Geochemistry and minerals at DSDP Hole 70-504B

In three veins from the lower part of Deep Sea Drilling Project Hole 504B, 298 meters below the top of basement, primary augite is replaced by aegirine-augite. This transformation occurs only in subophitic basalts, at the contact with veins which always include a dark-olive, Mg-rich clay mineral. Talc occurs in one of these veins; it can be regarded either as a vein constituent or as a product of augite alteration. Melanite (Ca,Fe,Ti-rich garnet) appears in only one of these three veins, where a Ca-carbonate is associated with a Mg-rich clay mineral. The occurrence of melanite in Hole 504B could be due to the conjunction of particular conditions: (1) basalt with a subophitic texture, (2) presence of hydrothermal fluids carrying Ca, Fe, Si, Ti, Al, Mg, and Na, (3) rather high temperatures. Possibly the melanite and aegirine-augite formed by deuteric alteration.

Magnetic properties and geochemistry in DSDP Holes 69-504B an d 69-505B

More than 60 basalt samples from two Deep Sea Drilling Project holes on the Costa Rica Rift were studied for magnetic properties and were found to have no properties significantly different from other DSDP basalts. Opaque mineralogical and thermomagnetic properties of these samples, however, to some extent show differences from normal submarine basalts; a new type of thermomagnetic curve and wide range of chemical compositions were recognized. Oxidized samples possibly containing incipient ilmenite exsolution lamellae were reduced and re-equilibrated during heating. The Curie temperatures of the re-equilibrated titanomagnetites are interpreted to be those of the original crystallized phase before oxidation.

Sedimentology on profiles from Lake Prespa, Greece

Hydro-acoustic surveys and coring campaigns at Lake Prespa were carried out between 2007 and 2009. This paper presents hydro-acoustic profiles and provide lithological and chronostratigraphical information from three up to 15.75 m long sediment sequences from the Macedonian side of the lake. The sediment sequences comprise glacial and interglacial sediments likely deposited from the end of Marine Isotope Stage (MIS) 5 to present day. The information implies a distinct change of sedimentation patterns at the Pleistocene/Holocene transition and the establishment of a relatively strong Holocene current system and deposition of channel-related contourite drift in Lake Prespa. Potential causes for the establishment of this current during the Holocene include significant lake level change, reduced winter ice cover, and/or higher aeolian activity.

Seismic velocities and elastic properties of gabbroic rocks from ODP Hole 118-735B

The nearly continuous recovery of 0.5 km of generally fresh, layer 3 gabbroic rocks at Hole 735B, especially near the bottom of the section, presents scientists an unusual opportunity to study the detailed elastic properties of the lower oceanic crust. Extending compressional-wave and density shipboard measurements at room pressure, Vp and Vs were measured at pressures from 20 to 200 MPa using the pulse transmission method. All of the rocks exhibit significant increases in velocity with increasing pressure up to about 150 MPa, a feature attributed to the closing of microcrack porosity. Measured velocities reflect the mineralogical makeup and microstructures acquired during the tectonic history of Hole 735B. Most of the undeformed and unaltered gabbros are approximately 65:35 plagioclase/clinopyroxene rocks plus olivine or oxide minerals, and the observed densities and velocities are fully consistent with the Voigt-Reuss-Hill (VRH) averages of the component minerals and their proportions. Depending on their olivine content, the predominant olivine gabbros at 200 MPa have average Vp = 7.1 ± 0.2 km/s, Vs = 3.9 ± 0.1 km/s, and grain densities of 2.95 ± 0.5 g/cm3. The less abundant iron-titanium (Fe-Ti) oxide gabbros average Vp = 6.75 ± 0.15 km/s, Vs = 3.70 ± 0.1 km/s, and grain densities of 3.22 ± 0.05 g/cm3, reflecting the higher densities and lower velocities of oxide minerals compared to olivine. About 30% of the core is plastically deformed, and the densities and directionally averaged velocities of these shear-zone tectonites are generally consistent with those of the gabbros, their protoliths. Three sets of observations indicate that the shear-zone metagabbros are elastically anisotropic: (1) directional variations in Vp, both vertical and horizontal and with respect to foliation and lineation; (2) discrepancies among Vp values for the horizontal cores and the VRH averages of the component minerals and their mineral proportions, suggesting preferred crystallographic orientations of anisotropic minerals; and (3) variations of Vs of up to 7%, with polarization directions parallel and perpendicular to foliation. Optical inspection of thin sections of the same samples indicates that plagioclase feldspar, clinopyroxene, and amphibole typically display crystallographic-preferred orientations, and this, plus the elastic anisotropy of these minerals, suggests that preferred orientations are responsible for much of the observed anisotropy, particularly at high pressure. Alteration tends to be localized to brittle faults and brecciated zones, and typical alteration minerals are amphibole and secondary plagioclase, which do not significantly change the velocity-density relationships.

