SeaWiFS (version R2010.0) Monthly Global 9 km Microplankton Fraction, links to NetCDF files

Phytoplankton cell size is important to biogeochemical and food web processes. The goal of this study is to estimate phytoplankton cell size distribution from satellite imagery of spectral remote sensing reflectance (Rrs(lambda)). Previous studies have indicated phytoplankton size classes have distinctive absorption spectra despite the physiological and taxonomic variability within an assemblage. For this study, the chlorophyll specific absorption spectra for phytoplankton size class extremes, pico- and microphytoplankton, are weighted by the percent microplankton (Sfm) and are the basis of phytoplankton size retrieval from SeaWiFS imagery. Satellite retrievals of Sfm are done through implementation of a forward optical model look-up table (LUT) that incorporates the range of absorption and scattering variability due to phytoplankton size, chlorophyll concentration ([Chl]) and dissolved and detrital matter (acdm(443)) in the global ocean from which Rrs(lambda) is calculated by the radiative transfer software, Hydrolight. The Hydrolight modeled Rrs(lambda) options for a given combination of [Chl] and acdm(443) within the LUT vary only due to Sfm. For a given pixel, the LUT search space was limited by satellite imagery of [Chl] and acdm(443). Within the narrowed search space, SeaWiFS Rrs(lambda) was matched with the closest LUT Rrs(lambda) option and the associated Sfm was assigned. Thresholds at which changes in Rrs(lambda) due to Sfm could be discerned were established in terms of [Chl] and acdm(443). In situ high-precision liquid chromatography-derived estimates of cell size are used in conjunction with matched daily satellite estimates of Sfm for validation and agree well. A single month is displayed as an example of the Sfm retrieval.

Geochemical analysis of surface sediments from the ocean floor and from sea ice in the northern Atlantic and Arctic Oceans

Barium in marine terrigenous surface sediments of the European Nordic Seas is analysed to evaluate its potential as palaeoproductivity proxy. Biogenic Ba is calculated from Ba and Al data using a conventional approach. For the determination of appropriate detrital Ba/Al ratios a compilation of Ba and Al analyses in rocks and soils of the catchments surrounding the Nordic Seas is presented. The resulting average detrital Ba/Al ratio of 0.0070 is similar to global crustal average values. In the southern Nordic Seas the high input of basaltic material with a low Ba/Al ratio is evident from high values of magnetic susceptibility and low Al/Ti ratios. Most of the Ba in the marine surface sediments is of terrigenous and not of biogenic origin. Variability in the lithogenic composition has been considered by the application of regionally varying Ba/Al ratios. The biogenic Ba values are comparable with those observed in the central Arctic Ocean, they are lower than in other oceanic regions. Biogenic Ba values are correlated with other productivity proxies and with oceanographic data for a validation of the applicability in paleoceanography. In the Iceland Sea and partly in the marginal sea-ice zone of the Greenland Sea elevated values of biogenic Ba indicate seasonal phytoplankton blooms. In both areas paleoproductivities may be reconstructed based on Ba and Al data of sediment cores.

