(Table II, page 668-669) Distribution of elements between minerals soluble in 1M Hydroxylamine hydrochloride (Reducible); in 1m HCL (Acid-soluble) and in the insoluble residue of manganese nodules

Attempts to classify pelagic sediments have been based either on appearance and composition, or on the ultimate origin of the components. In particular it appears feasible to distinguish minerals which crystallized in sea-water from those which formed in magmas, in hydrothermal solution, or by weathering under acidic conditions. It is the case of iron and manganese oxide mineral aggregates which constitute one of the major types of rock encountered on the ocean floor; according to Menard (unpublished) about 10% of the pelagic area of the Pacific is covered by such nodules. The nodules consist of intimately intergrown crystallites of different minerals among those identified, besides detrital minerals and organic matter, are opal, goethite, rutile, anatase, barite, nontronite, and at least three manganese oxide minerals of major importance. Arrhenius and Korkisch (1959) have attempted to separate from each other the different minerals constituting the nodules, in order to establish the details of their structure and the localization of the heavy metal ions. The results demonstrate (Table II) that copper and nickel are concentrated in the manganese oxide phases concentrated in the reducible fraction. Cobalt, part of the nickel and most of the chromium are distributed between these and the acid-soluble group of the non-manganese minerals, dominated by goethite and disordered FeOOH.

Magnetic extracts of three gravity cores located at the Ceará Rise, the Mid-Atlantic Ridge and the Sierra Leone Rise

The magnetic microparticle and nanoparticle inventories of marine sediments from equatorial Atlantic sites were investigated by scanning and transmission electron microscopy to classify all present detrital and authigenic magnetic mineral species and to investigate their regional distribution, origin, transport, and preservation. This information is used to establish source-to-sink relations and to constrain environmental magnetic proxy interpretations for this area. Magnetic extracts were prepared from sediments of three supralysoclinal open ocean gravity cores located at the Ceará Rise (GeoB 1523-1; 3°49.9'N/41°37.3'W), the Mid-Atlantic Ridge (GeoB 4313-2; 4°02.8'N/33°26.3'W), and the Sierra Leone Rise (GeoB 2910-1; 4°50.7'N/21°03.2'W). Sediments from two depths corresponding to marine isotope stages 4 and 5.5 were processed. This selection represents glacial and interglacial conditions of sedimentation for the western, central, and eastern equatorial Atlantic and avoids interferences from subsurface and anoxic processes. Crystallographic, elemental, morphological, and granulometric data of more than 2000 magnetic particles were collected by scanning and transmission electron microscopy. On basis of these properties, nine particle classes could be defined: detrital magnetite, titanomagnetite (fragmental and euhedral), titanomagnetite-hemoilmentite intergrowths, silicates with magnetic inclusions, microcrystalline hematite, magnetite spherules, bacterial magnetite, goethite needles, and nanoparticle clusters. Each class can be associated with fluvial, eolian, subaeric, and submarine volcanic, biogenic, or chemogenic sources. Large-scale sedimentation patterns are delineated as well: detrital magnetite is typical of Amazon discharge, fragmental titanomagnetite is a submarine weathering product of mid-ocean ridge basalts, and titanomagnetite-hemoilmenite intergrowths are common magnetic particles in West African dust. This clear regionalization underlines that magnetic petrology is an excellent indicator of source-to-sink relations. Hematite encrustations, magnetic spherules, and nanoparticle clusters were found at all investigated sites, while bacterial magnetite and authigenic hematite were only detected at the more oxic western site. At the eastern site, surface pits and crevices were seen on the crystal faces indicating subtle early diagenetic reductive dissolution. It was observed that paleoclimatic signatures of magnetogranulometric parameters such as the ratio of anhysteretic and isothermal remanent magnetizations can be formed either by mixing of multiple sources with separate, relatively narrow grain size ranges (western site) or by variable sorting of a single source with a broad grain size distribution (eastern site). Hematite, goethite, and possibly ferrihydrite nanoparticles occur in all sediment cores studied and have either high-coercive or superparamagnetic properties depending on their partly ultrafine grain sizes. These two magnetic fractions are generally discussed as separate fractions, but we suggest that they could actually be genetically linked.

