Geochemistry of sediments from the Eastern Cape Basin

Sediment cores retrieved in the Benguela coastal upwelling system off Namibia show very distinct enrichments of solid phase barium at the sulfate/methane transition (SMT). These barium peaks represent diagenetic barite (BaSO4) fronts which form by the reaction of upwardly diffusing barium with interstitial sulfate. Calculated times needed to produce these barium enrichments indicate a formation time of about 14,000 yr. Barium spikes a few meters below the SMT were observed at one of the investigated sites (GeoB 8455). Although this sulfate-depleted zone is undersaturated with respect to barite, the dominant mineral phase of these buried barium enrichments was identified as barite by scanning electron microscopy (SEM). This is the first study which reports the occurrence/preservation of pronounced barite enrichments in sulfate-depleted sediments buried a few meters below the SMT. At site GeoB 8455 high concentrations of dissolved barium in pore water as well as barium in the solid phase were observed. Modeling the measured barium concentrations at site GeoB 8455 applying the numerical model CoTReM reveals that the dissolution rate of barite directly below the SMT is about one order of magnitude higher than at the barium enrichments deeper in the sediment core. This indicates that the dissolution of barite at these deeper buried fronts must be retarded. Thus, the occurrence of the enrichments in solid phase barium at site GeoB 8455 could be explained by decreased dissolution rates of barite due to the changes in the concentration of barite in the sediment, as well as changes in the saturation state of fluids. Furthermore, the alteration of barite into witherite (BaCO3) via the transient phase barium sulfide could lead to the preservation of a former barite front as BaCO3. The calculations and modeling indicate that a relocation of the barite front to a shallower depth occurred between the last glacial maxium (LGM) and the Pleistocene/Holocene transition. We suggest that an upward shift of the SMT occurred at that time, most likely as a result of an increase in the methanogenesis rates due to the burial of high amounts of organic matter below the SMT.

Geochemical records of sediment cores from the Sea of Japan

Intervals of organic C- and carbonate-rich laminated sediments occur in the Sea of Japan with roughly the same frequency as temperature changes observed in Greenland ice cores, providing clear evidence of rapid oceanographic change during the past 36 kyr. Planktonic foraminiferal d18O data suggest that only the laminated sediments deposited during the Last Glacial Maximum (LGM), and perhaps one other interval formed during a period of increased water column stratification. Sedimentary Re and Mo data are consistent with bottom waters that were sulfidic during the LGM and suboxic during other laminated intervals. Results of a numerical model of Corg and Re burial are consistent with a mechanism whereby an increased Corg flux to the seafloor drove oxygen concentrations toward depletion during times of deposition of the suboxic laminated intervals. Such a process could have resulted from increased upwelling driven either by increased deep water formation due to colder and/or more saline surface waters or by stronger northeasterly monsoonal winds.

Age and oxygen isotope data for bulk carbonate from DSDP Sites 41-366 and 72-516 and ODP Sites 111-677A and 130-807

A numerical model which describes oxygen isotope exchange during burial and recrystallization of deep-sea carbonate is used to obtain information on how sea surface temperatures have varied in the past by correcting measured d18O values of bulk carbonate for diagenetic overprinting. Comparison of bulk carbonate and planktonic foraminiferal d18O records from ODP site 677A indicates that the oxygen isotopic composition of bulk carbonate does reflect changes in sea surface temperature and d18O. At ODP Site 690, we calculate that diagenetic effects are small, and that both bulk carbonate and planktonic foraminiferal d18O records accurately reflect Paleogene warming of high latitude surface oceans, biased from diagenesis by no more than 1°C. The same is likely to be true for other high latitude sites where sedimentation rates are low. At DSDP sites 516 and 525, the effects of diagenesis are more significant. Measured d18O values of Eocene bulk carbonates are more than 2? lower at deeply buried site 516 than at site 525, consistent with the model prediction that the effects of diagenesis should be proportional to sedimentation rate. Model-corrections reconcile the differences in the data between the two sites; the resulting paleotemperature reconstruction indicates a 4°C cooling of mid-latitude surface oceans since the Eocene. At low latitudes, the contrast in temperature between the ocean surface and bottom makes the carbonate d180 values particularly sensitive to diagenetic effects; most of the observed variations in measured d18O values are accounted for by diagenetic effects rather than by sea surface temperature variations. We show that the data are consistent with constant equatorial sea surface temperatures through most of the Cenozoic, with the possible exception of the early Eocene, when slightly higher temperatures are indicated. We suggest that the lower equatorial sea surface temperatures for the Eocene and Oligocene reported in other oxygen isotope studies are artifacts of diagenetic recrystallization, and that it is impossible to reconstruct accurately equatorial sea surface temperatures without explicitly accounting for diagenetic overprinting.

