Maastrichtian calcareous nannofossils of the Indian Ocean and Shatsky Rise

The biotic effects of volcanism have long been the unknown factors in creating biotic stress, and the contribution of the Deccan volcanism to the K-T mass extinction remains largely unknown. Detailed studies of the volcanic-rich sediments of Indian Ocean Ninetyeast Ridge Sites 216 and 217 and Wharton Basin Site 212 reveal that the biotic effects of late Maastrichtian volcanism on planktic foraminifera and calcareous nannofossils are locally as severe as those of the K-T mass extinction. The biotic expressions of these high stress environments are characterized by the Lilliput effect, which includes reduced diversity by eliminating most K-strategy species, and reduction in specimen size (dwarfing), frequently to less than half their normal adult size of both r-strategy and surviving K-strategy species. In planktic foraminifera, the most extreme biotic stress results are nearly monospecific assemblages dominated by the disaster opportunist Guembelitria, similar to the aftermath of the K-T mass extinction. The first stage of improving environmental conditions results in dominance of dwarfed low oxygen tolerant Heterohelix species and the presence of a few small r-strategy species (Hedbergella, Globigerinelloides). Calcareous nannofossil assemblages show similar biotic stress signals with the dominance of Micula decussata, the disaster opportunist, and size reduction in the mean length of subordinate r-strategy species particularly in Arkhangelskiella cymbiformis and Watznaueria barnesiae. These impoverished and dwarfed late Maastrichtian assemblages appear to be the direct consequences of mantle plume volcanism and associated environmental changes, including high nutrient influx leading to eutrophic and mesotrophic waters, low oxygen in the water column and decreased watermass stratification.

(Table 2) Organochlorine concentrations in polar bears (Ursus maritimus) from East Greenland 1999-2001

Persistent organochlorine (OC) contaminants (PCBs, DDTs, chlordanes (CHLs), dieldrin, hexachlorocyclohexanes (HCHs), chlorobenzenes (CBzs)) were determined in adipose tissue of 92 polar bears (Ursus maritimus) sampled between 1999 and 2001 in central East Greenland (69°00'N to 74°00'N). OC data were presented from subadults (S: females: <5 years and males: <6 years), adult females (F: >=5 years) and adult males (M: >=6 years). Summed chlorobiphenyl (SumCBs) concentrations (41 congeners including co-eluters), SumCHLs and SumDDTs were the dominant classes of OCs. SumCBs concentrations were found to be 6470, 8240 and 9100 ng/g lipid weight (lw) i subadults, adult females and adult males, respectively. The corresponding figures were: 2010 (S), 2220 (F) and 1710 (M) ng/ g lw for SumCHLs and 462 (S), 462 (F) and 559 (M) ng/g lw for SumDDTs. The dominant CB congeners were CB153 (32.3%), CB180 (21.4%), CB170 (12.2%) and CB138 (11.0%). The metabolite p,p'-DDE (88.2%) dominated the SumDDTs, while oxychlordane was the dominant (57.1%) CHL-related compound. Concentrations of SumCBs, SumCBzs, SumDDTs, mirex and dieldrin were highest in adult males, whereas concentrations of SumHCHs were lower than in adult females but not than those in subadults. Adult females had the lowest concentrations of SumCBzs, mirex and dieldrin. Concentrations of SumCHLs were lowest in adult males, intermediate in subadults and highest in adult females. SumCB, SumHCH and SumCHL concentrations showed high seasonal variability in adult females but remained relatively constant in adult males and subadults. In general, the OC levels in females appeared to be highest in March and lowest in January or September. Concentrations of SumCBzs and dieldrin showed seasonal variability in all three groups, with a maximum in March in adult females. SumCBz concentrations in adult males and subadults of both sexes peaked in April-July, and dieldrin concentrations peaked in April-July in subadults, but not until August in adult males. SumDDT concentrations increased from January to a maximum in April-July for subadults and in August for adults. Temporal trends within the last decade were examined by comparing the present data to the concentrations reported in samples from 1990 from the same region. SumCB, p,p'-DDE and SumHCH concentrations in 1999-2001 were 22.1%, 66.3% and 39.3% lower than the 1990 concentrations, respectively. in contrast, SumCHL and dieldrin concentrations showed differences amongst sex and age groups in the temporal trends, where present concentrations are between 24.4% to 69.3% and 27.0% to 69.0% lower, respectively, relative to the 1990 levels. However, power analysis suggested that firm conclusions could not be drawn regarding the general time trend based on these two sampling periods. The range of half-lives of the various OC classes were estimated to lie between 4.5 and 20.6 years depending on the age and sex groups considered.