Pore water and solid phase geochemistry of sediment core US5B

Studies of authigenic phosphorus (P) minerals in marine sediments typically focus on authigenic carbonate fluorapatite, which is considered to be the major sink for P in marine sediments and can easily be semi-quantitatively extracted with the SEDEX sequential extraction method. The role of other potentially important authigenic P phases, such as the reduced iron (Fe) phosphate mineral vivianite (Fe(II)3(PO4)*8H2O) has so far largely been ignored in marine systems. This is, in part, likely due to the fact that the SEDEX method does not distinguish between vivianite and P associated with Fe-oxides. Here, we show that vivianite can be quantified in marine sediments by combining the SEDEX method with microscopic and spectroscopic techniques such as micro X-ray fluorescence (µXRF) elemental mapping of resin-embedded sediments, as well as scanning electron microscope-energy dispersive spectroscopy (SEM-EDS) and powder X-ray diffraction (XRD). We further demonstrate that resin embedding of vertically intact sediment sub-cores enables the use of synchrotron-based microanalysis (X-ray absorption near-edge structure (XANES) spectroscopy) to differentiate between different P burial phases in aquatic sediments. Our results reveal that vivianite represents a major burial sink for P below a shallow sulfate/methane transition zone in Bothnian Sea sediments, accounting for 40-50% of total P burial. We further show that anaerobic oxidation of methane (AOM) drives a sink-switching from Fe-oxide bound P to vivianite by driving the release of both phosphate (AOM with sulfate and Fe-oxides) and ferrous Fe (AOM with Fe-oxides) to the pore water allowing supersaturation with respect to vivianite to be reached. The vivianite in the sediment contains significant amounts of manganese (~4-8 wt.%), similar to vivianite obtained from freshwater sediments. Our results indicate that methane dynamics play a key role in providing conditions that allow for vivianite authigenesis in coastal surface sediments. We suggest that vivianite may act as an important burial sink for P in brackish coastal environments worldwide.

Geochemical and stable isotope composition of Middle Campanian marl-limestone rhythmites of the Lehrte West Syncline near Hannover (Lower Saxony, northern Germany)

A cyclic marl-limestone succession of Middle-Late Campanian age has been investigated with respect to a Milankovitch-controlled origin of geochemical data. In general, the major element geochemistry of the marl-limestone rhythmites can be explained by a simple two-component mixing model with the end-members calcium carbonate and 'average shale'-like material. Carbonate content varies from 55 to 90%. Non-carbonate components are clay minerals (illite, smectite) and biogenic silica from sponge spicules, as well as authigenically formed zeolites (strontian heulandite) and quartz. The redox potential suggests oxidizing conditions throughout the section. Trace element and stable isotopic data as well as SEM investigations show that the carbonate mud is mostly composed of low-magnesium calcitic tests of planktic coccolithophorids and calcareous dinoflagellate cysts (calcispheres). Diagenetic overprint results in a decrease of 2% d18O and an increase in Mn of up to 250 ppm. However, the sediment seems to preserve most of its high Sr content compared to the primary low-magnesium calcite of co-occurring belemnite rostra. The periodicity of geochemical cycles is dominated by 413 ka and weak signals between 51 and 22.5 ka, attributable to orbital forcing. Accumulation rates within these cycles vary between 40 and 50 m/Ma. The resulting cyclic sedimentary sequence is the product of (a) changes in primary production of low-magnesium calcitic biogenic material in surface waters within the long eccentricity and the precession, demonstrated by the CaCO3 content and the Mg/Al, Mn/Al and Sr/Al ratios, and (b) fluctuations in climate and continental weathering, which changed the quality of supplied clay minerals (the illite/smectite ratio), demonstrated by the K/Al ratio. High carbonate productivity correlates with smectite-favouring weathering (semi-arid conditions, conspicuously dry and moist seasonal changes in warmer climates). Ti as the proxy indicator for the detrital terrigenous influx, as well as Rb, Si, Zr and Na, shows only low frequency signals, indicating nearly constant rates of supply throughout the more or less pure pelagic carbonate deposition of the long-lasting third-order Middle-Upper Campanian sedimentary cycle.

Age determinations on sediment cores from the North Atlantic

Sediments in the North Atlantic ocean contain as eries of layers that are rich in ice-rafted debris and unusally poor in foraminifera. Here we present evidence that the most recent six of the 'Heinrich layers', deposited between 14,000 and 70,000 years ago, record marked decreases in sea surface temperature and salinity, decreases in the flux of planktonic forminifera to the sediments, and short-lived, massive discharges of icebergs originating in eastern Canada. The path of the icebergs, clearly marked by the presence of ice-rafted detrital carbonate, can be traced for more than 3,000 km - a remarkable distance, attesting to extreme cooling of surface waters and enormous amounts of drifiting ice. The cause of these extreme events is puzzling. They may reflect repated rapid advances of the Laurentide ice sheet, perhaps associated with reductions in air temperatures, yet temperature records from Greenland ice cores appear to exhibit only a weak corresponding signal. Moreover, the 5-10,000-yr intervals between the events are inconsistent with Milankovitch orbital periodicities, raising the question of what the ultimate cause of the postulated cooling may have been.

