(Table 1) Chemical composition of plagioclase and amphibole-pyroxene containing samples from pyroxene-amphibole-asbestos rock collected in the Hess Deep

Recent sediments with distinct signs of hydrothermal alteration sampled in the Hess Deep(Galapagos Ridge, East Pacific Rise) contained a piece of ash-gray rock, which differed from other rock fragments by degree of consolidation, conchoidal fracture, and had properties of asbestos. Our studies found that the sample represented mixture of asbestos-like pyroxene of diopside-hedenbergite composition, amphibole of tremolite composition and a new mineral, which basic structure consisted of bands of triple pyroxene chains with the radical [Si6O16]. The latter can be regarded as intermediate between amphiboles and layered silicates. Also in some parts of the sample presence of trioctahedral vermiculite-chlorite was indicated. Genesis of the studied asbestos rock is considered from the standpoint of high-temperature hydrothermal-metasomatic alteration of sediment by post-magmatic mineralized halide solutions.

Geochemistry of recent sediments from the Indian Ocean

During the International Indian Ocean Expedition (1964/65) sediment cores were taken on six profiles off the western coast of the Indian Subcontinent. These profiles run approximately perpendicular to the coast, from the deep-sea over the continental slope to the continental shelf. Additional samples and cores were taken in a dense pattern in front of the delta of the Indus River. This pattern of sampling covered not only marine sediments, but also river and beach sediments in Pakistan. The marine samples were obtained with piston, gravity and box corers and by a Van Veen grab sampler. The longest piston core is about 5 meters long. 1. Distribution of the elements on the sediment surface The area of maximal carbonate values (aprox. 80-100% CaCO3) essentially coincides with the continental shelf. The highest Sr values were observed largely within this area, but only in the vicinity of the Gulf of Cambay. Mainly the aragonitic coprolites are responsible for those high Sr contents. The Mg contents of the carbonates are comparatively low; surprisingly enough the highest Mg concentrations were also measured in the coprolites. The maximum contents of organic matter (Core) were found along the upper part of the continental slope. They coincide with the highest porosity and water content of the sediments. Frequently the decomposition of organic matter by oxydation is responsible for the measured Corg contents. On the other side the quantity of originally deposited organic material is less important in most cases. The enrichment of the "bauxitophile" elements Fe, Ti, Cr and V in the carbonate- and quartz-free portions of the sediments is essentially due to the influence of coarse terrigenous detritus. For the elements Mn, Ni and Cu (in per cent of the carbonateand quartz-free sediment) a strong enrichment was observed in the deep-sea realm. The strong increase in Mn toward the deep-sea is explained by authigenesis of Mn-Fe-concretions. Mn-nodules form only under oxydizing conditions which obviously are possible only at very low rates of deposition. The Mg, B and, probably also Mn contents in the clay minerals increase with increasing distance from the continent. This can be explained by the higher adsorption of those elements from sea water because of increasing duration of the clay mineral transport. The comparison of median contents of some elements in our deep-sea samples with deep-sea sediments described by TUREKIAN & WEDEPOHL (1961) shows that clear differences in concentration exist only in the case of "bauxitophile" elements Cr and Be. The Cr and Be contents show a clear increase in the Indian Ocean deep-sea samples compared to those described by TUREKIAn & WEDEPOHL (1961) which can obviously be attributed to the enrichment in the lateritic and bauxitic parent rocks. The different behaviour of the elements Fe, Ti and Mn during decomposition of the source rocks, transport to the sea and during oxydizing and reducing conditions in the marine environment can be illustrated by Ti02/Fe and MnO/Fe ratios. The different compositions of the sediments off the Indus Delta and those of the remaining part of the area investigated are characterized by a different distribution of the elements Mn and Ti. 2. Chemical inhomogenities in the sediments Most longer cores show 3 intervals defined by chemical and sedimentological differences. The top-most interval is coarse-grained, the intermedial interval is fine grained and the lower one again somewhat coarser. At the same time it is possible to observe differences from interval to interval in the organogenic and detrital constituents. During the formation of the middle interval different conditions of sedimentation from those active during the previous and subsequent periods have obviously prevailed. Looking more closely at the organogenic constituents it is remarkable that during the formation of the finer interval conditions of a more intensive oxydation have prevailed that was the case before and after: Core decreases, whereas P shows a relative increase. This may be explained by slower sedimentation rate or by a vertical migration of the oxygen rich zone of the sea-water. The modifications of the elements from minerals in detrital portion of the sediments support an explanation ascribing this fact to modifications of the conditions of denudation and transportation which can come about through a climatic change or through tectonic causes. The paleontological investigations have shown (ZOBEL, in press) that in some of the cores the middle stratum of fine sedimentation represents optimal conditions for organic life. This fact suggests also oxydizing conditions during the sedimentation of this interval. In addition to the depositional stratification an oxydation zone characterized by Mn-enrichment can be recognized. The thickness of the oxidation zone decreases towards the coast and thins out along the middle part of the continental slope. At those places, where the oxydation zone is extremely thin, enrichment of Mn has its maximum. This phenomenon can probably be attributed to the migration of Mn taking place in its dissociated form within the sediment under reducing conditions. On the other side this Mn-migration in the sediment does not take place in the deep-sea, where oxydizing conditions prevail. 3. Interstitial waters in the sediments Already at very small core depths, the interstitial waters have undergone a distinct modification compared with the overlying sea water. This distinct modification applies both to total salinity and to the individual ions. As to the beginning of diagenesis the following conclusions can be drawn: a) A strong K-increase occurs already at an early stage. It may be attributable to a diffusion barrier or to an exchange of Mg-ions on the clays. Part of this increase may also originate from the decomposition of K-containing silicates (mica and feldspars). A K-decrease owing to the formation of illite (WEAVER 1967), however, occurs only at much greater sediment depth. b) Because of an organic protective coating, the dissolution of carbonate is delayed in recent organogenic carbonates. At the same time some Ca is probably being adsorbed on clay minerals. Consequently the Ca-content of the interstitial water drops below the Ca-content of the sea water. c) Already at an early stage the Mg adsorption on the clays is completed. The adsorbed Mg is later available for diagenetic mineral formations and transformations.