Calcium isotope ratios of pore fluids and solid phase of organic rich sediments

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (d44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of d44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, d44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the d44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.

Predicting bed form roughness: the influence of lee side angle

Flow transverse bedforms (ripples and dunes) are ubiquitous in rivers and coastal seas. Local hydrodynamics and transport conditions depend on the size and geometry of these bedforms, as they constitute roughness elements at the bed. Bedform influence on flow energy must be considered for the understanding of flow dynamics, and in the development and application of numerical models. Common estimations or predictors of form roughness (friction factors) are based mostly on data of steep bedforms (with angle-of-repose lee slopes), and described by highly simplified bedform dimensions (heights and lengths). However, natural bedforms often are not steep, and differ in form and hydraulic effect relative to idealised bedforms. Based on systematic numerical model experiments, this study shows how the hydraulic effect of bedforms depends on the flow structure behind bedforms, which is determined by the bedform lee side angle, aspect ratio and relative height. Simulations reveal that flow separation behind bedform crests and, thus, a hydraulic effect is induced at lee side angles steeper than 11 to 18° depending on relative height, and that a fully developed flow separation zone exists only over bedforms with a lee side angle steeper than 24°. Furthermore, the hydraulic effect of bedforms with varying lee side angle is evaluated and a reduction function to common friction factors is proposed. A function is also developed for the Nikuradse roughness (k s), and a new equation is proposed which directly relates k s to bedform relative height, aspect ratio and lee side angle.

(Table 1) Physical oceanography from several POLARSTERN cruises to the Arctic Ocean, 1993 - 2012

Freshwater in the Arctic Ocean plays an important role in the regional ocean circulation, sea ice, and global climate. From salinity observed by a variety of platforms, we are able, for the first time, to estimate a statistically reliable liquid freshwater trend from monthly gridded fields over all upper Arctic Ocean basins. From 1992 to 2012 this trend was 600±300 km**3/yr. A numerical model agrees very well with the observed freshwater changes. A decrease in salinity made up about two thirds of the freshwater trend and a thickening of the upper layer up to one third. The Arctic Ocean Oscillation index, a measure for the regional wind stress curl, correlated well with our freshwater time series. No clear relation to Arctic Oscillation or Arctic Dipole indices could be found. Following other observational studies, an increased Bering Strait freshwater import to the Arctic Ocean, a decreased Davis Strait export, and enhanced net sea ice melt could have played an important role in the freshwater trend we observed.

Sulphate concentrations and sulphur isotopic composition in pore fluids from ODP Leg 168 sites

A numerical model of sulfate reduction and isotopic fractionation has been applied to pore fluid SO4**2- and d34S data from four sites drilled during Ocean Drilling Program (ODP) Leg 168 in the Cascadia Basin at 48°N, where basement temperatures reach up to 62°C. There is a source of sulfate both at the top and the bottom of the sediment column due to the presence of basement fluid flow, which promotes bacterial sulfate reduction below the sulfate minimum zone at elevated temperatures. Pore fluid d34S data show the highest values (135 per mil) yet found in the marine environment. The bacterial sulfur isotopic fractionation factor, a, is severely underestimated if the pore fluids of anoxic marine sediments are assumed to be closed systems and Rayleigh fractionation plots yield erroneous values for a by as much as 15 per mil in diffusive and advective pore fluid regimes. Model results are consistent with a = 1.077+/-0.007 with no temperature effect over the range 1.8 to 62°C and no effect of sulfate reduction rate over the range 2 to 10 pmol/ccm/day. The reason for this large isotopic fractionation is unknown, but one difference with previous studies is the very low sulfate reduction rates recorded, about two orders of magnitude lower than literature values that are in the range of µmol/ccm/day to tens of nmol/ccm/day. In general, the greatest 34S depletions are associated with the lowest sulfate reduction rates and vice versa, and it is possible that such extreme fractionation is a characteristic of open systems with low sulfate reduction rates.

Physical oceanography and current measurements in the Filchner Depression (Weddell Sea, Antarctica) during Ernest Shackleton cruise ES060

Cold and dense ice shelf water (ISW) emerging from the Filchner-Ronne Ice Shelf cavity in the southwestern Weddell Sea flows northward through the Filchner Depression to eventually descend the continental slope and contribute to the formation of bottom water. New ship-born observations of hydrography and currents from Filchner Depression in January 2013 suggest that the northward flow of ISW takes place in a middepth jet along the eastern flank of the depression, thus questioning the traditional view with outflow along the western flank. This interpretation of the data is supported by results from a regional numerical model, which shows that ISW flowing northward along the eastern coast of Berkner Island turns eastward and crosses the depression to its eastern side upon reaching the Filchner ice front. The ice front represents a sudden change in the thickness of the water column and thus a potential vorticity barrier. Transport estimates of northward ISW flux based on observations ranges from 0.2 to 1.0 Sv.

