Manganese contents and accumulation rates in reduced bottom sediments of the Sea of Okhotsk

Manganese contents in reduced sediments and accumulation rates were investigated. Their values in sediments of most of cores are background (0.03-0.07 %).Anomalous concentrations (up to 2.5 %) and accumulation rates (up to 60 mg/cm**2/ka) occur near the known region of hydrothermal barite mineralization in the Derugin Basin. High accumulation rates of Mn (>10 mg/cm**2/ka) also occur in Holocene sediments to south-east from the Derugin Basin. It can be assumed that high Mn contents and accumulation rates occur there due to transportation of Mn-rich water from the Derugin Basin in the near-bottom layer under the lower border of the Sea of Okhotsk Intermediate Water. Intensive Mn accumulation is also typical for the South Okhotsk Basin near the Bussol Strait. Mn accumulation rates of glacial sediments of the second oxygen isotope stage are less significant, which is presumed to be caused by paleoceanological reasons.

Organofacies reconstruction and lipid geochemistry of sediments from the Galicia margin

Samples of Lower to middle Cretaceous rocks from ODP Sites 638, 640, and 641, drilled on the Galicia continental margin in the northeast Atlantic, have been investigated by organic geochemical methods (i.e., organic carbon determination, Rock-Eval pyrolysis, kerogen microscopy, gas chromatography, and gas chromatography/mass spectrometry) to define the Organofacies types and the depositional environments of these sediments. The results of this study fit well into the general picture drawn for the depositional history of the organic matter in Cretaceous organic-carbon-rich sediments in the North Atlantic from previous DSDP investigations. During the Valanginian to Albian, terrigenous organic carbon dominated the organic matter deposited on the Galicia continental margin. Cyclic changes in total organic carbon content were probably controlled by climatic-triggered changes in the supply of terrigenous organic matter from the nearby continent. A drastic change in depositional environment must have occurred near the Cenomanian/Turonian boundary. The preservation of large amounts of marine organic carbon in these sediments was probably caused by anoxic deep-water conditions during that time, rather than high productivity. All of the primary organic matter of the sediment samples investigated is thermally immature, as indicated by very low vitrinite reflectance values.

Organic geochemistry of late Cenozoic sediments from the eastern subtropical Atlantic

Detailed organic geochemical investigations have been performed on sediment samples from upwelling Site 658 and nonupwelling Sites 657 and 659. The major objective of this study has been the relationship between organic carbon accumulation and paleoclimatic and paleoceanographic conditions in the upwelling area off northwest Africa during late Cenozoic times. The study is based on results from organic carbon, nitrogen, and hydrogen analyses, Rock-Eval pyrolysis, kerogen microscopy, gas chromatography, and gas chromatography/mass spectrometry. In general, nonupwelling Sites 657 and 659 are characterized by low organic carbon values of less than 0.5%. At Site 657, four events of high organic carbon deposition (total organic carbon of 1%-3%) occur and represent turbidites and a slump interval. The upper Pliocene to Pleistocene sediments of upwelling Site 658 display high organic carbon contents of 0.5%-4%, with higher contents concentrated in the upper Pliocene. Accumulation rates of organic carbon vary between 0.1 and 0.5 gC/cm-**2/1000 yr, with maximum values between 3.5 and 3.1 Ma. Short-term cyclic ("Milankovitch-type") variations in organic carbon accumulation suggest climate-controlled mechanisms causing these fluctuations. The quality of organic matter at Site 658 is a mixture of kerogen type II and HI, with a dominance of the marine type. This is indicated by high hydrogen-index values of 200-400 mgHC/gC, low C/N ratios of 5-15, atomic H/C ratios of 1.0-1.5, and high amounts of marine macerals (alginite and liptodetrinite). We have estimated paleoproductivity for Sites 658 and 659 based on the amount of marine organic carbon. At open-marine Site 659, mean paleoproductivity varies between 20 and 50 gC/m**2/yr. At Site 658, mean paleoproductivity reaches high values of 160 to 320 gC/m**2/yr, very similar to those recorded in modern upwelling areas. The changes in productivity off northwest Africa are linked to changes in nutrient supply caused by both upwelling and fluvial input. The change from a dominantly humid climate to one characterized by fluctuations between humid and fully arid climates in northwest Africa occurs between 3.1 and 2.45 Ma.

