Iron (Fe) concentrations and fluxes in TALDICE ice core 0.6 to 314 ky BP

Atmospheric fluxes of iron (Fe) over the past 200 kyr are reported for the coastal Antarctic Talos Dome ice core, based on acid leachable Fe concentrations. Fluxes of Fe to Talos Dome were consistently greater than those at Dome C, with the greatest difference observed during interglacial climates. We observe different Fe flux trends at Dome C and Talos Dome during the deglaciation and early Holocene, attributed to a combination of deglacial activation of dust sources local to Talos Dome and the reorganisation of atmospheric transport pathways with the retreat of the Ross Sea ice shelf. This supports similar findings based on dust particle sizes and fluxes and Rare Earth Element fluxes. We show that Ca and Fe should not be used as quantitative proxies for mineral dust, as they all demonstrate different deglacial trends at Talos Dome and Dome C. Considering that a 20 ppmv decrease in atmospheric CO2 at the coldest part of the last glacial maximum occurs contemporaneously with the period of greatest Fe and dust flux to Antarctica, we confirm that the maximum contribution of aeolian dust deposition to Southern Ocean sequestration of atmospheric CO2 is approximately 20 ppmv.

Physics, geochemistry and bulk sedimentology on cores from the Peru Basin

Empirical relationships between physical properties determined non-destructively by core logging devices and calibrated by carbonate and opal measurements determined on discrete samples allow extraction of carbonate and opal records from the non-destructive measurements in biogenic settings. Contents of detrital material can be calculated as a residual. For carbonate and opal the correlation coefficients (r) are 0.954 and ?0.916 for sediment density, ?0.816 and 0.845 for compressional-wave velocity, 0.908 and ?0.942 for acoustic impedance, and 0.886 and ?0.865 for sediment color (lightness). Carbonate contents increase in concert with increasing density and acoustic impedance, decreasing velocity and lighter sediment color. The opposite is true for opal. The advantages of deriving the sediment composition quantitatively from core logging are: (i) sampling resolution is increased significantly, (ii) non-destructive data can be gathered rapidly, and (iii) laboratory work on discrete samples can be reduced. Applied to paleoceanographic problems, this method offers the opportunity of precise stratigraphic correlations and of studying processes related to biogenic sedimentation in more detail. Density is most promising because it is most strongly affected by changes in composition.

Upper Cenozoic dinoflagellate cysts from the continental slope and rise off New Jersey

This report contains the occurrence data for dinoflagellate cysts recorded from 163 samples taken from Sites 902 through 906, during Ocean Drilling Program (ODP) Leg 150. The dinoflagellate cyst (dinocyst) stratigraphy has been presented in Mountain, Miller, Blum, et al. (1994, doi:10.2973/odp.proc.ir.150.1994), and was based on these data. This report provides the full dinocyst data set supporting the dinocyst stratigraphic interpretations made in Mountain, Miller, Blum, et al. (1994). For Miocene shipboard dinocyst stratigraphy, I delineated 10 informal zones: pre-A, and A through I, in ascending stratigraphic order. These zones are defined in Shipboard Scientific Party (1994a, doi:10.2973/odp.proc.ir.150.103.1994), and are based on my studies of Miocene dinocyst stratigraphy in the Maryland and Virginia coastal plain (de Verteuil and Norris, 1991, 1992; de Verteuil, 1995). This zonation has been slightly revised (de Verteuil and Norris, 1996), and the new formal zone definitions are repeated below. Each new zone has an alpha-numeric abbreviation starting with "DN" (for Dinoflagellate Neogene). The equivalence between the informal zones reported in Mountain, Miller, Blum, et al. (1994), and the new DN zones is illustrated in Figure 1. For clarity, I delineated both zonations in the range charts that accompany this report (Tables 1-6). De Verteuil and Norris (1996a), using these and other data, correlated the DN zonation with the geological time scale of Berggren et al. (1995). Figure 2 summarizes these correlations and can be used to check the chronostratigraphic position of samples in this report, as determined by dinocyst stratigraphy. A thorough discussion of the basis for, and levels of uncertainty associated with, these correlations to the Cenozoic time scale can be found in de Verteuil and Norris (1996a). The Appendix lists all the dinocyst taxa recorded during shipboard analyses of Leg 150 samples. Open nomenclature is used for undescribed taxa. The range charts and Appendix also include reference to several new taxa that de Verteuil and Norris (1996b) described from Miocene coastal plain strata in Maryland and Virginia. Names of these taxa in Tables 1 through 6 and in the Appendix of this report are not intended for effective publication as defined in the International Code of Botanical Nomenclature (ICBN, Greuter et al., 1994). Therefore, taxonomic nomenclature contained in this report is not to be treated as meeting the conditions of effective and valid publication (ICBN; Article 29).

