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.

Uranium contents and isotope ratios of uranium and strontium in sediments, leachates and pore fluids from ODP Hole 162-984A

Bulk dissolution rates for sediment from ODP Site 984A in the North Atlantic are determined using the 234U/238U activity ratios of pore water, bulk sediment, and leachates. Site 984A is one of only several sites where closely spaced pore water samples were obtained from the upper 60 meters of the core; the sedimentation rate is high (11-15 cm/ka), hence the sediments in the upper 60 meters are less than 500 ka old. The sediment is clayey silt and composed mostly of detritus derived from Iceland with a significant component of biogenic carbonate (up to 30%). The pore water 234U/238U activity ratios are higher than seawater values, in the range of 1.2 to 1.6, while the bulk sediment 234U/238U activity ratios are close to 1.0. The 234U/238U of the pore water reflects a balance between the mineral dissolution rate and the supply rate of excess 234U to the pore fluid by a-recoil injection of 234Th. The fraction of 238U decays that result in a-recoil injection of 234U to pore fluid is estimated to be 0.10 to 0.20 based on the 234U/238U of insoluble residue fractions. The calculated bulk dissolution rates, in units of g/g/yr are in the range of 0.0000004 to 0.000002 1/yr. There is significant down-hole variability in pore water 234U/238U activity ratios (and hence dissolution rates) on a scale of ca. 10 m. The inferred bulk dissolution rate constants are 100 to 1000 times slower than laboratory-determined rates, 100 times faster than rates inferred for older sediments based on Sr isotopes, and similar to weathering rates determined for terrestrial soils of similar age. The results of this study suggest that U isotopes can be used to measure in situ dissolution rates in fine-grained clastic materials. The rate estimates for sediments from ODP Site 984 confirm the strong dependence of reactivity on the age of the solid material: the bulk dissolution rate (R_d) of soils and deep-sea sediments can be approximately described by the expression R_d ~ 0.1 1/age for ages spanning 1000 to 500,000,000 yr. The age of the material, which encompasses the grain size, surface area, and other chemical factors that contribute to the rate of dissolution, appears to be a much stronger determinant of dissolution rate than any single physical or chemical property of the system.

Grain size and chemical compositions of bottom sediments from the Amur Bay

Composition of clay minerals in the <0.001 mm size fraction from the uppermost layer of bottom sediments in the northern Amur Bay was determined by X-ray powder diffraction analysis, and enrichment of 33 elements in the <0.001 mm and <0.01 mm size fractions of surface sediments from a number of sites at the marginal filter of the Razdol'naya River were studied by ICP-MS. Fe, U, and chalcophile elements occur in the highest concentrations in sediments from all sampling sites within the filter. The bottom sediments are not enriched in trace, alkali, and alkaline earth elements. Maximum concentrations of chemical elements were found in deposits from the brackish part of the marginal filter, perhaps, because of formation of Fe and Mn (Al) hydroxides. Bottom sediments at the boundary between the brackish and marine parts of the filter contain the lowest concentrations of the examined elements.

Geochemistry and accumulation rates of the early Paleogene in the Weddel Sea, Maud Rise and Kerguelen Plateau

Marine biological productivity has been invoked as a possible climate driver during the early Paleogene through its potential influence on atmospheric carbon dioxide concentrations. However, the relationship of export productivity (the flux of organic carbon (C) from the surface ocean to the deep ocean) to organic C burial flux (the flux of organic C from the deep ocean that is buried in marine sediments) is not well understood. We examine the various components involved with atmosphere-to-ocean C transfer by reconstructing early Paleogene carbonate and silica production (using carbonate and silica mass accumulation rates (MARs)); export productivity (using biogenic barium (bio-Ba) MARs); organic C burial flux (using reactive phosphorus (P) MARs); redox conditions (using uranium and manganese contents); and the fraction of organic C buried relative to export productivity (using reactive P to bio-Ba ratios). Our investigations concentrate on Paleocene/Eocene sections of Sites 689/690 from Maud Rise and Site 738 from Kerguelen Plateau. In both regions, export productivity, organic C burial flux, and the fraction of organic C buried relative to export productivity decreased from the Paleocene/early Eocene to the middle Eocene. A shift is indicated from an early Paleogene two-gyre circulation in which nutrients were not efficiently recycled to the surface via upwelling in these regions, to a circulation more like the present day with efficient recycling of nutrients to the surface ocean. Export productivity was enhanced for Kerguelen Plateau relative to Maud Rise throughout the early Paleogene, possibly due to internal waves generated by the plateau regardless of gyre circulation.

