Ge/Si ratios in marine siliceous microfossils

A procedure is presented to separate diatoms and radiolaria from marine sediments and from each other, to purify them of elements associated with other phases, and to dissolve them to determine their elemental composition. The cleaning procedure eliminates artifacts due to the presence of detrital clays and the high sorption capacity of hydrated silica. The concentration of trace elements (Al, Fe, Mg, and Ba) that we find in alkaline dissolutions of clean diatoms are at least an order of magnitude lower than previously reported. The overall long-term precision in the determination of Ge/Si in a sub-standard of clean diatoms is ±0.024 * 10**-6 (1 sigma). Ge/Si measured in diatoms and radiolaria from core tops indicates that high-latitude Holocene diatoms accurately record the present-day oceanic Ge/Si, while radiolarian ratios are systematically lower and display more scatter. Evaluation of Ge/Si in diatoms and radiolaria from Hole DSDP 265 (Plio-Pleistocene) suggests that post-depositional alteration of the ratio does not occur at this site, but the average ratio carried by diatoms over this time interval was lower than that in the present ocean.

(Table 1) Carbohydrates in different sediment types of the Central Pacific

Total contents of carbohydrates were determined in samples of natural sediments of various genetic types. Analyses were made on board. Deep-sea pelagic sediments (red clays of various types including zeolite clays, and also radiolarian and carbonate oozes) were the main types of sediments studied. Contents of carbohydrates in pelagic oozes of the Central Pacific ranged from 214 to 1605 ppm, averaging 602 ppm of air-dried sediment. Organic matter of the group studied is a diagenetically stable complex, with polysaccharides apparently predominating.

Observation of ferromanganese deposits in the Baltic Sea

Baltic sediments have been studied by Behrens, Munthe, Küppers, Spethmann, Apstein, Sjöstedt, Pratje and the writer. The following types of sediments have been observed: varved and non-varved late-glacial clays, gray and black, post-glacial muds, and sands. The organic content of late-glacial clays ordinarily is less than 1.3 per cent, and of post-glacial muds more than 3 per cent. Sediments containing intermediate quantities are scarce. This can be explained as a result of the changed balance between organic and inorganic sedimentation when the glacial period ended; the abundance of fresh detritus then suddenly ceased and inorganic sedimentation became very much slower than before; consequently, the relative amount of organic detritus increased. As most of the material was not subjected to biological analysis, it has not been possible to distinguish different ages among post-glacial sediments.

Iron isotope and chemical compositions of sediments and basalts drilled seaward of the Mariana Trench

The purpose of this work is to study the mobility and budget of Fe isotopes in the oceanic crust and in particular during low-temperature interaction of seawater with oceanic basalt. We carried out this investigation using samples from Ocean Drilling Program (ODP) Site 801C drilled during Leg 129 and Leg 185 in Jurassic Pacific oceanic crust seaward of the Mariana Trench. The site comprises approximately 450 m of sediment overlying a section of 500 m of basalt, which includes intercalated pelagic and chemical sediments in the upper basaltic units and two low-temperature (10-30°C) ocherous Si-Fe hydrothermal deposits. Fe was chemically separated from 70 selected samples, and 57Fe/54Fe ratios were measured by MC-ICP-MS Isoprobe. The isotopic ratios were measured relative to an internal standard solution and are reported relative to the international Fe-standard IRMM-14. Based on duplicate measurements of natural samples, an external precision of 0.2? (2 sigma) has been obtained. The results indicate that the deep-sea sediment section has a restricted range of d57Fe, which is close to the igneous rock value. In contrast, large variations are observed in the basaltic section with positive d57Fe values (up to 2.05?) for highly altered basalts and negative values (down to ?2.49?) for the associated alteration products and hydrothermal deposits. Secondary Fe-minerals, such as Fe-oxyhydroxides or Fe-bearing clays (celadonite and saponite), have highly variable d57Fe values that have been interpreted as resulting from the partial oxidation of Fe(2+) leached during basalt alteration and precipitated as Fe(3+)-rich minerals. In contrast, altered basalts at Site 801C, which are depleted in Fe (up to 80%), display an increase in d57Fe values relative to fresh values, which suggest a preferential leaching of light iron during alteration. The apparent fractionation factor between dissolved Fe(2+) and Fe remaining in the mineral is from 0.5? to 1.3? and may be consistent with a kinetic isotope fractionation where light Fe is stripped from the minerals. Alternatively, the formation of secondary clays minerals, such as celadonite during basalt alteration may incorporate preferentially the heavy Fe isotopes, resulting in the loss of light Fe isotopes in the fluids. Because microbial processes within the oceanic crust are of potential importance in controlling rates of chemical reactions, Fe redox state and Fe-isotope fractionation, we evaluated the possible effect of this deep biosphere on Fe-isotope signatures. The Fe-isotope systematics presented in this study suggest that, even though iron behavior during seafloor weathering may be mediated by microbes, such as iron-oxidizers, d57Fe variations of more than 4? may also be explained by abiotic processes. Further laboratory experiments are now required to distinguish between various processes of Fe-isotope fractionation during seafloor weathering.

