Mineral and chemical composition of hydrothermally altered rocks and sediments from the Middle Valley, ODP Leg 139 data

The Middle Valley segment at the northern end of the Juan de Fuca Ridge is a deep extensional rift blanketed with 200-500 m of Pleistocene turbiditic sediment. Sites 857 and 858 were drilled during Ocean Drilling Program Leg 139 to determine whether these two sites were hydrologically linked end members of an active hydrothermal circulation system. Site 858 was placed in an area of active hydrothermal discharge with fluids up to 270°C venting through anhydrite-bearing mounds on top of altered sediment. The shallow basement of fine-grained basalt that underlies the vents at Site 858 is interpreted as a seamount that was subsequently buried by turbidites. Site 857 was placed 1.6 km south of the Site 858 vents in a zone of high heat flow and numerous seismically imaged ridge-parallel faults. Drilling at Site 857 encountered sediments that are increasingly altered with depth and that overlie a series of mafic sills at depths of 460-940 m below sea floor. Sill margins and adjacent baked sediment are highly altered to magnesian chlorite and crosscut with veins filled with quartz, chlorite, sulfides, epidote, and wairakite. The sill interiors vary from slightly altered, with unaltered plagioclase and clinopyroxene in a mesostasis replaced by chlorite, to local zones of intense alteration and brecciation. In these latter zones, the sill interiors are pervasively replaced by chlorite, epidote, quartz, pyrite, titanite, and rare actinolite. The most complete replacement is associated with brecciated horizons with low recovery and slickensides on fracture surfaces, which we interpret as intersections between faults and the sills. Geochemically, the alteration of the sill complex is reflected in significant whole-rock depletions in Ca, Sr, and Na with corresponding enrichments in Mg, Al, and most metals. The latter results from the formation of conspicuous sulfide poikiloblasts. In contrast, metamorphism of the Site 858 seamount includes incomplete albitization of plagioclase phenocrysts and replacement of sparse mafic phenocrysts. Much of the basement alteration at Site 858 is confined to crosscutting veins except for a highly altered and veined horizon at the contact between basaltic basement and the overlying sediment. The sill complex at Site 857 is more highly depleted in 18O (d18O = 2.4 per mil - 4.7 per mil) and more pervasively replaced by secondary minerals relative to the extrusives at Site 858 (d18O = 4.5 per mil - 5.5 per mil). There is no evidence of significant albitization of the plagioclase at Site 857, suggesting high Ca/Na in the pore fluids. Fluid-inclusion data from hydrothermal minerals in altered mafic rocks and veins at Sites 857 and 858 show a consistency of homogenization temperatures, varying from 245 to 270°C, which is within the range of temperatures observed for the fluids venting at Site 858. The consistency of the fluid inclusion temperatures, the lack of albitization within the Site 857 sills, and the apparently low water/rock ratio collectively suggest that the sill complex at Site 857 is in thermal equilibrium and being altered by a highly evolved Ca-rich fluid similar to the fluids now venting at Site 858. The alteration evident in these two deep crustal drillsites is a result of the ongoing hydrothermal circulation and is consistent with downhole logging results, instrumented borehole results, and hydrothermal fluid chemistry. The pervasive alteration of the laterally extensive sill-sediment complex at Site 857 determines the chemistry of the fluids that are venting at Site 858. The limited alteration of the Site 858 lavas suggests that this basement edifice acts as a penetrator or ventilator for the regional hydrothermal reservoir with much of the flow focussed at the highly altered and veined sediment-basalt contact.

Magnetic susceptibility parameters of ODP Leg 204 sites

In this paper, we present a rock magnetic data set produced for sediments from Hydrate Ridge recovered during Ocean Drilling Program Leg 204. Our data set is based on several artificially induced magnetic properties that can be used as a diagnostic for the presence of magnetic iron sulfides. The occurrence of magnetic iron sulfides within the gas hydrate stability zone in locations where gas hydrates are present seems to confirm previous interpretations linking formation of such minerals with generation of gas hydrate. Magnetic iron sulfides are also found at positions deeper than the gas hydrate stability zone. We suggest that these positions, which include intervals located just below the bottom-simulating reflector and also at deeper positions, may mark the former presence of gas hydrates that have been later dissociated as the gas hydrate stability zone moved upward through time. Detailed characterization of the magnetic iron sulfide mineralogy and comparison with sedimentological and geochemical data will be attempted for better determining the significance of magnetic iron sulfides in Hydrate Ridge sediments and their possible applications in the study of gas hydrates.