Oxygen and carbon isotope ratios of silicates and carbonates from exhumed peridotites in the Iberian Abyssal Plain

Legs 173 and 149 of the Ocean Drilling Program profiled a zone of exhumed mantle peridotite at the ocean-continent transition (OCT) beneath the Iberia Abyssal Plain. The zone of exhumed peridotite appears to be tens of kilometers wide and is situated between blocks of continental crust and the first products of ocean accretion. Exhumed peridotite is 95-100% serpentinised to probable depths of 2-3 km. Down core oxygen isotope profiles of serpentinised peridotite at Sites 1068 and 1070 (Leg 173) show evidence for two fluid infiltration events. The earlier event involved pervasive infiltration of comparatively warm (>175°C) sea water and accompanied serpentinisation. The later event involved structurally focused infiltration of comparatively cool (650-150°C) sea water and accompanied active mantle exhumation. We therefore conclude that the uppermost mantle was serpentinised before it was exhumed at the Iberian OCT. Implicit to this conclusion is that a sizeable region of serpentinised mantle existed directly beneath thinned but intact continental crust. Serpentinite has comparatively low density, low frictional strength and low permeability. The presence of such a "soft" layer may have localised deformation and consequently promoted detachment-style exhumation of the uppermost mantle. The low permeability of a serpentinite 'cap' layer might help to explain the lack of observed melt at the Iberian OCT.

(Table 1) Boron, carbon, magnesium and calcium isotope data, post-Marinoan Neoproterozoic carbonate sections, Namibia

A marked ocean acidification event and elevated atmospheric carbon dioxide concentrations following the extreme environmental conditions of the younger Cryogenian glaciation have been inferred from boron isotope measurements. Calcium and magnesium isotope analyses offer additional insights into the processes occurring during this time. Data from Neoproterozoic sections in Namibia indicate that following the end of glaciation the continental weathering flux transitioned from being of mixed carbonate and silicate character to a silicate-dominated one. Combined with the effects of primary dolomite formation in the cap dolostones, this caused the ocean to depart from a state of acidification and return to higher pH after climatic amelioration. Differences in the magnitude of stratigraphic isotopic changes across the continental margin of the southern Congo craton shelf point to local influences modifying and amplifying the global signal, which need to be considered in order to avoid overestimation of the worldwide chemical weathering flux.