Speciation of metals in bottom sediments from the south Kara Sea and Ob and Yenisei estuarine zones

Speciation of Fe, Mn, Zn, Cu, Co, Ni, Cr, Pb, and Cd was studied in 52 samples of bottom sediments collected during Cruise 49 of the R/V "Dmitry Mendeleev" to the estuaries of the Ob and Yenisei rivers and to the southwest Kara Sea. Immediately after sampling the samples were subjected to on-board consecutive extraction to separate metal species according to their modes of occurrence in the sediments: (1) adsorbed, (2) amorphous Fe-Mn hydroxides and related metals, (3) organic + sulfide, and (4) residual, or lithogenic. Atomic absorption spectroscopy of the extracts was carried out at a stationary laboratory. Distribution of Fe, Zn, Cu, Co, Ni, Cr, Pb, and Cd species is characterized by predominance of lithogenic or geochemically inert modes (70-95% of bulk contents), in which the metals are bound in terrigenous and clastic mineral particles and organic detritus. About half of total Mn amount and 15-30% of Zn and Cu are contained in geochemically mobile modes. Spatiotemporal variations in proportions of the metal species in the surface layer of sediments along sub-meridional sections and through vertical sections of bottom sediment cores testify that Mn and, to a lesser extent, Cu are the most sensitive to changes in sedimentation environment. The role of their geochemically mobile species notably increases under reducing conditions.

Clay mineralogy of late Eocene to early Miocene sediments of McMurdo Sound, Antarctica

The clay mineral assemblages of upper Eocene to lower Miocene sediments recovered at the CIROS-1 and MSSTS-1 drill sites on the McMurdo Sound shelf, Antarctica, were analyzed in order to reconstruct the Cenozoic Antarctic paleoclimate and ice dynamics. The assemblages are dominated by smectite and illite, with minor amounts of chlorite and kaolinite. The highest smectite amounts and best smectite crystallinities occur in the upper Eocene part of CIROS-1, below 425-445 mbsf. They indicate that during their deposition, chemical weathering conditions prevailed on the nearby continent. Large parts of East Antarctica were probably ice-free at that time, but some glaciers reached the sea and contributed to the glaciomarine sedimentation. In contrast, only minor total amounts of smectite are present in Oligocene and younger sediments due to the shift to mainly physical weathering on an ice-covered Antarctic continent. However, relative smectite percentages rise to more than 60% during two late Oligocene intervals (ca. 27.5-26.2 and 25.0-24.5 Ma) and during one early Miocene interval starting at ca. 23.3 Ma. These intervals are characterized by ice masses coming probably from the south, where volcanic rocks acted as a source, as also indicated by the composition of the sand and gravel fractions. During the other intervals, the ice came from the west, where the physical erosion of basement rocks and sedimentary rocks of the Beacon Supergroup in the Transantarctic Mountains provided high illite concentrations. Because the two drill sites are only 4 km apart, their clay mineral records can be correlated. This led to a new interpretation of the Oligocene paleomagnetic data of the MSSTS-1 site and to a more detailed lithostratigraphic correlation of the Miocene parts of the cores.

Geochemical analysis of sediments and interstitial water in sediment cores from the North-West African continental margin and from the Central Pacific