Geochemistry of sediment cores from the Rainbow vent site

A geochemical investigation was carried out on two sediment cores collected at 2 and 5 km from the Rainbow hydrothermal vent site. Bulk sediment compositions indicate that these cores record clear enrichments in Fe, Cu, Mn, V, P and As from hydrothermal plume fallout (Cave et al., 2002, doi:10.1016/S0016-7037(02)00823-2). Sequential dissolution of the bulk sediments has been used to discriminate between a leach (biogenic and oxy-hydroxide) component and a residual phase (detrital and sulphide/sulphate fractions). Major element data (Al, Fe, Ti, Mn, Mg, Ca, Si and index%) reveal that the hydrothermal input, as recorded in the leach phase, is much stronger than apparent from bulk sediment analyses alone. REE patterns for the leach phase record contributions from both biogenic carbonate (mimicking seawater REE patterns) and hydrothermal oxy-hydroxides, with the latter exhibiting positive Eu anomalies (hydrothermal derived) and negative Ce anomalies (seawater derived). Based on major element and REE data, the residue contains contributions from aeolian dust input, local MORB material and a hydrothermal component. Ternary REE mixing calculations indicate that most of the REE within the residual fraction (~80%) is derived from hydrothermal material, while detrital contributions to the REE budget, as deep-sea clay and volcanic debris, are <20%. By combining bulk and REE data for the various end-member components of the residue, we calculate that the chemical composition of the residue hydrothermal end-member is high in Ca (6-15%) and with a Nd/Sr ratio of 0.004. These characteristics indicate the presence of low-solubility hydrothermal sulphate (rather than sulphide) material within the residue component of Rainbow hydrothermal sediments.

Physical properties, velocity and attenuation characteristics, and mineralogy of gabbros from ODP Hole 176-735B

