Uranium and radioactive isotopes in bottom sediments and Fe-Mn nodules and crusts of seas and oceans

The main stages of the sedimentary cycle of uranium in modern marine basins are under consideration in the book. Annually about 18 thousand tons of dissolved and suspended uranium enters the ocean with river runoff. Depending on a type of a marine basin uranium accumulated either in sediments of deep-sea basins, or in sediments of continental shelves and slopes. In the surface layer of marine sediments hydrogenic uranium is predominantly bound with organic matter, and in ocean sediments also with iron, manganese and phosphorus. In diagenetic processes there occurs partial redistribution of uranium in sediments, as well as its concentration in iron-manganese, phosphate and carbonate nodules and biogenic phosphate detritus. Concentration of uranium in marine sediments of various types depending on their composition, as well as on forms of its entering, degree of differentiation and of sedimentation rates, on hydrochemical regime and water circulation, and on intensity of diagenetic processes.

Middle Miocene mineralogical events of Marion Plateau, northeast of Australia

Three ODP sites located on the Marion Plateau, Northeast Australian margin, were investigated for clay mineral and bulk mineralogy changes through the early to middle Miocene. Kaolinite to smectite (K/S) ratios, as well as mass accumulation rates of clays, point to a marked decrease in accumulation of smectite associated with an increase in accumulation of kaolinite starting at ~15.6 Ma, followed by a second increase in accumulation of kaolinite at ~13.2 Ma. Both of these increases are correlative to an increase in the calcite to detritus ratio. Comparison of our record with published precipitation proxies from continental Queensland indicates that increases in kaolinite did not correspond to more intense tropical-humid conditions, but instead to periods of greater aridity. Three mechanisms are explored to explain the temporal trends in clay on the Marion Plateau: sea-level changes, changes in oceanic currents, and denudation of the Australian continent followed by reworking and eolian transport of clays. Though low mass accumulation rates of kaolinite are compatible with a possible contribution of eolian material after 14 Ma, when Australia became more arid, the lateral distribution of kaolinite along slope indicates mainly fluvial input for all clays and thus rules out this mechanism as well as oceanic current transport as the main controls behind clay accumulation on the plateau. We propose a model explaining the good correlation between long-term sea-level fall, decrease in smectite accumulation, increase in kaolinite accumulation and increase in carbonate input to the distal slope locations. We hypothesize that during low sea level and thus periods of drier continental climate in Queensland, early Miocene kaolinite-rich lacustrine deposits were being reworked, and that the progradation of the heterozoan carbonate platforms towards the basin center favored input of carbonate to the distal slope sites. The major find of our study is that increase kaolinite fluxes on the Queensland margin during the early and middle Miocene did not reflect the establishment of a tropical climate, and this stresses that care must be taken when reconstructing Australian climate based on deep-sea clay records alone.

Grain counts and XRD mineralogy of turbidite sand and hemipelagic mud from ODP Leg 168 sites

Sequences of late Pliocene to Holocene sediment lap onto juvenile igneous crust within 20 km of the Juan de Fuca Ridge in northwestern Cascadia Basin, Pacific Ocean. The detrital modes of turbidite sands do not vary significantly within or among sites drilled during Leg 168 of the Ocean Drilling Program. Average values of total quartz, total feldspar, and unstable lithic fragments are Q = 35, F = 35, and L = 30. Average values of monocrystalline quartz, plagioclase, and K-feldspar are Qm = 46, P = 49, and K = 5, and the average detrital modes of polycrystalline quartz, volcanic-rock fragments, and sedimentary-rock plus metamorphic-rock fragments are Qp = 16, Lv = 43, and Lsm = 41. Likely source areas include the Olympic Peninsula and Vancouver Island; sediment transport was focused primarily through the Strait of Juan de Fuca, Juan de Fuca Channel, Vancouver Valley, and Nitinat Valley. Relative abundance of clay minerals (<2-µm-size fraction) fluctuate erratically with depth, stratigraphic age, and sediment type (mud vs. turbidite matrix). Mineral abundance in mud samples are 0%-35% smectite (mean = 8%), 18%-59% illite (mean = 40%), and 29%-78% chlorite + kaolinite (mean = 52%). We attribute the relatively low content of smectite to rapid mechanical weathering of polymictic source terrains, with little or no input of volcanic detritus from the Columbia River. The scatter in clay mineralogy probably was caused by converging of surface currents, turbidity currents, and near-bottom nepheloid clouds from several directions, as well as subtle changes in glacial vs. interglacial weathering products.