A. Continental slope sediments off Spanish-Sahara and Senegal contain up to 4% organic carbon and up to 0.4% total nitrogen. The highest concentrations were found in sediments from water depths between 1000 and 2000 m. The regional and vertical distribution of organic matter differs significantly. Off Spanish-Sahara the organic matter content of sediment deposited during glacial times (Wuerm, Late Riss) is high whereas sediments deposited during interglacial times (Recent, Eem) are low in organic matter. Opposite distribution was found in sediments off Senegal. The sediments contain 30 to 130 ppm of fixed nitrogen. In most sediments this corresponds to 2-8 % of the total nitrogen. Only in sediments deposited during interglacial times off Spanish-Sahara up to 20 % of the total nitrogen is contained as inorganically bound nitrogen. Positive correlations of the fixed nitrogen concentrations to the amounts of clay, alumina, and potassium suggest that it is primarily fixed to illites. The amino acid nitrogen and hexosamine nitrogen account for 17 to 26 % and 1.3 to 2.4 %, respectively of the total nitrogen content of the sediments. The concentrations vary between 200 and 850 ppm amino acid nitrogen and 20 to 70 ppm hexosamine nitrogen, both parallel the fluctiations of organic matter in the sediment. Fulvic acids, humic acids, and the total organic matter of the sediments may be clearly differentiated from one another and their amino acid and hexosamine contents and their amino acid composition: a) Fulvic acids contain only half as much amino acids as humic acids b) The molar amino acid/hexosamine ratios of the fulvic acids are half those of the humic acids and the total organic matter of the sediment c) The amino acid spectra of fulvic acids are characterized by an enrichment of aspartic acid, alanine, and methionine sulfoxide and a depletion of glycine, valine, isoleucine, leucine, tyrosine, phenylalanine, lysine, and arginine compared to the spectra of the humic acids and those of the total organic matter fraction of the sediment. d) The amino acid spectra of the humic acids and those of the total organic matter fraction of the sediments are about the same with the exception that arginine is clearly enriched in the total organic matter. In general, as indicated by the amino compounds humic acids resemble closer the total organic matter composition than the low molecular fulvic acids do. This supports the general idea that during the course of diagenesis in reducing sediments organic matter stabilizes from a fulvic-like structure to humic-like structure and finally to kerogen. The decomposition rates of single aminio acids differ significantly from one another. Generally amino acids which are preferentially contained in humic acids and the total organic matter fraction show a smaller loss with time than those preferably well documented in case of the basic amino acids lysine and arginine which- although thermally unstable- are the most stable amino acids in the sediments. A favoured incorporation of these compounds into high molecular substances as well as into clay minerals may explain their relatively high "stability" in the sediment. The nitrogen loss from the sediments due to the activity of sulphate-reducing bacteria amounts to 20-40 % of the total organic nitrogen now present. At least 40 % of the organic nitrogen which is liberated by sulphate-reducing bacteria can be explained ny decomposition of amino acids alone. B. Deep-sea sediments from the Central Pacific The deep-seas sediments contain 1 to 2 orders of magnitude less organic matter than the continental slope sediments off NW Africa, i.e. 0.04 to 0.3 % organic carbon. The fixed nitrogen content of the deep-sea sediments ranges from 60 to 270 ppm or from 20 to 45 % of the total nitrogen content. While ammonia is the prevailing inorganic nitrogen compound in anoxic pore waters, nitrate predominates in the oxic environment of the deep-sea sediments. Near the sediment/water interface interstital nitrate concentrations of around 30 µg-at. N/l were recorded. These generally increase with sediment depth by 10 to 15 µg-at. NO3- N/l. This suggests the presence of free oxygen and the activity of nitrifying bacteria in the interstitial waters. The ammonia content of the interstitial water of the oxic deep-sea sediments ranges from 2 to 60 µg-at. N/l and thus is several orders of magnitude less than in anoxic sediments. In contrast to recorded nitrate gradients towards the sediments/water interface, there are no ammonia concentration gradients. However, ammonia concentrations appear to be characteristic for certain regional areas. It is suggested that this regional differentiation is caused by ion exchange reactions involving potassium and ammonium ions rather than by different decomposition rates of organic matter. C. C/N ratios All estimated C/N ratios of surface sediments vary between 3 and 9 in the deep-sea and the continental margin, respectively. Whereas the C/N ratios generally increase with depth in the sediment cores off NW Africa they decrease in the deep-sea cores. The lowest values of around 1.3 were found in the deeper sections of the deep-sea cores, the highest of around 10 in the sediments off NW Africa. The wide range of the C/N ratios as well as their opposite behaviour with increasing sediment depth in both the deep-sea and continental margin sediment cores, can be attributed mainly to the combination of the following three factors: 1. Inorganic and organic substances bound within the latticed of clay minerals tend to decrease the C/N ratios. 2. Organic matter not protected by absorption on the clay minerals tends to increase C/N ratios 3. Diagenetic alteration of organic matter by micro-organisms tends to increase C/N ratios through preferential loss of nitrogen The diagenetic changes of the microbially decomposable organic matter results in both oxic and anoxic environments in a preferential loss of nitrogen and hence in higher C/N ratios of the organic fraction. This holds true for most of the continental margin sediments off NW Africa which contain relatively high amounts of organic matter so that factors 2 and 3 predominate there. The relative low C/N ratios of the sediments deposited during interglacial times off Spanish-Sahara, which are low in organic carbon, show the increasing influence of factor 1 - the nitrogen-rich organic substances bound to clay minerals. In the deep-sea sediments from the Central Pacific this factor completely predominates so that the C/N rations of the sediments approach that of the substance absorbed to clay minerals with decreasing organic matter content. In the deeper core sections the unprotected organic matter has been completely destroyed so that the C/N ratios of the total sediments eventually fall into the same range as those of the pure clay mineral fraction.

