Chemical and isotope compositions of interstitial water in sediments from Mediterranean basin at DSDP Sites 42-372 and 42-374

The Br/Cl, Li/Cl and B/Cl ratios and boron isotope compositions of hypersaline pore fluids from DSDP Sites 372 and 374 were measured in an attempt to evaluate the origin of the brines. In Site 374 the relationships between the Cl concentrations (up to 5000 mM) and Br/Cl (~0.012), Na/Cl (as low as 0.1), B/Cl (0.0025), and d11B values (43-55?) of the deep pore water between 380 and 405 mbsf, located within the Messinian sediments, reflect remnants of ~65-fold evaporated sea water. The original evaporated sea water was modified by: (1) dilution with overlying or less saline water by about 30%; and (2) slight dissolution of NaCl evaporites. The variations in d11B show a continuous increase in d11B values with depth in Site 374, up to 66.7? at a depth of 300 mbsf (Upper Pliocene marl sediments). The conspicuous 11B enrichment trend is consistent with elemental boron depletion, which was calculated from the expected boron concentrations of evaporated sea water with corresponding Br/Cl and Na/Cl ratios. Li/Cl variations also show a depletion of Li relative to evaporated sea water. The apparent depletions of B and Li, as well as the 11B enrichment, reflect uptake of these elements by clay minerals at low water/sediment ratios.

Concentrations of aliphatic hydrocarbons and hexachlorocyclohexane isomers in under-ice water, snow, and sea ice from the Greenland Sea

Data on concentrations of aliphatic hydrocarbons and isomers of hexachlorocyclohexane in specimens of various natural environments (water, snow, and ice) of the Greenland Sea obtained during field studies on the ice breaker Otto Shmidt are presented. Analyses were carried out with gas chromatographs using capillary and packed columns. Concentrations of aliphatic and chlorinated hydrocarbons were higher in snow and ice specimens than in sea water and were also higher in less saline water beneath ice. It is concluded that pollutants in this ocean area are at the background level.

(Table 1) Deuterium ratios, chloride content and hydrate volume of pore water and hydrate meltwater from ODP Site 164-996

Site 996 is located above the Blake Diapir where numerous indications of vertical fluid migration and the presence of hydrate existed prior to Ocean Drilling Program (ODP) Leg 164. Direct sampling of hydrates and visual observations of hydrate-filled veins that could be traced 30-40 cm along cores suggest a connection between fluid migration and hydrate formation. The composition of pore water squeezed from sediment cores showed large variations due to melting of hydrate during core recovery and influence of saline water from the evaporitic diapir below. Analysis of water released during hydrate decomposition experiments showed that the recovered hydrates contained significant amounts of pore water. Solutions of the transport equations for deuterium (d2H) and chloride (Cl-) were used to determine maximum (d2H) and minimum (Cl-) in situ concentrations of these species. Minimum in situ concentrations of hydrate were estimated by combining these results with Cl- and d2H values measured on hydrate meltwaters and pore waters obtained by squeezing of sediments, by the means of a method based on analysis of distances in the two-dimensional Cl- d2H space. The computed Cl- and d2H distribution indicates that the minimum hydrate amount solutions are representative of the actual hydrate amount. The highest and mean hydrate concentrations estimates from our model are 31% and 10% of the pore space, respectively. These concentrations agree well with visual core observations, supporting the validity of the model assumptions. The minimum in situ Cl- concentrations were used to constrain the rates of upward fluid migration. Simulation of all available data gave a mean flow rate of 0.35 m/k.y. (range: 0.125-0.5 m/k.y.).