Carbonate and Aluminium accumulation in the central equatorial Pacific Ocean

We examined the flux of Al to sediment accumulating beneath the zone of elevated productivity in the central equatorial Pacific Ocean, along a surface sediment transect at 135°W as well as downcore for a 650 kyr record at 1.3°N, 133.6°W. Across the surface transect, a pronounced, broadly equatorially symmetric increase in Al accumulation is observed, relative to Ti, with Al/Ti ratios reaching values 3-4 times that of potential detrital sources. The profile parallels biogenic accumulation and the modeled flux of particulate 234Th, suggesting rapid and preferential adsorptive removal of Al from seawater by settling biogenic particles. Normative calculations confirm that most Al is unsupported by the terrigenous fraction. The observed distributions are consistent with previous observations of the relative and absolute behavior of Al and Ti in seawater, and we can construct a reasonable mass balance between the amount of seawater-sourced Al retained in the sediment and the amount of seawater Al available in the overlying column. The close tie between Al/Ti and biogenic accumulation (as opposed to concentration) emphasizes that biogenic sedimentary Al/Ti responds to removal-transport phenomena and not bulk sediment composition. Thus, in these sediments dominated by the biogenic component, the bulk Al/Ti ratio reflects biogenic particle flux, and by extension, productivity of the overlying seawater. The downcore profile of Al/Ti at 1.3°N displays marked increases during glacial episodes, similar to that observed across the surface transect, from a background value near Al/Ti of average upper crust. The excursions in Al/Ti are stratigraphically coincident with maxima in both bulk and CaCO3 accumulation and the excess Al appears to not be preferentially affiliated with opaline or organic phases. Consistent with the similar behavioral removal of Al and 234Th, the latter of which responds to the total particle flux, the Al flux reflects carbonate accumulation only because carbonate comprises the dominant flux in these particular deposits. These results collectively indicate that (1) Al in biogenic sediment and settling biogenic particles is strongly affected by a component adsorbed from seawater. Therefore, the common tenet that Al is dominantly associated with terrestrial particulate matter, and the subsequent use of Al distributions to calculate the abundance and flux of terrestrial material in settling particles and sediment, needs to be reevaluated. (2) The Al/Ti ratio in biogenic sediment can be used to trace the productivity of the overlying water, providing a powerful new paleochemical tool to investigate oceanic response to climatic variation. (3) The close correlation between the Al/Ti productivity signal and carbonate maxima downcore at 1.3°N suggests that the sedimentary carbonate maxima in the central equatorial Pacific Ocean record increased productivity during glacial episodes.

Geochemistry, fluxes and nitrogen isotopic composition data of traps LP1 and EBC2-1 and cores GeoB4242-4 and Geo4301-1

We compare total and biogenic particle fluxes and stable nitrogen isotope ratios (d15N) at three mooring sites along a productivity gradient in the Canary Islands region with surface sediment accumulation rates and sedimentary d15N. Higher particle fluxes and sediment accumulation rates, and lower d15N were observed in the upwelling influenced eastern boundary region (EBC) compared to the oligotrophic sites north of Gran Canaria [European Station for Time-Series in the Ocean, Canary Islands (ESTOC]] and north of La Palma (LP). The impact of organic matter degradation and lateral particle advection on sediment accumulation was quantified with respect to the multi-year flux record at the ESTOC. Remineralisation of organic matter in the water column and at the sediment surface resulted in an organic carbon preservation of about 0.8% and total nitrogen preservation of about 0.4% of the estimated export production. Higher total and carbonate fluxes and accumulation rates in the lower traps and surface sediment compared to the upper traps indicated that at least 50% of the particulate matter at the ESTOC was derived from allochthonous sources. Low d15N values in the lower traps of the ESTOC and LP point to a source region influenced by coastal upwelling. We conclude from this study that the reconstruction of export production or nutrient regimes from sedimentary records in regions with strong productivity gradients might be biased due to the mixture of particles originating from autochthonous and allochthonous sources. This could result in an imprint of high productivity signatures on sedimentation processes in oligotrophic regions.