Chemistry of smectite and volcanic glass of ODP Site 159-959

The Ocean Drilling Program (ODP) Site 959 was drilled in the northern border of the Côte d'Ivoire-Ghana Ridge at a water depth of 2100 m. Pleistocene total thickness does not exceed 20 m. Winnowing processes resulted in a low accumulation rate and notable stratigraphic hiatuses. During the Late Pleistocene, bottom circulation was very active and controlled laminae deposition (contourites) which increased the concentration of glauconitic infillings of foraminifera, and of volcanic glass and blue-green grains more rarely, with one or several subordinate ferromagnesian silicates. Volcanic glass generally was X-ray amorphous and schematically classified as basic to intermediate (44-60% SiO2). Opal-A or opal-CT suggested the beginning of the palagonitisation process, and previous smectitic deposits may have been eroded mechanically. The blue-green grains presented two main types of mineralogic composition: (1) neoformed K, Fe-smectite associated with zeolite (like phillipsite) and unequal amounts of quartz and anorthite; (2) feldspathic grains dominated by albite but including quartz, volcanic glass and smectites as accessory components. They were more or less associated with the volcanic glass. On the basis of their chemical composition, the genetic relationship between the blue-green grains and the volcanic glass seemed to be obvious although some heterogeneous grains seemed to be primary ignimbrite and not the result of glass weathering. The most reasonable origin of these pyroclastic ejecta would be explosive events from the Cameroon Volcanic Ridge, especially from the Sao Thome and Principe Islands and Mount Cameroon area. This is supported both by grain geochemistry and the time of volcanic activity, i.e. Pleistocene. After westward wind transport (some 1200 km) and ash fall-out, the subsequent winnowing by bottom currents controlled the concentration of the volcanic grains previously disseminated inside the hemipelagic sediment. Palagonitisation, and especially phillipsite formation, may result from a relatively rapid reaction during burial diagenesis (<1 m.y.), in deep-sea deposits at relatively low sedimentation rate. However, it cannot be excluded that the weathering had begun widely on the Cameroon Ridge before the explosive event.

Major and trace element composition of sepentine muds and metabasic rocks of ODP Leg 195 and Leg 125 sites

New geochemical data on serpentinite muds and metamorphic clasts recovered during Ocean Drilling Program Legs 195 (Holes 1200A-1200E) and 125 (Holes 778A and 779A) provide insights into the proportions of rock types of various sources that compose the serpentinite mudflows and the fluid-rock interactions that predominate in these muds. We interpret the metamorphic rock fragments as derivatives of mostly metamorphosed mafic rocks from the descending Pacific oceanic crust. Based on their mid-ocean-ridge basalt (MORB)-like Al2O3, TiO2, CaO, Si/Mg, and rare earth element (REE) systematics, these metamorphic rocks are classified as metabasalts/metagabbros and, therefore, ~30-km depths represent an active subduction zone setting. The serpentinite muds from Holes 1200A and 1200E have slightly lower REE when compared to Hole 1200D, but overall the REE abundance levels range between 0.1-1 x chondrite (CI) levels. The chondrite-normalized patterns have [La/Sm]N ~ 2.3 and [Sm/Yb]N ~ 2. With the exception of one sample, the analyzed metamorphic clasts show flat to slightly depleted light REE patterns with 1.0-15 x CI levels, resembling MORBs. Visually, ~6 vol% of the serpentinized muds are composed of 'exotic' materials (metamorphic clasts [schists]). Our mixing calculations confirm this result and show that the serpentinite muds are produced by additions of ~5% metamafic materials (with flat and up to 10 x CI REE levels) to serpentinized peridotite clast material (with very low REE abundances and U-shaped chondrite-normalized patterns). The preferential incorporation of B, Cs, Rb, Li, As, Sb, and Ba into the structure of H2O-bearing sheet silicates (different than serpentine) in the Leg 125 and Leg 195 metamorphic clasts (chlorite, amphibole, and micas) have little effect on the overall fluid-mobile element (FME) enrichments in the serpentinite muds (average B = ~13 ppm; average Cs = ~0.05 ppm; average As = ~1.25 ppm). The extent of FME enrichment in the serpentinized muds is similar to that described for the serpentinized peridotites, both recording interaction with fluids very rich in B, Cs, and As originating from the subducting Pacific slab.

