Micropaleontological and geochemical proxy studies of sediment core GeoB7926-2

[1] The low-latitude upwelling regime off the Mauritanian coast in the subtropical NE Atlantic accounts for a significant part of global export production. Although productivity variations in coastal upwelling areas are usually attributed to changes in wind stress and upwelling intensity, productivity dynamics off Mauritania are less straightforward because of the complex atmospheric and hydrographic setting. Here we integrate micropaleontological (diatoms) and geochemical (bulk biogenic sediment components, X-ray fluorescence, and alkenones) proxies to examine on submillennial-to-millennial changes in diatom production that occurred off Mauritania, NW Africa, for the last 25 ka. During the Last Glacial Maximum (LGM, 19.0-23.0 ka B.P.), moderate silicate content of upwelled waters coupled with weakened NE trade winds determined moderate diatom productivity. No significant cooling is observed during the LGM, suggesting that our alkenone-based SST reconstruction represents a local, upwelling-related signal rather than a global insolation related one. Extraordinary increases in diatom and opal concentrations during Heinrich event 1 (H1, 15.5-18.0 ka B.P.) and the Younger Dryas (YD, 13.5-11.5 ka B.P.) are attributed to enhanced upwelling of silica-rich waters and an enlarged upwelling filament, due to more intense NE trade winds. The synchronous increase of CaCO3 and K intensity and the decreased opal and diatoms values mark the occurrence of the Bølling/Allerød (BA, 13.5-15.5 ka B.P.) due to weakened eolian input and more humid conditions on land. Although the high export of diatoms is inextricably linked to upwelling intensity off Mauritania, variability in the nutrient content of the thermocline also plays a decisive role.

Geological, geochemical and biogeochemical data on boundary zones of the Atlantic Ocean

Results of studies in two biogeochemically active zones of the Atlantic Ocean (the Benguela upwelling waters and the region influenced by the Congo River run-off) are reported in the book. A multidisciplinary approach included studies of the major elements of the ocean ecosystem: sea water, plankton, suspended matter, bottom sediments, interstitial waters, aerosols, as well as a wide complex of oceanographic studies carried out under a common program. Such an approach, as well as a use of new methodical solutions led to obtaining principally new information on different aspects of oceanology.

Geochemical composition and ages of sediment core BELQ300 obtained from Lake Belau, north Germany

Geochemical and palynological data from an annually laminated core sequence (Lake Belau, Schleswig-Holstein) are interpreted with respect to vegetation and settlement history on the basis of a chronostratigraphical model and archaeological evidence. Most settlement periods indicated by pollen and archaeological data can be geochemically identified in the sediment sequence using tracer elements such as K, Rb, Zr and the K/Zr ratio. Whilst air-borne pollen carry a more regional signal, the sedimentary flux of these trace elements is determined by the allogenic input from the catchment area of the lake and, therefore, provides information about the local history of settlement and agricultural land use in the lake's vicinity. This is exemplified for the period of the middle Neolithic Funnel Beaker Culture ('Iversen landnam'), where a time offset of 250 years between both signals has been detected. In contrast, both geochemical and pollen signals are highly synchronous during the Early Migration Period and the High Medieval Period. Additionally, the Fe/Ca and/or U/Fe ratio may serve as a sensitive tracer for human impact on the trophic state of the lake. The suggested impact of the Romans and the High Medieval civilization can clearly be seen (and quantified) from elevated lead input into Lake Belau sediments at this time. Effects of secular climatic changes on the sedimentary chemistry have not been detected and, if present, seem to have been obliterated by anthropogenic activity.

Utility of thallium and geochemical analysis of Mariana arc sediments from ODP Hole 129-801A and 129-801B