Particle analysis in the Kara Sea

In September 1999 two short-term moorings with cylindrical sediment traps were deployed to collect sinking particles in bottom waters off the Ob and Yenisei river mouths. Samples were studied for their bulk composition, pigments, phytoplankton, microzooplankton, fecal material, amino acids, hexosamines, fatty acids and sterols and compared to suspended matter and surface sediments in order to collect information about the nature and cycling of particulate matter in the water column. Results of all measured components in sinking particles point to an ongoing seasonality in the pelagic system from blooming diatoms in the first phase to a more retention system in the second half of trap deployment. Due to a phytoplankton bloom observed north of the Ob estuary, flux rates were generally higher in the trap deployed off the Ob than off the Yenisei. The Ob trap collected fresh surface-derived particulate matter. Particles from the Yenisei trap were more degraded and resembled deep water suspension. This material may partly have been derived from resuspended sediments.

Contents of P2O5, Corg, Sr, and Ba in phosphorites and host sediments from the Atlantic and Pacific oceans

Sr contents in phosphorites on shelves of the Southwest Africa, and of Chile and Peru increase with degree of their lithification, from 0.05 to 0.28% and from 0.13 to 0.16% respectively. Phosphorites from Pacific submarine seamounts have the average Sr content 0.11%, and bone phosphate from Pacific floor 0.13%. Shelf phosphorites are characterized by high correlation coefficients between Sr and P2O5 (R = +0.82) and constant Sr/P2O5 ratio (0.0084). In phosphorites from submarine sea-mounts and in bones from the ocean floor Sr/P2O5 ratio is only a little higher than a half of that in shelf phosphorites. This indicates specific and different genesis of phosphorites from submarine mountains. Ba content in recent phosphorites from the shelf of the Southwest Africa changes with increasing degree of lithification. At first their Ba contents rise from 0.031 to 0.188%, then they diminish to 0.016%, and thereafter again increase to 0.070%. This is due to successive predominance of one of the following processes going in different directions: co-precipitation with phosphate gels or formation of true separate Ba phase, loss of phosphate in crystallization and "self-purification" of concentrations, and surface adsorption. In Peru-Chile shelf phosphorites the average Ba content is 0.017%, in phosphorites from Pacific seamounts 0.192%, and in fossilized bones 0.010%.

Detailed measurements of radium inside a nodule of Albatross 1899-1900 - for Stations 13, 173 and 4658

Thanks to the courtesy of the British Museum of Natural History the author obtained from their Challenger collections two small nodules, and through a similar courtesy of the Mineralogical Department of the Riksmuseum in Stockholm one half of a much larger nodule, also from the Challenger Expedition. Results from his initial measurements of the radium contents of these samples convinced the author that the radium in the nodules is accumulated from the surrounding sediment. In the present paper the author conducted a much more thorough investigation on nodules obtained during the U.S. Albatross cruises of Dr. Agassiz. Detailed measurements of radium were conducted on individual layers and spots inside each nodule.

