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.

Miocene dissolution facies and microfacies at Northwest Atlantic Deep Sea Drilling Project Site 93-603

Depth fluctuations of the lysocline and calcite compensation depth (CCD) through time were investigated at Deep Sea Drilling Project Site 603, Leg 93. The CCD fell during the middle Miocene at the onset of the Western Boundary Undercurrent, correlated with seismic Horizon X. Subsequently deposited units show fluctuations of the dissolution curve. Major changes in dissolution facies correspond with lithologic boundaries.

Mineralogy and petrographic summary of ODP Leg 198 sites and DSDP Hole 62-463, Shatsky Rise

This petrological study of the lower Aptian Oceanic Anoxic Event (OAE1a) focused on the nature of the organic-rich interval as well as the tuffaceous units above and below it. The volcaniclastic debris deposited just prior to the OAE1a is consistent with reactivation of volcanic centers across the Shatsky Rise, concurrent with volcanism on the Ontong Java Plateau. This reactivation may have been responsible for the sub-OAE1a unconformity. Soon after this volcanic pulse, anomalous amounts of organic matter accumulated on the rise, forming a black shale horizon. The complex textures in the organic-rich intervals suggest a history of periodic anoxia, overprinted by bioturbation. Components include pellets, radiolarians, and fish debris. The presence of carbonate-cemented radiolarite under the OAE1a intervals suggests that there has been large-scale remobilization of carbonate in the system, which in turn may explain the absence of calcareous microfossils in the section. The volcanic debris in the overlying tuffaceous interval differs in that it is significantly epiclastic and glauconitic. It was likely derived from an emergent volcanic edifice.

(Table 1) Minerals found in vesicles and fractures from DSDP Leg 54 Holes basalts

A variety of secondary minerals, formed in response to different oxidation and hydration states, are found in vugs and on fracture surfaces of the basalt cores from DSDP Leg 54. The minerals are smectite (blue to grey), high-magnesium calcite, manganoan calcite, aragonite, iron oxides, phillipsite, todorokite, marcasite, and hydrobiotite. The relationship of the mineral assemblages to four depositional modes of the basalts are delineated. A definite sequence and genetic link exists between mineral type and host rock which is dependent upon the origin and subsequent cooling history of the basalt.

(Table 1) Mineralogical composition of sediments from DSDP Sites 69-504 and 69-505

We discuss the provenance of minerals detected by X-ray-diffraction analyses of sediments of Sites 504 and 505 of Deep Sea Drilling Project Leg 69. These are X-ray-amorphous material, opal-CT, calcite, quartz, feldspar, apatite, smectite, illite, kaolinite, magnetite, maghemite, pyrite, marcasite, barite, sepiolite, and clinoptilolite. Authigenic marcasite and clinoptilolite together with opal-CT are restricted to Site 504, indicating the special diagenetic conditions related to relatively high sediment temperatures at this site. Marcasite formation is likely dependent on the relatively low pH values of <7.1 found in interstitial waters of Site 504 sediments below 50 meters sub-bottom. Clinoptilolite evidently was formed by diagenetic alteration of rhyolitic volcanic glass or smectite plus biogenic silica within the chalk-limestone-chert sequence of Site 504, where opal-CT also reflects a high degree of silica dissolution and reprecipitation. This was a consequence of high temperatures (50-55 °C) at the base of the sediment column.

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.

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.

Sulphur chemistry of the ODP Site 206-1256 volcanic section

Sulfide mineralogy and the contents and isotope compositions of sulfur were analyzed in a complete oceanic volcanic section from IODP Hole 1256D in the eastern Pacific, in order to investigate the role of microbes and their effect on the sulfur budget in altered upper oceanic crust. Basalts in the 800 m thick volcanic section are affected by a pervasive low-temperature background alteration and have mean sulfur contents of 530 ppm, reflecting loss of sulfur relative to fresh glass through degassing during eruption and alteration by seawater. Alteration halos along fractures average 155 ppm sulfur and are more oxidized, have high SO4/Sum S ratios (0.43), and lost sulfur through oxidation by seawater compared to host rocks. Although sulfur was lost locally, sulfur was subsequently gained through fixation of seawater-derived sulfur in secondary pyrite and marcasite in veins and in concentrations at the boundary between alteration halos and host rocks. Negative d34S[sulfide-S] values (down to -30 per mil) and low temperatures of alteration (down to ~40 °C) point to microbial reduction of seawater sulfate as the process resulting in local additions of sulfide-S. Mass balance calculations indicate that 15-20% of the sulfur in the volcanic section is microbially derived, with the bulk altered volcanic section containing 940 ppm S, and with d34S shifted to -6.0 per mil from the mantle value (0 per mil). The bulk volcanic section may have gained or lost sulfur overall. The annual flux of microbial sulfur into oceanic basement based on Hole 1256D is 3-4 * 10**10 mol S/yr, within an order of magnitude of the riverine sulfate source and the sedimentary pyrite sink. Results indicate a flux of bacterially derived sulfur that is fixed in upper ocean basement of 7-8 * 10**-8 mol/cm**-2/yr1 over 15 m.y. This is comparable to that in open ocean sediment sites, but is one to two orders of magnitude less than for ocean margin sediments. The global annual subduction of sulfur in altered oceanic basalt lavas based on Hole 1256D is 1.5-2.0 * 10**11 mol/yr, comparable to the subduction of sulfide in sediments, and could contribute to sediment-like sulfur isotope heterogeneities in the mantle.

Composition of bottom sediments from the Guinea Basin

Geomorphology of the Guinea Basin is described along with sediments from cores collected on the abyssal plain, within the abyssal hill zone, and in the eastern part of the Chain Fracture Zone. Stratigraphic differentiation of deep-sea sediments was based on diatom analysis, geochemical and lithological data. Holocene and Pleistocene were identified by these criteria. The lower boundary of Holocene is was found from a marked decrease in CaCO3 concentration and total diatom count. Mineral and chemical compositions are given for coarse silt fraction of various Late Pleistocene sediments. It is shown that this facial complex is determined by tectonic position of the Guinea Basin.

Composition of hydrothermal manifestations in the World Ocean

The monograph summarizes results of studies of hydrothermal fields on the ocean floor, hydrothermal plumes and metalliferous sediments. Hydrothermal ore manifestations formed in different geodynamic settings, with different character of volcanism in different facial conditions of deposition are described. Causes of non-uniformity of hydrothermal system functioning in different parts of the ocean and therefore variability of hydrothermal deposits are under consideration. On the base of found relationships of these irregularities with geodynamics, volcanism and sedimentation a new classification of hydrothermal processes and genetic models of hydrothermal ore formation in the ocean have been created. Regularities of hydrothermal sedimentary material dispersion in bottom waters are discussed.