(Table 1) Minor and trace element concentrations in interstitial waters from ODP Leg 166 sites

Concentrations of minor and trace elements (Li, Rb, Sr, Ba, Fe, and Mn) in interstitial water (IW) were found in samples collected during Ocean Drilling Program (ODP) Leg 166 from Sites 1005, 1006, and 1007 on the western flank of the Great Bahama Bank (GBB). Concentrations of Li range from near-seawater values immediately below the sediment/water interface to a maximum of 250 µM deep in Site 1007. Concentrations determined during shore-based studies are substantially lower than the shipboard data presented in the Leg 166 Initial Reports volume (range of 28-439 µM) because of broad-band interferences from high dissolved Sr concentrations in the shipboard analyses. Rubidium concentrations of 1.3-1.7 µM were measured in IW from Site 1006 when salinity was less than 40 psu. A maximum of 2.5 µM is reached downhole at a salinity of 50 psu. Shipboard and shore-based concentrations of Sr2+ are in excellent agreement and vary from 0.15 mM near the sediment water interface to 6.8 mM at depth. The latter represent the highest dissolved Sr2+ concentrations observed to date in sediments cored during the Deep Sea Drilling Project (DSDP) or ODP. Concentrations of Ba2+ span three orders of magnitude (0.1-227µM). Concentrations of Fe (<0.1-14 µM) and Mn (0.1-2 µM) exhibit substantially greater fluctuations than other constituents. The concentrations of minor and trace metals in pore fluids from the GBB transect sites are mediated principally by changes in pore-water properties resulting from early diagenesis of carbonates associated with microbial degradation of organic matter, and by the abundance of detrital materials that serve as a source of these elements. Downcore variations in the abundance of detrital matter reflect differences in carbonate production during various sea-level stands and are more evident at the more proximal Site 1005 than at the more pelagic Site 1006. The more continuous delivery of detrital matter deep in Site 1007 and throughout all of Site 1006 is reflected in a greater propensity to provide trace elements to solution. Concentrations of dissolved Li+ derive principally from (1) release during dissolution of biogenic carbonates and subsequent exclusion during recrystallization and (2) release from partial dissolution of Li-bearing detrital phases, especially ion-exchange reactions with clay minerals. A third but potentially less important source of Li+ is a high-salinity brine hypothesized to exist in Jurassic age (unsampled) sediments underlying those sampled during Leg 166. The source of dissolved Sr2+ is almost exclusively biogenic carbonate, particularly aragonite. Concentrations of dissolved Sr2+ and Ba2+ are mediated by the solubility of their sulfates. Barite and detrital minerals appear to be the more important source of dissolved Ba2+. Concentrations of Fe and Mn2+ in anoxic pore fluids are mediated by the relative insolubility of pyrite and incorporation into diagenetic carbonates. The principal sources of these elements are easily reduced Fe-Mn-rich phases including Fe-rich clays found in lateritic soils and aoelian dust.

Geochemical parameters of bottom sediments from the Tajura Rift, Gulf of Aden

Results of a geochemical study of bottom sediments from the Tadjura rift zone are reported. The sediments were analyzed for CaCO3, Si, Al, Ti, Fe, Mn, Cu, Zn, Ni, Co, Cr, V, Zr, Ga, Yb and Y. It was found that formation of chemical composition of the sediments was controlled by factors being appropriate for a near-continental area of the arid climatic zone (aeolian supply of terrigenous material and high biological productivity), as well as by hydrothermal activity in the rift valley. It was shown that high Mn contents were typical for the sediments in study while maximal contents of Fe were found near supposed hydrothermal sources. Total flux of Mn into sediments was been calculated. Diagenetic redistribution gives the main contribution of Mn in surface layer sediments. Speciations of Fe, Mn, Cu, Zn, Ni, Co, and Al were studied. In the surface layer sediments iron and manganese were in hydroxides. Model calculations of contents of chemical elements in sediments of the area in study are given.

Concentrations and isotopic compositions of low molecular weight hydrocarbons in hydrothermal fluids from ODP Field, Middle Valley, northern Juan de Fuca Ridge

