and minerals of sediments at DSDP Leg 64 Holes

Mineralogical and oxygen isotopic analyses of samples from Deep Sea Drilling Project Sites 477, 481, and 477 in the Guaymas Basin indicate the existence of two distinct hydrothermal systems. In the first, at Sites 481 and 478, hot dolerite sills intruded into highly porous hemipelagic siliceous mudstones that were moderately rich in organic matter, thermally altered the adjacent sediments, and expelled hydrothermal pore fluids. The second, at Site 477 and active at present, is most probably caused by a recent igneous intrusion forming a magma chamber at shallow depth. In the first hydrothermal system, the main thermal reactions above and below the sills are dissolution of opal-A and formation of quartz, either directly or through opal-CT; formation of smectite; formation of analcime only above the sills; dissolution and recrystallization of calcite and occasional formation of dolomite or protodolomite. The d18O values of the hydrothermally altered sediments range from 9.9 to 12.2 per mil (SMOW). The d18O values of recrystallized calcites above the first sill complex, Site 481, indicate temperatures of 140° to 170°C. No fluid recharge is required in this system. The thickness of the sill complexes and the sequence and depth of intrusion into the sediment column determine the thickness of the alteration zones, which ranges from 2 or 3 to approximately 50 meters. Generally, the hydrothermally altered zone is thicker above than below the sill. In the second type, the sediments are extensively recrystallized. The characteristic greenschist-facies mineral assemblage of quartz-albite-chlorite-epidote predominates. Considerable amounts of pyrite, pyrrhotite, and sphene are also present. The lowest d18O value of the greenschist facies rocks is 6.6 per mil, and the highest d18O value of the associated pore fluids is +1.38 per mil (SMOW). The paragenesis and the oxygen isotopes of individual phases indicate alteration temperatures of 300 ± 50°C. On the basis of the oxygen isotopes of the solids and associated fluids, it is concluded that recharge of fluids is required. The water/rock ratio in wt.% is moderate, approximately 2/1 to 3/1 - higher than the calculated water/rock ratio of the hydrothermal system at the East Pacific Rise, 21 °N.

Mineralogy and geochemistry at DSDP Leg 64 Holes

At DSDP Site 477, late Quaternary diatomaceous muds and delta-derived silty-sand turbidites at 2000 meters water depth have been extensively and progressively altered by a deep-seated heat source beneath a sill. Bulk petrologic and microprobe analyses have identified a crudely zoned paragenesis within 260 meters sub-bottom which ranges from unaltered to slightly altered oozes (0-50 m), anhydrite-dolomite claystones (105-125 m), illite-chlorite-pyrite claystones (125-140 m), chlorite-pyrite-calcite-carbonaceous claystones with traces of K-feldspar, albite, epidote (140-190 m), and chlorite-epidote-quartz-albite-pyrrhotite-sphene sandstone (190-260 m). Several petrologic features suggest rapid processes of ocean floor metamorphism: (1) friable and porous textures, (2) abundant relict grains with overgrowths, (3) idiomorphic habits on epidotes, feldspars, and quartz, and (4) a steep gradient in levels of alteration. Many aspects of this hydrothermal assemblage are similar to hydrothermally metamorphosed sandstones of the Cerro Prieto, Mexico, geothermal area.