Chemical composition of ferromanganese nodules from the Black Sea

Ferruginate shells and tubular worm burrows from the oxygenated zone of the Black Sea (Kalamit Bay and Danube River mouth) are studied by transmission and scanning electron microscopy combined with analyses of elemental composition. Iron and manganese oxyhydroxide nodules considered here are enriched in phosphorus. They contain variable amounts of terrigenous and biogenic material derived from host sediments. Oxyhydroxides are mainly characterized by colloform structure, whereas globular and crystalline structures are less common. The dominating iron phase is represented by ferroxyhite and protoferroxyhite, whereas the manganese phase is composed of Fe-free vernadite. Concentrations of Mn, As, and Mo are 12-18 times higher relative to sediments, while concentrations of Fe, P, Ni, and Co increase 5-7 times during nodule formation.

Salinity estimation from Gulf of Guinea, sediment core MD03-2707

The isotopic composition of surface seawater is widely used to infer past changes in sea surface salinity using paired foraminiferal Mg/Ca and d18O from marine sediments. At low latitudes, paleosalinity reconstructions using this method have largely been used to document changes in the hydrological cycle. This method usually assumes that the modern seawater d18O (d18Osw)/salinity relationship remained constant through time. Modelling studies have shown that such assumptions may not be valid because large-scale atmospheric circulation patterns linked to global climate changes can alter the seawater d18Osw/salinity relationship locally. Such processes have not been evidenced by paleo-data so far because there is presently no way to reconstruct past changes in the seawater d18Osw/salinity relationship. We have addressed this issue by applying a multi-proxy salinity reconstruction from a marine sediment core collected in the Gulf of Guinea. We measured hydrogen isotopes in C37:2 alkenones (dDa) to estimate changes in seawater dD. We find a smooth, long-term increase of ~10 per mil in dDa between 10 and 3 kyr BP, followed by a rapid decrease of ~10 per mil in dDa between 3 kyr BP and core top to values slightly lighter than during the early Holocene. Those features are inconsistent with published salinity estimations based on d18Osw and foraminiferal Ba/Ca, as well as nearby continental rainfall history derived from pollen analysis. We combined dDa and d18Osw values to reconstruct a Holocene record of salinity and compared it to a Ba/Ca-derived salinity record from the same sedimentary sequence. This combined method provides salinity trends that are in better agreement with both the Ba/Ca-derived salinity and the regional precipitation changes as inferred from pollen records. Our results illustrate that changes in atmospheric circulation can trigger changes in precipitation isotopes in a counter-intuitive manner that ultimately impacts surface salinity estimates based on seawater isotopic values. Our data suggest that the trends in Holocene rainfall isotopic values at low latitudes may not uniquely result from changes in local precipitation associated with the amount effect.