Mineralogical (bulk rock and clay fraction) and stable isotope composition (d13C, d18O) of Aptian deposits of the Bir Oum Ali succession, central Tunisia

Alternations between siliciclastic, carbonate and evaporitic sedimentary systems, as recorded in the Aptian mixed succession of southern Tunisia, reflect profound palaeoceanographic and palaeoclimatic changes in this area of the southern Tethyan margin. The evolution from Urgonian-type carbonates (Berrani Formation, lower Aptian) at the base of the series, to intervals dominated by gypsum or detrital deposits in the remainder of the Aptian is thought to result from the interplay between climate change and tectonic activity that affected North Africa. Based on the evolution of clay mineral assemblages, the early Aptian is interpreted as having been dominated by slightly humid conditions, since smectitic minerals are observed. Near the early to late Aptian boundary, the onset of a gypsiferous sedimentation is associated with the appearance of palygorskite and sepiolite, which supports the installation of arid conditions in this area of the southern Tethyan margin. The evaporitic sedimentation may have also been promoted by the peculiar tectonic setting of the Bir Oum Ali area during the Aptian, where local subsidence may have been tectonically enhanced linked to the opening of northern and central Atlantic. Stress associated with the west and central African rift systems may have triggered the development of NW-SE, hemi-graben structures. Uplifted areas may have constituted potential new sources for clastic material that has been subsequently deposited during the late Aptian. Chemostratigraphic (d13C) correlation of the Bir Oum Ali succession with other peri-Tethyan regions complements biostratigraphic findings, and indicates that a potential expression of the Oceanic Anoxic Event (OAE) 1a may be preserved in this area of Tunisia. Although the characteristic negative spike at the base of this event is not recognized in the present study, a subsequent, large positive excursion with d13C values is of similar amplitude and absolute values to that reported from other peri-Tethyan regions, thus supporting the identification of isotopic segments C4-C7 of the OAE1a. The absence of the negative spike may be linked to either non preservation or non deposition: the OAE1a occurred in a global transgressive context, and since the Bir Oum Ali region was located in the innermost part of the southern Tethyan margin during most of the Aptian, stratigraphic hiatuses may have been longer than in other regions of the Tethys. This emphasizes the importance of integrating several stratigraphic disciplines (bio-, chemo- and sequence stratigraphy) when performing long-distance correlation.

Heavy mineral and bulk mineral compositions of cores from Kumano Basin

Coring during Integrated Ocean Drilling Program Expeditions 315, 316, and 333 recovered turbiditic sands from the forearc Kumano Basin (Site C0002), a Quaternary slope basin (Site C0018), and uplifted trench wedge (Site C0006) along the Kumano Transect of the Nankai Trough accretionary wedge offshore of southwest Japan. The compositions of the submarine turbiditic sands here are investigated in terms of bulk and heavy mineral modal compositions to identify their provenance and dispersal mechanisms, as they may reflect changes in regional tectonics during the past ca. 1.5 Myrs. The results show a marked change in the detrital signature and heavy mineral composition in the forearc and slope basin facies around 1 Ma. This sudden change is interpreted to reflect a major change in the sand provenance, rather than heavy mineral dissolution and/or diagenetic effects, in response to changing tectonics and sedimentation patterns. In the trench-slope basin, the sands older than 1 Ma were probably eroded from the exposed Cretaceous-Tertiary accretionary complex of the Shimanto Belt and transported via the former course of the Tenryu submarine canyon system, which today enters the Nankai Trough northeast of the study area. In contrast, the high abundance of volcanic lithics and volcanic heavy mineral suites of the sands younger than 1 Ma points to a strong volcanic component of sediment derived from the Izu-Honshu collision zones and probably funnelled to this site through the Suruga Canyon. However, sands in the forearc basin show persistent presence of blue sodic amphiboles across the 1 Ma boundary, indicating continuous flux of sediments from the Kumano/Kinokawa River. This implies that the sands in the older turbidites were transported by transverse flow down the slope. The slope basin facies then switched to reflect longitudinal flow around 1 Ma, when the turbiditic sand tapped a volcanic provenance in the Izu-Honshu collision zone, while the sediments transported transversely became confined in the Kumano Basin. Therefore, the change in the depositional systems around 1 Ma is a manifestation of the decoupling of the sediment routing pattern from transverse to long-distance axial flow in response to forearc high uplift along the megasplay fault.

