Dissolved Zinc in the Southern Ocean measured on water bottle samples during POLARSTERN cruise ANT-XXIV/3

The distribution of dissolved zinc (Zn) was investigated in the Atlantic sector of the Southern Ocean in the austral autumn of 2008 as part of the IPY GEOTRACES expedition ZERO & DRAKE. Research focused on transects across the major frontal systems along the Zero Meridian and across the Drake Passage. There was a strong gradient in surface zinc concentrations observed across the Antarctic Polar Front along both transects and high zinc levels were found in surface waters throughout the Southern Ocean. Vertical profiles for dissolved Zinc showed the presence of local minima and maxima in the upper 200 m consistent with significant uptake by phytoplankton and release by zooplankton grazing, respectively. Highest deep water zinc concentrations were found in the centre of the Weddell Gyre associated with Central Intermediate Water (CIW), a water mass which is depleted in O2, elevated in CO2 and is regionally a CFC minimum. Our data suggests that the remineralization of sinking particles is a key control on the distribution of Zn in the Southern Ocean. Disappearance ratios of zinc to phosphate (Zn:P) in the upper water column increased southwards along both transects and based on laboratory studies they suggest slower growth rates of phytoplankton due to iron or light limitation. Zinc and silicate were strongly correlated throughout the study region but the disappearance ratio (Zn:Si) was relatively uniform overall except for the region close to the ice edge on the Zero Meridian.

Stable oxygen and carbon isotopic composition of foraminifera and sea water from the Arctic Ocean

O18/O16 data on a depth profile of water samples from the Arctic Ocean reveal that near surface water is depleted in O18 by about 4 per mil, but water at depths greater than 350 meters reaches near normal open ocean water composition. The O18 profile very closely follows the salinity profile, with deltaO18 changing by about 0.8 per mil per 1 per mil salinity change. The results of deltaO18 measurements on the pelagic species Globigerina pachyderma from a composite core show that the deltaO18 value has not changed since the latter part of the last glacial period. This constancy we take to indicate that the temperature and the deltaO18 value of the water in which these foraminifera grew have not changed significantly since that time. Such a conclusion seems to imply that the present ice coverage in the Arctic Ocean has remained unchanged during the last 25,000 years. However, the deltaO18 value of benthonic foraminifera shows a shift of 1.2 per mil between the end of the last glacial period and the present warm period. This shift is consistent with the idea that the deep water mass of the Arctic Ocean is formed outside the Arctic basin. The information on the deltaO18 value of the benthonic foraminifera from the top of the core was used in conjunction with the data on deltaO18 and temperature of the bottom water to establish the constant in the empirical equation relating deltaO18 values to temperature for the preparation procedure used in our laboratory. Based on this calibration, the data confirm A. W. H. Bé's contention (personal communication, 1960) that G. pachyderma incorporates about one-half of its CaCO3 below 300 meters.

Nd isotopes an geochemistry of bulk deep sea sediments of the Atlantic Ocean

Nd isotopes preserved in fossil fish teeth and ferromanganese crusts have become a common tool for tracking variations in water mass composition and circulation through time. Studies of Nd isotopes extracted from Pleistocene to Holocene bulk sediments using hydroxylamine hydrochloride (HH) solution yield high resolution records of Nd isotopes that can be interpreted in terms of deep water circulation, but concerns about diagenesis and potential contamination of the seawater signal limit application of this technique to geologically young samples. In this study we demonstrate that Nd extracted from the > 63 µm, decarbonated fraction of older Ocean Drilling Program (ODP) sediments using a 0.02 M HH solution produces Nd isotopic ratios that are within error of values from cleaned fossil fish teeth collected from the same samples, indicating that the HH-extractions are robust recorders of deep sea Nd isotopes. This excellent correlation was achieved for 94 paired fish teeth and HH-extraction samples ranging in age from the Miocene to Cretaceous, distributed throughout the north, tropical and south Atlantic, and composed of a range of lithologies including carbonate-rich oozes/chalks and black shales. The strong Nd signal recovered from Cretaceous anoxic black shale sequences is unlikely to be associated with ferromanganese oxide coatings, but may be derived from abundant phosphatic fish teeth and debris or organic matter in these samples. In contrast to the deep water Nd isotopic signal, Sr isotopes from HH-extractions are often offset from seawater values, suggesting that evaluation of Sr isotopes is a conservative test for the integrity of Nd isotopes in the HH fraction. However, rare earth elements (REE) from the HH-extractions and fish teeth produce distinctive middle REE bulge patterns that may prove useful for evaluating whether the Nd isotopic signal represents uncontaminated seawater. Alternatively, a few paired HH-extraction and cleaned fish teeth samples from each site of interest can be used to verify the seawater composition of the HH-extractions. The similarity between isotopic values for the HH-extraction and fish teeth illustrates that the extensive cleaning protocol applied to fish teeth samples is not necessary in typical, carbonate-rich, deep sea sediments.

