Geochemistry of ferromanganese deposits from the Wombat Plateau

Ferromanganese crusts, nodules, and ferromanganese-rich sediments were recovered on the Wombat Plateau, northwest Australian continental margin, by dredging during Bureau of Mineral Resources cruise 56 of Rig Seismic and by drilling during ODP Leg 122 of JOWES Resolution. We report here the chemistry and mineralogy of the ferromanganese crusts, nodules, and associated ferromanganese-rich sediments. The ferromanganese deposits from the ODP sites are up to 40 cm thick and probably formed in Late Cretaceous to Eocene times. Those from outcrops usually formed in several phases, and their age is unconstrained except that the substrates are Mesozoic. The samples were recovered from present-day water depths of 2000-4600 m, on the Wombat Plateau adjacent to the Argo Abyssal Plain. Both the nodules and crusts are primarily vernadite (delta-MnO2) and are chemically and mineralogically similar, and not dissimilar from ferromanganese deposits found elsewhere on Australian and other marginal plateaus. They are markedly different from most deep-sea deposits. The only crystalline iron phase identified within the ferromanganese deposits is goethite. Concentrations of metals of potential economic interest are generally low compared to those from vernadite-rich seamount crusts and nodules and from abyssal nodules from areas of high resource potential in the Pacific Ocean. Maximum metal values reach 0.55% Co, 0.58% Ni, and 0.20% Cu in deposits containing 4.8% to 30.9% Fe and 4.4% to 21.1% Mn.

Grain-size distributions and bulk chemistry of sediment core MD00-2361

The terrigenous fraction of sediments from a deep-sea sediment core recovered from the northwestern Western Australian continental slope offshore North West Cape, SE Indian Ocean, reveals a history of Western Australian climate throughout the last 550 ka. End-member modelling of a data set of grain-size distributions (n = 438) of the terrigenous sediment fraction allows to interpret the record in terms of aeolian and fluvial sediment deposition, both related to palaeo-environmental conditions in the North West Cape area. The data set can be best described by two aeolian end members and one fluvial one. Changes in the ratio of the two aeolian end members over the fluvial one are interpreted as aridity variations in northwestern Western Australia. These grain-size data are compared with bulk geochemical data obtained by XRF scans of the core. Log-ratios of the elements Zr/Fe and Ti/Ca, which indicate a terrigenous origin, corroborate the grain-size data. We postulate that the mid- to late Quaternary near North West Cape climate was relatively arid during the glacial and relatively humid during the interglacial stages, owing to meridional shifts in the atmospheric circulation system. Opposite to published palaeo-environmental records from the same latitude (20°S) offshore Chile and offshore Namibia, the Australian aridity record does not show the typical southern hemisphere climate variability of humid glacials and dry interglacials, which we interpret to be the result of the relatively large land mass of the Australian continent, which emphasises a strong monsoonal climatic system.

(Table 1) Biological and chemical characteristics of surface water stations during Nathaniel B. Palmer cruise NBP06-08 to the Ross Sea

We present results from a field study of inorganic carbon (C) acquisition by Ross Sea phytoplankton during Phaeocystis-dominated early season blooms. Isotope disequilibrium experiments revealed that HCO3? was the primary inorganic C source for photosynthesis in all phytoplankton assemblages. From these experiments, we also derived relative enhancement factors for HCO3?/CO2 interconversion as a measure of extracellular carbonic anhydrase activity (eCA). The enhancement factors ranged from 1.0 (no apparent eCA activity) to 6.4, with an overall mean of 2.9. Additional eCA measurements, made using membrane inlet mass spectrometry (MIMS), yielded activities ranging from 2.4 to 6.9 U/[?g chl a] (mean 4.1). Measurements of short-term C-fixation parameters revealed saturation kinetics with respect to external inorganic carbon, with a mean half-saturation constant for inorganic carbon uptake (K1/2) of ~380 ?M. Comparison of our early springtime results with published data from late-season Ross Sea assemblages showed that neither HCO3? utilization nor eCA activity was significantly correlated to ambient CO2 levels or phytoplankton taxonomic composition. We did, however, observe a strong negative relationship between surface water pCO2 and short-term 14C-fixation rates for the early season survey. Direct incubation experiments showed no statistically significant effects of pCO2 (10 to 80 Pa) on relative HCO3? utilization or eCA activity. Our results provide insight into the seasonal regulation of C uptake by Ross Sea phytoplankton across a range of pCO2 and phytoplankton taxonomic composition.