Laboratory compressional wave (Vp) and shear wave (Vs) velocities were measured as a function of confining pressure for the gabbros from Hole 735B and compared to results from Leg 118. The upper 500 m of the hole has a Vp mean value of 6895 m/s measured at 200 MPa, and at 500 meters below seafloor (mbsf), Vp measurements show a mean value of 7036 m/s. Vs mean values in the same intervals are 3840 m/s and 3857 m/s, respectively. The mean Vp and Vs values obtained from log data in the upper 600 m are 6520 and 3518 m/s, respectively. These results show a general increase in velocity with depth and the velocity gradients estimate an upper mantle depth of 3.32 km. This value agrees with previous work based on dredged samples and inversion of rare element concentrations in basalts dredged from the conjugate site to the north of the Atlantis Bank. Laboratory measurements show Vp anisotropy ranging between 0.4% and 8.8%, with the majority of the samples having values less than 3.8%. Measurements of velocity anisotropy seem to be associated with zones of high crystal-plastic deformation with predominant preferred mineral orientations of plagioclase, amphiboles, and pyroxenes. These findings are consistent with results on gabbros from the Hess Deep area and suggest that plastic deformation may play an important role in the seismic properties of the lower oceanic crust. In contrast to ophiolite studies, many of the olivine gabbros show a small degree of anisotropy. Log derived Vs anisotropy shows an average of 5.8% for the upper 600 m of Hole 735B and tends to decrease with depth where the overburden pressure and the age of the crustal section suggests closure of cracks and infilling of fractures by alteration minerals. Overall the results indicate that the average shear wave splitting in Hole 735B might be influenced by preferred structural orientations and the average value of shear wave splitting may not be a maximum because structural dips are <90°. The maximum fast-wave orientation values could be influenced by structural features striking slightly oblique to this orientation or by near-field stress concentrations. However, flexural wave dispersion analyses have not been performed to confirm this hypothesis or to indicate to what extent the near-field stresses may be influencing shear wave propagation. Acoustic impedance contrasts calculated from laboratory and logging data were used to generate synthetic seismograms that aid in the interpretation of reflection profiles. Several prominent reflections produced by these calculations suggest that Fe-Ti oxides and shear zones may contribute to the reflective nature of the lower oceanic crust. Laboratory velocity attenuation (Q) measurements from below 500 m have a mean value of 35.1, which is consistent with previous vertical seismic profile (VSP) and laboratory measurements on the upper 500 m.

Geochemical data from pore water and solids from cores GS08-153-91GC12 and GS08-153-53-GC6, Arctic Mid-Ocean Ridge

Microbial communities and their associated metabolic activity in marine sediments have a profound impact on global biogeochemical cycles. Their composition and structure are attributed to geochemical and physical factors, but finding direct correlations has remained a challenge. Here we show a significant statistical relationship between variation in geochemical composition and prokaryotic community structure within deep-sea sediments. We obtained comprehensive geochemical data from two gravity cores near the hydrothermal vent field Loki's Castle at the Arctic Mid-Ocean Ridge, in the Norwegian-Greenland Sea. Geochemical properties in the rift valley sediments exhibited strong centimeter-scale stratigraphic variability. Microbial populations were profiled by pyrosequencing from 15 sediment horizons (59,364 16S rRNA gene tags), quantitatively assessed by qPCR, and phylogenetically analyzed. Although the same taxa were generally present in all samples, their relative abundances varied substantially among horizons and fluctuated between Bacteria- and Archaea-dominated communities. By independently summarizing covariance structures of the relative abundance data and geochemical data, using principal components analysis, we found a significant correlation between changes in geochemical composition and changes in community structure. Differences in organic carbon and mineralogy shaped the relative abundance of microbial taxa. We used correlations to build hypotheses about energy metabolisms, particularly of the Deep Sea Archaeal Group, specific Deltaproteobacteria, and sediment lineages of potentially anaerobic Marine Group I Archaea. We demonstrate that total prokaryotic community structure can be directly correlated to geochemistry within these sediments, thus enhancing our understanding of biogeochemical cycling and our ability to predict metabolisms of uncultured microbes in deep-sea sediments.

Geochemistry measured on sediment core GeoB12309-5

Laminated sediment records from the oxygen minimum zone in the Arabian Sea offer unique ultrahigh-resolution archives for deciphering climate variability in the Arabian Sea region. Although numerous analytical techniques are available it has become increasingly popular during the past decade to analyze relative variations of sediment cores' chemical signature by non-destructive X-ray fluorescence (XRF) core scanning. We carefully selected an approximately 5 m long sediment core from the northern Arabian Sea (GeoB12309-5: 24°52.3' N; 62°59.9' E, 956 m water depth) for a detailed, comparative study of high-resolution techniques, namely non-destructive XRF core scanning (0.8 mm resolution) and ICP-MS/OES analysis on carefully selected, discrete samples (1 mm resolution). The aim of our study was to more precisely define suitable chemical elements that can be accurately analyzed and to determine which elemental ratios can be interpretated down to sub-millimeter-scale resolutions. Applying the Student's t-test our results show significantly correlating (1% significance level) elemental patterns for all S, Ca, Fe, Zr, Rb, and Sr, as well as the K/Ca, Fe/Ti and Ti/Al ratios that are all related to distinct lithological changes. After careful consideration of all errors for the ICP analysis we further provide respective factors of XRF Core Scanner software error's underestimation by applying Chi-square-tests, which is especially relevant for elements with high count rates. As demonstrated by these new, ultra-high resolution data core scanning has major advantages (high-speed, low costs, few sample preparation steps) and represents an increasingly required alternative over the time consuming, expensive, elaborative, and destructive wet chemical analyses (e.g., by ICP-MS/OES after acid digestions), and meanwhile also provides high-quality data in unprecedented resolution.