We provide the first exploration of thallium (Tl) abundances and stable isotope compositions as potential tracers during arc lava genesis. We present a case study of lavas from the Central Island Province (CIP) of the Mariana arc, supplemented by representative sedimentary and altered oceanic crust (AOC) inputs from ODP Leg 129 Hole 801 outboard of the Mariana trench. Given the large Tl concentration contrast between the mantle and subduction inputs coupled with previously published distinctive Tl isotope signatures of sediment and AOC, the Tl isotope system has great potential to distinguish different inputs to arc lavas. Furthermore, CIP lavas have well-established inter island variability, providing excellent context for the examination of Tl as a new stable isotope tracer. In contrast to previous work (Nielsen et al., 2006b), we do not observe Tl enrichment or light epsilon 205Tl (where epsilon 205Tl is the deviation in parts per 10,000 of a sample 205Tl/203Tl ratio compared to NIST SRM 997 Tl standard) in the Jurassic-aged altered mafic ocean crust subducting outboard of the Marianas (epsilon 205Tl = - 4.4 to 0). The lack of a distinctive epsilon 205Tl signature may be related to secular changes in ocean chemistry. Sediments representative of the major lithologies from ODP Hole Leg 129 801 have 1-2 orders of magnitude of Tl enrichment compared to the CIP lavas, but do not record heavy signatures (epsilon 205Tl = - 3.0 to + 0.4), as previously found in similar sediment types (epsilon 205Tl > + 2.5; Rehkämper et al., 2004). We find a restricted range of epsilon 205Tl = - 1.8 to - 0.4 in CIP lavas, which overlaps with MORB. One lava from Guguan falls outside this range with epsilon 205Tl = + 1.2. Coupled Cs, Tl and Pb systematics of Guguan lavas suggests that this heavy Tl isotope composition may be due to preferential degassing of isotopically light Tl. In general, the low Tl concentrations and limited isotopic range in the CIP lavas is likely due to the unexpectedly narrow range of epsilon 205Tl found in Mariana subduction inputs, coupled with volcaniclastic, rather than pelagic sediment as the dominant source of Tl. Much work remains to better understand the controls on Tl processing through a subduction zone. For example, Tl could be retained in residual phengite, offering the potential exploration of Cs/Tl ratios as a slab thermometer. However, data for Tl partitioning in phengite (and other micas) is required before developing this application further. Establishing a database of Tl concentrations and stable isotopes in subduction zone lavas with different thermal parameters and sedimentary inputs is required for the future use of Tl as a subduction zone tracer.

Mineralogical, geochemical, and lipid biomarker study of cabonate precipitates at station GeoB9908-1

Carbonate precipitates recovered from 2,000 m water depth at the Dolgovskoy Mound (Shatsky Ridge, north eastern Black Sea) were studied using mineralogical, geochemical and lipid biomarker analyses. The carbonates differ in shape from simple pavements to cavernous structures with thick microbial mats attached to their lower side and within cavities. Low d13C values measured on carbonates (-41 to -32 per mill V-PDB) and extracted lipid biomarkers indicate that anaerobic oxidation of methane (AOM) played a crucial role in precipitating these carbonates. The internal structure of the carbonates is dominated by finely laminated coccolith ooze and homogeneous clay layers, both cemented by micritic high-magnesium calcite (HMC), and pure, botryoidal, yellowish low-magnesium calcite (LMC) grown in direct contact to microbial mats. d18O measurements suggest that the authigenic HMC precipitated in equilibrium with the Black Sea bottom water while the yellowish LMC rims have been growing in slightly 18O-depleted interstitial water. Although precipitated under significantly different environmental conditions, especially with respect to methane availability, all analysed carbonate samples show lipid patterns that are typical for ANME-1 dominated AOM consortia, in the case of the HMC samples with significant contributions of allochthonous components of marine and terrestrial origin, reflecting the hemipelagic nature of the primary sediment.

Geochemical data derived from an absolutely dated shell-based chronology for the Irish Sea

The identification in various proxy records of periods of rapid (decadal scale) climate change over recent millennia, together with the possibility that feedback mechanisms may amplify climate system responses to increasing atmospheric CO2, highlights the importance of a detailed understanding, at high spatial and temporal resolutions, of forcings and feedbacks within the system. Such an understanding has hitherto been limited because the temperate marine environment has lacked an absolute timescale of the kind provided by tree-rings for the terrestrial environment and by corals for the tropical marine environment. Here we present the first annually resolved, multi-centennial (489-year), absolutely dated, shell-based marine master chronology. The chronology has been constructed by detrending and averaging annual growth increment widths in the shells of multiple specimens of the very long-lived bivalve mollusc Arctica islandica, collected from sites to the south and west of the Isle of Man in the Irish Sea. The strength of the common environmental signal expressed in the chronology is fully comparable with equivalent statistics for tree-ring chronologies. Analysis of the 14C signal in the shells shows no trend in the marine radiocarbon reservoir correction (DR), although it may be more variable before ~1750. The d13C signal shows a very significant (R**2 = 0.456, p < 0.0001) trend due to the 13C Suess effect.