Sedimentology and geochemistry of surface sediments from the Pagassitikos Gulf

Volos city and its port are situated in the northern part of Pagassitikos Gulf, a shallow, semi-enclosed marine area in central Greece. A wastewater treatment plant (WWTP) and pipeline operate in the same area. Muddy sediments with low carbonate contents cover most of the seabed, except for the Volos embayment and the western part of the gulf where sandy carbonates prevail. Bulk organic carbon contents and the organic carbon contents of the clay fractions are high in the vicinity of Volos embayment. High element (Pb, Cu, and Zn) contents and Igeo (geoaccumulation index) values were found for the clay fractions in the northern part of Pagassitikos Gulf. This enrichment is attributed to the discharge of raw domestic and industrial effluents of Volos city and port before the WWTP was installed. The dispersal of pollutants is essentially controlled by diffusion from point sources (city, port and WWTP) and is limited to Volos Bay. Relatively high Mn levels are ascribed to diagenetic formation of manganese carbonates (authigenic phase), whereas Cr and Ni are elevated due to weathering of ultrabasic formations on land.

Clay mineralogy of South Atlantic surface sediments

Surface samples, mostly from abyssal sediments of the South Atlantic, from parts of the equatorial Atlantic, and of the Antarctic Ocean, were investigated for clay content and clay mineral composition. Maps of relative clay mineral content were compiled, which improve previous maps by showing more details, especially at high latitudes. Large-scale relations regarding the origin and transport paths of detrital clay are revealed. High smectite concentrations are observed in abyssal regions, primarily derived from southernmost South America and from minor sources in Southwest Africa. Near submarine volcanoes of the Antarctic Ocean (South Sandwich, Bouvet Island) smectite contents exhibit distinct maxima, which is ascribed to the weathering of altered basalts and volcanic glasses. The illite distribution can be subdivided into five major zones including two maxima revealing both South African and Antarctic sources. A particularly high amount of Mg- and Fe-rich illites are observed close to East Antarctica. They are derived from biotite-bearing crystalline rocks and transported to the west by the East Antarctic Coastal Current. Chiorite and well-crystallized dioctaedral illite are typical minerals enriched within the Subantarctic and Polarfrontal-Zone but of minor importance off East Antarctica. Kaolinite dominates the clay mineral assemblage at low latitudes, where the continental source rocks (West Africa, Brazil) are mainly affected by intensive chemical weathering. Surprisingly, a slight increase of kaolinite is observed in the Enderby Basin and near the Filchner-Ronne Ice shelf. The investigated area can be subdivided into ten, large-scale clay facies zones with characteristic possible source regions and transport paths. Clay mineral assemblages of the largest part of the South Atlantic, especially of the western basins are dominated by chlorite and illite derived from the Antarctic Peninsula and southernmost South America and supported by advection within the Circumantarctic Deep Water flow. In contrast, the East Antarctic provinces are relatively small. Assemblages of the eastern basins north of 30°S are strongly influenced by African sources, controlled by weathering regimes on land and by a complex interaction of wind, river and deep ocean transport. The strong gradient in clay mineral composition at the Brazilian slope indicate a relatively low contribution of tropically derived assemblages to the western basins.