14C ages of core top samples from Ontong-Java Plateau

Radiocarbon measurements on core tops from the Ontong-Java plateau confirm a previous finding by Berger and Killingley [1982] that at any given water depth, cores taken on the equator have higher accumulation rates and younger core top ages than their off-equator counterparts. Further, these new results fortify the conclusion by Broecker et al. [1991] that the increase in core top radiocarbon age with water depth rules out homogeneous dissolution within the pore waters as the dominant mechanism. Either most of the dissolution must occur prior to burial or it must occur during the first pass through the respiration-CO2-rich upper pore waters after which the calcite grains become armored against further dissolution. A puzzling aspect of this new data set is that despite the sizable difference in accumulation rate, the extent of dissolution as measured by either the CaCO3 content or the ratio of CaCO3 in the >150-µm size fraction to that in the < 63-µm fraction is no different off than on the equator. In order to reconcile the results of this study with those obtained by Hales and Emerson [1996] using in situ electrodes, it is necessary to call upon calcite armoring.

210Pb and AMS radiocarbon dates of sediment cores JM99-1197 and JM02-59 obtained in Malangen

A high-resolution sedimentary record from the subarctic Malangen fjord in northern Norway, northeastern North Atlantic has been investigated in order to reconstruct variations in influx of Atlantic Water for the last 2000 years. The fjord provides a regional oceanographic climatic signal reflecting changes in the North Atlantic heat flux at this latitude because of its deep sill and the relatively narrow adjoining continental shelf. The reconstructions are based on oxygen and carbon isotopic studies of benthic foraminifera from a high accumulation basin in the Malangen fjord, providing subdecadal time resolution. A comparison between instrumental measurements of bottom water temperatures at the core location and the reconstructed temperatures from benthic foraminiferal d18O for the same time period demonstrates that the stable isotope values reflect the bottom water temperatures very well. The reconstructed temperature record shows an overall decline in temperature of c. 1°C from c. 40 BC to ad 1350. This cooling trend is assumed to be driven by an orbital forced reduction in insolation. Superimposed on the general cooling trend are several periods of warmer or colder temperatures. The long-term fluctuations in the Malangen fjord are concurrent with fluctuations of Atlantic Water in the northern North Atlantic. Although they are not directly comparable, comparisons of atmospheric temperatures and marine records, indicate a close coupling between the climate systems. After ad l800 the record shows an unprecedented warming within the last 2000 years.

Chemical composition and accumulation rates of chemical elements in metalliferous sediments from axial zones of the East Pacific Rise and the Mid-Atlantic Ridge

In the monograph metalliferous sediments of the East Pacific Rise near 21°S are under consideration. Distribution trends of chemical, mineral and grain size compositions of metalliferous sediments accumulated near the axis of this ultrafast spreading segment of the EPR are shown. On the basis of lithological and geochemical investigations spatial and temporal variations of hydrothermal activity are estimated. Migration rates of hydrothermal fields along the spreading axis are calculated. The model of cyclic hydrothermal process is suggested as a result of tectono-magmatic development of the spreding centre.

Phosphorus partition and acumulation rates in sediments of ODP Legs 130 and 138

Understanding phosphorus (P) geochemistry and burial in oceanic sediments is important because of the role of P for modulating oceanic productivity on long timescales. We investigated P geochemistry in seven equatorial Pacific sites over the last 53 Ma, using a sequential extraction technique to elucidate sedimentary P composition and P diagenesis within the sediments. The dominant P-bearing component in these sediments is authigenic P (61-86% of total P), followed in order of relative dominance by iron-bound P (7-17%), organic P (3-12%), adsorbed P (2-9%), and detrital P (0-1%). Clear temporal trends in P component composition exist. Organic P decreases rapidly in younger sediments in the eastern Pacific (the only sites with high sample resolution in the younger intervals), from a mean concentration of 2.3 µmol P/g sediment in the 0-1 Ma interval to 0.4 µmol/g in the 5- 6 Ma interval. Over this same time interval, decreases are also observed for iron-bound P (from 2.1 to 1.1 µmol P/g) and adsorbed P (from 1.5 to 0.7 µmol P/g). These decreases are in contrast to increases in authigenic P (from 6.0-9.6 µmol P/g) and no significant changes in detrital P (0.1 µmol P/g) and total P (12 µmol P/g). These temporal trends in P geochemistry suggest that (1) organic matter, the principal shuttle of P to the seafloor, is regenerated in sediments and releases associated P to interstitial waters, (2) P associated with iron-rich oxyhydroxides is released to interstitial waters upon microbial iron reduction, (3) the decrease in adsorbed P with age and depth probably indicates a similar decrease in interstitial water P concentrations, and (4) carbonate fluorapatite (CFA), or another authigenic P-bearing phase, precipitates due to the release of P from organic matter and iron oxyhydroxides and becomes an increasingly significant P sink with age and depth. The reorganization of P between various sedimentary pools, and its eventual incorporation in CFA, has been recognized in a variety of continental margin environments, but this is the first time these processes have been revealed in deep-sea sediments. Phosphorus accumulation rate data from this study and others indicates that the global pre-anthropogenic input rate of P to the ocean (20x10**10 mol P/yr) is about a factor of four times higher than previously thought, supporting recent suggestions that the residence time of P in the oceans may be as short as 10000-20000 years.