Chemistry of bulk-rocks and minerals of ODP Hole 120-748C

Five hundred meters of a unique Upper Cretaceous Cr-rich glauconitic sequence (Unit III) that overlies a 3-m-thick alkali-basalt flow with underlying epiclastic volcanogenic sediments was drilled at ODP Leg 120 Site 748. The Cr-rich glauconitic sequence is lithostratigraphically and biostratigraphically divided into three subunits (IIIA, IIIB, IIIC) that can also be recognized by the Cr concentration of the bulk sediment, which is low (<200 ppm) in Subunits IIIC and IIIA and high (400-800 ppm) in Subunit IIIB. The Cr enrichment is caused by Cr-spinel, which is the only significant heavy mineral component beside Fe-Ti ores. Other Cr-bearing components are glauconite pellets and possibly some other clay minerals. The glauconitic sequence of Subunit IIIB was formed by reworking of glauconite and volcanogenic components that were transported restricted distances and redeposited downslope by mass-transportation processes. The site of formation was a nearshore, shallow inner shelf environment, and final deposition may have been on the outer part of a narrow shelf, at the slope toward the restricted, probably synsedimentary, faulted Raggatt Basin. The volcanic edifices uncovered on land were tholeiitic basalts (T-MORB), alkali-basaltic (OIB) and (?)silicic volcanic complexes, and ultramafic rocks. The latter were the ultimate source for the Cr-spinel contribution. Terrestrial aqueous solutions carried Fe, K, Cr, Si, and probably Al into the marine environment, where, depending on the redox conditions of microenvironments in the sediment, green (Fe- and K-rich) or brown (Al-rich) glauconite pellets formed. The Upper Cretaceous glauconitic sequence at Site 748 on the Southern Kerguelen Plateau constitutes the transition in space and time from terrestrial to marine, from magmatically active subaerial to magmatically passive submarine conditions, and from a tranquil platform to active rifting conditions.

Low-temperature magnetic remanence and hysteresis measurements on sediment core GeoB4901-8 from the Niger deep-sea fan