Description of recent sediments of Nile Delta, Red Sea and Gulf of Aden (Table 1-3)

The study of textural, structural, chemical, and physical properties of fine-grained recent marine sediments leads to the conclusion that only a few compositional factors are responsible for significant changes in mass physical characteristics in the upper meters below sea bottom. Fossil-induced porosity increases water content and liquid limit. It also seems to have partially influenced the plastic limit and plasticity index of calcareous sandy silts from the Red Sea and the western Gulf of Aden so that they become similar to the montmorillonite rich prodelta clays from the Nile Delta. Diagrams based on liquid limit and plasticity loose their original meaning in these cases. Activity of sediments rich in microorganisms can be higher than that of montmorillonitic clay. The shear strength-depth relationship of normally consolidated sediments is surprisingly little influenced by changes in sand or clay content and clay mineralogy. Only high lime content, submarine erosion and beginning cementation increase the strength considerably. Erosional disconformities near the present surface can be deduced from the strength-depth curve when as little as 1 or 2 m sediment have been removed. Flat or irregular strength-depth curves indicate beginning cementation and probably discontinuous sedimentation, provided the composition of the material remains in some degree constant. In our samples diagenetic pyrite, but no recristallisation of carbonates could be detected under the microscope. Underconsolidation and excess pore-water pressure, factors which tend to foster submarine slides, mud lumps, and diapiric folding, seem to be restricted Varito areas with mainly rapidly deposited, homogeneous or layered sediments. But where an abundance of burrowing organisms increases the vertical permeability of the sediment, normal consolidation and stable deposits are to be expected, at least in the upper meters below the present surface. According to 14C-determinations on calcareous microorganisms the rate of deposition of the investigated sediments seems to range from 26 to 167 cm per 1000 years.

(Table 1) Total organic carbon, calcium carbonate and nitrogen at DSDP Holes 80-559 and 80-550B

Concentrations of organic and inorganic nitrogen have been measured on Leg 80 sediments. The inorganic nitrogen content is relatively constant, 0.02-0.03 wt.%. Because most of the inorganic nitrogen occurs as NH3 or (NH4)+ fixed on clays, clay-poor sediments have lower inorganic nitrogen contents. Organic nitrogen content depends upon both the type and the quantity of organic matter present. In Leg 80 sediments, woody kerogens contain much less organic nitrogen than do kerogens of algal origin. Furthermore, pelagic samples of low organic carbon content have less organic nitrogen than predicted, because of loss during diagenesis. DSDP shipboard analytical procedures do not distinguish between organic and inorganic nitrogen. Great caution must therefore be exercised in interpreting C/N ratios.

(Table 19, page 199) Minor constituents of one of the San Clemente iron concretions and its metallic core

The chemical and mineralogical composition of pelagic sediments from the East Pacific Ocean has been determined with the aim of defining the ultimate sources and the mechanisms of formation of the solid phases. The distribution of elements between sea-water, the pore solution and the various solid components of the sediments permits interpretations of the variations in time and space of the gross chemical composition of pelagic clays. For example, manganese, present in sea-water in a divalent form, is apparently oxidized at the sediment-water interface to tetravalent species which subsequently become a part of the group of ferromanganese oxide minerals which are found in the marine environment. It is suggested the rate of manganese accumulation in sediments is some function of the length of time the sediment surface is in contact with sea-water. The contribution of chemical species from the different geospheres is considered. The quantitative importance of pelagic clays in the major sedimentary cycle is studied on the basis of the distribution of the weathered igneous rock products between continental and pelagic deposits and sea-water. These analyses of a wide variety of pelagic clays allow a reformulation of the geochemical balance and it is concluded that pelagic clays account for approximately 13 per cent of the total mass of sediments produced over geologic time.