Chert petrology and geochemistry at DSDP Leg 62 Holes

Sixty-five chert, porcellanite, and siliceous-chalk samples from Deep Sea Drilling Project Leg 62 were analyzed by petrography, scanning electron microscopy, analysis by energy-dispersive X-rays, X-ray diffraction, X-ray spectroscopy, and semiquantitative emission spectroscopy. Siliceous rocks occur mainly in chalks, but also in pelagic clay and marlstone at Site 464. Overall, chert probably constitutes less than 5% of the sections and occurs in deposits of Eocene to Barremian ages at sub-bottom depths of 10 to 820 meters. Chert nodules and beds are commonly rimmed by quartz porcellanite; opal-CT-rich rocks are minor in Leg 62 sediments 65 to 108 m.y. old and at sub-bottom depths of 65 to 520 meters. Chert ranges from white to black, shades of gray and brown being most common; yellow-brown and red-brown jaspers occur at Site 464. Seventy-eight percent of the studied cherts contain easily recognizable burrow structures. The youngest chert at Site 463 is a quartz cast of a burrow. Burrow silica maturation is always one step ahead of host-rock silicification. Burrows are commonly loci for initial silicification of the host carbonate. Silicification takes place by volume-f or-volume replacement of carbonate sediment, and more-clay-rich sediment at Site 464. Nannofossils are commonly pseudomorphically replaced by quartz near the edges of chert beds and nodules. Other microfossils, mostly radiolarians and foraminifers, whether in chalk or chert, can be either filled with or replaced by calcite, opal-CT, and (or) quartz. Chemical micro-environments ultimately control the removal, transport, and precipitation of calcite and silica. Two cherts from Site 465 contain sulfate minerals replaced by quartz. Site 465 was never subaerially exposed after sedimentation began, and the formation of the sulfate minerals and their subsequent replacement probably occurred in the marine environment. Several other cherts with odd textures are described in this paper, including (1) a chert breccia cemented by colloform opal-CT and chalcedony, (2) a transition zone between white porcellanite containing opal-CT and quartz and a burrowed brown chert, consisting of radial aggregates of opal-CT with hollow centers, and (3) a chert that consists of silica-replaced calcite pseudospherules interspersed with streaks and circular masses of dense quartz. X-ray-diffraction analyses show that when data from all sites are considered there are poorly defined trends indicating that older cherts have better quartz crystallinity than younger ones, and that opal-CT crystallite size increases and opal-CT cf-spacings decrease with depth of occurrence in the sections. In a general way, depth of burial and the presence of calcite promote the ordering in the opal-CT crystal structure which allows its eventual conversion to quartz. Opal-CT in porcellanites converts to quartz after reaching a minimum d-spacing of 4.07 Å. Quartz/opal-CT ratios and quartz crystallinity vary randomly on a fine scale across four chert beds, but quartz crystallinity increases from the edge to the center of a fifth chert bed; this may indicate maturation of the silica. Twenty-four rocks were analyzed for their major- and minor-element compositions. Many elements in cherts are closely related to major mineral components. The carbonate component is distinguished by high values of CaO, MgO, Mn, Ba, Sr, and (for unknown reasons) Zr. Tuffaceous cherts have high values of K and Al, and commonly Zn, Mo, and Cr. Pure cherts are characterized by high SiO2 and B. High B may be a good indicator of formation of chert in an open marine environment, isolated from volcanic and terrigenous materials.

Ages and geochemical and geophysical characteristics of sediment core MD99-2294, Lofoten Contourite Drift

A sediment core from the Lofoten Contourite Drift on the continental slope off Northern Norway, proximal to the former Vestfjorden-Trsnadjupet Ice Stream, details the development, variability and decline of marine margins of the northwestern Fennoscandian Ice Sheet during the time interval 25.3-14 cal ka BP, including the Last Glacial Maximum and onset of the deglaciation based on high-resolution IRD records. From the core interval between 25.3 and 17.7 cal ka BP we report data points with a mean time step of 10 years, between 17.7 cal ka BP and the Holocene time steps are typically 50 years. The core is divided into 7 informal ice-rafted debris (IRD) zones based on the variations in IRD including 7 major IRD maxima (A-G), inferred to represent periods of high iceberg production. Petrological identification reveals dominance of crystalline IRD (monocrystalline, plutonic and metamorphic rock fragments) accounting for 75-80% of total IRD assemblages, while sedimentary fragments generally account for 15-20%. The crystalline fragments (including eclogite and mangerite from a nearby terrestrial source) increase across the IRD peaks while the sedimentary fragments remain constant. This points to the importance of erosional products from icebergs originating from fast-flowing paleo-ice streams including the Vestfjorden-Trsnadjupet Ice Stream draining from the Fennoscandian mainland during the IRD maxima periods. Increased temperature of the adjacent surface water masses was probably an important external forcing factor on the Fennoscandian Ice Sheet behavior because some IRD maxima and plumite deposition from meltwater plumes post-date periods of increased sea surface temperatures. The peak IRD depositions occur in centennial and millennial time cycles (~200, 1030 and 3900 year) indicating some external forcing by solar variation. Both mechanisms could explain the observed synchronous instability of the northwestern Fennoscandian Ice Sheet to other European Ice Sheets.

Isotope composition of sulfur, oxygen and carbon in Black Sea sediments

Inversion of isotopic composition in the SO4(2-)-H2S system is shown to be universal in Neoeuxine sediments and an explanation of its occurrence is proposed. Change in isotopic composition of sulfate sulfur in Black Sea waters over last 10-15 thousand years is reconstructed. Periods of alteration between aerobic and anaerobic situations are identified, the beginning of entry of Mediterranean waters into the basin is dated, presence of authigenic carbonates in sediments of the sea is established and amounts are determined. Methane generation from carbon dioxide is shown to have been replaced by its generation from acetate in the paleo-Black Sea period.