Bulk geochemistry and grain-size composition of surface sediments from the SW Atlantic

Surface sediments from the South American continental margin surrounding tbe Argentine Basin were studied with respect to bulk geochemistry (Caeo) and C ) and grain-size composition (sand/silt/clay relation and terrigenous silt grain-size distribution). The grain-size distributions of the terrigenous silt fraction were unmixed into three end members (EMs), using an end-member modelling algorithm. Three unimodal EMs appear to satisfactorily explain the variations in the data set of the grain-size distributions ofterrigenous silt. The EMs are related to sediment supply by rivers, downslope transport, winnowing, dispersal and re-deposition by currents. The bulk geochemical composition was used to trace the distribution of prominent water masses within the vertical profile. The sediments of the eastern South American continental margin are generally divided into a coarse-grained and carbonate-depleted southwestern part, and a finer-grained and carbonate-rich northeastern part. The transition of both environments is located at the position of the Brazil Malvinas Confluence (BMC). The sediments below the confluence mixing zone of the Malvinas and Brazil Currents and its extensions are characterised by high concentrations of organic carbon, low carbonate contents and high proportions of the intennediate grain-size end member. Tracing these properties, the BMC emerges as a distinct north-south striking feature centered at 52-54°W crossing the continental margin diagonally. Adjacent to this prominent feature in the southwest, the direct detrital sediment discharge of the Rio de la Plata is clearly recognised by a downslope tongue of sand and high proportions of the coarsest EM. A similar coarse grain-size composition extends further south along the continental slope. However, it displays bener sorting due to intense winnowing by the vigorous Malvinas Current. Fine-grained sedimentary deposition zones are located at the southwestern deeper part of the Rio Grande Rise and the southern abyssal Brazil Basin, both within the AABW domain. Less conspicuous winnowing/accumulation panerns are indicated north of the La Plata within the NADW level according to the continental margin topography. We demonstrate that combined bulk geochemical and grain-size properties of surface sediments, unmixed with an end-member algorithm, provide a powerful tool to reconstruct the complex interplay of sedimentology and oceanography along a time slice.

Coccoliths and carbonate grain-size compositions in sediment samples from the Mid-Atlantic Ridge

This study presents a differentiated carbonate budget for marine surface sediments from the Mid-Atlantic Ridge of the South Atlantic, with results based on carbonate grain-size composition. Upon separation into sand, silt, and clay sub-fractions, the silt grain-size distribution was measured using a SediGraph 5100. We found regionally characteristic grain-size distributions with an overall minimum at 8 µm equivalent spherical diameter (ESD). SEM observations reveal that the coarse particles (>8 µm ESD) are attributed to planktic foraminifers and their fragments, and the fine particles (<8 µm ESD) to coccoliths. On the basis of this division, the regional variation of the contribution of foraminifers and coccoliths to the carbonate budget of the sediments are calculated. Foraminifer carbonate dominates the sediments in mesotropic regions whereas coccoliths contribute most carbonate in oligotrophic regions. The grain size of the coccolith share is constant over water depth, indicating a lower susceptibility for carbonate dissolution compared to foraminifers. Finally, the characteristic grain-size distribution in fine silt (<8 µm ESD) is set into context with the coccolith assemblage counted and biometrically measured using a SEM. The coccoliths present in the silt fraction are predominantly large species (length > 4 µm). Smaller species (length < 4 µm) belong to the clay fraction (<2 µm ESD). The average length of most frequent coccolith species is connected to prominent peaks in grain-size distributions (ESD) with a shape factor. The area below Gaussian distributions fitted to these peaks is suggested as a way to quantitatively estimate the carbonate contribution of single coccolith species more precisely compared to conventional volume estimates. The quantitative division of carbonate into the fraction produced by coccoliths and that secreted by foraminifers enables a more precise estimate for source/sink relations of consumed and released CO2 in the carbon cycle. The allocation of coccolith length and grain size (ESD) suggests size windows for the separation or accumulation of distinct coccolith species in investigations that depend on non to slightly-mixed signals (e.g., isotopic studies).

