Chemical composition of volcanic glass of some tephra layers in Northeastern Pacific Ocean

Five widespread upper Cenozoic tephra layers that are found within continental sediments of the western United States have been correlated with tephra layers in marine sediments in the Humboldt and Ventura basins of coastal California by similarities in major-and trace-element abundances; four of these layers have also been identified in deep-ocean sediments at DSDP sites 34, 36, 173, and 470 in the northeastern Pacific Ocean. These layers, erupted from vents in the Yellowstone National Park area of Wyoming and Idaho (Y), the Cascade Range of the Pacific Northwest (C), and the Long Valley area, California (L), are the Huckleberry Ridge ash bed (2.0 Ma, Y), Rio Dell ash bed (ca. 1.5 Ma, C), Bishop ash bed (0.74 Ma, L), Lava Creek B ash bed (0.62 Ma, Y), and Loleta ash bed (ca. 0.4 Ma, C). The isochronous nature of these beds allows direct comparison of chronologic and climatic data in a variety of depositional environments. For example, the widespread Bishop ash bed is correlated from proximal localities near Bishop in east-central California, where it is interbedded with volcanic and glacial deposits, to lacustrine beds near Tecopa, southeastern California, to deformed on-shore marine strata near Ventura, southwestern California, to deep-ocean sediments at site 470 in the eastern Pacific Ocean west of northern Mexico. The correlations allow us to compare isotopic ages determined for the tephra layers with ages of continental and marine biostratigraphic zones determined by magnetostratigraphy and other numerical age control and also provide iterative checks for available age control. Relative age variations of as much as 0.5 m.y. exist between marine biostratigraphic datums [for example, highest occurrence level of Discoaster brouweri and Calcidiscus tropicus (= C. macintyrei)], as determined from sedimentation rate curves derived from other age control available at each of several sites. These discrepancies may be due to several factors, among which are (1) diachronism of the lowest and highest occurrence levels of marine faunal and floral species with latitude because of ecologic thresholds, (2) upward reworking of older forms in hemipelagic sections adjacent to the tectonically active coast of the western United States and other similar analytical problems in identification of biostratigraphic and magnetostratigraphic datums, (3) dissolution of microfossils or selective diagenesis of some taxa, (4) lack of precision in isotopic age calibration of these datums, (5) errors in isotopic ages of tephra beds, and (6) large variations in sedimentation rates or hiatuses in stratigraphic sections that result in age errors of interpolated datums. Correlation of tephra layers between on-land marine and deep-ocean deposits indicates that some biostratigraphic datums (diatom and calcareous nannofossil) may be truly time transgressive because at some sites, they are found above and, at other sites, below the same tephra layers.

Abrupt shifts of the Sahara-Sahel boundary during Heinrich stadials demonstrated on a sediment core transect

Relict dune fields that are found as far south as 14° N in the modern-day African Sahel are testament to equatorward expansions of the Sahara desert during the Late Pleistocene. However, the discontinuous nature of dune records means that abrupt millennial-timescale climate events are not always resolved. High-resolution marine core studies have identified Heinrich stadials as the dustiest periods of the last glacial in West Africa although the spatial evolution of dust export on millennial timescales has so far not been investigated. We use the major-element composition of four high-resolution marine sediment cores to reconstruct the spatial extent of Saharan-dust versus river-sediment input to the continental margin from West Africa over the last 60 ka. This allows us to map the position of the sediment composition corresponding to the Sahara-Sahel boundary. Our records indicate that the Sahara-Sahel boundary reached its most southerly position (13° N) during Heinrich stadials and hence suggest that these were the periods when the sand dunes formed at 14° N on the continent. Heinrich stadials are associated with cold North Atlantic sea surface temperatures which appear to have triggered abrupt increases of aridity and wind strength in the Sahel. Our study illustrates the influence of the Atlantic meridional overturning circulation on the position of the Sahara-Sahel boundary and on global atmospheric dust loading.

(Table 1) Micro-inclusion counts and ion concentrations in the five GRIP ice-core sections

We provide the first direct evidence that a number of water-soluble compounds, in particular calcium sulfate (CaSO4 2H2O) and calcium carbonate (CaCO3), are present as solid, micron-sized inclusions within the Greenland GRIP ice core. The compounds are detected by two independent methods: micro-Raman spectroscopy of a solid ice sample, and energy-dispersive X-ray spectroscopy of individual inclusions remaining after sublimation. CaSO4 2H2O is found in abundance throughout the Holocene and the last glacial period, while CaCO3 exists mainly in the glacial period ice. We also present size and spatial distributions of the micro-inclusions. These results suggest that water-soluble aerosols in the GRIP ice core are dependable proxies for past atmospheric conditions.