Rockmagnetic investigations of IODP Site U1302-U1303

Integrated Ocean Drilling Program (IODP) Sites U1302-U1303, drilled on the SE flank of Orphan Knoll (Labrador Sea), preserve a record of detrital layers and other proxies of hydrographic change that extend the record of ice-sheet/ocean interactions through most of the Brunhes Chron. The age model is built by tandem matching of relative paleointensity (RPI) and oxygen isotope data (d18O) from Neogloboquadrina pachyderma (sin.) to reference records, indicating a mean Brunhes sedimentation rate of 14 cm/kyr. Sedimentation back to marine isotope stage (MIS) 18 is characterized by detrital layers that are detected by higher than background gamma-ray attenuation (GRA) density, peaks in X-ray fluorescence (XRF) indicators for detrital carbonate (Ca/Sr) and detrital silicate (Si/Sr), and an ice-rafted debris (IRD) proxy (wt.% >106 µm). The age model enables correlation of Site U1302/03 to IODP Site U1308 in the heart of the central Atlantic IRD belt where an age model and a similar set of detrital-layer proxies have already been derived. Ages of Heinrich (H) layers H1, H2, H4, H5 and H6 are within ~2 kyr at the two sites (H0, H3 and H5a are not observed at Site U1308), and agree with previous work at Orphan Knoll within ~3 kyr. At Site U1308, Brunhes detrital layers are restricted to peak glacials and glacial terminations back to marine isotope stage (MIS) 16 and have near-synchronous analogs at Site U1302/03. Detrital layers at Site U1302/03 are distributed throughout the record in both glacial and most interglacial stages. We distinguish Heinrich-like layers associated with IRD from detrital layers marked by multiple detrital-layer proxies (including Ca/Sr) but usually not associated with IRD, that may be attributed to lofted sediment derived from drainage and debris-flow events funneled down the nearby Northwest Atlantic Mid-Ocean Channel (NAMOC). The prominent detrital layers at Sites U1302/03 and U1308 can be correlated to millennial scale features in the Chinese speleothem (monsoon) record over the last 400 kyr, implying a link between monsoon precipitation and Laurentide Ice Sheet (LIS) instability. The detrital-layer stratigraphy at Site U1302/03 provides a long record of LIS dynamics against which other terrestrial and marine records can be compared.

Granulometry, mineralogy and geochemistry of ODP Holes 184-1147A and 184-1148A, South China Sea

Green clay layers are reported from the Pliocene-Holocene intervals in five of the six sites drilled in the South China Sea (SCS) during Leg 184. Centimeter-scale discrete, discontinuous, and bioturbated layers, constituted by stiff and porous green clays, were observed, sometimes associated with iron sulfides and pyrite. Detailed mineralogical and geochemical analyses indicate that they differentiate from the host sediments in their higher content of iron, smectite, and mixed-layered clays and lower amounts of calcite, authigenic phosphorus, quartz, and organic matter. Although no glauconite was observed, the mineralogy and geochemistry of green clay layers, along with their geometrical relation to background sediments, suggest that they most likely represent the result of the first steps of glauconitization. Correlation between green layers and volcanic ash layers was suggested for green laminae observed elsewhere in Pacific sediments but was not confirmed at SCS sites. Statistical analysis of the temporal distribution of green layers in the records of the last million years suggests that green clay layers have become more frequent since 600 ka. Only at Site 1148 does the green layer record show a statistically significant cyclicity which may be related to orbital eccentricity. A possible influence of sea level variations, related both to climatic changes and tectonism, is postulated.