Low-temperature (LT) magnetic remanence and hysteresis measurements, in the range 300-5 K, were combined with energy dispersive spectroscopy (EDS) in order to characterize the magnetic inventory of strongly diagenetically altered sediments originating from the Niger deep-sea fan. We demonstrate the possibility of distinguishing between different compositions of members of the magnetite-ulvöspinel and ilmenite-hematite solid solution series on a set of five representative samples, two from the upper suboxic and three from the lower sulfidic anoxic zone of gravity core GeoB 4901. Highly sensitive LT magnetic measurements were performed on magnetic extracts resulting in large differences in the magnetic behavior between samples from the different layers. This emphasizes that both Fe-Ti oxide phases occur in different proportions in the two geochemical environments. Most prominent are variations in the coercivity sensitive parameter coercive field (BC). At room-temperature (RT) hysteresis loops for all extracts are narrow and yield low coercivities (6-13 mT). With decreasing temperature the loops become more pronounced and wider. At 5 K an approximately 5-fold increase in BC for the suboxic samples contrasts a 20-25-fold increase for the samples from the anoxic zone. We demonstrate that this distinct increase in BC at LT corresponds to the increasing proportion of the Ti-rich hemoilmenite phase, while Fe-rich (titano-)magnetite dominates the magnetic signal at RT. This trend is also seen in the room-temperature saturation isothermal remanent magnetization (RT-SIRM) cycles: suboxic samples show remanence curves dominated by Fe-rich mineral phases while anoxic samples display curves clearly dominated by Ti-rich particles. We show that the EDS intensity ratios of the characteristic Fe Kalpha and Ti Kalpha lines of the Fe-Ti oxides may be used to differentiate between members of the magnetite-ulvöspinel and ilmenite-hematite solid solution series. Furthermore it is possible to calculate an approximate composition for each grain if the intensity ratios of natural particles are linked to well-known standards. Thus, element spectra with high Fe/Ti intensity ratios were found to be rather typical of titanomagnetite while low Fe/Ti ratios are indicative of hemoilmenite. The EDS analyses confirm the LT magnetic results, Fe-rich magnetic phases dominate in the upper suboxic environment whereas Ti-rich magnetic phases comprise the majority of particles in the lower anoxic domain: The mineral assemblage of the upper suboxic environments is composed of magnetite (~19%), titanomagnetite (~62%), hemoilmenite (~17%) and ~2% other particles. In the lower anoxic sediments, reductive diagenetic alteration has resulted in more extensive depletion of the (titano-)magnetite phase, resulting in a relative enrichment of the hemoilmenite phase (~66%). In these strongly anoxic sediments stoichiometric magnetite is barely preserved and only ~5% titanomagnetite was detected. The remaining ~28% comprises Ti-rich particles such as pseudobrookite or rutile.

Reflection microscopy and geochemistry at DSDP Leg 55 Holes

Magnetic properties of volcanic rocks are controlled mainly by the physical and chemical state of their constituent ferromagnetic minerals. The most important parameters determining magnetic properties are concentration, composition, grain size, and oxidation state. In sea floor basalts, the main ferromagnetic minerals are titanomagnetites which are either unoxidized or, more commonly, have undergone various degrees of posteruptive low-temperature oxidation to become cationdeficient titanomagnetites, or titanomaghemites. The effects of this low-temperature alteration are seen in the increase of Curie temperature and decrease of saturation magnetization and lattice parameter of ferromagnetic minerals (Readman and O'Reilly, 1972). It is now believed that titanomaghemitization of newly formed mid-ocean ridge crust proceeds with a time constant of about 1 m.y., accompanying drastic decrease of the intensity of the natural remanent magnetization (NRM) (Johnson and Atwater, 1977).

Mineralogy and textures of gabbros from ODP Hole 118-735B

Abundant iron-titanium (Fe-Ti) oxide gabbro, olivine gabbro, and troctolite were drilled at Hole 735B adjacent to the Atlantis II Fracture Zone of the Southwest Indian Ridge during Leg 118. The Fe-Ti oxide gabbro occurs as intrusive bodies into olivine gabbro with very sharp intrusive contacts. The size of the intrusive bodies varies from a millimeter to a few tens of meters. Mineralogical parameters, such as anorthite content of plagioclase and Mg/(Mg+Fe) ratios of mafic minerals exhibit bimodal distributions corresponding to olivine and Fe-Ti oxide gabbros, respectively. When the two major gabbro types are looked at separately, several downhole mineralogical cycles are recognized. The Fe-Ti oxide gabbros exhibit two such cycles with plagioclase becoming more sodic and mafic minerals becoming more iron-rich downward in the drill core. The olivine gabbros and troctolites, however, exhibit two cycles showing an upward increase in sodium in plagioclase and iron in mafic minerals. The mineralogical variations of these gabbros and the intrusive contact relationships probably resulted from downward intrusion of evolved magma into underlying solid or almost solidified olivine gabbros and troctolite. The dense evolved melt at the top of the cumulus pile probably formed from the crystallization of olivine gabbro cumulates followed by extreme fractional crystallization of residual melt in an isolated, ephemeral magma chamber. The interlayered occurrence of evolved and primitive gabbros from Hole 735B represents a typical section of lower ocean crust formed at a very slow spreading ridge.