(Table T1) Scanning electron microscope (SEM) analyses of IODP Site 321-U1338

The late Miocene to early Pliocene carbonate-rich sediments recovered at Integrated Ocean Drilling Program (IODP) Site U1338 during the Expedition 320/321 Pacific Equatorial Age Transect (PEAT) program contain abundant calcareous nanno- and microfossils. Geochemical proxies from benthic and planktonic foraminiferal and coccolithophore calcite could be very useful at this location; however, good preservation of the calcite is crucial for the proxies to be robust. Here, we evaluate the preservation of specific benthic and planktonic foraminifer species and coccolithophores in fine fraction sediment at Site U1338 using backscattered electron (topography mode) scanning electron microscopy (BSE-TOPO SEM). Both investigated foraminiferal species, Cibicidoides mundulus and Globigerinoides sacculifer, have undergone some alteration. The C. mundulus show minor evidence for dissolution, and only some specimens show evidence of overgrowth. The Gs. sacculifer show definite signs of alteration and exhibit variable preservation, ranging from fair to poor; some specimens show minor overgrowth and internal recrystallization but retain original features such as pores, spine pits, and internal test-wall growth structure, whereas in other specimens the recrystallization and overgrowth disguise many of the original features. Secondary electron and BSE-TOPO SEM images show that coccolith calcite preservation is moderate or moderate to poor. Slight to moderate etching has removed central heterococcolith features, and a small amount of secondary overgrowth is also visible. Energy dispersive spectroscopy analyses indicate that the main sedimentary components of the fine fraction sediment are biogenic CaCO3 and SiO2, with some marine barite. Based on the investigations in this data report, geochemical analyses on benthic foraminifers are unlikely to be affected by preservation, although geochemical analyses on the planktonic foraminifers should be treated cautiously because of the fair to poor and highly variable preservation.

Partial melting experiments on oceanic cumulated gabbros

We performed hydrous partial melting experiments at shallow pressures (0.2 GPa) under slightly oxidizing conditions (NNO oxygen buffer) on oceanic cumulate gabbros drilled by ODP (Ocean Drilling Program) cruises to evaluate whether the partial melting of oceanic gabbro can generate SiO2-rich melts with compositions typical of oceanic plagiogranites. The experimental melts of the low-temperature runs broadly overlap those of natural plagiogranites. At 940 °C, the normalized SiO2 contents of the experimental melts of all systems range between 60 and 61 wt%, and at 900 °C between 63 and 68 wt%. These liquids are characterized by low TiO2 and FeOtot contents, similar to those of natural plagiogranites from the plutonic section of the oceanic crust, but in contrast to Fe and Ti-rich low-temperature experimental melts obtained in MORB systems at ~950 °C. The ~1,500-m-long drilled gabbroic section of ODP Hole 735B (Legs 118 and 176) at the Southwest Indian Ridge contains numerous small plagiogranitic veins often associated with zones which are characterized by high-temperature shearing. The compositions of the experimental melts obtained at low temperatures match those of the natural plagiogranitic veins, while the compositions of the crystals of low-temperature runs correspond to those of minerals from high-temperature microscopic veins occurring in the gabbroic section of the Hole 735B. This suggests that the observed plagiogranitic veins are products of a partial melting process triggered by a water-rich fluid phase. If the temperature estimations for hightemperature shear zones are correct (up to 1,000 °C), and a water-rich fluid phase is present, the formation of plagiogranites by partial melting of gabbros is probably a widespread phenomenon in the genesis of the ocean crust.

(Table 1) Heavy minerals in silt and sand samples of IODP Site 301-U1301

The northwestern Cascadia Basin of western North America accumulated high-sedimentation-rate sequences during the Pleistocene sea-level low-stands. The continental shelf was largely exposed at that time, and rivers and estuaries delivered large sediment fluxes directly to the deep ocean. The IODP EXP1301 core, which was taken from the middle portion of the Cascadia Basin, is well preserved and exhibits the deeper and - more distal sedimentary facies. The lithology in this location is composed of two units, 1) hemipelagic mud with a thin sand layer and 2) thick, coarsening upward silt-sand turbidites with a small proportion of granules at the top. We will focus on the detailed sand-grain proportions in order to understand the origin of these sediments. We determined the modal proportions of the heavy minerals, and the chemical composition of olivine and orthopyroxene in fourteen samples. These are characterized by an abundance of amphibole, pyroxenes and epidote, and the presence of minerals derived from peridotite. There is no drastic change in the modal and mineral compositions of the sands and silts between the turbidite and hemipelagic sequences. There were two probable drainage systems on the continent, the Frazer and Columbia rivers, which shed turbidites into the Cascadia Basin after 1.6 Ma, especially at 0.46-0.76 Ma. Based on a comparison of the modal and mineral compositions, the Northern Cascadia Basin has been supplied with sediments, mainly from the Frazer River, through the Straits of Juan de Fuca, by Pleistocene to Holocene turbidites.

