Geochemistry of bulk sediment from the Cape Basin

A technique for onsite application of X-ray fluorescence (XRF) spectrometry to samples from sediment cores aboard a research vessel was developed and tested. The method is sufficiently simple, precise, and fast to be used routinely for high-resolution analyses of depth profiles as well as surface samples. Analyses were performed with the compact high-performance energy-dispersive polarisation X-ray fluorescence (EDPXRF) analyser Spectro Xepos. Contents of the elements Si, Ti, Al, Fe, Mn, Mg, Ca, K, Sr, Ba, Rb, Cu, Ni, Zn, P, S, Cl and Br were simultaneously determined on 200-225 samples of each core within 24 h of recovery. This study presents a description of the employed shipboard preparation and analysis technique, along with some example data. We show land-based datasets that support our decisions to use powder samples and to reduce the original measuring time for onboard analyses. We demonstrate how well the results from shipboard measurements for the various elements compare with the land-based findings. The onboard geochemical data enabled us to establish an element stratigraphy already during the cruise. Correlation of iron, calcium and silicon enrichment trends with an older reference core provided an age model for the newly retrieved cores. The Spectro Xepos instrument performed without any analytical and technical difficulties which could have been caused by rougher weather conditions or continuous movement and vibration of the research vessel. By now, this XRF technique has been applied during three RV Meteor cruises to approximately 5,000 Late Quaternary sediment samples from altogether 23 gravity cores, 25 multicorer cores and two box cores from the eastern South Atlantic off South Africa/Namibia and the eastern Atlantic off NW Africa.

Geochemistry on sediment profile PS69/335

During RV Polarstern cruise ANT-XXIII/4 in 2006, a gravity core (PS69/335-2) and a giant box core (PS69/335-1) were retrieved from Maxwell Bay off King George Island (KGI). Comprehensive geochemical (bulk parameters, quantitative XRF, Inductively Coupled Plasma Mass Spectrometry) and radiometric dating analyses (14C, 210Pb) were performed on both cores. A comparison with geochemical data from local bedrock demonstrates a mostly detrital origin for the sediments, but also points to an overprint from changing bioproductivity in the overlying water column in addition to early diagenetic processes. Furthermore, ten tephra layers that were most probably derived from volcanic activity on Deception Island were identified. Variations in the vertical distribution of selected elements in Maxwell Bay sediments further indicate a shift in source rock provenance as a result of changing glacier extents during the past c. 1750 years that may be linked to the Little Ice Age and the Medieval Warm Period. Whereas no evidence for a significant increase in chemical weathering rates was found, 210Pb data revealed that mass accumulation rates in Maxwell Bay have almost tripled since the 1940s (0.66 g cm-2 yr-1 in AD 2006), which is probably linked to rapid glacier retreat in this region due to recent warming.

Geochemistry at DSDP Holes 85-573B and 85-574C

Eocene-Oligocene metalliferous sediments and associated lithologies from the central equatorial Pacific are described in detail. Geochemical analyses of 54 sediment and 2 basalt samples are presented for 34 elements. Detailed stratigraphic and statistical analyses of these data, combined with mineralogic studies, indicate the presence of volcanic glass and seven main mineral phases: biogenic calcite and opal, Fe smectite, goethite, dMnO2, carbonate fluorapatite, and barite. Fe smectite formed by reactions between Fe oxyhydroxides and biogenic opal, causing the dissolution of calcite and the precipitation of barite. Diagenesis was oxic. Sediments have rare earth element distributions similar to those in seawater. The metal content of the sediments is related to competition between the supply rates of hydrothermal and biogenic particles, but has been enhanced by early diagenetic processes. Eocene-Oligocene metalliferous sediments compare closely to those currently being deposited in the Bauer Basin and on the flanks of the East Pacific Rise. There is, however, no evidence that they were deposited in close proximity to an active hydrothermal system.

Chemical composition of sediment core GeoB12309-5 from the northern Arabian Sea, its pore water profile and age depth relationship as well as CTD data obtained during cruise M74/3