Geological, geochemical and biogeochemical data on boundary zones of the Atlantic Ocean

Results of studies in two biogeochemically active zones of the Atlantic Ocean (the Benguela upwelling waters and the region influenced by the Congo River run-off) are reported in the book. A multidisciplinary approach included studies of the major elements of the ocean ecosystem: sea water, plankton, suspended matter, bottom sediments, interstitial waters, aerosols, as well as a wide complex of oceanographic studies carried out under a common program. Such an approach, as well as a use of new methodical solutions led to obtaining principally new information on different aspects of oceanology.

Stable isotope record, and abundances of ice rafted debris and Neogloboquadrina pachyderma in sediments of the Iberian margin

This paper documents the migration of the Polar Front (PF) over the Iberian margin during some of the cold climatic extremes of the last 45 ka. It is based on a compilation of robust and coherent paleohydrological proxies obtained from eleven cores distributed between 36 and 42°N. Planktonic delta18O (Globigerina bulloides), ice-rafted detritus concentrations, and the relative abundance of the polar foraminifera Neogloboquadrina pachyderma sinistral were used to track the PF position. These three data sets, compared from core to core, show a consistent evolution of the sea surface paleohydrology along the Iberian margin over the last 45 ka. We focused on five time slices representative of cold periods under distinct paleoenvironmental forcings: the 8.2 ka event and the Younger Dryas (two recent cold events occurring within high values of summer insolation), Heinrich events 1 and 4 (reflecting major episodes of massive iceberg discharges into the North Atlantic), and the Last Glacial Maximum (typifying the highest ice volume accumulated in the Northern Hemisphere). For each event, we generated schematic maps mirroring past sea surface hydrological conditions. The maps revealed that the Polar Front presence along the Iberian margin was restricted to Heinrich events. The sea surface conditions during the Last Glacial Maximum were close to those at present day, except for the northern sites which briefly experienced subarctic conditions.

Grain size, mineral and chemical compositions of modern deposits fron the northern Caspian Sea and the Volga River delta

Comprehensive investigations revealed that modern deposits in the northern Caspian Sea involve terrigenous sands and aleurites with admixture of detritus and intact bivalve shells, including coquina. Generally, these deposits overlay dark grayish viscous clays. Similar geological situation occurs in the Volga River delta; however, local deposits are much poorer in biogenic constituents. Illite prevails among clay minerals. In coarse aleurite fraction (0.100-0.050 mm) heavy transparent minerals are represented mostly by epidotes, while light minerals - mostly by quartz and feldspars. Sedimentary material in the Volga River delta is far from completely differentiated into fractions due to abundant terrigenous inflows. Comparatively better grading of sediments from the northern Caspian Sea is due to additional factors such as bottom currents and storms. When passing from the Volga River delta to the northern Caspian Sea, sediments are enriched in rare earth elements (except Eu), Ca, Au, Ni, Se, Ag, As, and Sr, but depleted in Na, Rb, Cs, K, Ba, Fe, Cr, Co, Sc, Br, Zr, ??, U, and Th. Concentrations of Zn remain almost unchanged. Sedimentation rates and types of recent deposits in the northern Caspian Sea are governed mainly by abundant runoff of the Volga River.