Stable isotope and Magnesium/Calcium ratios of 4 profiles from the equatorial Pacific/Caribbean

This thesis examines the closure history of the Central American Seaway (CAS) and its effect on changes in ocean circulation and climate during the time interval from ~6 - 2.5 Ma. It was accomplished within the DFG Research Unit "Impact of Gateways on Ocean Circulation, Climate and Evolution" at the University of Kiel. Proxy records from Ocean Drilling Program (ODP) Sites 999 and 1000 (Caribbean), and from ODP Sites 1237, 1239 and 1241 (low-latitude east Pacific) are developed and examined. In addition, previously established proxy data from Atlantic Sites 925/926 (Ceara Rise) and 1006 (western Great Bahama Bank) and from two east Pacific sites (851, 1236) are included for interpretations. The main objectives of this study are (1) to acquire a consistent stratigraphic framework for all sites, (2) to reconstruct Pliocene changes in Caribbean and tropical east Pacific upper ocean water masses (i.e. temperature, salinity, thermocline depth), and (3) to identify potential underlying forcing mechanisms.

Haemolymph inorganic ion composition, physiology and behaviour dependent on temperature and ambient magnesium concentration in early life history stages of Paralomis granulosa (Decapoda, Anomura, Lithodidae)

Marine brachyuran and anomuran crustaceans are completely absent from the extremely cold (-1.8 °C) Antarctic continental shelf, but caridean shrimps are abundant. This has at least partly been attributed to low capacities for magnesium excretion in brachyuran and anomuran lithodid crabs ([Mg2+]HL = 20-50 mmol/L) compared to caridean shrimp species ([Mg2+]HL = 5-12 mmol/L). Magnesium has an anaesthetizing effect and reduces cold tolerance and activity of adult brachyuran crabs. We investigated whether the capacity for magnesium regulation is a factor that influences temperature-dependent activity of early ontogenetic stages of the Sub-Antarctic lithodid crab Paralomis granulosa. Ion composition (Na+, Mg2+, Ca2+, Cl-, [SO4]2-) was measured in haemolymph withdrawn from larval stages, the first and second juvenile instars (crabs I and II) and adult males and females. Magnesium excretion improved during ontogeny, but haemolymph sulphate concentration was lowest in the zoeal stages. Neither haemolymph magnesium concentrations nor Ca2+:Mg2+ ratios paralleled activity levels of the life stages. Long-term (3 week) cold exposure of crab I to 1 °C caused a significant rise of haemolymph sulphate concentration and a decrease in magnesium and calcium concentrations compared to control temperature (9 °C). Spontaneous swimming activity of the zoeal stages was determined at 1, 4 and 9 °C in natural sea water (NSW, [Mg2+] = 51 mmol/L) and in sea water enriched with magnesium (NSW + Mg2+, [Mg2+] = 97 mmol/L). It declined significantly with temperature but only insignificantly with increased magnesium concentration. Spontaneous velocities were low, reflecting the demersal life style of the zoeae. Heart rate, scaphognathite beat rate and forced swimming activity (maxilliped beat rate, zoea I) or antennule beat rate (crab I) were investigated in response to acute temperature change (9, 6, 3, 1, -1 °C) in NSW or NSW + Mg2+. High magnesium concentration reduced heart rates in both stages. The temperature-frequency curve of the maxilliped beat (maximum: 9.6 beats/s at 6.6 °C in NSW) of zoea I was depressed and shifted towards warmer temperatures by 2 °C in NSW + Mg2+, but antennule beat rate of crab I was not affected. Magnesium may therefore influence cold tolerance of highly active larvae, but it remains questionable whether the slow-moving lithodid crabs with demersal larvae would benefit from an enhanced magnesium excretion in nature.