Organic geochemistry and Rock-Eval pyrolysis at DSDP Leg 79 and 41 Holes

Cenozoic and Mesozoic sediments ranging in age from Pleistocene to Early Jurassic/late Triassic were recovered on DSDP Leg 79, off Morocco at Sites 544 to 547 in front of the Mazagan Plateau. The main zone of oil genesis should be reached at Site 547 within the Jurassic section. Organic material of marine origin with good petroleum potential characterizes the late Eocene slumps of Site 547 and originates from reworked organic matter of Cretaceous origin. Organic enrichment also occurs at Site 545 during the middle to late Albian period. Since the organic matter appears to be autochthonous, reducing environments of deposition are inferred. In the other Cretaceous deposits, variably altered organic matter of the same origin predominates. Finally, a transect including Site 370 off the Agadir Canyon, is studied: detrital organic matter and reducing environments of deposition were more developed during Albian time for Site 370 than for Site 545.

Mineralogy, geochemistry and elemental ratios of ODP Core 171B-1049C-8X

Inorganic geochemistry and mineralogy of Core 171B-1049C-8X, containing a Cretaceous/Tertiary boundary section, was investigated by X-ray fluorescence (XRF) and X-ray diffraction (XRD). The ages of samples analyzed stretched from the latest Maastrichtian into the Danian. XRD measurements were made using the peak height method. A reduction in low-magnesium calcite and an increase in quartz were found above the spherule layer. Substantial amounts of dolomite were noted just above the spherule layer. XRF analyses were performed using the RHSMALL program to measure the abundance of major and minor elements. Replicate analyses for each technique were performed to assess the precision of the results. The section above the spherule bed was found to be characterized by peaks in many elements, including Si, Al, Fe, and Mg, as well as the following elemental ratios: Fe/Al, Ni/Al, Zr/Rb, and Rb/Sr'. Above the spherule bed, there were significant reductions in Ca, Sr/Ca, Ti/Al, K/Al, Rb/Al, Cr/Al, Ba/Al, biogenic Ba, and excess P.

(Table DR1) Argon isotope data and dating for individual >63 µm amphibole grains from Labrador Sea sediments, ODP Hole 105-647A

Variations of global and regional silicate weathering rates and paleo-ocean circulation patterns are estimated by using radiogenic isotope records, but the effects of changes in provenance are generally ignored. Here sediment provenance has been constrained through the use of Ar-Ar ages for individual detrital minerals from the Labrador Sea, which can be compared directly to the radiogenic isotope compositions from the same core material. Dramatic changes in the radiogenic isotope composition of North Atlantic Deep Water through the Quaternary Period are shown to reflect discrete changes in both sources and weathering processes accompanying Northern Hemisphere glaciation. Changes in the different radiogenic isotope systems reflect the influence of source, physical weathering, and chemical weathering, and not simply changes in the underlying weathering rate or ocean circulation patterns that are typically inferred.

(Appendix A) Geochemistry of Oligocene sediments of ODP Site 177-1090

Ocean Drilling Program (ODP) Site 1090, on the Agulhas Ridge in the South Atlantic sector of the Southern Ocean, is ideally located to capture changes in Southern Ocean circulation patterns. Using samples taken from cored sediments, we construct multiproxy records of productivity (biogenic barium (Baex), opal, and CaCO3 mass accumulation rates (MARs)), nutrient and organic carbon burial (reactive phosphorus (Pr) MARs), and redox conditions (U and Mn enrichments) to investigate hydrographic conditions associated with climatic shifts from the Oligocene through the early Miocene. Orbitally induced cyclicity in U and Mn enrichments (100 kyr) suggests shifts in deepwater characteristics. However, CaCO3 dissolution coincident with low U and Mn enrichments does not indicate low-oxygen, corrosive waters similar to modern conditions. These observations indicate that a well-developed "modern-type" Antarctic Circumpolar Current (ACC) did not yet exist over the period from 30 to 20 Ma, with two potential consequences: The Southern Ocean was not functioning as a silica trap, permitting a broader distribution of silica that may have facilitated organic carbon burial in the ocean in general, and the lack of a deeply mixing ACC may have facilitated organic carbon burial in the Southern Ocean. Both the relative (high opal MARs coincident with low CaCO3 MARs) and absolute (high Pr MARs) burial of organic carbon suggest a powerful mechanism for pCO2 drawdown.