(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.

Radiolarians of DSDP Site 136-842 and Hole 136-843C

Deep-sea cores recovered at Sites 842 and 843 on Leg 136 of the Ocean Drilling Program have yielded assemblages of Quaternary, Eocene, and Cretaceous radiolarians from the Hawaiian Arch region of the northern equatorial Pacific Ocean. Reddish-brown clays from Hole 842A (0-9.6 mbsf), Hole 842B (0-6.3 mbsf), and Hole 843C (0-4.2 mbsf) contain abundant and diverse assemblages of Quaternary radiolarians consisting of more than 80 species typical of the equatorial Pacific region. Quaternary radiolarians at these sites are assignable to the Quaternary Collosphaera tuberosa Interval Zone and Amphirhopalum ypsilon Interval Zone. The boundary between these zones cannot be determined precisely because of the rarity of zonal markers below surface sediments. Correlations have been made between radiolarian occurrences and magnetostratigraphic events elsewhere in the Pacific Ocean, but similar correlations are difficult at Sites 842 and 843 because of poor subsurface preservation. Chert samples collected from intervals in Cores 842B-10X and 842C-1W have yielded radiolarian ages of lower Cenomanian to Santonian and lower Cenomanian, respectively. Radiolarian assemblages in volcanic sand layers in Sections 6 and 7 of Core 842A-1H (7.5-9.6 mbsf) contain lower and middle Eocene radiolarians admixed with abundant Quaternary faunas. Reworked Eocene radiolarians appear to be restricted to thin layers of volcanic sands within the cores, suggesting deposition by turbidity currents.

Rock eval analysis of organic matter in sediment core 159-959D

The Cretaceous Equatorial Atlantic Gateway between the Central and South Atlantic basins is of interest not only for paleoceanographic and paleoclimatic studies, but also because it provided particularly favourable conditions for the accumulation and preservation of organic-rich sediments. Deposition of carbonaceous sediments along the Côte d'Ivoire-Ghana Transform Margin (Ocean Drilling Program Leg 159) was intimately linked to the plate tectonic and paleoceanographic evolution of this gateway. Notably, the formation of a marginal basement ridge on the southeastern border of the transform margin provided an efficient shelter of the landward Deep Ivorian Basin against erosive and potentially oxidizing currents. Different subsidence histories across the transform margin were responsible for the development of distinct depositional settings on the crest and on both sides of the basement ridge. Whereas the southern, oceanward flank of the basement ridge was characterized by rapid, continuous deepening since last Albian-early Cenomanian, marine sedimentation on the northern, landward flank was interrupted by a period of uplift and erosion in the late Albian, and rapid subsidence started after the early Coniacian. Organic-rich sediments occur throughout almost the entire Cretaceous section, but hydrogen-rich marine black shales were exclusively recovered from core sections above an uplift-related unconformity. These black shales formed when separation of Africa and South America was sufficient to allow permanent oceanic midwater exchange after the late Albian. Four periods of black shale accumulation are recovered, some of them are correlated with the global oceanic anoxic events: in the last Albian-earliest Cenomanian, at the Cenomanian-Turronian boundary, during the middle Coniacian-early Campanian, and in the mid-Maastrichtian. These periods were characterized by increasing carbon flux to the seafloor, induced by enhanced palaeoproductivity and intensified supply of terrestrial organic matter. Black shale depostion appears to be intimately linked to periods of rising or maximum eustatic sea level and to the expansion of the oxygen minimum zone, as indicated by foraminiferal biofacies. Intervals between black shales units, in contrast, indicate a shrinking oxygen minimum zone and enhanced detrital flux rates, probably related to lowering sea level. Upper Cretaceous detritral limestones with high porosities may provide excellent hydrocarbon reservoirs, alsthough their areal extent appears to be limited. Palaeogene porcellanites, capped by Neogene pelagic marls and clays, extend over a wider area and max provide another target for hydrocarbon exploration.

