Nd concentrations and isotopic composition in the western Mediterranean Sea

The concentration and isotopic composition of Nd in water and particles collected in the western Mediterranean Sea are studied by two complementary approaches. The first examines local vertical profiles and time series; the second considers the global Nd budget of the whole western Mediterranean Sea. These two approaches are used to quantify the Nd inputs and the dissolved/particulate exchange processes in the water column. Two profiles of Nd in seawater in the Ligurian Sea taken in May and October 1992 show an average epsilon-Nd(0) = -9.6 ± 0.5. Seawater from the Strait of Sicily, representative of the eastern waters flowing into the western basin, is more radiogenic [epsilon-Nd(0) = -7.7 ± 0.6]. Profiles of particulate matter collected in sediment traps in coastal (Gulf of Lions) and offshore (Ligurian Sea) environments are also shown. Particles are enriched in Nd and are more radiogenic near the coast than offshore. Measurements of Nd concentration and epsilon-Nd(0) of external sources to the western Mediterranean Sea compared with the literature data demonstrate that particulate flux of atmospheric Saharan origin are more rich ([Nd] = 38 ± 10 µg/g) and less radiogenic [epsilon-Nd(0) = -13.0 ± 1.0] than riverine particulate discharge ([Nd] = 21.5 ± 4.4 µg/g; epsilon-Nd(0) = -10.1 ± 0.5), allowing to trace Nd particulate inputs in the water column. Nd atmospheric flux appears to be the major source into the whole western basin, although lateral advection of riverine material is the prevailing process in the coastal environment. Offshore, the vertical propagation of an important Saharan dust event has been recorded for two months in sediment traps at 80, 200 and 1000 m. The evolution of the resulting negative epsilon-Nd(0) peak along depth and time shows that the particles reach 200 m on a time scale of one week. For the first time, the Nd budget in the western Mediterranean basin is constrained by both concentrations and isotopic compositions measured in particles and seawater. Surface budget requires a remobilization of 30 ± 20% of particulate Nd input. In deep water, dissolved Nd concentrations are balanced by a scavenging of 10 ± 20% of the sinking particulate flux. On the other hand, the deep isotopic compositions suggest an exchange between 30 ± 20% of the sinking particles and the deep waters. The hypothesis of a non-stationary regime for the surface waters in the Ligurian Sea is also considered.

Chemical and isotopic composition of interstitial waters and hydrocarbon composition at ODP Site 184-1146

Bottom-simulating reflectors were observed beneath the southeastern slope of the Dongsha Islands in the South China Sea, raising the potential for the presence of gas hydrate in the area. We have analyzed the chemical and isotopic compositions of interstitial water, headspace gas, and authigenic siderite concretions from Site 1146. Geochemical anomalies, including a slight decrease of chlorine concentration in interstitial water, substantial increase of methane concentration in headspace gas, and 18O enrichment in the authigenic siderite concretion below 400 meters below seafloor are probably caused by the decomposition of gas hydrate. The low-chlorine pore fluids contain higher molecular-weight hydrocarbons and probably migrate to Site 1146 along faults or bedded planes.

Elemental and stable isotopic composition of some metalliferous and pelagic sediments at DSDP Leg 70 Holes

Nontronite, the main metalliferous phase of the Galapagos mounds, occurs at subsurface depths of about 2 to 20 meters; Mn-oxide material is limited to the upper 2 meters of the mounds. The nontronite forms intervals of up to a few meters' thickness, consisting essentially of 100% nontronite granules, which alternate with intervals of normal pelagic sediment. Electron microprobe analyses of nontronite granules from different core samples indicate that: (1) there is little difference in major element composition between nontronites from varying locations within the mounds, with adjacent granules from a given sample having very similar compositions; (2) individual granules show little internal variation in composition. This indicates that the granules are composed of a single mineral of essentially constant composition, consistent with relatively uniform conditions of Eh and composition during nontronite formation. Mn-oxide crusts have very low Fe contents, a feature characteristic of rapidly deposited Mn-oxide crusts formed under hydrothermal influences. The rare-earth element (REE) abundances of the nontronites are generally extremely low, totalling less than several ppm. Two samples have the negatively Ce anomaly typical of authigenic precipitates formed relatively rapidly from seawater. A Mn-oxide crust sample has low REE contents, typical of Mn-oxide crusts formed under hydrothermal influences, but no negative Ce anomaly. A sample of unusual Mn-Fe-oxide mud has relatively high REE concentrations and a seawater-type pattern; both of these features are also found for metalliferous sediments from the East Pacific Rise. The oxygen and hydrogen isotopic composition of the nontronites define a restricted field within a d18O-dD plot. In manganiferous sediments, d18O and dD appear to decrease with increase in the Mn-oxide content of the sediment. From the d18O values of the nontronites, formation temperatures in the range of about 20-30°C have been estimated. By comparison, temperatures of up to 11.5 °C at a 9-meter depth have been directly measured within the mounds (Corliss et al., 1979), and heat-flow data suggest present basement/sediment interface temperatures of 15-25°C. In a plot of Fe + Mn vs. d18O, the Mn-oxide crust and Mn-Fe-ooze plot near the tie-lines for authigenic Mn nodules and silicate phases, implying that they have formed in isotopic equilibrium with seawater at or close to bottom-water temperatures.

