ALBERT

Description: Chemical disparities at the interface between subducting oceanic crustal rocks and the harzburgitic mantle lead to the formation of reaction zones in the mantle above the subducting slabs composed of hybrid rocks that may carry exotic trace-element patterns and isotopic signatures. Subsequent burial of these metasomatised rocks as part of the progressively subducted slab could deliver trace elements and volatiles to the source region of arc magma. A natural laboratory to study reactions at the slab–mantle interface maybe found in exhumed high-pressure mélanges, where sedimentary, mafic and ultramafic lithologies are juxtaposed and metamorphosed at high-P/T conditions. A mélange zone of that type is found in northern Syros, where metasomatic reaction zones (“blackwalls”) formed on a metre scale at the contact of metasedimentary blueschists and serpentinite. Five different zones within such a contact display the assemblages (I) glaucophane+garnet+phengite+epidote, (II) glaucophane+epidote+chlorite, (III) chlorite+epidote+omphacite±albite (IV) chlorite±titanite±rutile±apatite and (V) serpentine+chromite. Accessory phases, such as apatite, allanite, rutile, titanite, tourmaline, zircon and monazite are abundant in zones II to IV. The observed succession of assemblages together with whole-rock major and trace-element compositions reflect the two dominant processes that are thought to have operated along the lithological contact: (A) diffusion of chemical components driven by the compositional contrast of the juxtaposed rocks, and (B) flux of hydrous fluids along the contact, which depleted (e.g., LILE, SiO2) or enriched (e.g., B, LREE) certain elements in various zones. Thermodynamic modelling is able to closely predict the succession of mineral assemblages as they are expected from diffusion of Mg and Ca across the contact zone. Employed to various P–T conditions and different juxtaposed rock types, this type of modelling could be used to access and evaluate larger portions of the subduction system. Our results support existing models that suggest that mixing and redistribution of major and trace elements in subduction zones may be related to the formation of hybrid rocks in mélange zones

Description: Prompted by recent data analyses suggesting that the flux of particulate organic carbon sinking into deep waters is determined by fluxes of mineral ballasts, we undertook a study of the relationships among organic matter (OM), calcium carbonate, opal, lithogenic material, and excess aluminum fluxes as part of the MedFlux project. We measured fluxes of particulate components during Spring and Summer of 2003, and Spring of 2005, using a swimmer-excluding sediment trap design capable of measuring fluxes both in a time-series (TS) mode and in a configuration for obtaining particle settling velocity (SV) profiles. On the basis of these studies, we suggest that distinct OM–ballast associations observed in particles sinking at a depth of ∼200 m imply that the mechanistic basis of the organic matter–ballast association is set in the upper water column above the Twilight Zone, and that the importance of different ballast types follows the seasonal succession of phytoplankton. As in other studies, carbonate appears to enhance the flux of organic matter over opal. Particles must be at least half organic matter before their settling velocity is affected by ballast concentration. This lack of change in ballast composition with SV in particles with 〈40% OM content suggests that particle SV reaches a maximum because of the increasing importance of inertial drag. Relative amounts of OM and opal decrease with depth due to decomposition and dissolution; carbonates and lithogenic material contribute about the same amount to total mass, or increase slightly, throughout the water column. The high proportion of excess Al cannot be explained by its incorporation into diatom opal or reverse weathering, so Al is most likely adsorbed to particulate oxides. On shorter time scales, dust appears to increase particle flux through its role in aggregation rather than by nutrient inputs enhancing productivity. We suggest that the role of dust as a catalyst in particle formation may be a central mechanism in flux formation in this region, particularly when zooplankton fecal pellet production is low.

Description: Distributions of dissolved vitamin B12 and total dissolved Co were measured to gain an understanding of the cycling of these interdependent micronutrients in six marine settings including; an upwelling location, a semi-enclosed bay, two urban coastal systems, and two open ocean locations. Along the coast of Baja California, Mexico, concentrations of B12 and dissolved Co varied from 0.2 to 11 pM and 180 to 990 pM, respectively. At a nearby upwelling station, vitamin B12 and Co concentrations ranged from 0.3 to 7.0 pM and 22 to 145 pM, and concentrations did not correlate with upwelling intensity. Concentrations of B12 were highest within Todos Santos Bay, a semi-enclosed bay off the coast of Baja California, Mexico, during a dinoflagellate bloom, ranging from 2 to 61 pM, while Co concentrations varied between 61 and 194 pM. In the anthropogenically impacted Long Island Sound, NY, U.S.A., B12 levels were between 0.1 and 23 pM and Co concentrations varied from 60 to 1900 pM. However, anthropogenic inputs were not evident in B12 levels in the San Pedro Basin, located outside Los Angeles, Ca, U.S.A., where concentrations of B12 were 0.2–1.8 pM, approximating observed open ocean B12 concentrations. In the Southern Ocean and North Atlantic Ocean, B12 levels were 0.4–4 pM and 0.2–2 pM, respectively. Total Co concentrations in the Southern Ocean and North Atlantic tended to be low; measuring 26–59 pM and 15–80 pM, respectively. These low Co concentrations may limit B12 synthesis and its availability to B12-requiring phytoplankton because the total dissolved Co pool is not necessarily entirely bioavailable.