Radionuclide measurements in sediments and water of the Kara Sea

In this report, the results of a 2000-2001 radiogeoecological investigation are presented for the region of the Ob and Yenisei estuaries and the adjacent Kara Sea. In order to study the behaviour and migration of Cs, Sr and Pu radionuclides in a river - sea system experimental research on the distribution of these radionuclides in the water column and surface sediments has been carried out. In addition, the role of suspended and dissolved organic matter on the behaviour of radionuclides in water solutions has been studied. The 137Cs and 239,240Pu concentrations in the upper 0-2cm layer of the sediments varied between 1,4 and 50,0 Bq/kg, with a mean of 12,4 Bq/kg, and between 0,065-1,96 Bq/kg, with a mean of 0,62 Bq/kg, respectively. There is a direct relationship of a specific radioactivity of 137Cs and 239,240Pu in the sediments and the content of clay fraction. The 137Cs, 90Sr and 239,240Pu concentrations in the water samples varied between 0,4 and 7,0 Bq/m**3 (mean of 3,6 Bq/m**3), 0,4 and 9,7 Bq/m**3 (mean of 3,3 Bq/m**3), and 0,01-0,3 Bq/m**3 (mean of 0,02 Bq/m**3), respectively. In the water samples the concentration of the water-soluble species l37Cs increases with increasing salinity, whereas the concentration of the 90Sr-radionuclide decreases with increasing salinity. This may be related to the physico-chemical behaviour of these radionuclides in water solutions and the influence of several sources on radioactive pollution in this basin. In sea water the suspended matter may absorb up to 10% 137Cs, 90Sr and 239,240Pu, in river water samples these values may reach 15-30%. More than 50% 90Sr and 239,240Pu is able to form complexes with dissolved organic matter. This effect is smaller in saline water. The comparison of the data of 137Cs radioactivity in the surface sediments in 1995 and 2000-2001 showed that the level of radioactivity has decreased.

Stable isotope ratios from foraminfera in Kara Sea sediments

Ostracods secrete their valve calcite within a few hours or days, therefore, its isotopic composition records ambient environmental conditions of only a short time span. Hydrographic changes between the calcification of individuals lead to a corresponding range (max.-min.) in the isotope values when measuring several (>=5) single valves from a specific sediment sample. Analyses of living (stained) ostracods from the Kara Sea sediment surface revealed high ranges of >2per mil of d18O and d13C at low absolute levels (d18O: <3per mil, d13C: <-3per mil) near the river estuaries of Ob and Yenisei and low ranges of not, vert, similar1per mil at higher absolute levels (d18O: 2-5.4per mil, d13C: -3 per mil to -1.5per mil) on the shelf and in submarine paleo-river channels. Comparison with a hydrographic data base and isotope measurements of bottom water samples shows that the average and the span of the ostracod-based isotope ranges closely mirror the long-term means and variabilities (standard deviation) of bottom water temperature and salinity. The bottom hydrography in the southern part of the Kara Sea shows strong response to the river discharge and its extreme seasonal and interannual variability. Less variable hydrographic conditions are indicative for deeper shelf areas to the north, but also for areas near the river estuaries along submarine paleo-river channels, which act as corridors for southward flowing cold and saline bottom water. Isotope analyses on up to five single ostracod valves per sample in the lower section (8-7 cal. ka BP) of a sediment core north of Yenisei estuary revealed d18O and d13C values which on average are lower by 0.6? in both, d18O and d13C, than in the upper core section (<5 cal. ka BP). The isotope shifts illustrate the decreasing influence of isotopically light river water at the bottom as a result of the southward retreat of the Yenisei river mouth from the coring site due to global sea level rise. However, the ranges (max.-min.) in the single-valve d18O and d13C data of the individual core samples are similar in the upper and in the lower core section, although a higher hydrographic variability is expected prior to 7 cal. ka BP due to river proximity. This lack of variability indicates the southward flow of cold, saline water along a submarine paleo-river channel, formerly existing at the core location. Despite shallowing of the site due to sediment filling of the channel and isostatic uplift of the area, the hydrographic variability at the core location remained low during the Late Holocene, because the shallowing proceeded synchronously with the retreat of the river mouth due to the global sea level rise

Physical oceanography during UPAT cruise to the Amvrakikos Gulf, August 2009

Oceanographic research in the Amvrakikos Gulf in Western Greece, a semi-enclosed embayment isolated from the Ionian Sea by a narrow, shallow sill, has shown that it is characterised by a fjord-like oceanographic regime. The Gulf is characterised by a well-stratified two layer structure in the water column made up of a surface layer and a bottom layer that are separated by a strong pycnocline. At the entrance over the sill, there is a brackish water outflow in the surface water and a saline water inflow in the near-bed region. This morphology and water circulation pattern makes the Amvrakikos Gulf the only Mediterranean Sea fjord. The investigations have also shown that the surface layer is well oxygenated, whereas in the pycnocline, the dissolved oxygen (DO) declines sharply and finally attains a value of zero, thus dividing the water column into oxic, dysoxic and anoxic environments. At the dysoxic/anoxic interface, at a depth of approximately 35 m, a sharp redox cline develops with Eh values between 0 and 120 mV occurring above and values between 0 and -250 mV occurring below, where oxic and anoxic biochemical processes prevail, respectively. On the seafloor underneath the anoxic waters, a black silt layer and a white mat cover resembling Beggiatoa-like cells are formed. The dysoxic/anoxic conditions appeared during the last 20 to 30 years and have been caused by the excessive use of fertilisers, the increase in animal stocks, intensive fish farming and domestic effluents. The inflicted dysoxia/anoxia has resulted in habitat loss on the seafloor over an area that makes up just over 50% of the total Gulf area and approximately 28% of the total water volume. Furthermore, anoxia is also considered to have been responsible for the sudden fish mortality which occurred in aquaculture rafts in the Gulf in February 2008. Therefore, anoxic conditions can be considered to be a potential hazard to the ecosystem and to the present thriving fishing and mariculture industry in the Gulf.