The Arabian Sea off the Pakistan continental margin is characterized by one of the world's largest oxygen minimum zones (OMZ). The lithology and geochemistry of a 5.3 m long gravity core retrieved from the lower boundary of the modern OMZ (956 m water depth) were used to identify late Holocene changes in oceanographic conditions and the vertical extent of the OMZ. While the lower part of the core (535 - 465 cm, 5.04 - 4.45 cal kyr BP, Unit 3) is strongly bioturbated indicating oxic bottom water conditions, the upper part of the core (284 - 0 cm, 2.87 cal kyr BP to present, Unit 1) shows distinct and well-preserved lamination, suggesting anoxic bottom waters. The transitional interval from 465 to 284 cm (4.45 - 2.87 cal kyr BP, Unit 2) contains relicts of lamination which are in part intensely bioturbated. These fluctuations in bioturbation intensity suggest repetitive changes between anoxic and oxic/suboxic bottom-water conditions between 4.45 - 2.87 cal kyr BP. Barium excess (Baex) and total organic carbon (TOC) contents do not explain whether the increased TOC contents found in Unit 1 are the result of better preservation due to low BWO concentrations or if the decreased BWO concentration is a result of increased productivity. Changes in salinity and temperature of the outflowing water from the Red Sea during the Holocene influenced the water column stratification and probably affected the depth of the lower boundary of the OMZ in the northern Arabian Sea. Even if we cannot prove certain scenarios, we propose that the observed downward shift of the lower boundary of the OMZ was also impacted by a weakened Somali Current and a reduced transport of oxygen-rich Indian Central Water into the Arabian Sea, both as a response to decreased summer insolation and the continuous southward shift of the Intertropical Convergence Zone during the late Holocene.

(Table T1) Geochemical composition of xenoliths and host rocks from ODP Hole 193-1188A and dredge haul MD-138, PACMANUS field

A number of intensely altered, dark xenoliths with palimpsest quench textures were recorded within altered dacitic host rocks at Site 1189 (Roman Ruins, PACMANUS) during Ocean Drilling Program (ODP) Leg 193. Several of these displayed puzzling marginal fringes, apparently of altered plagioclase with variolitic texture, protruding into adjacent host rocks. Despite their alteration, the xenoliths were interpreted as fragments of rapidly chilled, possibly olivine-bearing basalts incorporated into the dacitic magmas either within the crustal plumbing system or during eruption at the seafloor (figures F15, F16, F17, F42, and F43 in Shipboard Scientific Party, 2002, doi:10.2973/odp.proc.ir.193.104.2002). An additional example of formerly spinifex-textured xenolith, the first from Site 1188 (Snowcap) and the first from the upper cristobalite-bearing zone of alteration, has been revealed by postcruise studies. Furthermore, a pristine sample of the parent lithology has been found within a dredge haul (MD-138, Binatang-2000 Cruise of Franklin; 3°43.60'S, 151°40.35'E, 1688 meters below sea level) from the Satanic Mills hydrothermal field at PACMANUS, near ODP Site 1191. The purpose of this report is to document these discoveries and thereby to confirm and build on shipboard interpretations. To my knowledge, similar xenoliths have never before been found in modern island arc or backarc volcanic sequences. Spinifex textures are most common in Archean komatiites, some of which are bimodally associated with calc-alkaline felsic volcanic rocks.

Composition of bottom sediments, rocks, and ores from the Tropical Atlantic

Geological features of some areas of the Tropical Atlantic (stratigraphy, tectonic structure, lithology, distribution of ore components in bottom sediments, petrography of bedrocks, etc.) are under consideration in the book. Regularities of concentration of trace elements in iron-manganese nodules, features of these nodules in bottom sediments, distribution of phosphorite nodules and other phosphorites have been studied. Much attention is paid to rocks of the ocean crust. A wide range of mineralization represented by magnetite, chromite, chalcopyrite, pyrite, pentlandite, and other minerals has been found.

Geochemical composition and atomic formulas of saponites, celadonites and clays from ODP Leg 168 sites

A drilling transect across the sedimented eastern flank of the Juan de Fuca Ridge, conducted during Leg 168 of the Ocean Drilling Program, resulted in the recovery of samples of volcanic basement rocks (pillow basalts, massive basalts, and volcanic glass breccias) that exhibit the effects of low-temperature hydrothermal alteration. Secondary clays are ubiquitous, with Mg-rich and Fe-rich saponite and celadonitic clays commonly accounting for several percent, and up to 10%-20% by volume. Present-day temperatures of the basement sites vary from 15° to 64°C, with the coolest site being about 0.8 Ma, and the warmest site being about 3.5 Ma. Whereas clays are abundant at sites that have been heated to present temperatures of 23°C and higher, the youngest site at 15°C has only a small trace of secondary clay alteration. Alteration increases as temperatures increase and as the volcanic basement ages. The chemical compositions of secondary clays were determined by electron microprobe, and additional trace element data were determined by both conventional nebulization inductively coupled plasma-mass spectroscopy (ICP-MS) and laser-ablation ICP-MS. Trioctahedral saponite and pyrite are characteristic of the interior of altered rock pieces, forming under conditions of low-oxygen fugacity. Dioctahedral celadonite-like clays along with iron oxyhydroxide and Mg-saponite are characteristic of oxidized haloes surrounding the nonoxidized rock interiors. Chemical compositions of the clays are very similar to those determined from other deep-sea basalts altered at low temperature. The variable Mg:Fe of saponite appears to be a systematic function both of the Mg:Fe of the host rock and the oxidation state during water-rock interaction.