(Table 1) Gypsum, pyrite and glauconite at DSDP Hole 36-329

Authigenic gypsum, pyrite, and glauconite are disseminated throughout an unusually long (346 m) Miocene section of mixed biogenic carbonate and diatomaceous ooze drilled on the Falkland Plateau at DSDP Site 329 (water depth, 1519 m). The present organic carbon content of the sediment is low, ranging between 0.1 and 0.7%. Gypsum occurs as euhedral single or twinned crystals of selenite up to 5 mm in diameter, sometimes in the form of gypsum rosettes. These crystals are intact and unabraded, comprising up to 4% of the washed sample. The authigenic nature of the gypsum is demonstrated by the presence of diatoms and radiolarians embedded within the gypsum crystals. The gypsum co-occurs with pyrite and glauconite in these samples. The pyrite occurs as framboids, foraminiferal infillings, rods, and granular sheetlike masses composed of pyrite octahedra. The glauconite occurs as foraminiferal infillings and as free grains. The gypsum and pyrite were identified by energy-dispersive X-ray analysis and scanning electron micrographs. Some of the gypsum has grown on pyrite, indicating that it precipitated after the pyrite, perhaps in response to a change in pH conditions. The formation of the mineral suite can be explained by current models of in situ sulfide and sulfate precipitation coincident with diagenesis and oxidation of much of the original organic carbon.

Composition and crystal parameters of carbonate-apatites from animal teeth and bones and from phosphate rocks of the ocean bottom

Samples of recent to Miocene fish and marine mammal bones from the bottom of the Atlantic and Pacific Oceans and Miocene Maikop deposits (Transcaspian region) are studied by X-ray diffraction technique combined with chemical and energy-dispersive analyses. Changes of lattice parameters and chemical composition of bioapatite during fossilization and diagenesis suggest that development of skeletal apatite proceeds from dahllite-type hydroxyapatite to francolite-type carbonate-fluorapatite. It is assumed that jump-type transition from dahllite to francolite during initial fossilization reflects replacement of biogeochemical reactions in living organisms, which are subject to nonlinear laws of nonequilibrium thermodynamics, by physicochemical processes according to the linear equilibrium thermodynamics.

Low-temperature experiments of sediment core GeoB6229-6 at the South American continental margin off the Rio de la Plata estuary

With various low-temperature experiments performed on magnetic mineral extracts of marine sedimentary deposits from the Argentine continental slope near the Rio de la Plata estuary, a so far unreported style of partial magnetic self-reversal has been detected. In these sediments the sulphate-methane transition (SMT) zone is situated at depths between 4 and 8 m, where reductive diagenesis severely alters the magnetic mineral assemblage. Throughout the sediment column magnetite and ilmenite are present together with titanomagnetite and titanohematite of varying compositions. In the SMT zone (titano-)magnetite only occurs as inclusions in a siliceous matrix and as intergrowths with lamellar ilmenite and titanium-rich titanohematite, originating from high temperature deuteric oxidation within the volcanic host rocks. These abundant structures were visualized by scanning electron microscopy and analysed by energy dispersive spectroscopy. Warming of field-cooled and zero-field-cooled low-temperature saturation remanence displays magnetic phase transitions of titanium-rich titanohematite below 50 K and the Verwey transition of magnetite. A prominent irreversible decline characterizes zero-field cooling of room temperature saturation remanence. It typically sets out at ~210 K and is most clearly developed in the lower part of the SMT zone, where low-temperature hysteresis measurements identified ~210 K as the blocking temperature range of a titanohematite phase with a Curie temperature of around 240 K. The mechanism responsible for the marked loss of remanence is, therefore, sought in partial magnetic self-reversal by magnetostatic interaction of (titano-)magnetite and titanohematite. When titanohematite becomes ferrimagnetic upon cooling, its spontaneous magnetic moments order antiparallel to the (titano-)magnetite remanence causing an drastic initial decrease of global magnetization. The loss of remanence during subsequent further cooling appears to result from two combined effects (1) magnetic interaction between the two phases by which the (titano-)magnetite domain structure is substantially modified and (2) low-temperature demagnetization of (titano-)magnetite due to decreasing magnetocrystalline anisotropy. The depletion of titanomagnetite and superior preservation of titanohematite is characteristic for strongly reducing sedimentary environments. Typical residuals of magnetic mineral assemblages derived from basaltic volcanics will be intergrowths of titanohematite lamellae with titanomagnetite relics. Low-temperature remanence cycling is, therefore, proposed as a diagnostic method to magnetically characterize such alteration (palaeo-)environments.

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.

Sedimentary climate indicators of sediment core MD08-3167 and GeoB1711-4, southwestern Africa

The past climate evolution of southwestern Africa is poorly understood and interpretations of past hydrological changes are sometimes contradictory. Here we present a record of leaf-wax dD and View the MathML source taken from a marine sediment core at 23°S off the coast of Namibia to reconstruct the hydrology and C3 versus C4 vegetation of southwestern Africa over the last 140 000 years (140 ka). We find lower leaf-wax dD and higher View the MathML source (more C4 grasses), which we interpret to indicate wetter Southern Hemisphere (SH) summer conditions and increased seasonality, during SH insolation maxima relative to minima and during the last glacial period relative to the Holocene and the last interglacial period. Nonetheless, the dominance of C4 grasses throughout the record indicates that the wet season remained brief and that this region has remained semi-arid. Our data suggest that past precipitation increases were derived from the tropics rather than from the winter westerlies. Comparison with a record from the Congo Basin indicates that hydroclimate in southwestern Africa has evolved in antiphase with that of central Africa over the last 140 ka.