Oceanographic data in the Greenland Sea and around Svalbard in 1991-1993

The Arctic Ocean is connected with the North Atlantic Ocean by the Fram Strait between Greenland and Svalbard. The strait is located in the northern part of the Greenland Sea. In the eastern part of the strait, warm saline water flows northward as the West Spitsbergen Current; while in the western part, cold less-saline water flows southward as the East Greenland Current. The northwestern part of the Greenland Sea is normally covered with sea ice even in summer. Furthermore, this region is regarded as a major area where the Arctic sea ice is discharged into mid latitude oceans. Thus, this area plays an important role in heat and salt exchange processes in the Arctic marine system. The reveal exchange processes of water masses and ocean-atmosphere interaction in high-latitude oceans, a number of international research programs have been focused on the Greenland Sea and its surrounding waters. As one of the international Arctic research programs, oceanographic studies have been executed in cooperation with the Norsk Polarinstitutt and other institutes under the leadership of the National Institute of Polar Research since 1991. Japanese scientists have been carrying out field observations in and around Svalbard. The observations include not only physical measurements but also biological surveys. This report presents physical oceanographic data obtained in the Greenland Sea in 1992 and 1993, and data around Svalbard from 1991 to 1993.

Seismic multichannel reflection profiles from the Gulf of Cadiz, IODP Expedition 339

Sediments cored along the southwestern Iberian margin during Integrated Ocean Drilling Program Expedition 339 provide constraints on Mediterranean Outflow Water (MOW) circulation patterns from the Pliocene epoch to the present day. After the Strait of Gibraltar opened (5.33 million years ago), a limited volume of MOW entered the Atlantic. Depositional hiatuses indicate erosion by bottom currents related to higher volumes of MOW circulating into the North Atlantic, beginning in the late Pliocene. The hiatuses coincide with regional tectonic events and changes in global thermohaline circulation (THC). This suggests that MOW influenced Atlantic Meridional Overturning Circulation (AMOC), THC, and climatic shifts by contributing a component of warm, saline water to northern latitudes while in turn being influenced by plate tectonics.

(Table 1) Sea ice and snow characteristics and heat fluxes observed during R/V Aurora Australis cruise to East Antarctica in September/October 2007

The properties of snow on East Antarctic sea ice off Wilkes Land were examined during the Sea Ice Physics and Ecosystem Experiment (SIPEX) in late winter of 2007, focusing on the interaction with sea ice. This observation includes 11 transect lines for the measurement of ice thickness, freeboard, and snow depth, 50 snow pits on 13 ice floes, and diurnal variation of surface heat flux on three ice floes. The detailed profiling of topography along the transects and the d18O, salinity, and density datasets of snow made it possible to examine the snow-sea-ice interaction quantitatively for the first time in this area. In general, the snow displayed significant heterogeneity in types, thickness (mean: 0.14 +- 0.13 m), and density (325 +- 38 kg/m**3), as reported in other East Antarctic regions. High salinity was confined to the lowest 0.1 m. Salinity and d18O data within this layer revealed that saline water originated from the surface brine of sea ice in 20% of the total sites and from seawater in 80%. From the vertical profiles of snow density, bulk thermal conductivity of snow was estimated as 0.15 W/K/m on average, only half of the value used for numerical sea-ice models. Although the upward heat flux within snow estimated with this value was significantly lower than that within ice, it turned out that a higher value of thermal conductivity (0.3 to 0.4 W/K/m) is preferable for estimating ice growth amount in current numerical models. Diurnal measurements showed that upward conductive heat flux within the snow and net long-wave radiation at the surface seem to play important roles in the formation of snow ice from slush. The detailed surface topography allowed us to compare the air-ice drag coefficients of ice and snow surfaces under neutral conditions, and to examine the possibility of the retrieval of ice thickness distribution from satellite remote sensing. It was found that overall snow cover works to enhance the surface roughness of sea ice rather than moderate it, and increases the drag coefficient by about 10%. As for thickness retrieval, mean ice thickness had a higher correlation with ice surface roughness than mean freeboard or surface elevation, which indicates the potential usefulness of satellite L-band SAR in estimating the ice thickness distribution in the seasonal sea-ice zone.