Amino acids in interstitial waters from ODP Sites 126-790 and 126-791

Sites 790 and 791 lie in the eastern half graben of the Sumisu Rift, a backarc graben west of the active Izu-Bonin arc volcanoes Sumisu Jima and Tori Shima, at 30°54.96'N, 139°50.66'E, in 2223 m water depth and 30°54.97'N, 139°52.20'E, in 2268 m water depth, respectively. A small decrease in the sulfate concentration in the interstitial waters from these sites suggests fairly low microbial activity by sulfate-reducing bacteria. The values of the dissolved free amino acids (DFAA) in the interstitial waters from both sites range from 1.26 to 6.82 µmol/L, with an average of 3.81 µmol/L. The acidic, basic, neutral, aromatic, and sulfur-containing amino acids have average values of 0.32, 0.50, 2.71, 0.15, and 0.09 µmol/L, respectively. The relative abundances of the acidic, basic, neutral, aromatic, and sulfur-containing amino acids average 8, 13,72, 4, and 1 mol%, respectively. Glycine, serine, alanine, ornithine, and aspartic acid are major constituent amino acids. The dissolved combined amino acids (DCAA) values range between 1.25 and 44.35 µmol/L, with an average of 10.36 µmol/L. The mean concentrations and relative abundances of the acidic, basic, neutral, aromatic, and sulfur-containing amino acids are 2.29 (22 mol%), 0.60 (6 mol%), 6.70 (65 mol%), 0.09 (1 mol%), and 0.00 µmol/L (0 mol%), respectively. Glycine is the most abundant amino acid residue, followed by glutamic acid, serine, and alanine. The predominance of DCAA over DFAA present in the interstitial waters from Sites 790 and 791 is consistent with previous results from interstitial-water and seawater analyses. The most plausible source for the DCAA is biogenic calcareous debris. A much greater depletion of aspartic acid and the basic fraction, except for ornithine, is found in the DCAA. The decomposition of the basic amino acid fraction or its incorporation to clay minerals would result in a decrease in its relative abundance, whereas ornithine is produced during early diagenesis. The characteristics of the amino acids in the interstitial waters are (1) a greater depletion of the acidic amino acid fraction in the DFAA than in the DCAA and (2) the enrichment of glycine and serine in both. The adsorption or reaction of the amino acids in interstitial waters with biogenic carbonates would be responsible for the lower relative abundance of the acidic fraction of the DFAA. The production of glycine during early diagenesis and its stability in solution would raise its relative abundance in the interstitial waters.

Sea surface temperature estimation for MIS 16 of IODP Site 306-U1313

Hudson Strait (HS) Heinrich Events, ice-rafting events in the North Atlantic originating from the Laurentide ice sheet (LIS), are among the most dramatic examples of millennial-scale climate variability and have a large influence on global climate. However, it is debated as to whether the occurrence of HS Heinrich Events in the (eastern) North Atlantic in the geological record depends on greater ice discharge, or simply from the longer survival of icebergs in cold waters. Using sediments from Integrated Ocean Drilling Program (IODP) Site U1313 in the North Atlantic spanning the period between 960 and 320 ka, we show that sea surface temperatures (SSTs) did not control the first occurrence of HS Heinrich(-like) Events in the sedimentary record. Using mineralogy and organic geochemistry to determine the characteristics of ice-rafting debris (IRD), we detect the first HS Heinrich(-like) Event in our record around 643 ka (Marine Isotope Stage (MIS) 16), which is similar as previously reported for Site U1308. However, the accompanying high-resolution alkenone-based SST record demonstrates that the first HS Heinrich(-like) Event did not coincide with low SSTs. Thus, the HS Heinrich(-like) Events do indicate enhanced ice discharge from the LIS at the end of the Mid-Pleistocene Transition, not simply the survivability of icebergs due to cold conditions in the North Atlantic.