Mineralogical and geochemical analyses of serpentines from ODP Hole 125-778A

Thirty-five samples from Hole 778A were prepared for X-ray diffraction (XRD) mineralogical analyses and for chemical analyses of major and trace elements. Most of the selected samples were silt- and sand-sized sedimentary serpentinites or microbreccias except for a soft clast of mafic rock, a hard clast of massive serpentinized peridotite, and a pebble of consolidated, undeformed serpentine microbreccia that contained planktonic foraminifers. Both mineralogical and geochemical analyses allow discrimination of three groups among the analyzed samples. These groups correspond to three stratigraphic intervals present along the drilled section. Group A contains the upper samples (lithologic Unit I). These consist of poorly consolidated serpentine muds carrying hard-rock clasts (serpentinized peridotites, metabasalts). They are characterized by the following mineralogical assemblage: serpentine, Fe-oxides and hydroxides, aragonite, and halite. They exhibit variable SiO2, MgO contents, but are characterized by a SiO2/MgO ratio near 1. CaO content is high in relation to development of aragonite. Al2O3 content is low. Relatively high K2O, Na2O, and Sr contents are present, presumably in relation to interactions with seawater. Group B (30-77 mbsf) contains samples exhibiting very homogeneous chemical and mineralogical compositions. They consist of serpentinite microbreccias exhibiting frequent shear structures. Hard-rock clasts are also present (serpentinized peridotites, metabasalts, one possible chert fragment). The mineralogy of the Group B samples is characterized by the presence of serpentine and authigenic minerals: hydroxycarbonates and hydrogrossular. Calcite and chlorite are also present, but all the samples lack aragonite. Their chemical compositions are remarkably similar to compositions of their parent rocks. Group C contains silt- and sand-sized serpentine and serpentine microbreccias, which are locally rich in red clasts, probably strongly altered (oxidized?) mafic fragments. Intervals having clasts of more diverse origin than those higher in the section were recovered. Clast lithology includes serpentinized peridotites, metabasalts, metavolcaniclastite, meta-olivine gabbro, and amphibolite sandstone. Mineralogy and geochemistry reflect these compositions. Serpentine content of the samples is less than in previous groups. Correlatively, sepiolite, palygorskite, and chlorite-smectite are mineral phases present in the analyzed samples. Accessory igneous minerals (amphiboles, pyroxenes, hematite) also were found. The chemical compositions of most of Group C samples differ from that of massive serpentinized peridotites. The main differences are (1) higher SiO2, CaO, TiO2 and Al2O3 contents, (2) a SiO2/MgO ratio greater than 1, and (3) a negative correlation between Al2O3, and MgO, Cr, and Ni. These characteristics suggest new constraints relative to the flow structure of the flank of Conical Seamount.

Whole-rock geochemical analyses of serpentinized harzburgites from ODP Site 209-1270

Small-scale shear zones are present in drillcore samples of abyssal peridotites from the Mid-Atlantic ridge at 15°20'N (Ocean Drilling Program Leg 209). The shear zones act as pathways for both evolved melts and hydrothermal fluids. We examined serpentinites directly adjacent to such zones to evaluate chemical changes resulting from melt-rock and fluid-rock interaction and their influence on the mineralogy. Compared to fresh harzburgite and melt-unaffected serpentinites, serpentinites adjacent to melt-bearing veins show a marked enrichment in rare earth elements (REE), strontium and high field strength elements (HFSE) zirconium and niobium. From comparison with published chemical data of variably serpentinized and melt-unaffected harzburgites, one possible interpretation is that interaction with the adjacent melt veins caused the enrichment in HFSE, whereas the REE contents might also be enriched due to hydrothermal processes. Enrichment in alumina during serpentinization is corroborated by reaction path models for interaction of seawater with harzburgite-plagiogranite mixtures. These models explain both increased amounts of alumina in the serpentinizing fluid for increasing amounts of plagiogranitic material mixed with harzburgite, and the absence of brucite from the secondary mineralogy due to elevated silica activity. By destabilizing brucite, nearby melt veins might fundamentally influence the low-temperature alteration behaviour of serpentinites. Although observations and model results are in general agreement, due to absence of any unaltered protolith a quantification of element transport during serpentinization is not straightforward.