(Table 3) Oxygen isotope ratios of benthic foraminifera from DSDP Hole 80-548

Presently, the intermediate depths of the North Atlantic Ocean are occupied by a great lens of warm, saline water whose source is the Mediterranean Sea. This water flows both westward and northward, finally entering the Norwegian Sea where it may contribute to the formation of North Atlantic Deep Water. The Late Neogene history of Mediterranean Outflow in the Atlantic can be monitored at DSDP-IPOD Site 548 on the continental slope Southwest of Ireland using benthic Foraminifera oxygen isotope values. Isotopic data from 154 samples indicate that Mediterranean water was absent from the mid-depth North Atlantic from 3.4 to 3.2 Ma ago. However, at about 2.9 Ma ago the isotopic values at Site 548 diverge from those recorded from the deep North Atlantic and they can be interpreted to indicate the appearance of a new water mass, possibly Mediterranean water, in the North Atlantic water column. This appearance may be related to climatic changes that occurred around the Mediterranean Basin at about 2.9 Ma ago. The analysis of 189 samples for grain-size distributions shows that a significant increase in the silt-size fraction occurs at the same level that isotopic analysis indicates a change in bottom waters at Site 548. The grainsize data support the hypothesis that mid-depth water-mass changes occurred at about 2.9 Ma ago.

Stable oxygen isotope record and benthic foraminiferal abundances in Cretaceous sediments of Demerara Rise

During the mid-Cretaceous period, the global subsurface oceans were relatively warm, but the origins of the high temperatures are debated. One hypothesis suggests that high sea levels and the continental configuration allowed high-salinity waters in low-latitude epicontinental shelf seas to sink and form deep-water masses (Brass et al., 1982, doi:10.1038/296620a0; Arthur and Natland, 1979; Chamberlin, 1906). In another scenario, surface waters in high-latitude regions, the modern area of deep-water formation, were warmed through greenhouse forcing (Bice and Marotzke, 2001, doi:10.1029/2000JC000561), which then propagated through deep-water circulation. Here, we use oxygen isotopes and Mg/Ca ratios from benthic foraminifera to reconstruct intermediate-water conditions in the tropical proto-Atlantic Ocean from 97 to 92 Myr ago. According to our reconstruction, intermediate-water temperatures ranged between 20 and 25 °C, the warmest ever documented for depths of 500-1,000 m. Our record also reveals intervals of high-salinity conditions, which we suggest reflect an influx of saline water derived from epicontinental seas around the tropical proto-North Atlantic Ocean. Although derived from only one site, our data indicate the existence of warm, saline intermediate waters in this silled basin. This combination of warm saline intermediate waters and restricted palaeogeography probably acted as preconditioning factors for the prolonged period of anoxia and black-shale formation in the equatorial proto-North Atlantic Ocean during the Cretaceous period.

Hydrology dataset based on 111 CTD stations in the North Aegean Sea during June 1998 from the project INTERREGAEGEAN

The combination of two research projects offered us the opportunity to perform a comprehensive study of the seasonal evolution of the hydrological structure and the circulation of the North Aegean Sea, at the northern extremes of the eastern Mediterranean. The combination of brackish water inflow from the Dardanelles and the sea-bottom relief dictate the significant differences between the North and South Aegean water columns. The relatively warm and highly saline South Aegean waters enter the North Aegean through the dominant cyclonic circulation of the basin. In the North Aegean, three layers of distinct water masses of very different properties are observed: The 20-50 m thick surface layer is occupied mainly by Black Sea Water, modified on its way through the Bosphorus, the Sea of Marmara and the Dardanelles. Below the surface layer there is warm and highly saline water originating in the South Aegean and the Levantine, extending down to 350-400 m depth. Below this layer, the deeper-than-400 m basins of the North Aegean contain locally formed, very dense water with different i/S characteristics at each subbasin. The circulation is characterised by a series of permanent, semi-permanent and transient mesoscale features, overlaid on the general slow cyclonic circulation of the Aegean. The mesoscale activity, while not necessarily important in enhancing isopycnal mixing in the region, in combination with the very high stratification of the upper layers, however, increases the residence time of the water of the upper layers in the general area of the North Aegean. As a result, water having out-flowed from the Black Sea in the winter, forms a separate distinct layer in the region in spring (lying between "younger" BSW and the Levantine origin water), and is still traceable in the water column in late summer.