Geochemistry of sediment cores GeoB4901-3 and GeoB4901-8 from the southern flank of the Niger Fan

Time series of terrigenous source elements (Al, K, Ti, Zr) from core GeoB4901-8 recovered from the deep-sea fan of the Niger River record variations in riverine sediment discharge over the past 245,000 yr. Although the flux rates of all the elements depend on physical erosion, which is mainly controlled by the extent of vegetation coverage in central Africa, element/Al ratios reflect conditions for chemical weathering in the river basin. Maximum sediment input to the ocean occurs during cold and arid periods, when precipitation intensity and associated freshwater runoff are reduced. High carbonate contents during the same periods indicate that the sediment supply has a positive effect on river-induced marine productivity. In general, variations in the terrestrial signals contain a strong precessional component in tune with changes in low-latitude solar radiation. However, the terrestrial signal lags the insolation signal by several thousand years. K/Al, Ti/Al, and Zr/Al records reveal that African monsoonal precipitation depends on high-latitude forcing. We attribute the shift between insolation cycle and river discharge to the frequently reported nonlinear response of African climate to primary orbital configurations, which may be caused by a complex interaction of the secondary control parameters, such as surface albedo and/or thermohaline circulation.

(Table 1) Chemical and isotopic composition of pore fluids in cores TGC-1 and TGC-6

The role of sediment diagenesis in the marine cycles of Li and B is poorly understood. Because Li and B are easily mobilized during burial and are consumed in authigenic clay mineral formation, their abundance in marine pore waters varies considerably. Exchange with the overlying ocean through diffusive fluxes should thus be common. Nevertheless, only a minor Li sink associated with the low-temperature alteration of volcanic ash has been observed. We describe a low-temperature diagenetic environment in the Black Sea dominated by the alteration of detrital plagioclase feldspars. Fluids expelled from the Odessa mud volcano in the Sorokin Trough originate from shallow (~100-400 m deep) sediments which are poor in volcanic materials but rich in anorthite. These fluids are depleted in Na+, K+, Li+, B, and 18O and enriched in Ca2+ and Sr2+, indicating that anorthite is dissolving and authigenic clays are forming. Using a simple chemical model, we calculate the pH and the partial pressure of CO2 (PCO2) in fluids associated with this alteration process. Our results show that the pH of these fluids is up to 1.5 pH units lower than in most deep marine sediments and that PCO2 levels are up to several hundred times higher than in the atmosphere. These conditions are similar to those which favor the weathering of silicate minerals in subaerial soil environments. We propose that in Black Sea sediments enhanced organic matter preservation favors CO2 production through methanogenesis and results in a low pore water pH, compared to most deep sea sediments. As a result, silicate mineral weathering, which is a sluggish process in most marine diagenetic environments, proceeds rapidly in Black Sea sediments. There is a potential for organic matter-rich continental shelf environments to host this type of diagenesis. Should such environments be widespread, this new Li and B sink could help balance the marine Li and Li isotope budgets but would imply an apparent imbalance in the B cycle.

(Table 1) Water chemistry of groundwater and snow samples from three sites in Ontario, Canada

Snow samples collected from hand-dug pits at two sites in Simcoe County, Ontario, Canada were analysed for major and trace elements using the clean lab methods established for polar ice. Potentially toxic, chalcophile elements are highly enriched in snow, relative to their natural abundance in crustal rocks, with enrichment factor (EF) values (calculated using Sc) in the range 107 to 1081 for Ag, As, Bi, Cd, Cu, Mo, Pb, Sb, Te, and Zn. Relative to M/Sc ratios in snow, water samples collected at two artesian flows in this area are significantly depleted in Ag, Al, Be, Bi, Cd, Cr, Cu, Ni, Pb, Sb, Tl, V, and Zn at both sites, and in Co, Th and Tl at one of the sites. The removal from the waters of these elements is presumably due to such processes as physical retention (filtration) of metal-bearing atmospheric aerosols by organic and mineral soil components as well as adsorption and surface complexation of ionic species onto organic, metal oxyhydroxide and clay mineral surfaces. In the case of Pb, the removal processes are so effective that apparently ''natural'' ratios of Pb to Sc are found in the groundwaters. Tritium measurements show that the groundwater at one of the sites is modern (ie not more than 30 years old) meaning that the inputs of Pb and other trace elements to the groundwaters may originally have been much higher than they are today; the M/Sc ratios measured in the groundwaters today, therefore, represent a conservative estimate of the extent of metal removal along the flow path. Lithogenic elements significantly enriched in the groundwaters at both sites include Ba, Ca, Li, Mg, Mn, Na, Rb, S, Si, Sr, and Ti. The abundance of these elements can largely be explained in terms of weathering of the dominant silicate (plagioclase, potassium feldspar, amphibole and biotite) and carbonate minerals (calcite, dolomite and ankerite) in the soils and sediments of the watershed. Arsenic, Mo, Te, and especially U are also highly enriched in the groundwaters, due to chemical weathering: these could easily be explained if there are small amounts of sulfides (As, Mo, Te) and apatite (U) in the soils of the source area. Elements neither significantly enriched nor depleted at both sites include Fe, Ga, Ge, and P.