(Table 1) Water column silicic acid concentrations and Si isotopic composition during Marion Dufresne cruise MD166 off South Africa

Silicon isotopic signatures (d30Si) of water column silicic acid (Si(OH)4) were measured in the Southern Ocean, along a meridional transect from South Africa (Subtropical Zone) down to 57° S (northern Weddell Gyre). This provides the first reported data of a summer transect across the whole Antarctic Circumpolar Current (ACC). d30Si variations are large in the upper 1000 m, reflecting the effect of the silica pump superimposed upon meridional water transfer across the ACC: the transport of Antarctic surface waters northward by a net Ekman drift and their convergence and mixing with warmer upper-ocean Si-depleted waters to the north. Using Si isotopic signatures, we determine different mixing interfaces: the Antarctic Surface Water (AASW), the Antarctic Intermediate Water (AAIW), and thermoclines in the low latitude areas. The residual silicic acid concentrations of end-members control the d30Si alteration of the mixing products and with the exception of AASW, all mixing interfaces have a highly Si-depleted mixed layer end-member. These processes deplete the silicic acid AASW concentration northward, across the different interfaces, without significantly changing the AASW d30Si composition. By comparing our new results with a previous study in the Australian sector we show that during the circumpolar transport of the ACC eastward, the d30Si composition of the silicic acid pools is getting slightly, but significantly lighter from the Atlantic to the Australian sectors. This results either from the dissolution of biogenic silica in the deeper layers and/or from an isopycnal mixing with the deep water masses in the different oceanic basins: North Atlantic Deep Water in the Atlantic, and Indian Ocean deep water in the Indo-Australian sector. This isotopic trend is further transmitted to the subsurface waters, representing mixing interfaces between the surface and deeper layers. Through the use of d30Si constraints, net biogenic silica production (representative of annual export), at the Greenwich Meridian is estimated to be 5.2 ± 1.3 and 1.1 ± 0.3 mol Si/m**2 for the Antarctic Zone and Polar Front Zone, respectively. This is in good agreement with previous estimations. Furthermore, summertime Si-supply into the mixed layer of both zones, via vertical mixing, is estimated to be 1.6 ± 0.4 and 0.1 ± 0.5 mol Si/m**2, respectively.

Sediment and pore water chemistry and physical oceanography of samples obtained during Baltic Sea research cruises

Sediment samples from approximately 40 stations in the Western, middle and eastern Baltic Sea were investigated for manganese and iron content. In a series of interstitial water samples and numerous deep and surface water samples, the manganese content was likewise determined. A strong enrichment of these elements in the basin sediments was shown. In many instances, several percent manganese were present. As a maximum value, 13% was found in a 1 mm thick layer. Furthermore, a distinct decrease in manganese content with increasing sediment depth was shown in the upper 10 to 20 cm of the Sediment at almost all stations. Both phenomena may be explained by the release of manganese from the Sediment through diffusion. In the flat parts of the Baltic and those parts having good bottom water circulation, this diffusion progresses especially vigorously as a result of a steep gradient of the Mn++ concentration in the interstitial water-deep water interface. The manganese which hereby passes into the water overlying the bottom (manganese contents between 10 and 100 y Mn/l were determined in numerous deep water samples) is partly reprecipitated on the Sediment surface, and partly carried by currents into the deeper basins where it is finallv deposited. It is bound there as a manganese-rich mixed carbonate, the composition of which can be proved chemically and by x-ray methods. Iron is likewise of higher content in the basinal sediments, however, the extent of its enrichment is far less since it is less soluble than manganese under the reducing conditions in the sediments. The fine bands of manganese- and iron-rich layers in the basin sediments may likewise be explained as a result of diffusion.