Biomagnetostratigraphy of ODP Leg 189 sites

Late Cretaceous (Maastrichtian)-Quaternary summary biostratigraphies are presented for Ocean Drilling Program (ODP) Leg 189 Sites 1168 (West Tasmanian Margin), 1170 and 1171 (South Tasman Rise), and 1172 (East Tasman Plateau). The age models are calibrated to magnetostratigraphy and integrate both calcareous (planktonic foraminifers and nannofossils) and siliceous (diatoms and radiolarians) microfossil groups with organic walled microfossils (organic walled dinoflagellate cysts, or dinocysts). We also incorporate benthic oxygen isotope stratigraphies into the upper Quaternary parts of the age models for further control. The purpose of this paper is to provide a summary age-depth model for all deep-penetrating sites of Leg 189 incorporating updated shipboard biostratigraphic data with new information obtained during the 3 yr since the cruise. In this respect we provide a report of work to November 2003, not a final synthesis of the biomagnetostratigraphy of Leg 189, yet we present the most complete integrated age model for these sites at this time. Detailed information of the stratigraphy of individual fossil groups, paleomagnetism, and isotope data are presented elsewhere. Ongoing efforts aim toward further integration of age information for Leg 189 sites and will include an attempt to correlate zonation schemes for all the major microfossil groups and detailed correlation between all sites.

Stable isotope record of foraminifera from the subarctic Pacific

Benthic (Uvigerina spp., Cibicidoides spp., Gyroidinoides spp.) and planktonic (N. pachyderma sinistral, G. bulloides) stable isotope records from three core sites in the central Gulf of Alaska are used to infer mixed-layer and deepwater properties of the late glacial Subarctic Pacific. Glacial-interglacial amplitudes of the planktonic delta18O records are 1.1-1.3 per mil, less than half the amplitude observed at core sites at similar latitudes in the North Atlantic; these data imply that a strong, negative deltaw anomaly existed in the glacial Subarctic mixed layer during the summer, which points to a much stronger low-salinity anomaly than exists today. If true, the upper water column in the North Pacific would have been statically more stable than today, thus suppressing convection even more efficiently. This scenario is further supported by vertical (i.e., planktic versus benthic) delta18O and delta13C gradients of >1 per mil, which suggest that a thermohaline link between Pacific deep waters and the Subarctic Pacific mixed layer did not exist during the late glacial. Epibenthic delta13C in the Subarctic Pacific is more negative than at tropical-subtropical Pacific sites but similar to that recorded at Southern Ocean sites, suggesting ventilation of the deep central Pacific from mid-latitude sources, e.g., from the Sea of Japan and Sea of Okhotsk. Still, convection to intermediate depths could have occurred in the Subarctic during the winter months when heat loss to the atmosphere, sea ice formation, and wind-driven upwelling of saline deep waters would have been most intense. This would be beyond the grasp of our planktonic records which only document mixed-layer temperature-salinity fields extant during the warmer seasons. Also we do not have benthic isotope records from true intermediate water depths of the Subarctic Pacific.

Geochemistry of dark-light rhythm sediments of the Japan Sea

Ocean Drilling Program Legs 127 and 128 in the Japan Sea have revealed the existence of numerous dark-light rhythms of remarkable consistency in sediments of late Miocene, latest Pliocene, and especially Pleistocene age. Light-colored units within these rhythms are massive or bioturbated, consist of diatomaceous clays, silty clays, or nannofossil-rich clays, and are generally poor in organic matter. Dark-colored units are homogeneous, laminated, or thinly bedded and include substantial amounts of biogenic material such as well-preserved diatoms, planktonic foraminifers, calcareous nannofossils, and organic matter (maximum 7.4 wt%). The dark-light rhythms show a similar geometrical pattern on three different scales: First-order rhythms consist of a cluster dominated by dark-colored units followed by a cluster dominated by light-colored units (3-5 m). Spectral analysis of a gray-value time series suggests that the frequencies of the first-order rhythms in sediments of latest Pliocene and Pleistocene age correlate to the obliquity and the eccentricity cycles. The second-order dark-light rhythms include a light and a dark-colored unit (10-160 cm). They were formed in time spans of several hundred to several ten thousand years, with variance centering around 10,500 yr. This frequency may correspond to half the precessional cycle. Third-order rhythms appear as laminated or thinly bedded dark-light couplets (2-15 mm) within the dark-colored units of the second-order rhythms and may represent annual frequencies. In interpreting the rhythms, we have to take into account that (1) the occurrence of the first- and second-order rhythms is not necessarily restricted to glacial or interglacial periods as is shown by preliminary stable-isotope analysis and comparison with the published d18O record; (2) they appear to be Milankovitch-controlled; and (3) a significant number of the rhythms are sharply bounded. The origin of the dark-light rhythms is probably related to variations in monsoonal activity in the Japan Sea, which show annual frequencies, but also operates in phase with the orbital cycles.