Description: The dissolution of in-situ generated methane hydrate in undersaturated, synthetic seawater (S = 35) was investigated in a series of laboratory-based experiments at P-/T-conditions within the hydrate stability field. A controlled flow field was generated across the smooth hydrate surface to test if, in addition to thermodynamic variables, the dissolution rate is influenced by changing hydrodynamic conditions. The dissolution rate was found to be strongly dependent on the friction velocity, showing that hydrate dissolution in undersaturated seawater is a diffusion-controlled process. The experimental data was used to obtain diffusional mass transfer coefficients kd, which were found to correlate linearly with the friction velocity, u★. The resulting kd/u★-correlation allows predicting the flux of methane from natural gas hydrate exposures at the sediment/seawater interface into the bulk water for a variety of natural P, T and flow conditions. It also is a tool for estimating the rate of hydrate regrowth at locations where natural hydrate outcrops at the seafloor persist in contact with undersaturated seawater

Description: Nd concentration and isotope data have been obtained for the Canada, Amundsen, and Makarov Basins of the Arctic Ocean. A pattern of high Nd concentrations (up to 58 pM) at shallow depths is seen throughout the Arctic, and is distinct from that generally seen in other oceans where surface waters are relatively depleted. A range of isotopic variations across the Arctic and within individual depth profiles reflects the different sources of waters. The dominant source of water, and so Nd, is the Atlantic Ocean, with lesser contributions from the Pacific and Arctic Rivers. Radiogenic isotope Nd signatures (up to epsilon(Nd) = -6.5) can be traced in Pacific water flowing into the Canada Basin. Waters from rivers draining older terrains provide very unradiogenic Nd (down to epsilon(Nd) = -14.2) that can be traced in surface waters across much of the Eurasian Basin. A distinct feature of the Arctic is the general influence of the shelves on the Nd concentrations of waters flowing into the basins, either from the Pacific across the Chukchi Sea, or from across the extensive Siberian shelves. Water-shelf interaction results in an increase in Nd concentration without significant changes in salinity in essentially all waters in the Arctic, through processes that are not yet well understood. In estuarine regions other processes modify the Nd signal of freshwater components supplied into the Arctic Basin, and possibly also contribute to sedimentary Nd that may be subsequently involved in sediment-water interactions. Mixing relationships indicate that in estuaries, Nd is removed from major river waters to different degrees. Deep waters in the Arctic are higher in Nd than the inflowing Atlantic waters, apparently through enrichments of waters on the shelves that are involved in ventilating the deep basins. These enrichments generally have not resulted in major shifts in the isotopic compositions of the deep waters in the Makarov Basin (epsilon(Nd) similar to -10.5), but have created distinctive Nd isotope signatures that were found near the margin of the Canada Basin (with epsilon(Nd) similar to -9.0). The deep waters of the Amundsen Basin are also distinct from the Atlantic waters (with epsilon(Nd) = -12.3), indicating that there has been limited inflow from the adjacent Makarov Basin through the Lomonosov Ridge. (C) 2009 Elsevier Ltd. All rights reserved.

Description: δ18O values of nine tropical–subtropical planktonic foraminiferal species with different preferential habitat depths collected from 62 core–top samples along an east–west transect across the tropical Atlantic/Caribbean were used to test the applicability of interspecific δ18O gradients for reconstructions of tropical upper ocean stratification. In general, the δ18O difference (Δδ18O) between intermediate- and shallow-dwelling species decreases, and Δδ18O between deep and intermediate dwellers increases with increasing thermocline depth towards the west. The statistical significance of regional differences in Δδ18O highlights Δδ18O between the intermediate dwellers (in particular Globorotalia scitula and Globorotalia tumida) and the shallow dweller Globigerinoides ruber pink, as well as Δδ18O between the deep dwellers Globorotalia crassaformis or Globorotalia truncatulinoides dextral and intermediate dwellers as most sensitive to changes in tropical Atlantic thermocline depth. Based on the observed regional variations in interspecific Δδ18O, we propose a multispecies stratification index “STRAtrop” = (δ18Ointermediate − δ18Oshallow) / (δ18Odeep − δ18Oshallow) for the tropical ocean. Statistically significant differences in STRAtrop values between the E-Atlantic and the Caribbean suggest that this index may be a useful tool to monitor variations in tropical upper ocean stratification in the geological record.