North Atlantic IODP Site 303-U1308 Middle Pleistocene Heinrich Events record

Heinrich events are well documented for the last glaciation, but little is known about their occurrence in older glacial periods of the Pleistocene. Here we report scanning XRF and bulk carbonate d18O results from Integrated Ocean Drilling Program Site U1308 (reoccupation of Deep Sea Drilling Project Site 609) that are used to develop proxy records of ice-rafted detritus (IRD) for the last ~1.4 Ma. Ca/Sr is used as an indicator of IRD layers that are rich in detrital carbonate (i.e., Heinrich layers), whereas Si/Sr reflects layers that are poor in biogenic carbonate and relatively rich in detrital silicate minerals. A pronounced change occurred in the composition and frequency of IRD at ~640 ka during marine isotope stage (MIS) 16, coinciding with the end of the middle Pleistocene transition. At this time, "Hudson Strait" Heinrich layers suddenly appeared in the sedimentary record of Site U1308, and the dominant period of the Si/Sr proxy shifted from 41 ka prior to 640 ka to 100 ka afterward. The onset of Heinrich layers during MIS 16 represents either the initiation of surging of the Laurentide Ice Sheet (LIS) off Hudson Strait or the first time icebergs produced by this process survived the transport to Site U1308. We speculate that ice volume (i.e., thickness) and duration surpassed a critical threshold during MIS 16 and activated the dynamical processes responsible for LIS instability in the region of Hudson Strait. We also observe a strong coupling between IRD proxies and benthic d13C variation at Site U1308 throughout the Pleistocene, supporting a link between iceberg discharge and weakening of thermohaline circulation in the North Atlantic.

Sedimentology on two core from the Bransfield Strait area

The raw material for these investigations are samples from marine (sub)surface sediments around the northern part of the Antarctic Peninsula. They had been sampled in the years 1981 to 1986 during several expeditions of the research vessels Meteor, Polarstern and Walther Herwig. 83 box core, gravity core and dredge samples from the area of the Bransfield Strait, the Powell Basin and the northern Weddell Sea have been examined for their grain-size distribution, their mineralogical and petrographical composition. Silt prevails and its clay proportions exceed 25% wt. in water depths greater than 2000 m. The granulometrical results reveal some typical sedimentation processes within the area of investigation. While turbiditic processes together with sediment input from melting icebergs control the sedimentation in the Weddell Sea, the South Orkney Island Plateau and the Powell Basin, the fine grained material from Bransfield Strait mainly relies on marine currents in the shelf area. In addition, the direct sediment input of coarse shelf sediments from the Bransfield Strait into the Powell Basin through submarine canyons could be proven. Variations in the grain-size composition with sediment depth are smalI. The mineral composition of the clay and fine silt fractions is quite uniform in all samples. There are (in decreasing order): illite, montmorillonite, chlorite, smectite, mixed-Iayers, as well as detrital quartz and feldspars. A petrographically based sediment stratigraphy can be established in using the considerable changes in the chlorite- and Ca-plagioclase portions in samples from Core 224. For this sedimentation area a mean sedimentation rate of 7 cm/1000 a is assumed. Remarkable changes in the portions of amorphous silica components - diatom skeletons and volcanic glass shards - appear all over the area of investigation. They contribute between 4-83 % to the clay and fine silt fraction. Several provinces according to the heavy mineral assemblages in the fine sand fraction can be distinguished: (i) a province remarkably influenced by minerals of volcanic origin south and north of the South Shetland Islands; (ii) a small strip with sediment dominated by plutonic material along the western coast of the Antarctic Peninsula and (iii) a sediment controlled by metamorphic minerals and rock fragments in the area of the Weddell Sea and Elephant Island. While taking the whole grain-size spectrum into account a more comprehensive interpretation can be given: the accessoric but distinct appearance of tourmaline, rutile and zircon in the heavy mineral assembly along the northwestern coast of the Antarctic Peninsula is in agreement with the occurrence of acid volcanic rock pieces in the coarse fraction of the ice load detritus in this region. In the vicinity of the South Shetland Islands chlorite appears in remarkable portions in the clay fraction in combination with leucoxene, sphene and olivine, and pumice as well as pyroclastic rocks in the medium and coarse grain fractions, respectively. Amphiboles and amphibole-schists are dominant on the South Orkney Island Plateau. In the sediments of the northwestern Weddell Sea the heavy mineral phases of red spinel, garnet, kyanite and sillimanite in connection with medium to highgrade metamorphic rocks especially granulitic gneisses, are more abundant. A good conformity between the ice rafted rock sampIes and the rocks in the island outcrops could be proven, especially in the vicinity of offshore islands nearby. On the continent enrichments of rock societies and groups appear in spacious outlines: acid effusive rocks in the west of the ice divide on the Antarctic Peninsula, clastic sedimentites at the tip of the Antarctic Peninsula and granoblastic gneisses in central and eastern Antarctica. Coarse grain detritus with more than 1 cm of diameter must have been rafted by icebergs. These rock fragments are classified as rock types, groups and societies. The spacial distribution of their statistically determined weight relations evidently shows the paths of the iceberg drift and in nexus with already known iceberg routes also point to the possible areas of provenance, provided that the density of sample locations and the number of rock pieces are sufficient.