The presence of sedimentary organic matter blanketing midocean ridge crests has a potentially strong impact on metal transport in hydrothermal vent fluids. To constrain the role of organic matter in metal mobility during hydrothermal sediment alteration, we reacted organic-rich diatomaceous ooze from Guaymas Basin, Gulf of California, and organic-poor hemipelagic mud from Middle Valley, northern Juan de Fuca Ridge, with seawater and a Na-Ca-K-Cl fluid of seawater chlorinity, at 275° to 400°C, 350 to 500 bars, and initial fluid: sediment mass ratios ranging from 1.6 to 9.8. Reaction of these fluids with both sediment types released CO2 and high concentrations of ore-forming metals (Fe, Mn, Zn, Pb) to solution. Relatively low concentrations of Cu were observed in solution and likely reflect the reducing conditions that resulted from the presence of sedimentary organic matter. Both the concentrations of CO2 and dissolved metals were lower in fluids reacted with Middle Valley sediment compared with aqueous concentrations in fluids reacted with Guaymas Basin sediment. During alteration of both sediment types, metal concentrations varied strongly as a function of temperature, increasing by up to an order of magnitude over the 75°C range of each experiment. Major element fluid chemistry and observed alteration assemblages suggest that during hydrothermal alteration of organic-lean sediment from Middle Valley a feldspar-quartz-illite mineral assemblage buffered in situ pH. In contrast, data from the experimental alteration of organic-rich Guaymas Basin sediment suggest that a calcite-plagioclase-quartz assemblage regulated in situ pH. Fluid speciation calculations suggest that in situ pH during Guaymas Basin sediment alteration was lower than during alteration of Middle Valley sediment and accounts for the substantially greater metal mobility at a given temperature and pressure during the former experiment. Comparison of our results with the results of basalt alteration experiments indicate that except for Cu, hydrothermal sediment alteration results in equal or greater concentrations of ore-forming metals at a given temperature and pressure. Accordingly, the presence of ore-forming metals in fluids currently venting from sediment-covered hydrothermal systems at concentrations substantially lower than in fluids from bare-rock systems may reflect chemical reequilibration during subsurface cooling within the sediment pile.

(Table 1, page 661) Average composition of fossil nodules from three localities studied in the Transdanubian Central Mountains of Hungary

Fossil manganese nodules and encrustations from seamount' and basin' localities in the Transdanubian Central Mountains of Hungary are lithologically, mineralogically and chemically similar to some modern marine ferromanganese oxide deposits, and show no evidence of postdepositional changes other than cementation. Five groups of deposits were encountered: Fe/Mn nodules, encrusted shells, pavements, stains, and Fe oxide encrusted intraclasts, the first three of which are specific to the 'seamount' environment and the last to the basins'. Optical and electron microprobe investigation of the samples shows them to exhibit many similarities with modern ferromanganese oxide deposits, and that many of the nodules are surrounded by a halo of dispersed ferromanganese oxides, strongly suggesting that they continued to accrete metals through the pore waters of unlithified sediments for a period after burial. By contrast, pavements which appear to have grown on hardgrounds at the sea floor show little or no evidence of derivation of metals from underlying sediments. Geochemical investigations on the deposits show the seamount' varieties to be closer in composition to most modern nodules and crusts than the basin' varieties, and that the latter are essentially manganese and trace-element-poor ferruginous deposits. Nevertheless, all can be more or less compositionally equated with modern ferromanganese oxide deposits forming in marginal Atlantic environments, which would be in accord with the proposed depositional environment of the Transdanubian Central Mountains based on other evidence.

Investigation of manganese nodules from the Malvinas (Falkland) Plateau

Manganese nodules occurring within marine sediments of presumably Upper Miocene-Lower Pliocene age from cores obtained by the Argentine oceanographic vessel ARA Islas Orcadas in 1977 on the Malvinas (Falkland) Plateau and neighbouring Scotia Sea were studied with the aim of comparing them with other fossil nodules found on the mainland of Argentina that were also ascribed to the marine environment. After optical mineralogical, chemical, X-ray and trace element analysis, the studied "nodules" proved to be actually wacke clasts cemented by manganese oxides with a high Fe/Mn ratio corresponding to a continental environment. The studied "nodules" thus differ from the Argentine mainland nodules and are supposed to have been transported from continental environments and then deposited in the marine realms. The wacke clasts became then nuclei for the deposition of the marine manganese oxides of the coatings. The proportion of trace elements, which is high, suggests the growth of the nodules in the marine environment.

(Table 3) Barium barite and excess comparison, accumulation rates and productivity from surface sediments

Since Dymond et al. (1992, doi:10.1029/92PA00181) proposed the paleoproductivity algorithm based on "Bio-Ba", which relies on a strong correlation between Ba and organic carbon fluxes in sediment traps, this proxy has been applied in many paleoproductivity studies. Barite, the main carrier of particulate barium in the water column and the phase associated with carbon export, has also been suggested as a reliable paleoproductivity proxy in some locations. We demonstrate that Ba(excess) (total barium minus the fraction associated with terrigenous material) frequently overestimates Ba(barite) (barium associated with the mineral barite), most likely due to the inclusion of barium from phases other than barite and terrigenous silicates (e.g., carbonate, organic matter, opal, Fe-Mn oxides, and hydroxides). A comparison between overlying oceanic carbon export and carbon export derived from Ba(excess) shows that the Dymond et al. (1992) algorithm frequently underestimates carbon export but is still a useful carbon export indicator if all caveats are considered before the algorithm is applied. Ba(barite) accumulation rates from a wide range of core top sediments from different oceanic settings are highly correlated to surface ocean 14C and Chlorophyll a measurements of primary production. This relationship varies by ocean basin, but with the application of the appropriate f ratio to 14C and Chlorophyll a primary production estimates, the plot of Ba(barite) accumulation and carbon export for the equatorial Pacific, Atlantic, and Southern Ocean converges to a global relationship that can be used to reconstruct paleo carbon export.