Description: The skill of numerical Lagrangian drifter trajectories in three numerical models is assessed by comparing these numerically obtained paths to the trajectories of drifting buoys in the real ocean. The skill assessment is performed using the two-sample Kolmogorov-Smirnov statistical test. To demonstrate the assessment procedure, it is applied to three different models of the Agulhas region. The test can either be performed using crossing positions of one-dimensional sections in order to test model performance in specific locations, or using the total two-dimensional data set of trajectories. The test yields four quantities: a binary decision of model skill, a confidence level which can be used as a measure of goodness-of-fit of the model, a test statistic which can be used to determine the sensitivity of the confidence level, and cumulative distribution functions that aid in the qualitative analysis. The ordering of models by their confidence levels is the same as the ordering based on the qualitative analysis, which suggests that the method is suited for model validation. Only one of the three models, a 1/10 degree two-way nested regional ocean model, might have skill in the Agulhas region. The other two models, a 1/2 degree global model and a 1/8 degree assimilative model, might have skill only on some sections in the region.

Description: We critically evaluate the applicability of Ca-isotope ratios in planktonic foraminifers as proxy for past sea surface temperatures (SST) and isotope composition of paleo-seawater (δ44Casw) reconstructions. Previous studies have shown discrepancies regarding the temperature sensitivity of Ca isotope fractionation in foraminifers of more than one order of magnitude. We present new data from the planktonic foraminifer species Orbulina universa, Globigerinoides sacculifer and Neogloboquadrina pachyderma (sinistral) from culture experiments, multinet deployments and coretop samples. Specimens of G. sacculifer cultured at low salinities (33–34.5) show predominantly no major temperature dependent Ca isotope fractionation, in contrast to previous individuals cultured at higher salinities of 34.5–36. The new data of O. universa are consistent with previously published results, revealing a small but significant temperature sensitivity. Calcium isotope fractionation in tests of N. pachyderma shows a significant variation with temperature, which is not uniform over the total investigated temperature range (−1.6 °C to +10 °C), possibly reflecting the influence of additional controlling factors besides temperature. Controlled dissolution experiments in the laboratory indicate that the Ca-isotope composition of G. sacculifer and N. pachyderma is relatively insensitive to partial dissolution of their tests. Calcium isotope ratios in the planktonic foraminifers G. sacculifer and N. pachyderma (s) reveal a complex Ca isotope fractionation behaviour, which is not yet fully understood. Additional validation studies are crucial to enhance the basic understanding of the calcium isotope systematics in planktic foraminifer shells, and the potential for applying Ca-isotope ratios as proxies for seawater temperature and the oceanic Ca budget.

Description: The first isotopic compositions of dissolved hafnium in seawater from across the Arctic Ocean are reported. Most samples from the four sub-basins of the Arctic Ocean have values within error of an average of epsilon(Hf) = +0.8. Combined Hf-Nd isotope compositions do not fall on the well-established positive correlation for mantle and crustal rocks. Instead, Arctic waters have Hf that is more radiogenic than that typically found in rocks with similar Nd isotope compositions, a feature previously found in ferromanganese crusts and waters from the Pacific Ocean. Arctic seawater samples generally fall on the lower part of the ferromanganese crust array, reflecting influences of inputs from Arctic rivers and interactions of shelf waters with underlying sediments. Arctic rivers have much higher Hf concentrations (7-30 pM) than Arctic seawater (0.36-4.2 pM). Water from the Mackenzie River has the least radiogenic Hf, with epsilon(Hf) = -7.1 +/- 1.7, and plots furthest away from the ferromanganese crust array, while waters from the Ob, Yenisey, and Lena Rivers have values that are indistinguishable from most Arctic waters. In the Amundsen, Makarov, and Canada basins, Hf concentrations are highest at the surface and lowest in the deeper waters, reflecting the influences of riverine inputs and of waters that have flowed over the extensive Siberian continental shelves and have Nd and Hf characteristics that reflect water-sediment interactions. This is in contrast to the relatively low near surface Hf concentrations reported for locations elsewhere. The Pacific water layer in the Canada Basin exhibits the highest value of epsilon(Hf) = +6.8 +/- 1.8, reflecting the Hf isotopic composition of waters entering the Arctic from the Pacific Ocean. Mixing relationships indicate that a substantial fraction of the Hf in the Mackenzie River is lost during estuarine mixing; the behaviour of Hf from other rivers is less constrained. (C) 2009 Elsevier Ltd. All rights reserved.