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.

Sedimentation in the vicinity of Leg 92 Drill Sites: Studies of site survey cores

Surveys of the areas surrounding the sites drilled on the Leg 92 19°S transect showed that sedimentation at all except the oldest site is dominated by calcium carbonate deposition. The sediments in the area of the oldest site, west of the Austral Fracture Zone, are being deposited beneath the calcium carbonate compensation depth and are dominated by terrigenous and metal-rich hydrogenous and hydrothermal sediments. The noncarbonate sediments in all of the areas east of the Austral Fracture Zone are dominated by hydrothermal sediment similar in composition to that presently being deposited at the East Pacific Rise. Although no biogenic microfossils were present in smear slides of the sediment, geochemical partitioning suggests that a remnant signal of siliceous biogenic deposition may be preserved, especially in gravity core (GC) 8, which was collected from a high heat flow zone near Site 600. The siliceous sediment may also result from the deposition of amorphous hydrothermal silica from the higher concentrations of pore water SiO2 characteristic of the upwelling waters. Sedimentation on the broad plateaus that characterize each area is quite uniform and suggests that sites on these plateaus will be broadly representative of pelagic sedimentation in the area.

Mineralogy of ODP Site 105-645

Cores from the upper 70 meters below seafloor (mbsf) (upper Pleistocene) at Ocean Drilling Program (ODP) Site 645 in Baffin Bay show dramatic meter-scale changes in color and mineralogy. Below this interval, mineralogical changes are more gradual to the top of the Miocene at about 550 mbsf. The Pliocene-Pleistocene section can be divided into five facies: Facies 1 - massive, poorly sorted, gravel-bearing muds; Facies 2 - gray silty clays and silty muds; Facies 3 - laminated detricarbonate silty muds; Facies 4 - silty sand and sandy silt; and Facies 5 - poorly sorted muddy sands and silty muds. Facies 4 and 5 are restricted to the Pliocene section below depths of about 275 mbsf. The mineralogical/color cycles in the upper 70 mbsf are the result of alternations between Facies 2 and three lithotypes of Facies 1: lithotype A - tan-colored, carbonate-rich, gravel-bearing mud; lithotype B - weak, red-colored, gravel-bearing mud rich in sedimentary rock fragments; and lithotype C - gray, gravel-bearing mud. A fourth lithotype, D, is restricted to depths of 168-275 mbsf and is dark gray, carbonate-poor, gravel-bearing mud. We believe that all lithotypes of Facies 1 and the sand and gravel fractions of Facies 2 and 3 were deposited by ice rafting. Depositional processes for Facies 4 and 5 probably include ice rafting and bottom- and turbidity-current transport. Data from petrographic analyses of light and heavy sand-sized grains and X-ray analyses of silt- and clay-size fractions suggest that tan-colored sediments (lithotype A of Facies 1; Facies 3) were derived mainly from Paleozoic carbonates of Ellesmere, Devon, and northern Baffin islands. Weak red sediments (lithotype B) contain significant red sedimentary clasts, reworked quartzarenite grains and clasts, and rounded colorless garnets, all derived from Proterozoic sequences of the Borden and Thule basins, and from minor Mesozoic red beds. Other sediments in the upper 335 mbsf at Site 645 contain detritus from a heterogeneous mixture of sources, including Precambrian shield terranes around Baffin Bay. Sediments from 335 to 550 mbsf (Facies 5) are rich in friable sedimentary clasts and detrital micas and contain glauconite and, in a few samples, reworked diatoms. These components suggest derivation from poorly consolidated Mesozoic-Tertiary sediments in coastal outcrops and beneath the modern shelves of northeastern Baffin Island and western Greenland. For the upper Pleistocene section (about 0-100 mbsf), marked mineralogical cyclicity is attributed to fluctuating glacial margins, calving rates, and iceberg melting rates, particularly around the northern end of Baffin Bay. Tan-colored, carbonate-rich units were derived at times of maximum advance of glaciers on Ellesmere and Devon islands, during relatively warm intervals induced by incursion of warm Atlantic surface water into the bay. At the beginning of these warmer episodes, most icebergs were contributed by glaciers near sea level around the Arctic channels, which resulted in deposition of weak red, ice-rafted units rich in Proterozoic sedimentary clasts.