Inorganic geochemical record of ODP Holes 117-722B and 117-724C

High-resolution sampling from late Pleistocene (last 400 k.y.) sediments of Site 722 (upper 16 m) and Site 724 (upper 70 m), and subsequent inorganic geochemical analysis, has defined the history of productivity in the northwest Arabian Sea. Eolian dust input from the Arabian Peninsula and Somalia is characterized by the record of Ti/Al and Cr/Al. This dust record displays strong precessional periodicity (cycles at 25 k.y.) suggesting the Southwest Monsoon and associated winds play a key role in transporting terrigenous material from the land. High biological productivity results in the accumulation of biogenic CaCO3 and opal in the sediments, the latter having an unexpectedly minor contribution to the total mass flux. Due to dilution of the CaCO3 record by the terrigenous component, the record of biological productivity is best exemplified by Ba. Its record, together with that of other metals recording biological association and redox variability (Cu, Ni, Zn, V, U) clearly identifies the interglacial episodes as being more biologically productive. The striking agreement between Ba and the d18O record in planktonic foraminifers suggests that the supply of nutrients during these periods of high productivity is linked to ocean-wide changes in ocean fertility, and not just local upwelling conditions. High levels of phosphate accumulation in interglacial sediments is attributed to both diagenetic phosphorite formation and biogenic skeletal debris. This study provides a detailed record of productivity variation in the northwest Arabian Sea during the late Pleistocene.

Composition of sedimemts from the Transpacific profile

The book is devoted to comprehensive study of composition of sediments from the North Pacific Ocean. The sediments have been divided characterized by their lithologic and facial types, grain size composition and mineralogy. Influence of volcanism on formation of mineral and chemical composition of these sediments has been shown. Regularities of distribution of sediment accumulation rates and of a number of chemical elements on the Transpacific profile have been found. Determining role of mechanical fractionation in their localization has been shown.

Geochemistry, lithology, and bulk density of Cricket Flat paleosol samples

The high-resolution marine isotope climate record indicates pronounced global cooling during the Langhian (16-13.8 Ma), beginning with the warm middle Miocene climatic optimum and ending with significant Antarctic ice sheet expansion and the transition to "icehouse" conditions. Terrestrial paleoclimate data from this interval is sparse and sometimes conflicting. In particular, there are gaps in the terrestrial record in the Pacific Northwest during the late Langhian and early Serravallian between about 14.5 and 12.5 Ma. New terrestrial paleoclimate data from this time and region could reconcile these conflicting records. Paleosols are particularly useful for reconstructing paleoenvironment because the rate and style of pedogenesis is primarily a function of surface environmental conditions; however, complete and well-preserved paleosols are uncommon. Most soils form in erosive environments that are not preserved, or in environments such as floodplains that accumulate in small increments; the resulting cumulic soils are usually thin, weakly developed, and subject to diagenetic overprinting from subsequent soils. The paleosol at Cricket Flat in northeastern Oregon is an unusually complete and well-preserved paleosol from a middle Miocene volcanic sequence in the Powder River Volcanic Field. An olivine basalt flow buried the paleosol at approximately 13.8 ± 0.6 Ma, based on three 40Ar/39Ar dates on the basalt. We described the Cricket Flat paleosol and used its physical and chemical profile and micromorphology to assess pedogenesis. The Cricket Flat paleosol is an Ultisol-like paleosol, chemically consistent with a high degree of weathering. Temperature and rainfall proxies suggest that Cricket Flat received 1120 ± 180 mm precipitation y-1 and experienced a mean annual temperature of 14.5 ± 2.1 °C during the formation of the paleosol, significantly warmer and wetter than today. This suggests slower cooling after the middle Miocene climatic optimum than is seen in the existing paleosol record.

Description and chemical composition of ferromanganese deposits from Oneida Lake, New York

Saucer-shaped iron-manganese crusts occur adjacent to gravel shoal areas in Oneida lake in central New York. The crusts usually have a crude concentric banding owing to an alternation of orange, iron-rich layers and black, iron-poor layers. Materials from both types of layers are x-ray amorphous. The Oneida lake crusts, like most other freshwater manganese nodules, contain about the same Mn concentration as marine manganese nodules, but are usually higher in Fe and lower in trace metals than their marine equivalents. Although Fe and Mn may be precipitating directly from the lake water, it is more likely that the oxidate crusts are the result of precipitation of Fe and Mn when reduced sediment pore water comes in contact with well oxygenated bottom waters. Organisms, particularly bacteria, may play a role in the formation of the crusts, but to date no evidence of this has been found.