(Table 1) 137Cs and 90Sr concentrations, salinity, and temperature in waters of the southeastern Baltic Sea on October 16, 2001

An analysis of variations in 137Cs and 90Sr concentrations in Baltic Sea surface waters after the accident at the Chernobyl nuclear power plant was performed. Instability of 137Cs concentrations during the short-term observations was found, when they differed 2- to 3-fold. Concentrations of 90Sr appeared to be more stable; meanwhile, their deviations sometimes exceeded ranges of experimental errors. By variations in the monthly average values of radionuclide concentrations in surface waters of the Baltic Sea in 1989-1995, no trend of water self-purification was observed. Theoretical results obtained confirmed a potential of formation and propagation of patches with increased concentrations of 137Cs in the southeastern Baltic Sea. The most reliable factor that controlled the process of self-purification of Baltic Sea water appeared to be the mean annual value of radionuclide concentration. Pronounced divergences were obtained between the measured and calculated mean annual concentrations of 137Cs and 90Sr in surface waters of the Baltic Sea in 1989-2001. These divergences are explained by potential influence of waters from the Gulf of Bothnia and by other additional supplies of radionuclides to marine environment, which were not included into mathematical models.

(Table 1) Composition of manganese-iron accumulates in the Kiel Bay, western Baltic Sea

Manganese-iron accumulates in the Kiel Bay were investigated with regard to their occurence, chemical composition and formation. Three morphologically different types were identified: a) growth on mussels, b) spherical nodules (ca. 1-3 cm) and c) disshaped symetrical and asymetrical nodules (up to 10 cm). Average values from 110 accumulates representing the three types were: Mn 29.3%, Fe 10.0%, Co 77 ppm, Ni 97 ppm, Cu 21 ppm and Zn 340 ppm. Accumulates on mussels showed the highest trace metal concentrations. A growth rate of ca. 0.6 mm/yr for type (a) was estimated. Heavy metal concentrations were determined in ca. 60 sediment and 30 pore water samples, and in 110 Baltic sea water samples. During certain periods, large increases in Mn values (up to 400 (µg/l) were found in the deeper waters. These concentrations develop during periods of strong stagnant conditions in the sediments where dissolution of Mn oxides, and diffusion mobilizes the Mn into the overlying waters. The manganese is then reprecipitated close to the boundary of the O2-enriched surface waters. This critical O2-concentration was found to be 40% saturation. In the Kiel Bay, Mn-Fe-accumulates are found in a zone which marks the upper limit sometimes reached by the deep waters of lower O2-concentration. Additionally, the availability of larger particles (especially stones or mussels) on the sediment surface is necessary. These conditions are met in the Kiel Bay in a water depth of 20-28 m at several places.

Census of calcareous nannofossil taxa expressed as percent of total number of individuals counted, ODP Legs 113, 114, 119, 120

Quantitative analysis of upper Eocene-upper Oligocene calcareous nannofossil assemblages from five Ocean Drilling Program sites in the Atlantic and Indian Ocean sectors of the Southern Ocean reveals an abrupt increase in cool-water taxa at the top of magnetic Subchron C13R ca. 35.9 Ma, coincident with an enrichment of ~1? d18O in the planktonic foraminifers at these sites. The synchrony of the abrupt increase in cool-water taxa in the Southern Ocean renders this event a useful biostratigraphic datum at southern high latitudes. This earliest Oligocene cool-water taxa increase was the sharpest and largest during the late Eocene-late Oligocene interval and indicates a drop in surface-water temperature of more than 3°C in the Southern Ocean. This suggests that the earliest Oligocene d18O shift represents primarily a temperature signal; a small portion (~0.2?) is attributable to a global ice-volume increase.