Sedimentology and geochemistry of ODP Leg 129 siliceous deposits

Siliceous deposits drilled on Ocean Drilling Program Leg 129 accumulated within a few degrees of the equator during the Jurassic through early Tertiary, as constrained by paleomagnetic data. During the Jurassic and Early Cretaceous, radiolarian ooze, mixed with a minor amount of pelagic clay, was deposited near the equator, and overall accumulation rates were moderate to low. At a smaller scale, in more detail, periods of relatively higher accumulation rates alternated with periods of very low accumulation rates. Higher rates are represented by radiolarite and limestone; lower rates are represented by radiolarian claystone. Our limited data from Leg 129 suggests that accumulation of biogenic deposits was not symmetrical about the equator or consistent over time. In the Jurassic, sedimentation was siliceous; in the Cretaceous there was significant calcareous deposition; in the Tertiary claystone indicates significantly lower accumulation rates at least the northern part of the equatorial zone. Accumulation rates for Leg 129 deposits in the Cretaceous were higher in the southern part of the equatorial zone than in the northern part, and the southern side of this high productivity zone extended to approximately 15°S, while the northern side extended only to about 5°N. Accumulation rates are influenced by relative contributions from various sediment sources. Several elements and element ratios are useful for discriminating sedimentary sources for the equatorial depositional environments. Silica partitioning calculations indicate that silica is dominantly of biogenic origin, with a detrital component in the volcaniclastic turbidite units, and a small hydrothermal component in the basal sediments on spreading ridge basement of Jurassic age at Site 801. Iron in Leg 129 sediments is dominantly of detrital origin, highest in the volcaniclastic units, with a minor hydrothermal component in the basal sediments at Site 801. Manganese concentrations are highest in the units with the lowest accumulation rates. Fe/Mn ratios are >3 in all units, indicating negligible hydrothermal influence. Magnesium and aluminum concentrations are highest in the volcaniclastic units and in the basal sediments at Site 801. Phosphorous is very low in abundance and may be detrital, derived from fish parts. Boron is virtually absent, as is typical of deep-water deposits. Rare earth element concentrations are slightly higher in the volcaniclastic deposits, suggesting a detrital source, and lower in the rest of the lithologic units. Rare earth element abundances are also low relative to "average shale." Rare earth element patterns indicate all samples are light rare earth element enriched. Siliceous deposits in the volcaniclastic units have patterns which lack a cerium anomaly, suggesting some input of rare earth elements from a detrital source; most other units have a distinct negative Ce anomaly similar to seawater, suggesting a seawater source, through adsorption either onto biogenic tests or incorporation into authigenic minerals for Ce in these units. The Al/(Al + Fe + Mn) ratio indicates that there is some detrital component in all the units sampled. This ratio plotted against Fe/Ti shows that all samples plot near the detrital and basalt end-members, except for the basal samples from Site 801, which show a clear trend toward the hydrothermal end-member. The results of these plots and the association of high Fe with high Mg and Al indicate the detrital component is dominantly volcaniclastic, but the presence of potassium in some samples suggests some terrigenous material may also be present, most likely in the form of eolian clay. On Al-Fe-Mn ternary plots, samples from all three sites show a trend from biogenic ooze at the top of the section downhole to oceanic basalt. On Si-Fe-Mn ternary plots, the samples from all three sites fall on a trend between equatorial mid-ocean spreading ridges and north Pacific red clay. Copper-barium ratios show units that have low accumulation rates plot in the authigenic field, and radiolarite and limestone samples that have high accumulation rates fall in the biogenic field.