Radionuclides measured on 27 water bottle profiles during POLARSTERN cruise ANT-XXIV/3

As part of the GEOTRACES Polarstern expedition ANT XXIV/3 (ZERO and DRAKE) we have measured the vertical distribution of 234Th on sections through the Antarctic Circumpolar Current along the zero meridian and in Drake Passage and on an EW section through the Weddell Sea. Steady state export fluxes of 234Th from the upper 100m, derived from the depletion of 234Th with respect to its parent 238U, ranged from 621±105 dpm/m**2/d to 1773±90 dpm/m**2/d. This 234Th flux was converted into an export flux of organic carbon ranging from 3.1-13.2 mmolC/m**2/d (2.1-9.0 mmolC/m**2/d) using POC/234Th ratio of bulk (respectively >50 µm) suspended particles at the export depth (100 m). Non-steady state fluxes assuming zero flux under ice cover were up to 23% higher. In addition, particulate and dissolved 234Th were measured underway in high resolution in the surface water with a semi-automated procedure. Particulate 234Th in surface waters is inversely correlated with light transmission and pCO2 and positively with fluorescence and optical backscatter and is interpreted as a proxy for algal biomass. High resolution underway mapping of particulate and dissolved 234Th in surface water shows clearly where trace elements are absorbed by plankton and where they are exported to depth. Quantitative determination of the export flux requires the full 234Th profile since surface depletion and export flux become decoupled through changes in wind mixed layer depth and in contribution to export from subsurface layers. In a zone of very low algal abundance (54-58 °S at the zero meridian), confirmed by satellite Chl-a data, the lowest carbon export of the ACC was observed, allowing Fe and Mn to maintain their highest surface concentrations (Klunder et al., this issue, Middag et al., this issue). An ice-edge bloom that had developed in Dec/Jan in the zone 60-65 °S as studied during the previous leg (Strass et al., in prep) had caused a high export flux at 64.5 °S when we visited the area two months later (Feb/March). The ice-edge bloom had then shifted south to 65-69 °S evident from uptake of CO2 and dissolved Fe, Mn and 234Th, without causing export yet. In this way, the parallel analysis of 234Th can help to explain the scavenging behaviour of other trace elements.

(Table 2) Chemical composition of bottom sediments from the Equatorial East Pacific

Fe, Mn, Cu, Ni, and Co contents in bottom sediment samples from the Clarion Clipperton fracture zone and Guatemala Basin were studied; maps of their distribution in the upper layer of sediments were prepared. At some stations contents of these elements were also measured in Pleistocene and Oligocene sediments. Elevated contents of five ore elements (except for Zn) were found at the East Pacific Rise and in the Clarion-Clipperton province; and of Mn, Ni, and Cu in the Guatemala basin. Increased zinc contents occur only in sediments of the East Pacific Rise and Guatemala Basin. Enrichment of sediments in these elements results from under¬water hydrothermal activity and high biological productivity.

Chemical composition of oxide-phosphorite pavement from the Blake Plateau under various preparation treatment

Sample preparation technique is critical for valid chemical analyses. A main source of error comes from the fact that the great specific surface area of crusts or nodules enhances their tendency to retain or attract hygroscopic moisture. Variable treatment of this moisture can in extreme cases lead to analytical value differences as great as 40-50 %. In order to quantify these influences, samples of ferromanganese oxide-phosphorite pavement from the Blake Plateau have been subjected to various drying techniques before analysis using X-ray fluorescence.

Heavy metals and carbon isotope concentrations in recent Baltic Sea sediments

Recent sediment cores of the western Baltic Sea were analyzed for heavy metal and carbon isotope contents. The sedimentation rate was determined from radiocarbon dates to be 1.4 mm/yr. The 'recent age' of the sediment was about 850 yr. Within the upper 20 cm of sediment, certain heavy metals became increasingly enriched towards the surface; Cd, Pb, Zn and Cu increased 7-, 4-, 3- and 2-fold, respectively, whereas Fe, Mn, Ni and Co remained unchanged. Simultaneously, the radiocarbon content decreased by about 14 per cent. The enrichment in heavy metals as well as the decrease in the 14C-concentration during the last 130 ± 30yr parallels industrial growth as reflected in European fossil fuel consumption within that same period of time. The near-surface sediments are affected by residues released from fossil fuels at the rate of about 30 g/m**2 yr for the past two decades. The residues have a pronounced effect on the heavy metal and carbon isotope composition of the most Recent sediments allowing estimates to be made for sedimentation, erosion and heavy metal pollution.