Paleomagnetic of ODP Holes 122-762B and 122-763A

The magnetostratigraphy of Neogene sediments from Holes 762B and 763A are presented in this paper. Hole 762B contains 17 reversals. All reversals above the base of the Gilbert are correlated with the magnetic polarity time scale (Haq et al., 1988). Hole 763A yields a record of about 20 reversals that can be correlated to the magnetic polarity time scale, documenting all reversals to the base of Chron 4A. Based on the correlation, the sediment accumulation vs. time for Holes 762B and 763A are determined. The age-depth curves obtained show a similar pattern of sedimentation rate since 6.8 Ma. The study also indicates a correlation between the fluctuations in the magnetic parameters (natural remanent magnetization intensity and susceptibility), the lithologic changes, and changes in iron content at both holes. This correlation suggests that the natural remanent magnetization intensity and susceptibility changes observed in Holes 762B and 763A are controlled by changes in depositional processes probably associated with climatic variations.

Stable isotope and trace element geochemistry of carbonate sediments at DSDP Holes 87-577 and 6-47.2

Detailed analyses of well-preserved carbonate samples from across the Cretaceous/Tertiary boundary in Hole 577 have revealed a significant decline in the d13C values of calcareous nannoplankton from the Maestrichtian to the Danian Age accompanied by a substantial reduction in carbonate accumulation rates. Benthic foraminifers, however, do not exhibit a shift in carbon composition similar to that recorded by the calcareous nannoplankton, but actually increase slightly over the same time interval. These results are similar to the earlier findings at two North Pacific Deep Sea Drilling Project locations, Sites 47.2 and 465, and are considered to represent a dramatic decrease in oceanic phytoplankton production associated with the catastrophic Cretaceous/Tertiary boundary extinctions. In addition, the change in carbon composition of calcareous nannoplankton across the Cretaceous/Tertiary boundary at Hole 577 is accompanied by only minor changes in the oxygen isotope trends of both calcareous nannoplankton and benthic foraminifers, suggesting that temperature variations in the North Pacific from the late Maestrichtian to the early Danian Age were insignificant.

Mineralogy and pyrolysis at DSDP Hole 62-463

A 15-meter sequence of early Aptian organic-matter-rich sediments, cored at Deep Sea Drilling Project Site 463 (western Mid-Pacific Mountains) has been submitted for detailed mineralogical studies (XRD, SEM) and organiccarbon characterization. Although intense diagenesis has obscured the sedimentary record of depositional conditions, the history has been tentatively reconstructed. Through sustained volcanic activity and alteration processes on the archipelago, large amounts of silica were released into the sea water, resulting in a "bloom" of radiolarians. Hard parts settled in large amounts, yielding a hypersiliceous sediment; amorphous silica was diagenetically transformed into chalcedony, opal-CT and clinoptilolite through dissolution and recrystallization. Oxidization of part of the radiolarian soft parts (1) depleted the sea water in dissolved oxygen, allowing the burial of organic matter, and (2) generated carbon dioxide which led to dissolution of most of the calcareous tests. Moderate depositional depth and a high sedimentation rate are though to have prevailed during this episode. An immature stage of evolution is assigned to the studied organic matter, which is of two origins: autochthonous marine material, and allochthonous humic compounds and plant debris. Rhythmic sedimentation characterizes the distribution of the organic matter; each sequence shows (1) an upward progressive increase in organic-carbon content, and (2) an upward enrichment in marine organic matter.

Geochemistry, sediment components, and paleoproductivity reconstruction for the Miocene to early Pliocene sediments