Composition and age of volcanic rocks from the Sinii Utes Depression, Southern Primoye

New data are reported on structure of sections, chemical composition, and age of volcano-sedimentary and volcanic rocks from the Sinii Utes Depression in the Southern Primorye region. The Sinii Utes Depression is filled with two sequences: the lower sequence composed of sedimentary-volcanogenic coaliferous rocks (the stratotype of the Sinii Utes Formation) and the upper sequence consisting of tephroid with overlying basalts. This work considers chemical composition and problems of K-Ar dating of basalts. The uppermost basaltic flow has K-Ar age 22.0±1.0 Ma. The dates obtained for the middle and upper parts of lava flows are underestimated. It is explained by their heating due to combustion of brown coals of the Sinii Utes Formation underlying the lava flow. Calculations show that argon could only partly have been removed from the basalts owing to conductive heat transfer and was lost largely due to infiltration of hot gases in heterogeneous fissured medium. Basaltic volcanism on continental margins of the southern Primorye region and the adjacent Korean and Chinese areas at the Oligocene-Miocene boundary preceded Early-Middle Miocene spreading and formation of the Sea of Japan basin. Undifferentiated moderately alkaline basalts of intraplate affinity developed in the Amba Depression and some other structures of the southern Primorye region and intraplate alkali basalts of the Phohang Graben in the Korean Peninsula serve as indicators of incipient spreading regime in the Sea of Japan. Potassic basalt-trachybasalt eruptions occurred locally in riftogenic depressions and shield volcanoes. In some structures this volcanism was terminated by eruptions of intermediate and acid lavas. Such evolution of volcanism is explained by selective contamination of basaltic melts during their interaction with crustal acid material and generation of acid anatectic melts.

Isotopic ratios, concentration of noble gases and mineral and bulk composition of extraterrestrial dust particles in Dome Fuji ice core, East Antarctica

Two silicate-rich dust layers were found in the Dome Fuji ice core in East Antarctica, at Marine Isotope Stages 12 and 13. Morphologies, textures, and chemical compositions of constituent particles reveal that they are high-temperature melting products and are of extraterrestrial origin. Because similar layers were found ~2000 km east of Dome Fuji, at EPICA (European Project for Ice Coring in Antarctica)-Dome C, particles must have rained down over a wide area 434 and 481 ka. The strewn fields occurred over an area of at least 3 × 10**6 km**2. Chemical compositions of constituent phases and oxygen isotopic composition of olivines suggest that the upper dust layer was produced by a high-temperature interaction between silicate-rich melt and water vapor due to an impact explosion or an aerial burst of a chondritic meteoroid on the inland East Antarctic ice sheet. An estimated total mass of the impactor, on the basis of particle flux and distribution area, is at least 3 × 10**9 kg. A possible parent material of the lower dust layer is a fragment of friable primitive asteroid or comet. A hypervelocity impact of asteroidal/cometary material on the upper atmosphere and an explosion might have produced aggregates of sub-µm to µm-sized spherules. Total mass of the parent material of the lower layer must exceed 1 × 10**9 kg. The two extraterrestrial horizons, each a few millimeters in thickness, represent regional or global meteoritic events not identified previously in the Southern Hemisphere.

Physical oceanography and ADCP measurements during METEOR cruise M71/3

Work on M71-3 aimed to answer the question whether phosphate loss and incomplete utilisation of nitrate on the one hand, or dinitrogen fixation on the other hand are responsible for unusual nutrient ratios in the water column of the eastern Mediterranean Sea. We investigated the reason for unusually depleted 15N/14N ratios in dissolved nitrate, suspended matter and surface sediments of that oligotrohic ocean basin. During a total of 18 days of ship time on R/V METEOR, Leg 3 OF M71 performed water column and surface sediment work in the eastern Mediterranean Sea (Heraklion-Istanbul). Stations will be aligned on one E-W and two N-S transects and sampled all major basins and water masses. On stations, CTD casts were obtained and water samples for nutrient concentrations were taken. These samples and those of suspended matter and surface sediment will be analysed for the stable nitrogen isotope composition of dissolved nitrate, suspended matter, and surface sediments. In addition, phytoplankton samples were be taken and experiments were be carried out to determine N2 fixation rates, genetic expressions of nitrogen fixation, and the composition of microbial and algal assemblages. One mooring of sediment traps (Ierapetra Deep) was be deployed and will be recovered in September 2007 to monitor changes in particle flux and its isotope signature over a seasonal cycle.

(Table 2) Comparison of annual mass fluxes measured with shallower and deeper sediment traps off Cape Blanc (CB)

