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.

Nd and Pb isotope signatures of the clay-size fraction of sediment core MD99-2227

Nd and Pb isotopes were measured on the fine fraction of one sediment core drilled off southern Greenland. This work aims to reconstruct the evolution of deep circulation patterns in the North Atlantic during the Holocene on the basis of sediment supply variations. For the last 12 kyr, three sources have contributed to the sediment mixture: the North American Shield, the Pan-African and Variscan crusts, and the Mid-Atlantic Ridge. Clay isotope signatures indicate two mixtures of sediment sources. The first mixture (12.2-6.5 ka) is composed of material derived from the North American shield and from a "young" crustal source. From 6.5 ka onward the mixture is characterized by a young crustal component and by a volcanic component characteristic of the Mid-Atlantic Ridge. Since the significant decrease in proximal deglacial supplies, the evolution of the relative contributions of the sediment sources suggests major changes in the relative contributions of the deep water masses carried by the Western Boundary Undercurrent over the past 8.4 kyr. The progressive intensification of the Western Boundary Undercurrent was initially associated mainly with the transport of the Northeast Atlantic Deep Water mass until 6.5 ka and with the Denmark Strait Overflow Water thereafter. The establishment of the modern circulation at 3 ka suggests a reduced influence of the Denmark Strait Overflow Water, synchronous with the full appearance of the Labrador Seawater mass. Our isotopic data set emphasizes several changes in the relative contribution of the two major components of North Atlantic Deep Water throughout the Holocene.

Chemical composition of siderites and clay minerals from DSDP Holes 70-506G and 70-507B

As soon as they are emplaced on the sea floor, oceanic basalts go through a low-temperature alteration process which produces black halos concentrical with exposed surfaces and cracks, whereas the grey internal parts of the basaltic pieces apparently remain unaltered. This paper reports for the first time the occurrence of authigenic siderite and ankerite in oceanic basalts and more particularly in the grey internal parts of the latter. Small (8-50 µm) crystals of zoned siderite and ankerite have been observed in ten vesicles of two samples recovered from DSDP Holes 506G and 507B drilled south of the Galápagos Spreading Center (GSC). These Fe-carbonates show a large range of chemical composition (FeCO3 = 47-88%; CaCO3 = 5-40%; MgCO3 = 1-20%; MnCO3 = 0-11%). Most of them are Ca-richer than siderite reported in the literature. The chemical composition of the carbonate clearly reflects the fluctuation of the fluid chemical composition during crystallization. Mn and at least part of the Fe are thought to be hydrothermal in origin, whereas Mg and probably Ca were provided by seawater. It is proposed that siderite and ankerite formed at relatively low temperature (<85°C) and is metastable. The alteration of the GSC basalts seems to have proceeded in two stages: during the first, reducing stage, pyrite precipitated from hydrothermal fluids. A little further in the rock, siderite precipitated from the fluid which had already been modified by the formation of pyrite, and thus in a microenvironment where particular conditions prevailed (high P_CO2, increasing p_S**2- or increasing pH or increasing or decreasing pe). During the second, oxidizing, stage of alteration, a seawater-dominated fluid allowed crystallization of mixtures of Fe-rich smectites and micas, and Fe-hydroxides forming the black halos in the external portion of the basalt pieces and locally oxidizing pyrite and siderite in their innermost part. It is shown in this paper that, even at its earliest stage, and at low temperature, alteration of the upper oceanic crust (lavas) involves fluids enriched in Fe and Mn, interpreted to be of hydrothermal origin.

Clay mineral and heavy metal composition of sea-bed surface sediments and pre-Holocene sediment samples taken during POLARSTERN cruise ANT-XXIII/9

Surface mineralogical compositions and their association to modern processes are well known from the east Atlantic and south-west Indian sectors of the Southern Ocean, but data from the interface of these areas - the Prydz Bay-Kerguelen region - is still missing. The objective of our study was to provide mineralogical data of reference samples from this region and to relate these mineralogical assemblages to hinterland geology, weathering, transport and depositional processes. Clay mineral assemblages were analysed by means of X-ray diffraction technique. Heavy mineral assemblages were determined by counting of gravity-separated grains under a polarizing microscope. Results show that by use of clay mineral assemblages four mineralogical provinces can be subdivided: i) continental shelf, ii) continental slope, iii) deep sea, iv) Kerguelen Plateau. Heavy mineral assemblages in the fine sand fraction are relatively uniform except for samples taken from the East Antarctic shelf. Our findings show that mineralogical studies on sediment cores from the study area have the potential to provide insights into past shifts in ice-supported transport and activity and provenance of different water masses (e.g. Antarctic slope current and deep western boundary current) in the Prydz Bay-Kerguelen region.