Characteristics of light and dark alternations in Owen Ridge sediments (Appendix)

Clay mineral relative abundances in approximately 450 samples from cores recovered during ODP Leg 117 in the Arabian Sea have been used to examine the paleoclimatic, paleoenvironmental, and tectonic histories of the Indus Fan, Owen Ridge, Oman margin, and adjacent continental source regions. Geographic variations in the relative abundances of minerals and correlations with depositional processes support previous interpretations that smectite has been supplied from weathering of the Deccan Traps; illite and chlorite have been supplied either from the Himalayas via marine transport or from the Iran-Makran region by winds; and palygorskite has been supplied from the Arabian peninsula and Somalia by winds. Pleistocene sediments of the Indus Fan record two modes of deposition: turbidites supplied from the Indus drainage and dominated by illite and chlorite, and pelagic carbonates containing smectites and wind-transported palygorskite. Local and regional causes for shifts between these depositional processes cannot be demonstrated conclusively with the data available, but sea-level fluctuations probably exerted a significant control on the rate of turbidite influx. Lower Miocene sediments on the Owen Ridge are also turbidites supplied by the Indus drainage; in the middle Miocene, a shift to pelagic carbonates records the uplift of the Owen Ridge, and is accompanied by the increased relative importance of wind-transported palygorskite. Associations of palygorskite and biosiliceous components in middle to upper Miocene sediments are interpreted to record vigorous monsoonal circulation and accompanying upwelling-produced biological productivity. Mineralogic and geochemical data indicate that light/dark color alternations in upper Miocene sediments on the Owen Ridge record climatic fluctuations, but the climatic significance of similar alternations in Pliocene-Pleistocene sediments is unclear. Palygorskite is the dominant clay on the Oman margin, reflecting proximity to its source areas. On the Oman margin, clay mineral relative abundances are most variable at structurally complex sites, indicating that local depositional settings have been influenced by their tectonic histories since the Miocene.

Soil properties and microbial indicators of samples from Lake Wellman, Darwin Mountains, Antarctica

Four pedons on each of four drift sheets in the Lake Wellman area of the Darwin Mountains were sampled for chemical and microbial analyses. The four drifts, Hatherton, Britannia, Danum, and Isca, ranged from early Holocene (10 ka) to mid-Quaternary (c. 900 ka). The soil properties of weathering stage, salt stage, and depths of staining, visible salts, ghosts, and coherence increase with drift age. The landforms contain primarily high-centred polygons with windblown snow in the troughs. The soils are dominantly complexes of Typic Haplorthels and Typic Haploturbels. The soils were dry and alkaline with low levels of organic carbon, nitrogen and phosphorus. Electrical conductivity was high accompanied by high levels of water soluble anions and cations (especially calcium and sulphate in older soils). Soil microbial biomass, measured as phospholipid fatty acids, and numbers of culturable heterotrophic microbes, were low, with highest levels detected in less developed soils from the Hatherton drift. The microbial community structure of the Hatherton soil also differed from that of the Britannia, Danum and Isca soils. Ordination revealed the soil microbial community structure was influenced by soil development and organic carbon.