Methane concentration profiles and isotopic composition of sediment cores from the Black Sea

We present high resolution profiles for the methane concentration and the carbon isotope composition of methane from surface sediments and from the sediment-water transition in the Black Sea. At shallow water sites methane migrates from the sediment into the water column, and the magnitude of this upward migrating flux depends on the depth of the sulfate-methane transition (SMT) in the sediment. The isotope data reveal that the sediments at shallow water sites are a source for methane depleted in 13C relative to the isotope composition of methane in the water column. At deep water sites the methane concentration first decreases with depth in the sediment to reach lowest values at the Unit I to Unit II transition. Below this transition the concentration increases again. Numerical modeling of methane concentration and isotope data shows that high methane oxidation rates occur in the surface sediment layer, indicating that the removal of methane in the surface sediments is not related to the anaerobic oxidation of methane coupled to sulfate reduction that occurs a few meters deep in the sediment, at the SMT. Instead, near-surface methane consumption in the euxinic Black Sea sediments appears to be related to lithological stratification. Furthermore, a map of the diffusive methane fluxes in the Black Sea surface sediments indicates that approximately half of the Black Sea seafloor acts as a sink for methane and thus limits the flux of methane to the atmosphere.

Sulfur speciation and isotopic composition in waters and sediments from river and seawater mixing zones

Studies of sulfur behavior in the water column and in sediments in river and seawater mixing zone were conducted in three areas of the Black and Azov Seas. These investigations showed constancy of sulfate concentrations versus chlorinity. Sulfur isotope composition in sulfates of surface, bottom, and pore waters depended on sulfate contents and salinity. The dependence was complicated by partial sulfate depletion in pore water due to bacterial sulfate reduction and also by alteration of isotope composition. Surface sediments in mixing zones are characterized by intensive sulfate reduction, great variability of content and isotopic composition of reduced sulfur, and a low mean isotopic fractionation factor of sulfur.

Biostratigraphy and Sr isotopic composition of sediments from DSDP Legs 12, 14, 15, 17, 20-22, and 30

We present the data used to construct the Cenozoic and Cretaceous portion of the Phanerozoic curve of seawater 87Sr/86Sr that had been given in summary form by W.H. Burke co-workers. All Cenozoic samples (128) and 22 Cretaceous samples are foram-nannofossil oozes and limestones from DSDP cores distributed among 13 sites in the Atlantic, Pacific and Indian Oceans, and the Caribbean Sea. Non-DSDP Cretaceous samples (126) include limestone, anhydrite and phosphate samples from North America, Europe and Asia. Determination of the 87Sr/86Sr value of seawater at particular times in the past is based on comparison of ratios derived from coeval marine samples from widely separated geographic areas. These samples are characterized by a wide variety of diagenetic and burial histories. The large size and cosmopolitan nature of the data set decreases the likelihood that, among coeval data, systematic error has been introduced by a similar pattern of diagenetic alteration of the ratios. There is good clustering of data points throughout the Cenozoic and Cretaceous curve. The consistency of data is illustrated by Cenozoic and Cretaceous data plots that include a separate symbol for each DSDP site and non-DSDP sample location. More than 98% of the data points are enclosed by upper and lower lines that define a narrow band. For any given time, the correct seawater ratio probably lies within this band. A line drawn within the band represents our estimate of the actual seawater ratio as a function of time. The general configuration of the Cenozoic and Cretaceous curve appears to be strongly influenced by the history of plate interactions and sea-floor spreading. Specific rises and falls in the 87Sr/86Sr of seawater, however, may be caused by a variety of factors such as variation in lithologic composition of the crust exposed to weathering, configuration and topographic relief of continents, volcanic activity, rate of sea-floor spreading, extent of continental inundation by epeiric seas, and variations in both climate and paleooceanographic conditions. Many or all of these factors are probably related to global tectonic processes, yet their combined effect on the temporal variation of seawater 87Sr/86Sr can complicate a direct platetectonic interpretation for portions of the seawater curve.