Silicate in marine sediments from the Emerland Basin, North Atlantic

A method was developed to measure porosity and dissolved interstitial silicate at millimeter intervals or less in a sediment core. In cores from Emerald Basin (Scotian Shelf), interstitial concentrations near the sediment surface did not drop rapidly to bottom-water concentrations as measured in bottle casts (28 µM) but remained as high as 166 µM in the upper 0.5 mm of sediment High rates of benthic silicate release were measured which could not be accounted for by interstitial concentration gradients or by ventilation of macro-invertebrate burrows. The silicate discontinuity observed between the sediments and water column suggests that a diffusive sublayer exists in a zone of viscous flow above the sediment surface. This is possible only if a surface reaction is primarily responsible for silicate release. By assuming a linear concentration gradient across this diffusive sublayer, the silicate release rates were used to estimate the thickness of the sublayer to be about 2 mm.

Iron and phosphorus speciations in DSDP Leg 92 sediments

We present a detailed study of the co-diagenesis of Fe and P in hydrothermal plume fallout sediments from ~19°S on the southern East Pacific Rise. Three distal sediment cores from 340-1130 km from the ridge crest, collected during DSDP Leg 92, were analysed for solid phase Fe and P associations using sequential chemical extraction techniques. The sediments at all sites are enriched in hydrothermal Fe (oxyhydr)oxides, but during diagenesis a large proportion of the primary ferrihydrite precipitates are transformed to the more stable mineral form of goethite and to a lesser extent to clay minerals, resulting in the release to solution of scavenged P. However, a significant proportion of this P is retained within the sediment, by incorporation into secondary goethite, by precipitation as authigenic apatite, and by readsorption to Fe (oxyhydr)oxides. Molar P/Fe ratios for these sediments are significantly lower than those measured in plume particles from more northern localities along the southern East Pacific Rise, and show a distinct downcore decrease to a depth of ~12 m. Molar P/Fe ratios are then relatively constant to a depth of ~35 m. The Fe and P speciation data indicate that diagenetic modification of the sediments is largely complete by a depth of 2.5 m, and thus depth trends in molar P/Fe ratios can not solely be explained by losses of P from the sediment by diffusion to the overlying water column during early diagenesis. Instead, these sediments are likely recording changes in dissolved P concentrations off the SEPR, possibly as a result of redistribution of nutrients in response to changes in oceanic circulation over the last 10 million years. Furthermore, the relatively low molar P/Fe ratios observed throughout these sediments are not necessarily solely due to losses of scavenged P by diffusion to the overlying water column during diagenesis, but may also reflect post-depositional oxidation of pyrite originating from the volatile-rich vents of the southern East Pacific Rise. This study suggests that the molar P/Fe ratio of oxic Fe-rich sediments may serve as a proxy of relative changes in paleoseawater phosphate concentrations, particularly if Fe sulfide minerals are not an important component during transport and deposition.

Oxygen isotope and Mg/Ca record of planktonic foraminifera of sediment core MD01-2390

Changes in the local freshwater budget over the last 22,000 years have been estimated from a sediment core located in the southern South China Sea (SCS) using a combined approach of Mg/Ca and oxygen isotopes on the planktonic foraminifera Globigerinoides ruber (white) sensu stricto (s.s.). Core MD01-2390 (06°28,12N, 113°24,56E; water depth 1591 m) is located near the glacial paleo-river mouths of the Baram, Rajang and North Sunda/Molengraaff Rivers that drained the exposed Sunda Shelf. The delta18Oseawater record reveals lower average values (-0.96±0.18 per mil) during the Last Glacial Maximum (LGM) when compared with modern values (-0.54±0.18 per mil). Low salinity during the LGM is interpreted to reflect a higher freshwater contribution due to a greater proximity of the core site to the mouths of the Baram, Rajang and North Sunda/Molengraaff Rivers at that time. A general deglacial increasing trend in salinity due to the progressive landward displacement of the coastline during deglacial shelf flooding is punctuated by several short-term shifts towards higher and lower salinity that are likely related to abrupt changes in the intensity of the East Asian summer monsoon. Thus, the deglacial delta18Oseawater changes reflect the combined effects of sea-level-induced environmental changes on the shelf (e.g. phases of retreat and breakdown of the shelf drainage systems) and East Asian monsoon climate change. Lower salinity than at present during the Early Holocene may be attributed to an increase in summer monsoonal precipitation that is corroborated by previous marine and terrestrial studies that report a Preboreal-Early Holocene monsoon optimum in the Asian monsoon region.