Chemistry of very young basalts from ODP Hole 106-648B

Basalts in Hole 648B, located in the rift valley of the Mid-Atlantic Ridge at 23°N in crust estimated to be less than 100,000 years old, are mainly fresh, but small amounts of secondary phases are found on fracture surfaces and in alteration halos within the rocks. The halos are defined by dark bands 1-4 mm thick that have developed parallel to fracture surfaces or pillow margins and which in some cases have migrated some centimeters into the rock. The dark bands are the principal locus of secondary phases. The secondary phases are olive-green and yellow protoceladonites, of composition and structure intermediate between celadonite and iron-rich saponite, red (Mn-poor) to opaque (Mn-rich) iron oxyhydroxides, mixtures of protoceladonite and iron oxyhydroxide, and rare manganese oxides. These phases occur mainly as linings or fillings of open spaces in the basalt within the dark bands. Sulfides and intersertal glass are the only primary phases that can be seen to have been altered. Where dark bands have migrated into the rock, the rock behind the advancing band is almost devoid of secondary phases, implying redissolution. The potassium and magnesium in the secondary phases could have been supplied from ambient seawater. The aluminum in the protoceladonites must have been derived from local reaction of intergranular glass. The source of iron and silica could have been intergranular glass or low temperature mineralizing solutions of the type responsible for the formation of deposits of manganese oxides and iron oxyhydroxides and silicates on the seafloor.

Pore water and solid-phase data from site Scharendijke (Lake Grevelingen, NL)

Will be submitted by the author

Downcore rock-magnetic properties of ICDP Core 5045-1, Lake Ohrid

The bulk magnetic mineral record from Lake Ohrid, spanning the past 637 kyr, reflects large-scale shifts in hydrological conditions, and, superimposed, a strong signal of environmental conditions on glacial-interglacial and millennial timescales. A shift in the formation of early diagenetic ferrimagnetic iron sulfides to siderites is observed around 320 ka. This change is probably associated with variable availability of sulfide in the pore water. We propose that sulfate concentrations were significantly higher before ~320 ka, due to either a higher sulfate flux or lower dilution of lake sulfate due to a smaller water volume. Diagenetic iron minerals appear more abundant during glacials, which are generally characterized by higher Fe/Ca ratios in the sediments. While in the lower part of the core the ferrimagnetic sulfide signal overprints the primary detrital magnetic signal, the upper part of the core is dominated by variable proportions of high- to low-coercivity iron oxides. Glacial sediments are characterized by high concentration of high-coercivity magnetic minerals (hematite, goethite), which relate to enhanced erosion of soils that had formed during preceding interglacials. Superimposed on the glacial-interglacial behavior are millennial-scale oscillations in the magnetic mineral composition that parallel variations in summer insolation. Like the processes on glacial-interglacial timescales, low summer insolation and a retreat in vegetation resulted in enhanced erosion of soil material. Our study highlights that rock-magnetic studies, in concert with geochemical and sedimentological investigations, provide a multi-level contribution to environmental reconstructions, since the magnetic properties can mirror both environmental conditions on land and intra-lake processes.

Chemical composition and stable sulfur isotope record of Black Sea sediments

The main terminal processes of organic matter mineralization in anoxic Black Sea sediments underlying the sulfidic water column are sulfate reduction in the upper 2-4 m and methanogenesis below the sulfate zone. The modern marine deposits comprise a ca. 1-m-deep layer of coccolith ooze and underlying sapropel, below which sea water ions penetrate deep down into the limnic Pleistocene deposits from >9000 years BP. Sulfate reduction rates have a subsurface maximum at the SO4[2-]-CH4 transition where H2S reaches maximum concentration. Because of an excess of reactive iron in the deep limnic deposits, most of the methane-derived H2S is drawn downward to a sulfidization front where it reacts with Fe(III) and with Fe2+ diffusing up from below. The H2S-Fe2+ transition is marked by a black band of amorphous iron sulfide above which distinct horizons of greigite and pyrite formation occur. The pore water gradients respond dynamically to environmental changes in the Black Sea with relatively short time constants of ca. 500 yr for SO4[2-] and 10 yr for H2S, whereas the FeS in the black band has taken ca. 3000 yr to accumulate. The dual diffusion interfaces of SO4[2-]-CH4 and H2S-Fe2+ cause the trapping of isotopically heavy iron sulfide with delta34S = +15 to +33 per mil at the sulfidization front. A diffusion model for sulfur isotopes shows that the SO4[2-] diffusing downward into the SO4[2-]-CH4 transition has an isotopic composition of +19 per mil, close to the +23 per mil of H2S diffusing upward. These isotopic compositions are, however, very different from the porewater SO4[2-] (+43 per mil) and H2S (-15 per mil) at the same depth. The model explains how methane-driven sulfate reduction combined with a deep H2S sink leads to isotopically heavy pyrite in a sediment open to diffusion. These results have general implications for the marine sulfur cycle and for the interpretation of sulfur isotopic data in modern sediments and in sedimentary rocks throughout earth's history.