Analysis of Mn nodules from cruise GH72-2

The GH72-2 shipborne survey was carried out in the northwest Pacific during 31 days under the 'Basic investigations for exploration of deep sea mineral resources' program. The sediments encountered could be classified as follows: 1) Most of the brown clays occur on the abyssal plain of the basins at depth over 4500m. 2) Calcareous oozes are predominant at the top, slope and foot of seamounts and guyots. 3) Terrigeneous sediments are distributed near islands. The concentrated zone of ferromanganese nodules was located in the Magellan seamounts area. However, the metal contents in Mn, Cu, Ni and Co for these nodules are relatively poor, and these ferromanganese deposits occur at a depth over 5000m. It is interesting to note that the shape of the nodules is sometimes nearly spherical, and that the chemical composition of the nodules is characterized by the low ratio Mn/Fe and Co/Ni.

Planktonic foraminifera in sediments of the Ibero-Moroccan Continental Margin

Recent clays cover the East Atlantic continental slopes. They are gray and poor in sand off Portugal (Cape Sines), but reddish brown to reddish gray and richer in sand off Morocco (Cape Mazagan). The majority of the 19 sediment cores, which were taken mainly on two profiles (Fig. 3), can be correlated by means of planktonic foraminifera (Figs. 27, 28). The following parameters seem to be well suited for this purpose: qualitative and quantitative distribution of the planktonic foraminiferal species and faunas, coiling ratios of three Globorotalia-species: G. crassaformis, G. hirsuta and G. truncatulinoides. Sediments from about 2000 m water depth show highest sedimentation rates off Portugal (> 20 cm/1000 yrs.), but off Morocco the lowest sedimentation rates (about 3 cm/1000 yrs.). The sediments are dated with planktonic foraminifera and 31 radiocarbon analyses and the stratigraphic interpretation is supported by the lithostratigraphy. Holocene faunas are distinguished from the Pleistocene ones by differences in species composition, lower dominances and higher diversities. The Holocene sediments show smaller differences of the foraminiferal numbers than the Pleistocene ones. During Holocene and Pleistocene the temperatures of the surface water masses (indicated by the planktonic foraminiferal faunas) show similar values nearshore and offshore off Morocco. Likewise, there is no apparent temperature gradient in the Pleistocene off Portugal; whereas here values increase offshore during the Holocene. The proportion of species indicating warmer water masses is generally higher off Morocco. The plankton/benthos ratio increases with water depth and reaches maximum values already at about 1000 m. The production rate for planktonic foraminifera is higher in the continental slope regions than in the open ocean, but their shells show typical solution phenomena already in water depths of less than 1000 m. A higher solutional rate was found in sediments from the Tagus Abyssal Plain, while sediments from Horse Shoe and Seine Abyssal Plain seem to be better preserved. In the Tagus Abyssal Plain solution is less important during late Pleistocene than during Holocene.

Age model of ODP Site 184-1146 (Table 1)

Clay mineral assemblages at ODP Site 1146 in the northern South China Sea are used to investigate sediment source and transport processes and to evaluate the evolution of the East Asian monsoon over the past 2 Myr. Clay minerals consist mainly of illite (22-43%) and smectite (12-48%), with associated chlorite (10-30%), kaolinite (2-18%), and random mixed-layer clays (5-22%). Hydrodynamic and mineralogical studies indicate that illite and chlorite sources include Taiwan and the Yangtze River, that smectite and mixed-layer clays originate predominantly from Luzon and Indonesia, and that kaolinite is primarily derived from the Pearl River. Mineral assemblages indicate strong glacial-interglacial cyclicity, with high illite, chlorite, and kaolinite content during glacials and high smectite and mixed-layer clay content during interglacials. During interglacials, summer enhanced monsoon (southwesterly) currents transport more smectite and mixed-layer clays to Site 1146 whereas during glacials, enhanced winter monsoon (northerly) currents transport more illite and chlorite from Taiwan and the Yangtze River. The ratio (smectite+mixed layers)/(illite+chlorite) was adopted as a proxy for East Asian monsoon variability. Higher ratios indicate strengthened summer-monsoon winds and weakened winter-monsoon winds during interglacials. In contrast, lower ratios indicate a strongly intensified winter monsoon and weakened summer monsoon during glacials. Spectral analysis indicates the mineral ratio was dominantly forced by monsoon variability prior to the development of large-scale glaciation at 1.2 Myr and by both monsoon variability and the effects of changing sea level in the interval 1.2 Myr to present.