Grain size analysis and sedimentation rates of ODP Hole 175-1085A off the Namibian coast

Sediments from the ODP Site 1085A were studied to investigate the impacts of global cooling in the Middle and Late Miocene on the climate in Southwestern Africa. The size composition of the sediment was analysed emphasising the silt fraction. A comparison with the modern grain size distribution and suitable transport processes made it possible to assign specific transport processes to the grain size composition. Three processes are considered for transport of terrigeneous silt: while there was no evidence found for (1) transport by ocean currents, the analyses showed signals of (2) wind transport indicating dry conditions associated with a cool climate and (3) fluvial transport that points to humid and warm conditions. Three climatic phases were defined. The first phase from 13.8 to 11.8 Myr reveals a stable humid climate in Southwest Africa independent of the Antarctic glaciations. During the second phase from 11.8 to 10.4 Myr the regional climate cooled considerably but was not drier. Additionally, the climate during this phase reacted to the Antarctic glaciations. This cooling-trend continued during phase 3 from 10.4 to 9.0 Myr with a significant increase in dust input, pointing to overall drier conditions. However, fluvial transport still remained as the main source.

(Table 1) Dissolved and particulate organic carbon, phosphorus, and nitrogen in waters of the Sea of Japan

Concentrations of dissolved and particulate organic carbon (DOC and POC, respectively), phosphorus (DP and PP, respectively) and particulate organic nitrogen (PON) were determined at Station VITYAZ6656 in the Sea of Japan in 12 sea water samples collected in June 1972 with a 200-liter sampling bottle. Mean weighted concentrations from the surface to 2000 m were: DOC - 1.58 mg/l, POC - 17.9 µg/l, DP - 13.9 µg/l, PP - 0.185 µg/l, PON - 2.7 µg/l, the ratios were DOC:DP=100:9 and POC:PON:PP=100:14:1. Relation between POC (µg/l)and the light attenuation index "e" (1/m) for the visible part of the spectrum is described by the equation POC = ca. 170e. The maximum of POC in the upper layer correlated with the maxima of phyto- and bacterioplankton and protozoa.

Cenozoic record of continental mineral deposit on Broken and Ninetyeast Ridges, Indian Ocean

The mineral component of pelagic sediments recovered from the Indian Ocean provides both a history of eolian deposition related to climatic changes in southern Africa and a record of terrigenous input related to sediment delivery from the Himalayas. A composite Cenozoic dust flux record from four sites in the central Indian Ocean is used to define the evolution of the Kalahari and Namib desert source regions. The overall record of dust input is one of very low flux for much of the Cenozoic indicating a long history of climate stability and regional hyperaridity. The most significant reduction in dust flux occurred near the Paleocene/Eocene boundary and is interpreted as a shift from semiarid climates during the Paleocene to more arid conditions in the early Eocene. Further aridification is recorded as stepwise reductions in the input of dust material which occur from about 35 to 40 Ma, 27 to 32 Ma, and 13 to 15 Ma and correlate to significant enrichments in benthic foraminifer delta18O values. The mineral flux in sediments from the northern Indian Ocean, site 758, records changes in the terrigenous input apparently related to the erosion of the Himalayas and indicates a rapid late Cenozoic uplift history. Three major pulses of increased terrigeneous sediment flux are inferred from the depositional record. The initial increase began at about 9.5 Ma and continued for roughly 1.0 million years. A second pulse with approximately the same magnitude occurred from about 7.0 to 5.6 Ma. The largest pulse of enhanced terrigenous influx occurred during the Pliocene from about 3.9 to 2.0 Ma when average flux values were severalfold greater than at any other time in the Cenozoic.

Description and geochemical composition of tephra layers from ODP Hole 186-1150A and Site 186-1151

The sediments collected at Sites 1150 and 1151 during Leg 186 included many tephra layers and volcaniclastic detritus. In order to identify these tephras, the major oxide compositions of individual glass shards were determined by electron probe microanalyzer. The uppermost four tephras in sediments from Hole 1150A are correlated with the Towada-Hachinohe tephra (To-H; Tohoku district), Shikotsu Daiichi (1st) tephra (Spfa-1; Hokkaido district), Narugo-Yanagisawa tephra (Nr-Y; Tohoku district), and Aso-4 tephra (Kyushu district), respectively. The uppermost tephra in Hole 1151C is correlated with To-H tephra. To-H, Spfa-1, and Aso-4 tephras are also present in piston core KH94-3, LM-8, collected between Sites 1150 and 1151. Eruptive ages of To-H and Spfa-1 estimated from the oxygen isotopic Stages of core KH94-3, LM-8 are between 14.9-15.3 and 39.5-40.1 ka.