The ocean off NW Africa is the second most important coastal upwelling system with a total annual primary production of 0.33 Gt of carbon per year (Carr in Deep Sea Res II 49:59-80, 2002). Deep ocean organic carbon fluxes measured by sediment traps are also fairly high despite low biogenic opal fluxes. Due to a low supply of dissolved silicate from subsurface waters, the ocean off NW Africa is characterized by predominantly carbonate-secreting primary producers, i.e. coccolithophorids. These algae which are key primary producers since millions of years are found in organic- and chlorophyll-rich zooplankton fecal pellets, which sink rapidly through the water column within a few days. Particle flux studies in the Mauretanian upwelling area (Cape Blanc) confirm the hypothesis of Armstrong et al. (Deep Sea Res II 49:219-236, 2002) who proposed that ballast availability, e.g. of carbonate particles, is essential to predict deep ocean organic carbon fluxes. The role of dust as ballast mineral for organic carbon, however, must be also taken into consideration in the coastal settings off NW Africa. There, high settling rates of larger particles approach 400 m day**-1, which may be due to a particular composition of mineral ballast. An assessment of particle settling rates from opal-production systems in the Southern Ocean of the Atlantic Sector, in contrast, provides lower values, consistent with the assumptions of Francois et al. (Global Biogeochem Cycles 16(4):1087, 2002). Satellite chlorophyll distributions, particle distributions and fluxes in the water column off NW Africa as well as modelling studies suggest a significant lateral flux component and export of particles from coastal shelf waters into the open ocean. These transport processes have implications for paleo-reconstructions from sediment cores retrieved at continental margin settings.

Major components and major and trace elements from ODP Site 175-1085

We have analyzed 33 Pliocene bulk sediment samples from Ocean Drilling Program Site 1085 in the Cape Basin, located offshore of western Africa in the Angola-Benguela Current system, for 17 major and trace elements, and interpreted their associations and temporal variations in the context of an allied data set of CaCO3, opal, and Corg. We base our interpretations on elemental ratios, accumulation rates, inter-element correlations, and several multi-element statistical techniques. On the basis of qualitative assessment of downhole changes in the distributions of P and Ba, utilized as proxies of export production, we conclude that highs in bulk and biogenic accumulation that occur at 3.2 Ma, 3.0 Ma, 2.4 Ma, and 2.25 Ma were caused by increases in export production as well as terrigenous flux, and record a greater sequestering of organic matter during these time periods. Studies of refractory elements and other indicator proxies (SiO2, Al2O3, TiO2, Fe2O3, MgO, V, Cr, Sr, and Zr) strongly suggest that the terrigenous component of the bulk sediment is composed of two compositional end-members, one being 'basaltic' in composition and the other similar to an 'average shale'. The basaltic end-member comprises approximately 10-15% of the total bulk sediment and its presence is consistent with the local geology of source material in the drainage basin of the nearby Orange River. The increase in bulk accumulation at 2.4 Ma appears to reflect a greater relative increase in basaltic input than the relative increase in shale-type input. Although studies such as this cannot precisely identify the transport mechanisms of the different terrigenous components, these results are most consistent with variations in sea level (and associated changes in shelf geometry and fluvial input) being responsible for the changing depositional conditions along the Angolan Margin during this time period.

Diurnal fluctuations in seawater pH influence the response of a calcifying macroalga to ocean acidification

Coastal ecosystems that are characterized by kelp forests encounter daily pH fluctuations, driven by photosynthesis and respiration, which are larger than pH changes owing to ocean acidification (OA) projected for surface ocean waters by 2100. We investigated whether mimicry of biologically mediated diurnal shifts in pH-based for the first time on pH time-series measurements within a kelp forest-would offset or amplify the negative effects of OA on calcifiers. In a 40-day laboratory experiment, the calcifying coralline macroalga, Arthrocardia corymbosa, was exposed to two mean pH treatments (8.05 or 7.65). For each mean, two experimental pH manipulations were applied. In one treatment, pH was held constant. In the second treatment, pH was manipulated around the mean (as a step-function), 0.4 pH units higher during daylight and 0.4 units lower during darkness to approximate diurnal fluctuations in a kelp forest. In all cases, growth rates were lower at a reduced mean pH, and fluctuations in pH acted additively to further reduce growth. Photosynthesis, recruitment and elemental composition did not change with pH, but ?(13)C increased at lower mean pH. Including environmental heterogeneity in experimental design will assist with a more accurate assessment of the responses of calcifiers to OA.

Benthic oxygen isotopes, Zr/Al and grain size fractions over the Miocene-Pliocene boundary in the Gulf of Cadiz

During the latest Messinian, hemipelagic sediments exhibiting precession-induced climate variability were deposited. These are overlain by Pliocene sediments deposited at a much higher sedimentation rate, with much higher and more variable XRF-scanning Zr/Al ratios than the underlying sediment, and that show evidence of winnowing, particle sorting and increasing grain size, which we interpret to be related to the increasing flow of MOW. Pliocene sedimentary cyclicity is clearly visible in both the benthic d18O record and the Zr/Al data and is probably also precessionally controlled. On the basis of these results, we conclude that contouritic sedimentation, associated with weak Mediterranean-Atlantic exchange, began in the Gulf of Cadiz virtually at or shortly after the Miocene-Pliocene boundary, with two contouritic bigradational sandy-beds within the fourth precession cycle after the Miocene-Pliocene boundary.