We reconstruct paleoproductivity at three sites in the Atlantic Ocean (Ocean Drilling Program Sites 982, 925, and 1088) to investigate the presence and extent of the late Miocene to early Pliocene 'biogenic bloom' from 9 to 3 Ma. Our approach involves construction of multiple records including benthic foraminiferal and CaCO3 accumulation rates, Uvigerina counts, dissolution proxies, and geochemical tracers for biogenic and detrital fluxes. This time interval also contains the so-called late Miocene carbon isotope shift, a well-known decrease in benthic foraminiferal d13C values. We find that the timing of paleoproductivity maxima differs among the three sites. At Site 982 (North Atlantic), benthic foraminifera and CaCO3 accumulation were both at a maximum at ~5 Ma, with smaller peaks at ~6 Ma. The paleoproductivity maximum was centered earlier (~6.6-6.0 Ma) in the tropical Atlantic (Site 925). In the South Atlantic (Site 1088), paleoproductivity increased even earlier, between 8.2 Ma and 6.2 Ma, and remained relatively high until ~5.4 Ma. We note that there is some overlap between the interval of maximum productivity between Sites 925 and 1088, as well as the minor productivity increase at Site 982. We conclude that the paleoproductivity results support hypotheses aiming to place the biogenic bloom into a global context of enhanced productivity. In addition, we find that at all three sites the d13C shift is accompanied by carbonate dissolution. This observation is consistent with published studies that have sought a relationship between the late Miocene carbon isotope shift and carbonate preservation.

Pleistocene and late Miocene Calcareous nannofossil biostratigraphy of ODP Hole 150-905A

Continental rise Site 905 yielded upper Miocene and Pliocene uniform hemipelagic mud (a contourite) from approximately 215 to 540 meters below seafloor. The nannofossil biostratigraphy of this interval was reexamined using closely spaced samples from core interiors. Additionally, total nannofossil abundances and dominant species and species group abundances were determined to evaluate the potential of this section for extracting sequence stratigraphic information. The data indicate that the putative hiatuses at the end of the late Pliocene (Zones NN17 and NN18) and in the early Pliocene (Zones NN13 and NN14) probably are condensed intervals, but the base of the late Miocene is almost certainly marked by an unconformity. Judging from carbonate content and sedimentation rate both, nannofossil abundance may be governed by carbonate dissolution or by siliciclastic dilution. Consequently, condensed sections cannot be identified by the abundance of pelagic component in the sediment alone, as is possible in equivalent age Gulf of Mexico sediments. Where nannofossil preservation is adequate in consecutive samples, as in the early Pliocene and latest late Miocene, total nannofossil abundance fluctuates regularly and with a periodicity of less than 105 yr, which suggests that dilution of the pelagic component occurred with a frequency probably related to astronomical forcing.

Chemical, isotope and mineral composition of hydrothermally altered upper oceanic crust drilled at ODP Site 129-801C

ODP Hole 801C penetrates >400 m into 170-Ma oceanic basement formed at a fast-spreading ridge. Most basalts are slightly (10-20%) recrystallized to saponite, calcite, minor celadonite and iron oxyhydroxides, and trace pyrite. Temperatures estimated from oxygen isotope data for secondary minerals are 5-100°C, increasing downward. At the earliest stage, dark celadonitic alteration halos formed along fractures and celadonite, and quartz and chalcedony formed in veins from low-temperature (<100°C) hydrothermal fluids. Iron oxyhydroxides subsequently formed in alteration halos along fractures where seawater circulated, and saponite and pyrite developed in the host rock and in zones of restricted seawater flow under more reducing conditions. Chemical changes include variably elevated K, Rb, Cs, and H2O; local increases in FeT, Ba, Th, and U; and local losses of Mg and Ni. Secondary carbonate veins have 87Sr/86Sr = 0.706337 - 0.707046, and a negative correlation with d18O results from seawater-basalt interaction. Carbonates could have formed at any time since the formation of Site 801 crust. Variable d13C values (-11.2? to 2.9?) reflect the incorporation of oxidized organic carbon from intercalated sediments and changes in the d13C of seawater over time. Compared to other oceanic basements, a major difference at Site 801 is the presence of two hydrothermal silica-iron deposits that formed from low-temperature hydrothermal fluids at the spreading axis. Basalts associated with these horizons are intensely altered (60-100%) to phyllosilicates, calcite, K-feldspar, and titanite; and exhibit large increases in K, Rb, Cs, Ba, H2O, and CO2, and losses of FeT, Mn, Mg, Ca, Na, and Sr. These effects may be common in crust formed at fast-spreading rates, but are not ubiquitous. A second important difference is that the abundance of brown oxidation halos along fractures at Site 801 is an order of magnitude less than at some other sites (2% vs. 20-30%). Relatively smooth basement topography (<100 m) and high sedimentation rate (8 m/Ma) probably restricted the access of oxygenated seawater. Basement lithostratigraphy and early low-temperature hydrothermal alteration and mineral precipitation in fractures at the spreading axis controlled permeability and limited later flow of oxygenated seawater to restricted depth intervals.