U-Pb, trace element, and Hf isotope analysis for Macquarie Island detrital zircon

Oceanic zircon trace element and Hf-isotope geochemistry offers a means to assess the magmatic evolution of a dying spreading ridge and provides an independent evaluation of the reliability of oceanic zircon as an indicator of mantle melting conditions. The Macquarie Island ophiolite in the Southern Ocean provides a unique testing ground for this approach due to its formation within a mid-ocean ridge that gradually changed into a transform plate boundary. Detrital zircon recovered from the island records this change through a progressive enrichment in incompatible trace elements. Oligocene age (33-27 Ma) paleo-detrital zircon in ophiolitic sandstones and breccias interbedded with pillow basalt have trace element compositions akin to a MORB crustal source, whereas Late Miocene age (8.5 Ma) modern-detrital zircon collected from gabbroic colluvium on the island have highly enriched compositions unlike typical oceanic zircon. This compositional disparity between age populations is not complimented by analytically equivalent eHf data that primarily ranges from 14 to 13 for sandstone and modern-detrital populations. A wider compositional range for the sandstone population reflects a multiple pluton source provenance and is augmented by a single cobble clast with eHf equivalent to the maximum observed composition in the sandstone (~17). Similar sandstone and colluvium Hf-isotope signatures indicate inheritance from a similar mantle reservoir that was enriched from the depleted MORB mantle average. The continuity in Hf-isotope signature relative to trace element enrichment in Macquarie Island zircon populations, suggests the latter formed by reduced partial melting linked to spreading-segment shortening and transform lengthening along the dying spreading ridge.

The magnesium isotope composition of diagenetic dolomites from ODP Hole 112-685A and 201-1230A of the Peru Margin

The magnesium isotope composition of diagenetic dolomites and their adjacent pore fluids were studied in a 250 m thick sedimentary section drilled into the Peru Margin during Ocean Drilling Program (ODP) Leg 201 (Site 1230) and Leg 112 (Site 685). Previous studies revealed the presence of two types of dolomite: type I dolomite forms at ~ 6 m below seafloor (mbsf) due to an increase in alkalinity associated with anaerobic methane oxidation, and type II dolomite forms at focused sites below ~ 230 mbsf due to episodic inflow of deep-sourced fluids into an intense methanogenesis zone. The pore fluid delta 26Mg composition becomes progressively enriched in 26Mg with depth from values similar to seawater (i.e. -0.8 per mil, relative to DSM3 Mg reference material) in the top few meters below seafloor (mbsf) to 0.8 ± 0.2 per mil within the sediments located below 100 mbsf. Type I dolomites have a delta 26Mg of -3.5 per mil, and exhibit apparent dolomite-pore fluid fractionation factors of about -2.6 per mil consistent with previous studies of dolomite precipitation from seawater. In contrast, type II dolomites have delta 26Mg values ranging from -2.5 to -3.0 per mil and are up to -3.6 per mil lighter than the modern pore fluid Mg isotope composition. The enrichment of pore fluids in 26Mg and depletion in total Mg concentration below ~ 200 mbsf is likely the result of Mg isotope fractionation during dolomite formation, The 26Mg enrichment of pore fluids in the upper ~ 200 mbsf of the sediment sequence can be attributed to desorption of Mg from clay mineral surfaces. The obtained results indicate that Mg isotopes recorded in the diagenetic carbonate record can distinguish near surface versus deep formed dolomite demonstrating their usefulness as a paleo-diagenetic proxy.

Pliocene and Pleistocene diatom datum levels of the Northwest Pacific

Thick sections of Pliocene and Pleistocene biosiliceous clay and ooze were recovered by the Hydraulic Piston Corer (I-IPC) at three northwest Pacific sites (DSDP Sites 578, 579, and 580). They contain a well-preserved paleomagnetic record which made it possible to evaluate diatom events used in low and high latitudes in the transitional region of the northwest Pacific. Equatorial Pacific events are usually isochronons between the equatorial and subarctic regions. However, species which have short ranges in low latitudes tend to have diachronous first and last appearances in higher latitudes. All subarctic North Pacific datum species are present in the sediments at three sites which lie north and south across the subarctic front, but their ranges become shorter in southern regions. They do not penetrate into the equatorial region. Spatial distributions of these events are influenced by the paleo-position of the subarctic front. The migration of species from their home-area outwards, in the form of the first appearance, is related to the fluctuations of the subarctic front. The last appearance of species is a response to the change of the surface water temperature that is beyond the limit of tolerance of the species, or an unstable oceanic environment due to major change of climate.