Nitrogen cycling driven by organic matter export in the South Pacific oxygen minimum zone

Oxygen minimum zones are expanding globally, and at present account for around 20-40% of oceanic nitrogen loss. Heterotrophic denitrification and anammox-anaerobic ammonium oxidation with nitrite-are responsible for most nitrogen loss in these low-oxygen waters. Anammox is particularly significant in the eastern tropical South Pacific, one of the largest oxygen minimum zones globally. However, the factors that regulate anammox-driven nitrogen loss have remained unclear. Here, we present a comprehensive nitrogen budget for the eastern tropical South Pacific oxygen minimum zone, using measurements of nutrient concentrations, experimentally determined rates of nitrogen transformation and a numerical model of export production. Anammox was the dominant mode of nitrogen loss at the time of sampling. Rates of anammox, and related nitrogen transformations, were greatest in the productive shelf waters, and tailed off with distance from the coast. Within the shelf region, anammox activity peaked in both upper and bottom waters. Overall, rates of nitrogen transformation, including anammox, were strongly correlated with the export of organic matter. We suggest that the sinking of organic matter, and thus the release of ammonium into the water column, together with benthic ammonium release, fuel nitrogen loss from oxygen minimum zones.

Respiration and dissolution in sediments of the western Atlantic

We present in situ microelectrode measurements of sediment formation factor and porewater oxygen and pH from six stations in the North Atlantic varying in depth from 2159 to 5380 m. A numerical model of the oxygen data indicates that fluxes of oxygen to the sediments are as much as an order of magnitude higher than benthic chamber flux measurements previously reported in the same area. Model results require dissolution driven by metabolic CO2 production within the sediments to explain the pH data; even at the station with the most undersaturated bottom waters >60% of the calcite dissolution occurs in response to metabolic CO2. Aragonite dissolution alone cannot provide the observed buffering of porewater pH, even at the shallowest station. A sensitivity test of the model that accounts for uncertainties in the bottom water saturation state and the stoichiometry between oxygen consumption and CO2 production during respiration constrains the dissolution rate constant for calcite to between 3 and 30% day**-1, in agreement with earlier in situ determinations of the rate constant. Model results predict that over 35% of the calcium carbonate rain to these sediments dissolves at all stations, confirmed by sediment trap and CaCO3 accumulation data.

Table 2: Firn temperature, ram resistance, mass balance and submergence velo city measurements on Colle Gnifetti

Distributional patterns of glaciological parameters at the Colle Gnifetti core drilling site are described and their interrelationships are brietly discussed. Observations within a stake network established in 1980 furnish information about snow accumulation (short term balance), submergence velocity of ice tlow (long term balance), ram hardness (melt layer stratigraphy), and firn temperature. In addition, a numerical model was used to estimate local variations of available radiant energy. Melt layer formation is considerably more intensive on the south facing parts of the firn saddie where incoming radiation is high. These melt layers seem to effectively protect some of the fallen snow from wind erosion. As a result, balance ist up to one order of magnitude larger on south facing slopes. Heat applied to the surface is therefore positively correlated with balance, whereas the relation between solar radiation and firn temperature is less dear. Distributional patterns of submergence velocity confirm that the observed spatial variability of surface balance is representative for longer time periods and greatly intluences the time scale and the stratigraphy of firn and ice cores from Colle Gnifetti.

(Table 1) Oxygen isotopic composition of interstitial waters from ODP Hole 161-976

Interstitial waters recovered from Ocean Drilling Program, Leg 161, site 976 in the western Mediterranean Sea are used in conjunction with a numerical model to constrain the delta18O of seawater in the basin since the Last Glacial Maximum, including Sapropel Event 1. To resolve the oxygen isotopic composition of the deep Mediterranean, we use a model that couples fluid diffusion with advective transport, thus producing a profile of seawater delta18O variability that is unaffected by glacial-interglacial variations in marine temperature. Comparing our reconstructed seawater delta18O to recent determinations of 1.0 per mil for the mean ocean change in glacial-interglacial delta18O due to the expansion of global ice volume, we calculate an additional 0.2 per mil increase in Mediterranean delta18O caused by local evaporative enrichment. This estimate of delta18O change, due to salinity variability, is smaller than previous studies have proposed and demonstrates that Mediterranean records of foraminiferal calcite delta18O from the last glacial period include a strong temperature component. Paleotemperatures determined in combination with a stacked record of foraminiferal calcite depict almost 9°C of regional cooling for the Last Glacial Maximum. Model results suggest a decrease of ~1.1 per mil in seawater delta18O relative to the modern value caused by increased freshwater input and reduced salinity accompanying the formation of the most recent sapropel. The results additionally indicate the existence of isotopically light water circulating down to bottom water depths, at least in the western Mediterranean, supporting the existence of an 'anti-estuarine' thermohaline circulation pattern during Sapropel Event 1.