Mineralogical-sedimentological and chemical investigation of sediments from Cross Bank off Florida

The sediments of a core of.1.55 m length taken on the windward side of the Cross Bank, Florida Bay, are clearly subdivided into two portions, as shown by grain size analysis: silt-sized particles predominate in the relatively homogeneous lower two thirds of the core. This is succeeded abruptly by a thin layer of sand, containing fragments of Halimeda. They indicate a catastrophic event in the Florida Bay region, because Halimeda does not grow within Florida Bay. Above this layer, the amount of sand decreases at first and then continuously increases right to the present sediment-water-interface. The median and skewness increase simultaneously with the increase in the sand and granule portion. We assume that the changing grain size distribution was determined chiefly by the density of the marine flora: during the deposition of the lower two thirds of the core a dense grass cover acted as a sediment catcher for the fine-grained detritus washed out of the shallow basins of the Florida Bay, and simultaneously prohibited renewed reworking. Similar processes go on today on the surface of most mud banks of Florida Bay. The catastrophic event indicated by the sand layer probably changed the morphology of the bank to such an extent that the sampling point was shifted more to the windward side of the bank. This side is characterized by less dense plant growth. Therefore, less detritus could be caught and the material deposited could be reworked. The pronounced increase in skewness in the upper third of the core certainly indicates a strong washing out of the smaller-sized particles. The sediments are predominantly made up of carbonates, averagely 88.14 percent. The average CaCO3-content is 83.87 percent and the average MgCO3-content amounts to 4.27 percent. The chief carbonate mineral is aragonite making up 60.1 percent of the carbonate portion in the average, followed by high-magnesian calcite (33.8 percent) and calcite (6.1 percent). With increasing grain size the aragonite clearly increases at the cost of high-magnesian calcite in the upper third of the core. Chemically, this is shown by an increase of the CaCO3 : MgCO3-ratio. This increase is mainly caused by the more common occurrence of aragonitic fragments of mollusks in the coarse grain fractions. The bulk of the carbonates is made up of mollusks, foraminifera, ostracods, and - to a much lesser extent - of corals, worm-tubes, coccolithophorids, and calcareous algae, as shown by microscopic investigations. The total amount of the carbonate in the sediments is biogenic detritus with the possible exception of a very small amount of aragonite needles in the clay and fine silt fraction. The individual carbonate components of the gravel and sand fraction can be relatively easy identified as members of a particular animal or plant group. This becomes very difficult in the silt and clay fraction. Brownish aggregates are very common in the coarse and medium silt fraction. It was not always possible to clarify their origin (biogenic detritus, faecal pellets or carbonate particles cemented by carbonates or organic slime, etc.). Organic matter (plant fragments, rootlets), quartz, opal (siliceous sponge needles), and feldspar also occur in the sediments, besides carbonates. The lowermost part of the core has an age of 1365 +/- 90 years, as shown by 14C analysis.