Haemolymph inorganic ion composition, physiology and behaviour dependent on temperature and magnesium in adult Paralomis granulosa (Decapoda, Anomura, Lithodidae)

A low capacity for regulation of extracellular Mg2+ has been proposed to exclude reptant marine decapod crustaceans from temperatures below 0°C and thus to exclude them from the high Antarctic. To test this hypothesis and to elaborate the underlying mechanisms in the most cold-tolerant reptant decapod family of the sub-Antarctic, the Lithodidae, thermal tolerance was determined in the crab Paralomis granulosa (Decapoda, Anomura, Lithodidae) using an acute stepwise temperature protocol (-1°, 1°, 4°, 7°, 10°, and 13°C). Arterial and venous oxygen partial pressures (Po2) in hemolymph, heartbeat and ventilation beat frequencies, and hemolymph cation composition were measured at rest and after a forced activity (righting) trial. Scopes for heartbeat and ventilation beat frequencies and intermittent heartbeat and scaphognathite beat rates at rest were evaluated. Hemolymph [Mg2+] was experimentally reduced from 30 mmol/L to a level naturally observed in Antarctic caridean shrimps (12 mmol/L) to investigate whether the animals remain more active and tolerant to cold (-1°, 1°, and 4°C). In natural seawater, righting speed was significantly slower at -1° and 13°C, compared with acclimation temperature (4°C). Arterial and venous hemolymph Po2 increased in response to cooling even though heartbeat and ventilation beat frequencies as well as scopes decreased. At rest, ionic composition of the hemolymph was not affected by temperature. Activity induced a significant increase in hemolymph [K+] at -1° and 1°C. Reduction of hemolymph [Mg2+] did not result in an increase in activity, an increase in heartbeat and ventilation beat frequencies, or a shift in thermal tolerance to lower temperatures. In conclusion, oxygen delivery in this cold-water crustacean was not acutely limiting cold tolerance, and animals may have been constrained more by their functional capacity and motility. In contrast to earlier findings in temperate and subpolar brachyuran crabs, these constraints remained insensitive to changing Mg2+ levels.

Magnesium/Calcium ratios measured on planktonic foraminifera of the LGM

As part of the Multi-proxy Approach for the Reconstruction of the Glacial Ocean (MARGO) incentive, published and unpublished temperature reconstructions for the Last Glacial Maximum (LGM) based on planktonic foraminiferal Mg/Ca ratios have been synthesised and made available in an online database. Development and applications of Mg/Ca thermometry are described in order to illustrate the current state of the method. Various attempts to calibrate foraminiferal Mg/Ca ratios with temperature, including culture, trap and core-top approaches have given very consistent results although differences in methodological techniques can produce offsets between laboratories which need to be assessed and accounted for where possible. Dissolution of foraminiferal calcite at the sea-floor generally causes a lowering of Mg/Ca ratios. This effect requires further study in order to account and potentially correct for it if dissolution has occurred. Mg/Ca thermometry has advantages over other paleotemperature proxies including its use to investigate changes in the oxygen isotopic composition of seawater and the ability to reconstruct changes in the thermal structure of the water column by use of multiple species from different depth and or seasonal habitats. Presently available data are somewhat limited to low latitudes where they give fairly consistent values for the temperature difference between Late Holocene and the LGM (2-3.5 °C). Data from higher latitudes are more sparse, and suggest there may be complicating factors when comparing between multi-proxy reconstructions.

Geochemistry of minerals in medium-grained diabase from ODP Holes 137-504B and 140-504B