Stable isotope ratios measured on carbonate tests from the Kara Sea

River discharge of Ob and Yenisei to the Kara Sea is highly variable on seasonal and interannual time scales. River water dominates the shallow bottom water near the river mouths, making it warmer and less saline but seasonally and interannually more changeable than bottom water on the deeper shelf. This hydrographic pattern shows up in measurements and modelling, and in stable isotope records (delta18O, delta13C) along the growth axis of bivalve shells and in multiple analyses of single benthic foraminiferal shells. Average isotope ratios increase, but sample-internal variability decreases with water depth and distance from river mouths. However, isotope records of bivalves and foraminifera of a sediment core from a former submarine channel of Yenisei River reveal a different pattern. The retreat of the river mouth from this site due to early Holocene sea level rise led to increasing average isotope values up core, but not to the expected decrease of the in-sample isotope variability. Southward advection of cold saline water along the palaeo-river channel probably obscured the hydrographic variability during the early Holocene. Later, when sediment filled the channel, the hydrographic variability at the core location remained low, because the shallowing proceeded synchronously with the retreat of the river mouth.

Magnesium/calcium and stable isotope ratios of planktonic foraminifera from the Timor Sea

We present sea surface and upper thermocline temperature records (60-100 yr temporal resolution) spanning Marine Isotope Stage 3 (~24-62 kyr BP) from IMAGES Core MD01-2378 (121°47.27'E and 13°04.95'S; 1783 m water depth) located in the outflow area of the Indonesian Throughflow within the Timor Sea. Stable isotopes and Mg/Ca of the near surface dwelling planktonic foraminifer Globigerinoides ruber (white) and the upper thermocline dwelling Pulleniatina obliquiloculata reveal rapid changes in the thermal structure of the upper ocean during Heinrich Events. Thermocline warming and increased delta18Oseawater (P. obliquiloculata record) during Heinrich Events 3, 4, and 5 reflect weakening of the relatively cool and fresh thermocline flow and reduced export of less saline water from the North Pacific and Indonesian Seas to the tropical Indian Ocean. Three main factors influenced Indonesian Throughflow variability during Marine Isotope Stage 3: (1) global slow-down in thermohaline circulation during Heinrich Events triggered by northern hemisphere cooling; (2) increased freshwater export from the Java Sea into the Indonesian Throughflow controlled by rising sea level from ~60 to 47 ka and (3) insolation related changes in Australasian monsoon with associated migration of hydrological fronts between Indian Ocean and Indonesian Throughflow derived water masses at ~46-40 ka.

Stable isotope analysis on planktic foraminifera in sediment cores from the eastern Mediterranean sapropel formation

During the late Pleistocene, sapropels (layers of organic-carbon rich sediment) formed throughout the entire Eastern Mediterranean Basin in close association with glacial/interglacial transitions. The current theory for the mechanism of sapropel formation involves a density stratification of the water column, due to the invasion of a large quantity of low-saline water, which resulted in oxygen depletion of the bottom waters. Most workers believe that this low-salinity water was glacial meltwater that entered the Mediterranean via the Black Sea and a series of interconnected glacial lakes, but the suggestion also has been made that the freshwater originated from the Nile River. In this study the oxygen isotope values of planktonic foraminifera,Globigerinoides ruber, have been examined in six gravity cores and one piston core from the southern Levantine Basin, and compared with the oxygen isotope records ofG. ruber from other areas of the Eastern Mediterranean. This study deals mainly with the latest sapropel which was deposited approximately 7000 to 9000 years ago. Results indicate that Nile discharge probably does reduce salinities somewhat in the immediate area surrounding the mouth of the Nile, but this water is rapidly mixed with the highly saline waters of the easternmost Mediterranean. Using a mixing equation and surface water salinity limitations, an approximate oxygen isotope balance of surface waters was calculated for the time of latest sapropel deposition. This calculation shows that neither Nile River discharge nor Black Sea input (nor both together) are large enough to account for the large-scale oxygen isotope depletion associated with latest sapropel deposition in the Eastern Mediterranean. This suggests that part of the isotopic change at Termination I is probably due to increased surface water salinities during the last glacial maximum. In addition, evidence from the timing of sapropel 1 deposition and the dissolved oxygen balance indicates that deposition of the latest sapropel is associated with increased surface water production of biogenic material, as much as three times higher than that of present day.