Quartz grain microtextures of sediments from ODP Hole 188-1166A (Table 1)

This paper presents the results of the scanning electron microscopic (SEM) analysis of quartz grains from a selection of samples at Site 1166. Ocean Drilling Program Leg 188 drilled Site 1166 on the Prydz Bay continental shelf, Antarctica, to document onset and fluctuations of East-Antarctic glaciation. This site recovered Upper Pliocene-Holocene glacial sediments directly above Cretaceous through Lower Oligocene sediments recording the transition from preglacial to early glacial conditions. SEM analysis of quartz grains at Site 1166 was used to characterize the glacial and preglacial sediments by their diagnostic textures. Angular edges, edge abrasion as well as arcuate to straight steps, are the most frequent features in glacial deposits. The highest frequency of grains with round edges is present in Middle-Late Eocene fluvio-deltaic sands. However, angular outlines, fractured plates with subparallel linear fractures and edge abrasion indicating glacier influence are also present. Preglacial carbonaceous mudstone and laminated gray claystone show distinctive high relief quartz grains and some chemical weathering on grain surfaces. The results of the microtextural analysis of quartz grains are used to verify some critical periods of ice sheet evolution, such as the transition from the East Antarctic preglacial to glacial conditions on the continental shelf from Middle/Late Eocene to Late Eocene/Early Oligocene time.

Modern major element concentrations and ratios measured in Atlantic surface sediments (36°N-49°S)

Numerous studies use major element concentrations measured on continental margin sediments to reconstruct terrestrial climate variations. The choice and interpretation of climate proxies however differ from site to site. Here we map the concentrations of major elements (Ca, Fe, Al, Si, Ti, K) in Atlantic surface sediments (36°N-49°S) to assess the factors influencing the geochemistry of Atlantic hemipelagic sediments and the potential of elemental ratios to reconstruct different terrestrial climate regimes. High concentrations of terrigenous elements and low Ca concentrations along the African and South American margins reflect the dominance of terrigenous input in these regions. Single element concentrations and elemental ratios including Ca (e.g., Fe/Ca) are too sensitive to dilution effects (enhanced biological productivity, carbonate dissolution) to allow reliable reconstructions of terrestrial climate. Other elemental ratios reflect the composition of terrigenous material and mirror the climatic conditions within the continental catchment areas. The Atlantic distribution of Ti/Al supports its use as a proxy for eolian versus fluvial input in regions of dust deposition that are not affected by the input of mafic rock material. The spatial distributions of Al/Si and Fe/K reflect the relative input of intensively weathered material from humid regions versus slightly weathered particles from drier areas. High biogenic opal input however influences the Al/Si ratio. Fe/K is sensitive to the input of mafic material and the topography of Andean river drainage basins. Both ratios are suitable to reconstruct African and South American climatic zones characterized by different intensities of chemical weathering in well-understood environmental settings.

Table 1. Concentration of rare earth elements in ferromanganese nodule (crust), sediment and rock of the South China Sea

Based on the X-ray fluorescence spectrum analysis of 15 rare earth elements in 6 ferromanganese nodu1es and 5 ferro mangane se crusts from the South China Sea, their abundances, distribution patterns, sources and relationships with associated elements are discussed in detail in this paper. The results show that: 1) The average abundance of rare earth elements in ferromanganese nodu1es and crusts is 1. 625 g/kg and 2. 167 g/kg respectively, which is 1-2 tim es , 5-6 times and 15-20 times higher than that in the Pacific, in the sediments of the North Pacific and the South China Sea, respectively; 2) The distribution patterns of rare earth elements standardized by the globular aerolite in ferro mangane se nodules and crusts are basically similar, that is, Ce is positively abnormal and Eu is in deficit slightly; 3) The relationships between rare earth elements and associated elements, sediments and rocks show that the source of rare earth elements in ferromanganese nodules and crusts have mainly come from slow deposition caused by weathering and leaching of medium acidic rock of the South China Sea.