Iridium and other element concentrations and magnetostratigraphy across the Cretaceous/Tertiarty boundary in ODP Hole 122-761C

Samples from Ocean Drilling Program Hole 761C, collected on both sides of the Cretaceous/Tertiary boundary have been analyzed for their chemical and mineralogical content. The sediment consists of nannofossil ooze with variable amounts of clay. The boundary is marked by a color change associated with a nearly step-like decrease of the carbonate fraction. Paleomagnetic data and the drop of the carbonate content indicate that a strong reduction of the sedimentation rate occurred at the boundary and persisted for million of years. An iridium anomaly of 80 ng/cm**2, together with overabundances of Cr and Fe, are found in close coincidence with the planktonic crisis. These enrichments can be explained by the infall of =0.16 g/cm2 of Cl-like chondritic material. Co and Ni enrichments and a great quantity of Ni-rich magnetites are also observed in the basal Danian. These elements and minerals excepted, the composition of the insoluble fraction appears to be nearly unchanged across the boundary. Chemical and mineralogical observations support a cosmic origin for the Cretaceous/Tertiary event but do not reveal the presence of any significant impact ejecta.

Chemical composition of bottom sediments at DSDP Sites 91-595 and 91-596 and ODP Sites 114-701 and 129-801

Subducted sediments play an important role in arc magmatism and crust-mantle recycling. Models of continental growth, continental composition, convergent margin magmatism and mantle heterogeneity all require a better understanding of the mass and chemical fluxes associated with subducting sediments. We have evaluated subducting sediments on a global basis in order to better define their chemical systematics and to determine both regional and global average compositions. We then use these compositions to assess the importance of sediments to arc volcanism and crust-mantle recycling, and to re-evaluate the chemical composition of the continental crust. The large variations in the chemical composition of marine sediments are for the most part linked to the main lithological constituents. The alkali elements (K, Rb and Cs) and high field strength elements (Ti, Nb, Hf, Zr) are closely linked to the detrital phase in marine sediments; Th is largely detrital but may be enriched in the hydrogenous Fe-Mn component of sediments; REE patterns are largely continental, but abundances are closely linked to fish debris phosphate; U is mostly detrital, but also dependent on the supply and burial rate of organic matter; Ba is linked to both biogenic barite and hydrothermal components; Sr is linked to carbonate phases. Thus, the important geochemical tracers follow the lithology of the sediments. Sediment lithologies are controlled in turn by a small number of factors: proximity of detrital sources (volcanic and continental); biological productivity and preservation of carbonate and opal; and sedimentation rate. Because of the link with lithology and the wealth of lithological data routinely collected for ODP and DSDP drill cores, bulk geochemical averages can be calculated to better than 30% for most elements from fewer than ten chemical analyses for a typical drill core (100-1000 m). Combining the geochemical systematics with convergence rate and other parameters permits calculation of regional compositional fluxes for subducting sediment. These regional fluxes can be compared to the compositions of arc volcanics to asses the importance of sediment subduction to arc volcanism. For the 70% of the trenches worldwide where estimates can be made, the regional fluxes also provide the basis for a global subducting sediment (GLOSS) composition and flux. GLOSS is dominated by terrigenous material (76 wt% terrigenous, 7 wt% calcium carbonate, 10 wt% opal, 7 wt% mineral-bound H2O+), and therefore similar to upper continental crust (UCC) in composition. Exceptions include enrichment in Ba, Mn and the middle and heavy REE, and depletions in detrital elements diluted by biogenic material (alkalis, Th, Zr, Hf). Sr and Pb are identical in GLOSS and UCC as a result of a balance between dilution and enrichment by marine phases. GLOSS and the systematics of marine sediments provide an independent approach to the composition of the upper continental crust for detrital elements. Significant discrepancies of up to a factor of two exist between the marine sediment data and current upper crustal estimates for Cs, Nb, Ta and Ti. Suggested revisions to UCC include Cs (7.3 ppm), Nb (13.7 ppm), Ta (0.96 ppm) and TiO2 (0.76 wt%). These revisions affect recent bulk continental crust estimates for La/Nb and U/Nb, and lead to an even greater contrast between the continents and mantle for these important trace element ratios. GLOSS and the regional sediment data also provide new insights into the mantle sources of oceanic basalts. The classical geochemical distinction between 'pelagic' and 'terrigenous' sediment sources is not valid and needs to be replaced by a more comprehensive understanding of the compositional variations in complete sedimentary columns. In addition, isotopic arguments based on surface sediments alone can lead to erroneous conclusions. Specifically, the Nd/Hf ratio of GLOSS relaxes considerably the severe constraints on the amount of sediment recycling into the mantle based on earlier estimates from surface sediment compositions.