Mineralogy, isotopic composition of oxygen, hydrogen and carbon, and oxygen isotopic temperature of deep-sea silica and coexisting carbonates (Table 1)

Water extracted from opal-CT ("porcellanite", "cristobalite"), granular microcrystalline quartz (chert), and pure fibrous quartz (chalcedony) in cherts from the JOIDES Deep Sea Drilling Project is 56? to 87? depleted in deuterium relative to the water in which the silica formed. This large fractionation is similar in magnitude and sign to that observed for hydroxyl in clay minerals and suggests that water extracted from these forms of silica has been derived from hydroxyl groups within the silica. Delta18O-values for opal-CT at sites 61, 64, 70B and 149 vary from 34.3? to 37.2? and show no direct correlation with depth of burial. Granular microcrystaUine quartz in these cores is 0.5 ? depleted in 18O relative to coexisting opal-CT at sediment depths of 100 m and the depletion increases to 2? for sediments buried below 384 m. These relationships suggest that opal-CT forms before significant burial while granular microcrystalline quartz forms during deeper burial at warmer temperatures. The temperature at which opal-CT forms is thus probably approximately equal to the temperature of the overlying bottom water. Isotopic temperatures deduced for opal-CT formation are preliminary and very approximate, but yield Eocene deep-water temperatures of 5-13°C, and 6°C for the upper Cretaceous sample. Pure euhedral quartz crystals lining a cavity in opal-CT at 388 m in core 8-70B-4-CC have a ~delta18O value of +29.8? and probably formed near maximum burial. The isotopic temperature is approximately 32 ° C.

Food selectivity and processing by the cold-water coral Lophelia pertusa

Cold-water corals form prominent reef ecosystems along ocean margins that depend on suspended resources produced in surface waters. In this study, we investigated food processing of 13C and 15N labelled bacteria and algae by the cold-water coral Lophelia pertusa. Coral respiration, tissue incorporation of C and N and metabolic-derived C incorporation into the skeleton were traced following the additions of different food concentrations (100, 300, 1300 µg C/l) and two ratios of suspended bacterial and algal biomass (1:1, 3:1). Respiration and tissue incorporation by L. pertusa increased markedly following exposure to higher food concentrations. The net growth efficiency of L. pertusa was low (0.08±0.03), which is consistent with their slow growth rates. The contribution of algae and bacteria to total coral assimilation was proportional to the food mixture in the two lowest food concentrations, but algae were preferred over bacteria as food source at the highest food concentration. Similarly, the stoichiometric uptake of C and N was coupled in the low and medium food treatment, but was uncoupled in the high food treatment and indicated a comparatively higher uptake or retention of bacterial carbon as compared to algal nitrogen. We argue that behavioural responses for these small-sized food particles, such as tentacle behaviour, mucus trapping and physiological processing, are more likely to explain the observed food selectivity as compared to physical-mechanical considerations. A comparison of the experimental food conditions to natural organic carbon concentrations above CWC reefs suggests that L. pertusa is well adapted to exploit temporal pulses of high organic matter concentrations in the bottom water caused by internal waves and down-welling events.

Fossil associations from the middle and upper Eocene strata of the Pamplona Basin and surrounding areas (Navarre, western Pyrenees)

Fossil associations from the middle and upper Eocene (Bartonian and Priabonian) sedimentary succession of the Pamplona Basin are described. This succession was accumulated in the western part of the South Pyrenean peripheral foreland basin and extends from deep-marine turbiditic (Ezkaba Sandstone Formation) to deltaic (Pamplona Marl, Ardanatz Sandstone and Ilundain Marl formations) and marginal marine deposits (Gendulain Formation). The micropalaeontological content is high. It is dominated by foraminifera, and common ostracods and other microfossils are also present. The fossil ichnoasssemblages include at least 23 ichnogenera and 28 ichnospecies indicative of Nereites, Cruziana, Glossifungites and ?Scoyenia-Mermia ichnofacies. Body macrofossils of 78 taxa corresponding to macroforaminifera, sponges, corals, bryozoans, brachiopods, annelids, molluscs, arthropods, echinoderms and vertebrates have been identified. Both the number of ichnotaxa and of species (e. g. bryozoans, molluscs and condrichthyans) may be considerably higher. Body fossil assemblages are comparable to those from the Eocene of the Nord Pyrenean area (Basque Coast), and also to those from the Eocene of the west-central and eastern part of South Pyrenean area (Aragon and Catalonia). At the European scale, the molluscs assemblages seem endemic from the Pyrenean area, although several Tethyan (Italy and Alps) and Northern elements (Paris basin and Normandy) have been recorded. Palaeontological data of studied sedimentary units fit well with the shallowing process that throughout the middle and late Eocene occurs in the area, according to the sedimentological and stratigraphical data.