Sedimentological and clay mineralogical analysis of ODP sites in the central Fram Strait

This study presents the results of high-resolution sedimentological and clay mineralogical investigations on sediments from ODP Sites 908A and 909AlC located in the central Fram Strait. The objective was to reconstruct the paleoclimate and paleoceanography of the high northern latitudes since the middle Miocene. The sediments are characterised in particular by a distinctive input of ice-rafted material, which most probably occurs since 6 Ma and very likely since 15 Ma. A change in the source area at 1 1.2 Ma is clearly marked by variations within clay mineral composition and increasing accumulation rates. This is interpreted as a result of an increase in water mass exchange through the Fram Strait. A further period of increasing exchange between 4-3 Ma is identified by granulometric investigations and points to a synchronous intensification of deep water production in the North Atlantic during this time interval. A comparison of the components of coarse and clay fraction clearly shows that both are not delivered by the Same transport process. The input of the clay fraction can be related to transport mechanisms through sea ice and glaciers and very likely also through oceanic currents. A reconstruction of source areas for clay minerals is possible only with some restrictions. High smectite contents in middle and late Miocene sediments indicate a background signal produced by soil formation together with sediment input, possibly originating from the Greenland- Scotland Ridge. The applicability of clay mineral distribution as a climate proxy for the high northern latitudes can be confirmed. Based on a comparison of sediments from Site 909C, characterised by the smectite/illite and chlorite ratio, with regional and global climatic records (oxygen isotopes), a middle Miocene cooling phase between 14.8-14.6 Ma can be proposed. A further cooling phase between 10-9 Ma clearly shows similarities in its Progress toward drastic decrease in carbonate sedimentation and preservation in the eastern equatorial Pacific. The modification in sea water and atmosphere chemistry may represent a possible link due to the built-up of equatorial carbonate platforms. Between 4.8-4.6 Ma clay mineral distribution indicates a distinct cooling trend in the Fram Strait region. This is not accompanied by relevant glaciation, which would otherwise be indicated by the coarse fraction. The intensification of glaciation in the northern hemisphere is distinctly documented by a rapid increase of illite and chlorite starting from 3.3 Ma, which corresponds to oxygen isotope data trends from North Atlantic.

Clay mineral assemblages in the western Baltic Sea

Surface samples and nine cores from the western Baltic Sea and marginal water bodies were investigated for clay mineral composition. The clay mineral assemblages of recent sediments are rather homogeneous. Variations result mainly from the erosion of different glacial source deposits. High percentages of illite and low kaolinite/chlorite and quartz/feldspar ratios are characteristic for this glacial source. Advection of kaolinite-rich suspensions from the North Sea is believed to account for higher kaolinite/chlorite ratios in the Mecklenburg Bight. A contribution of the rivers Trave and Oder to the western Baltic Sea is indicated by increased smectite values in marginal water bodies. They correspond to increased kaolinite/chlorite and quartz/feldspar ratios. In the main basins the river signal is diluted beyond recognition. Cores from the Arkona, Bornholm and Gotland Basins penetrate through post-Littorina muds and sediments of the Ancylus Lake/Yoldia Sea into Late Glacial sediments of the Baltic Ice Lake. Clay mineral assemblages are characterized by an increase in kaolinite/chlorite ratios from Late Glacial to Holocene sediments, with a distinct shift at each facies change. This allows the distinction and core to core correlation of main lithological units with kaolinite/chlorite ratios. Kaolinite enrichment of Holocene muds corresponds to a brackish-marine facies and may reflect influx of kaolinite-rich suspensions from the North Sea. Cores from the lagoon of the Oderhaff show fluctuations in the contributions of the two main sediment sources: river suspension and glacial deposits during the Late Glacial and Postglacial sequence. Lacustrine sediments, which were deposited prior to 5500 years B.P. are characterized by smectite, kaolinite and quartz from the drainage area of the Oder river. Erosion of coastal and offshore glacial boulder clays with the Littorina transgression supplied a marine component rich in illite, chlorite and feldspars to the brackish muds of the Oderhaff.