(Table 1) Chemical composition of Central Pacific manganese micronodules containing birnessite as a major component

Detailed mineralogical characterization of micronodules is given. The main regularities of variations in composition of micronodules from Central Pacific sedimentary rocks of different ages are revealed. New data on structure and structural features of manganese minerals are reported.

(Table 1) Major and trace element composition of sediment core PS 70/306-3, Gakkel Ridge

The paper presents data on the chemical composition of Late Pleistocene-Holocene sediments in the Gakkel Ridge according to data on sediment core PS 70/306-3, offers a hypothetical litho-stratigraphic model, and provides data on chemo-stratigraphic horizons distinguished based on the distribution of carbonates, organic carbon, metals (Fe, Mn, Cu, Zn, Co, Ni, V, Pb), As, and P in the core. Chemical transformations of sediments at the redox barrier are discussed, along with relations between the composition of the sediments and the facies sedimentation conditions.

Geochemistry of the Japan Trench sediments at DSDP Legs 56-57 Holes

The main objective of this investigation was to study distribution of main chemical constituents and several minor elements in sediment sections drilled during DSDP Legs 56 and 57 in the Japan Trench, in order to infer geochemical features of different lithologic types of sediments, and to find out how the geochemistry is associated with major lithologic constituents, such as terrigenous detrital matter, clay, volcanic ash, and biogenic particles. The geochemical data may help to indicate the nature of the sediments and to interpret sedimentation processes. The analyzed samples seem to be representative of most lithologic units, sub-units, and sediment types drilled at all sites on both legs, except for some shallow-water deposits at Sites 438 and 439. We analyzed bulk-sediment composition by X-ray fluorescence (Kuzmina and Turanskaya) and routine wet-chemical methods (Mikhailov); amorphous SiO2, extracted in a boiling sodium carbonate solution (Analythical Laboratory, P. P. Shirshov Institute of Oceanology); Cr, Zn, Cu, Ni, Co, and Al by atomic absorption (Gordeev); and Sn, Pb, Zn, Cu, Ni, Co, Cr, V, B, and Ag by quantitative spectrographic analyses in both bulk samples and granulometric fractions (Mikhailov). In addition, Fe, Ti, Mn, and CaCO3 have been determined in selected samples by routine wet-chemical methods (Analytical Laboratory, P. P. Shirshov Institute of Oceanology). Murdmaa was responsible for interpretation of the results.

Contents of metal cations exchange capacity of ore minerals in ferromanganese micronodules from the Atlantic, Indian and Pacific Oceans

Results of experimental studies of ion exchange properties of manganese and iron minerals in micronodules from diverse bioproductive zones of the World Ocean were considered. It was found that sorption behavior of these minerals was similar to that of ore minerals from ferromanganese nodules and low-temperature hydrothermal crusts. The exchange complex of minerals in the micronodules includes the major (Na**+, K**+, Ca**2+, Mg**2+, and Mn**2+) and subordinate (Ni**2+, Cu**2+, Co**2+, Pb**2+, and others) cations. Reactivity of theses cations increases from Pb**2+ and Co**2+ to Na**+ and Ca**2+. Exchange capacity of micronodule minerals increases from alkali to heavy metal cations. Capacity of iron and manganese minerals in oceanic micronodules increases in the following series: goethite < goethite + birnessite < todorokite + asbolane-buserite + birnessite < asbolane-buserite + birnessite < birnessite + asbolane-buserite < birnessite + vernadite ~= Fe-vernadite + Mn-feroxyhyte. Obtained data supplement available information on ion exchange properties of oceanic ferromanganese sediments and refine the role of sorption processes in redistribution of metal cations at the bottom water - sediment interface during micronodule formation and growth.

Raw and normalized X-ray fluorescence (XRF) scannings of IODP Expedition 321, Site U1338

We used X-ray fluorescence (XRF) scanning on Site U1338 sediments from Integrated Ocean Drilling Program Expedition 321 to measure sediment geochemical compositions at 2.5 cm resolution for the 450 m of the Site U1338 spliced sediment column. This spatial resolution is equivalent to ~2 k.y. age sampling in the 0-5 Ma section and ~1 k.y. resolution from 5 to 17 Ma. Here we report the data and describe data acquisition conditions to measure Al, Si, K, Ca, Ti, Fe, Mn, and Ba in the solid phase. We also describe a method to convert the data from volume-based raw XRF scan data to a normalized mass measurement ready for calibration by other geochemical methods. Both the raw and normalized data are reported along the Site U1338 splice.