Chemical and isotopic compositions of altered MORB from ODP Holes 187-1154A, 187-1155B, and 187-1160B

Boron and Pb isotopic compositions together with B-U-Th-Pb concentrations were determined for Pacific and Indian mantle-type mid-ocean ridge basalts (MORB) obtained from shallow drill holes near the Australian Antarctic Discordance (AAD). Boron contents in the altered samples range from 29.7 to 69.6 ppm and are extremely enriched relative to fresh MORB glass with 0.4-0.6 ppm B. Similarly the d11B values range from 5.5? to 15.9? in the altered basalts and require interaction with a d11B enriched fluid similar to seawater ~39.5? and/or boron isotope fractionation during the formation of secondary clays. Positive correlations between B concentrations and other chemical indices of alteration such as H2O CO2, K2O, P2O5, U and 87Sr/86Sr indicate that B is progressively enriched in the basalts as they become more altered. Interestingly, d11B shows the largest isotopic shift to +16? in the least altered basalts, followed by a continual decrease to +5-6? in the most altered basalts. These observations may indicate a change from an early seawater dominated fluid towards a sediment-dominated fluid as a result of an increase in sediment cover with increasing age of the seafloor. The progression from heavy d11B towards lighter values with increasing degrees of alteration may also reflect increased formation of clay minerals (e.g., saponite). A comparison of 238U/204Pb and 206Pb/204Pb in fresh glass and variably altered basalt from Site 1160B shows extreme variations that are caused by secondary U enrichment during low temperature alteration. Modeling of the U-Pb isotope system confirms that some alteration events occurred early in the 21.5 Ma history of these rocks, even though a significant second pulse of alteration happened at ~12 Ma after formation of the crust. The U-Pb systematics of co-genetic basaltic glass and variably low temperature altered basaltic whole rocks are thus a potential tool to place age constraints on the timing of alteration and fluid flow in the ocean crust.

Impact of CO2 enrichment on organic matter dynamics during nutrient induced coastal phytoplankton blooms

A mesocosm experiment was conducted to investigate the impact of rising fCO2 on the build-up and decline of organic matter during coastal phytoplankton blooms. Five mesocosms (~38 m³ each) were deployed in the Baltic Sea during spring (2009) and enriched with CO2 to yield a gradient of 355-862 µatm. Mesocosms were nutrient fertilized initially to induce phytoplankton bloom development. Changes in particulate and dissolved organic matter concentrations, including dissolved high-molecular weight (>1 kDa) combined carbohydrates, dissolved free and combined amino acids as well as transparent exopolymer particles (TEP), were monitored over 21 days together with bacterial abundance, and hydrolytic extracellular enzyme activities. Overall, organic matter followed well-known bloom dynamics in all CO2 treatments alike. At high fCO2, higher dPOC:dPON during bloom rise, and higher TEP concentrations during bloom peak, suggested preferential accumulation of carbon-rich components. TEP concentration at bloom peak was significantly related to subsequent sedimentation of particulate organic matter. Bacterial abundance increased during the bloom and was highest at high fCO2. We conclude that increasing fCO2 supports production and exudation of carbon-rich components, enhancing particle aggregation and settling, but also providing substrate and attachment sites for bacteria. More labile organic carbon and higher bacterial abundance can increase rates of oxygen consumption and may intensify the already high risk of oxygen depletion in coastal seas in the future.

Investigations on seven sediment cores from the New Ireland Basin, east of Papua New Guinea

Sediment cores were recovered from the New Ireland Basin, east of Papua New Guinea, in order to investigate the late Quaternary eruptive history of the Tabar-Lihir-Tanga-Feni (TLTF) volcanic chain. Foraminifera d18O profiles were matched to the low-latitude oxygen isotope record to date the cores, which extend back to the early part of d18O Stage 9 (333 ka). Sedimentation rates decrease from >10 cm/1000 yr in cores near New Ireland to ~2 cm/1000 yr further offshore. The cores contain 36 discrete ash beds, mostly 1-8 cm thick and interpreted as either fallout or distal turbidite deposits. Most beds have compositionally homogeneous glass shard populations, indicating that they represent single volcanic events. Shards from all ash beds have the subduction-related pattern of strong enrichment in the large-ion lithophile elements relative to MORB, but three distinct compositional groups are apparent: Group A beds are shoshonitic and characterised by >1300 ppm Sr, high Ce/Yb and high Nb/Yb relative to MORB, Group B beds form a high-K series with MORB-like Nb/Yb but high Ce/Yb and well-developed negative Eu anomalies, whereas Group C beds are transitional between the low-K and medium-K series and characterised by flat chondrite-normalised REE patterns with low Nb/Yb relative to MORB. A comparison with published data from the TLTF chain, the New Britain volcanic arc and backarc including Rabaul, and Bagana on Bougainville demonstrates that only Group A beds share the distinctive phenocryst assemblage and shoshonitic geochemistry of the TLTF lavas. The crystal- and lithic-rich character of the Group A beds point to a nearby source, and their high Sr, Ce/Yb and Nb/Yb match those of Tanga and Feni lavas. A youthful stratocone on the eastern side of Babase Island in the Feni group is the most probable source. Group A beds younger than 20 ka are more fractionated than the older Group A beds, and record the progressive development of a shallow level magma chamber beneath the cone. In contrast, Group B beds represent glass-rich fallout from voluminous eruptions at Rabaul, whereas Group C beds represent distal glass-rich fallout from elsewhere along the volcanic front of the New Britain arc.