Phosphorus geochemistry of eastern equatorial Pacific Ocean sediments

We determined phosphorus (P) concentrations in Leg 138 sediment samples from Sites 844, 846, and 851, using a sequential extraction technique to identify the P associated with five sedimentary components. Total concentrations of P (sum of the five components) ranged from 4 to 35 µmol P/g sediment, with mean values relatively similar between the three sites (11, 14, and 12 for Sites 844,846, and 851, respectively). Authigenic/biogenic P was the most important component in terms of percentage of total P (about 75%), with iron-bound P (13%), adsorbed P (2%-9%), and organic P (4%) of secondary importance; detrital P was a minor P sink (1%) in these sediments. Profiles of adsorbed P and iron-bound P show decreasing concentrations with age, indicating that these components have been affected by diagenesis and reorganization of P. A peak in iron-bound P may reflect higher fluxes of hydrothermally derived Fe to eastern equatorial Pacific Ocean sediments from 11 to 8 Ma. Lower detrital P values for western Site 851 reflect a greater distance of this site from a terrigenous source area, compared to that of Sites 844 and 846. Phosphorus mass accumulation rates (P-MARs; units of µmol P/cm**2/k.y.) were calculated using total P concentrations (not including the minor and oceanically unreactive detrital P component) and sedimentation rates and dry-bulk densities averaged over time intervals of 0.5 m.y. P-MARs generally decrease from 17 Ma to the present. Eastern transect Sites 844 and 846 display a decrease in P-MARs from about 30 to 10 in the interval from 17 to 8 Ma, while western transect Site 851 is highly variable during this interval. P-MARs increase to about 45 and stay relatively high from 8 to 6 Ma, then decrease toward the present to some of the lowest values of the record (about 10). The general trend of high P-MARs at about 6 Ma and decreasing values toward the present is correlated with other geochemical and sedimentary trends through this interval and may reflect (1) a change in net sediment and P burial, (2) a reorganization of fluxes with no change of net burial, or (3) a combination of the two.

(Table 1) Phosphorus and carbon chemistry of ODP Holes 169-1033B and 169-1034B

Uncertainty currently exists about the removal of carbon (C) and phosphorus (P) from the oceanic reservoir, especially in low oxygen settings. In this paper, the cycling of C and P is examined in sediments from the anoxic Saanich Inlet, cored by Ocean Drilling Program (ODP) Leg 169S in 1996 at two sites. Although Corg/Porg ratios are high and increase with depth in the Saanich Inlet, this effect is due largely to a remobilization of P from an organic matter sink to an authigenic sink. Reducible sedimentary components act as temporary shuttles in this process even in this anoxic setting, with the ultimate burial sink for the remobilized P being carbonate fluorapatite. The effective Corg/Preactive molar ratio appears to be about 150-200, indicating some preferential loss of P compared to C during organic matter degradation, but not approaching previously reported values of over 3000 in black shales. Reactive P accumulation rates in this basin range from 10,000-60,000 µmol/cm**2/kyr, greatly exceeding the range of 500-8000 µmol/cm**2/kyr found in most continental-margin settings, including regions of modern phosphogenesis. The initiation of marine sedimentation in the Saanich Inlet occurred after deglaciation, and the high rates of P burial seen here may provide an end-member example of the effects of sea level and margin sedimentation on the distribution of P within the marine P cycle.