Evolution of neodymium isotopic signature of seawater during the Late Cretaceous: Implications for intermediate and deep circulation

Neodymium isotopic compositions (εNd) have been largely used for the last fifty years as a tracer of past ocean circulation, and more intensively during the last decade to investigate ocean circulation during the Cretaceous period. Despite a growing set of data, circulation patterns still remain unclear during this period. In particular, the identification of the deep-water masses and their spatial extension within the different oceanic basins are poorly constrained. In this study we present new deep-water εNd data inferred from the Nd isotope composition of fish remains and Fe-Mn oxyhydroxide coatings on foraminifera tests, along with new εNd data of residual (partly detrital) fraction recovered from DSDP sites 152 (Nicaraguan Rise), 258 (Naturaliste Plateau), 323 (Bellinghausen Abyssal Plain), and ODP sites 690 (Maud Rise) and 700 (East Georgia Basin, South Atlantic). The presence of abundant authigenic minerals in the sediments at sites 152 and 690 detected by XRD analyses may explain both middle rare earth element enrichments in the spectra of the residual fraction and the evolution of residual fraction εNd that mirror that of the bottom waters at the two sites. The results point towards a close correspondence between the bottom water εNd values of sites 258 and 700 from the late Turonian to the Santonian. Since the deep-water Nd isotope values at these two sites are also similar to those at other proto-Indian sites, we propose the existence of a common intermediate to deep-water water mass as early as the mid-Cretaceous. The water mass would have extended from the central part of the South Atlantic to the eastern part of proto-Indian ocean sites, beyond the Kerguelen Plateau. Furthermore, data from south and north of the Rio Grande Rise-Walvis Ridge complex (sites 700 and 530) are indistinguishable from the Turonian to Campanian, suggesting a common water mass since the Turonian at least. This view is supported by a reconstruction of the Rio Grande Rise-Walvis Ridge complex during the Turonian, highlighting the likely existence of a deep breach between the Rio Grande Rise and the proto-Walvis Ridge at that time. Thus deep-water circulation may have been possible between the different austral basins as early as the Turonian, despite the presence of potential oceanic barriers. Comparison of new seawater and residue εNd data on Nicaraguan Rise suggest a westward circulation of intermediate waters through the Caribbean Seaway during the Maastrichtian and Paleocene from the North Atlantic to the Pacific. This westward circulation reduced the Pacific water influence in the Atlantic, and was likely responsible for more uniform, less radiogenic εNd values in the North Atlantic after 80 Ma. Additionally, our data document an increasing trend observed in several oceanic basins during the Maastrichtian and the Paleocene, which is more pronounced in the North Pacific. Although the origin of this increase still remains unclear, it might be explained by an increase in the contribution of radiogenic material to upper ocean waters in the northern Pacific. By sinking to depth, these waters may have redistributed to some extent more radiogenic signatures to other ocean basins through deep-water exchanges.

Limited mid-water scavenging of trawl discards

The consumption or scavenging of fish in the water column at depths from 75 to 275 m in Algarve (southern Portugal) trawl fishing grounds was evaluated. Longlines were used to suspend baits throughout the water column while electric fishing reels were used to simulate sinking discards. Eighteen species were caught, with higher catch rates near the surface than near the bottom. However, scavenging rates were generally highest near the bottom and lowest in the middle of the water column. At depths less than 100 m the majority or all the fish were scavenged throughout the water column, while at depths greater than 200 m most of the fish were untouched after periods of time greater than would be required for them to sink to the bottom. Since other studies have shown that most small fish discards are scavenged at the surface by sea birds and most of the discarded species that sink are either too large or not attractive to pelagic predators, these results suggest that mid-water scavenging of trawl discards in deep water is relatively unimportant.