Ages, sedimentation rates and geochemical composition of ODP Site 162-983 sediments

A geochemical study of sediments from Ocean Drilling Program Site 983 was conducted to examine low-frequency variations in carbonate content as expressed by blue-band reflectance (450-500 nm) over the last 1.2 Ma. Sedimentary percent organic carbon, percent carbonate, and excess barium (Ba[ex]) were used as the primary tools to evaluate the factors responsible for these long-term changes. We observe positive correlation between the mass-accumulation rate of various biogenic components and the mass-accumulation rate of Ba(ex), especially in sediments younger than ~600 ka. Deeper in the section (~600-1200 ka), the correlation between Ba(ex) and the other biogenic tracers is weak. The lack of correlation between Ba(ex) and biogenic carbonate likely results either from a higher supply of terrigenous material at that time (which confounds Ba[ex] estimation), or remobilization of Ba resulting from low pore-water sulfate ion concentrations, or both. Nonbiogenic sediments at Site 983, represented by Th, K2O, and the molar Ti/Al ratio, exhibit cyclic variations that represent mixing between continental and oceanic (i.e., basaltic) terrigenous sources. The timing of these cycles matches that of the major glacial-interglacial cycles, which suggests that they result from the supply of continental material as ice-rafted debris during glacial periods and fine-grained basaltic material by bottom currents during interglacial periods. Given these observations, the most likely causes for the low-frequency carbonate variations observed in the Site 983 sediments are shifts in surface productivity and, to a lesser extent, dilution by the input of terrigenous material.

Geochemical and isotopic composition of basalts from the axial Mid-Atlantic Ridge, South Atlantic

One of the essential problems of oceanic tectonics is estimation of the influence of plumes of the deep hot mantle on processes in the axial spreading zone. Areas of two giant (St. Helena and Tristan da Cunha) plumes in the Mid-Atlantic Ridge (MAR) rift zone (South Atlantic) are characterized by the effusion of basalts that differ from typical depleted riftogenic tholeiites by anomalously high contents of lithophile components and specific isotopic compositions. Moreover, the rift valley floor with basalt effusion is significantly uplifted above the adjacent sectors of the rift. The formation of the St. Helena Seamount located 400 km east of the MAR axis is related to magmatism that is active to this day. St. Helena Island is a member of the structural ensemble of large volcanic seamounts (Bonaparte, Bagration, and Kutuzov). Like St. Helena Island, each seamount incorporates a series of smaller rises of different morphologies and dimensions. Thus, a system of subparallel series of NE-trending (~45°) rises extend from the seamount ensemble to the African continent. According to the plate tectonics concept, the seamount series represent hotspots related to a deep mantle plume that can be projected onto the present-day St. Helena Island area (St. Helena plume). At the same time, the inferred topographic map based on satellite altimetry data shows that the seamount series also extend along the opposite southwestern direction (~225°) toward the axial MAR and even intersect the latter structure. This fact cannot be explained by the hotspot hypothesis, which suggests stationary positions of plumes relative to the mobile oceanic plate. In the course of Cruise 10 of the R/V Akademik Ioffe (2002), detailed geological and geophysical investigations were carried out at the junction of one structural series with the MAR rift zone located near the Martin Vaz Fracture Zone (Martin Vaz test area, 19°-20° S). The present communication is devoted to the study of lithology, geochemistry, and isotopy of basalts dredged at the test area.

Geochemical studies of the Cretaceous-Tertiary boundary in ODP Holes 113-689B and 113-690C

In a study of ODP Hole 689B no iridium (Ir) anomaly was found in Sections 1 through 6 of Core 25X or in Core 26X from the top down to section 2, 3-12 cm. The background Ir abundance averaged 11 parts per trillion (ppt) and a clay-enriched region had nearly the same average, 26 ± 12 ppt. If the Cretaceous-Tertiary (K-T) contact is in the region studied, then sedimentation was not continuous, and the K-T boundary was probably either not deposited or it was eroded away. In a study of Cores 15X and 16X of ODP Hole 690C, an iridium peak with a maximum abundance of 1566 ± 222 ppt was found in Section 4 of Core 15X at 39-40 cm with a half-width of 6.6 cm. Background abundances were ~15 ppt and distinctly higher Ir abundances were observed from 119 cm below to 72 cm above the main peak. The Ir distribution below the main peak is attributed to bioturbation by organisms with burrows extending at least 0.4 m. The Ir distribution above the main peak may be due to the same cause but other explanations may be significant. There are variable enrichments of clay in the mainly CaCO3 sediment of Core 15X, and the stratigraphically lowest part of the most abundant clay deposits is found (within 2 cm) in the same position as the main Ir peak. The clay deposit, which is estimated to be about 50% of the sediment, extends upward ~19 cm and then slowly decreases to a background level of 10% over 1 m. The degree of homogeneity of the clay-rich interval suggests it was not due to episodic volcanism but may have been due to a decrease of the CaCO3 deposition rate which was possibly triggered by the impact of a large asteroid or comet on the Earth.