Samples recovered from Hole 504B during Leg 140 include a number of medium-grained, holocrystalline diabases that appear to represent the cores of thick dikes. The plagioclase and pyroxene in these samples occur in a variety of crystal morphologies. Plagioclase occurs as phenocrysts, microphenocrysts, elongate crystals, skeletal crystals, and branching radial clusters. Pyroxene occurs as phenocrysts, microphenocrysts, ophitic crystals, and poikilitic crystals. Plagioclase compositions became progressively poorer in anorthite and MgO and progressively richer in FeO as crystallization proceeded, while the average grain volume decreased and the aspect ratio of individual grains increased. Pyroxene compositions are largely independent of crystal morphology. The diabase dikes recovered from Hole 504B during Leg 140 appear to have crystallized in situ. Crystal compositions and morphologies are consistent with a rapid cooling rate and solidification times for individual dikes on the order of hours or days. The crystallization rate and nucleation rate of plagioclase lagged behind the cooling rate so that the degree of undercooling progressively increased as crystallization proceeded. Plagioclase crystal morphologies indicate much greater degrees of supersaturation than do pyroxene or olivine crystal morphologies. The 504B diabase magmas appear to have been emplaced with abundant preexisting pyroxene and olivine nuclei, but with few preexisting plagioclase nuclei. The suppression of plagioclase nucleation and crystallization relative to that of pyroxene and olivine could provide a mechanism by which the actual fractionation assemblage is more pyroxene-rich and plagioclase-poor than that predicted from thermodynamic models, or that observed in isothermal crystallization experiments.

Chemical composition of ultrabasites and composing minerals from the Tonga Trench

A petrologic-geochemical study (petrochemistry, contents of siderophile and certain lithophile elements, composition of rock-forming silicates and accessory chrome spinels) of ultrabasic rocks dredged from the arc side in the northern end of the Tonga deep-sea trench has been carried out. The ultrabasites included harzburgites and dunites. Peridotites show clearly manifested material characteristics of ultrabasic relicts strongly depleted in low-temperature basaltic components. It is suggested that they have arose in the high degree of partial melting (about 30%) of a matrix mantle source of the lherzolite type. Great similarity of the rocks studied with ultrabasites of many ophiolites that are widespread in folded belts indicates that young island arcs are among the most likely geodynamic environments of ophiolite generation.

Chemical and isotopical analsyes of DSDP Hole 34-321 basalts

A blue-green smectite (iron-rich saponite) and green mica (celadonite) are the dominant sheet silicates in veins within the 10.5 m of basalt cored during DSDP Leg 34, Site 32l, in the Nazca plate. Oxygen isotopic analyses of these clays, and associated calcite, indicate a formation temperature of <25°C. Celadonite contains appreciable Fe2O3, K2O and SiO2, intermediate MgO, and very little Al2O3. Celadonite is commonly associated with goethite and hematite, which suggests that this phase formed by precipitation within a dominantly oxygenated environment of components leached from basalt and provided by seawater. A mass balance estimate indicates that celadonite formation can remove no more than 15% of the K annually transported to the oceans by rivers. In contrast, iron-rich saponite containing significant Al2O3 appears to have precipitated from a nonoxidizing, distinctly alkaline fluid containing a high Na/K ratio relative to unmodified seawater. Seawater-basalt interaction at low temperatures, resulting in the formation of celadonite and smectite may explain chemical gradients observed in interstitial waters of sediments overlying basalts.

Geochemistry of primary and secondary mineral phases in ODP Leg 209 sediments

Primary and secondary mineral phases from Holes 1268A (11 samples), 1272A (9 samples), and 1274A (12 samples) were analyzed by electron microprobe in Bonn and Cologne (Germany). Bulk rock powders of these samples were also analyzed geochemically, including major and trace elements (Paulick et al., 2006, doi:10.1016/j.chemgeo.2006.04.011). Ocean Drilling Program (ODP) Leg 209 Holes 1268A, 1272A, and 1274A differ remarkably in alteration intensity and mineralogy, and details regarding their lithologic characteristics are presented in Bach et al. (2004, doi:10.1029/2004GC000744) and Shipboard Scientific Party (2004, doi:10.2973/odp.proc.ir.209.101.2004). Because of the least altered character of peridotite in Hole 1274A, abundant clinopyroxene, orthopyroxene, olivine, and spinel were analyzed at this site. In Hole 1272A, primary silicates are rare and analyses were restricted to some samples that contain traces of olivine and orthopyroxene. Because of the intensity of alteration, Hole 1268A is devoid of primary phases except spinel. Commonly, alteration is pseudomorphic and serpentinization of olivine and orthopyroxene can be distinguished. Accordingly, compositional variations of the alteration minerals with regard to the precursor minerals are one of the issues investigated in this data report.