Geochemistry of recent sediments of the East African continental margin, Arabian Sea

Chemical analyses have been carried out on 40 samples from the sediment surface and 210 samples from cores that were taken from the edge of the African continental block at the Arabian Sea (coasts of Somalia and Kenya, from Cape Guardafui to Mombasa) on the occasion of the Indian Ocean Expedition of the German research vessel "Meteor" during the years 1964/65. The carbonate content shows its maximum on the northern part of the continental shelf of Africa, where fossil reef debris furnish the detritic portion of carbonate. In the southern part of the continental shelf of Africa the portion of carbonate is low, as it is heavily diluted by the non-carbonatic detritus. It is also in the deep-sea that a lower carbonate content is encountered below the calcite compensation depth. Trace elements in the carbonates: On the shelf and in its vicinity Sr and Mg are enriched. The enrichment has been brought about by the portion of reef debris, as this latter contains aragonite (enrichment of Sr) as well as high-magnesium calcite. The greatest part of the slope contains carbonates that are poor in trace elements and mainly made up of foraminifera (and of coccoliths). Below the carbonate compensation depth another enrichment of Mg takes place in the carbonates, which is probably due to a selective dissolution of calcite in comparison to dolomite. The iron and manganese contents of the carbonates are high (iron higher in coast proximity, manganese higher in the depth), but not genuine, as they come about in the course of the extraction of the carbonates as a result of the dissolution of authigenic Mn-Fe-minerals. Non-carbonatic portion of the sediments: In coast proximity an enrichment of quartz comes about. Within the quartz-rich zone it is the elements V, Cr, Fe, Ti, and B that have been enriched in the non-carbonatic components. This enrichment must be attributed to an elevated content of heavy minerals. In the case of Ti and Fe the preliminary enrichment brought about by processes of lateritisation on the continent plays a certain role. Toward the deep-sea an enrichment of the elements Mn Ni, Cu, and Zn takes place; these enrichments must be explained by authigenic Mn-Fe-minerals. Within the Mn-rich zone a belt running parallel to the coast stands out that shows an increased Mn-enrichment. However, this increase in enrichment does not apply to the elements Ni, Cu, and Zn. It is probable that this latter increased enrichment comes about as a result of the migration of manganese to the sediment surface. (Within the sediments there prevail reductive conditions, in the presence of which Mn is capable of migration, whereas at the sediment surface its precipitation comes about under oxidizing conditions). The quantity of organic matter mainly is dependent on grain size and on the rate of sedimentation. On the shelf an impoverishment of organic matter is to be encountered, as the sediments are coarse-grained. In the depth the impoverishment must be explained on the strength of a small rate of sedimentation. Between those two ranges organic substance is enriched. P and N show an enrichment in comparison to Corg with this applying all the more the smaller the absolute quantity of Corg is. In this particular case one has to do with an enrichment coming about during the diagenetic processes of organic matter. A comparison with the sediments from the Indian and Pakistani continental border in Arabian Sea shows as follows: on the African continental border the coarse detrital material has been transported farther out to deep-sea, which has something to do with the greater inclination of the surface of sedimentation. Carbonate is found in greater abundance on the African side. Its chemical composition is influenced by reef-debris which is missing by Indian-Pakistani side. The content of organic matter is lower on the African side. Contrary to that, the enrichments of N and P compared to organic matter are of an equal order of magnitude on both sides of the Arabian Sea.