Dissolved Iron, Aluminium, and Dissolved Inorganic Phosphorus in the (Sub-)Tropical Atlantic Surface Ocean

Inorganic nitrogen depletion restricts productivity in much of the low-latitude oceans, generating a selective advantage for diazotrophic organisms capable of fixing atmospheric dinitrogen (N2). However, the abundance and activity of diazotrophs can in turn be controlled by the availability of other potentially limiting nutrients, including phosphorus (P) and iron (Fe). Here we present high-resolution data (~0.3°) for dissolved iron, aluminum, and inorganic phosphorus that confirm the existence of a sharp north-south biogeochemical boundary in the surface nutrient concentrations of the (sub)tropical Atlantic Ocean. Combining satellite-based precipitation data with results from a previous study, we here demonstrate that wet deposition in the region of the intertropical convergence zone acts as the major dissolved iron source to surface waters. Moreover, corresponding observations of N2 fixation and the distribution of diazotrophic Trichodesmium spp. indicate that movement in the region of elevated dissolved iron as a result of the seasonal migration of the intertropical convergence zone drives a shift in the latitudinal distribution of diazotrophy and corresponding dissolved inorganic phosphorus depletion. These conclusions are consistent with the results of an idealized numerical model of the system. The boundary between the distinct biogeochemical systems of the (sub)tropical Atlantic thus appears to be defined by the diazotrophic response to spatial-temporal variability in external Fe inputs. Consequently, in addition to demonstrating a unique seasonal cycle forced by atmospheric nutrient inputs, we suggest that the underlying biogeochemical mechanisms would likely characterize the response of oligotrophic systems to altered environmental forcing over longer timescales.

Case studies of the effects of a total solar eclipse on weather with varying degrees of cloud cover using a local numerical weather prediction model

The importance of renewable energies for the European electricity market is growing rapidly. This presents transmission grids and the power market in general with new challenges which stem from the higher spatiotemporal variability of power generation. This uncertainty is due to the fact that renewable power production results from weather phenomena, thus making it difficult to plan and control. We present a sensitivity study of a total solar eclipse in central Europe in March. The weather in Germany and Europe was modeled using the German Weather Service's local area models COSMO-DE and COSMO-EU, respectively (http://www.cosmo-model.org/). The simulations were performed with and without considering a solar eclipse for the following 3 situations: 1. An idealized, clear-sky situation for the entire model area (Europe, COSMO-EU) 2. A real weather situation with mostly cloudy skies (Germany, COSMO-DE) 3. A real weather situation with mostly clear skies (Germany, COSMO-DE) The data should help to evaluate the effects of a total solar eclipse on the weather in the planetary boundary layer. The results show that a total solar eclipse has significant effects particularly on the main variables for renewable energy production, such as solar irradiation and temperature near the ground.

Lagrangian back-tracing results for Kohnen station; output of time dependent numerical experiment with a 3D nested Antarctic ice sheet model

A nested ice flow model was developed for eastern Dronning Maud Land to assist with the dating and interpretation of the EDML deep ice core. The model consists of a high-resolution higher-order ice dynamic flow model that was nested into a comprehensive 3-D thermomechanical model of the whole Antarctic ice sheet. As the drill site is on a flank position the calculations specifically take into account the effects of horizontal advection as deeper ice in the core originated from higher inland. First the regional velocity field and ice sheet geometry is obtained from a forward experiment over the last 8 glacial cycles. The result is subsequently employed in a Lagrangian backtracing algorithm to provide particle paths back to their time and place of deposition. The procedure directly yields the depth-age distribution, surface conditions at particle origin, and a suite of relevant parameters such as initial annual layer thickness. This paper discusses the method and the main results of the experiment, including the ice core chronology, the non-climatic corrections needed to extract the climatic part of the signal, and the thinning function. The focus is on the upper 89% of the ice core (appr. 170 kyears) as the dating below that is increasingly less robust owing to the unknown value of the geothermal heat flux. It is found that the temperature biases resulting from variations of surface elevation are up to half of the magnitude of the climatic changes themselves.