Chemical composition of waters, suspended matter, bottom sediments, and benthic organisms along a section from the Ob River estuary (Obskaya Guba) to the central Kara Sea

Biogeochemical behavior of a group of heavy metals and metalloids in water (including their dissolved and suspended particulate forms), bottom sediments, and zoobenthos was studied in the Ob River estuary (Obskaya Guba) - Kara Sea section on the basis of data obtained during Cruise 54 of R/V Akademik Mstislav Keldysh in September-October 2007. Changes in ratios of dissolved and particulate forms of Fe, Mn, Zn, Cu, Pb, Cd, and As were shown, as well as growth of adsorbed fractions of the elements in near-bottom suspended matter under mixing of riverine and marine waters. Features of chemical element accumulation in typical benthic organisms of the Obskaya Guba and the Kara Sea were revealed, and their concentrating factors were calculated based on specific conditions of the environment. It was shown that shells of bivalves possessing higher biomass compared to other groups of organisms in the Obskaya Guba play an important role in deposition of heavy metals. In the Obskaya Guba mollusks accumulate Cd and Pb at the background level, whereas Cu and Zn contents appear to be higher than the background level.

Chemical measurements from the EPICA Dome C core

Sea ice and dust flux increased greatly in the Southern Ocean during the last glacial period. Palaeorecords provide contradictory evidence about marine productivity in this region, but beyond one glacial cycle, data were sparse. Here we present continuous chemical proxy data spanning the last eight glacial cycles (740,000 years) from the Dome C Antarctic ice core. These data constrain winter sea-ice extent in the Indian Ocean, Southern Ocean biogenic productivity and Patagonian climatic conditions. We found that maximum sea-ice extent is closely tied to Antarctic temperature on multi-millennial timescales, but less so on shorter timescales. Biological dimethylsulphide emissions south of the polar front seem to have changed little with climate, suggesting that sulphur compounds were not active in climate regulation. We observe large glacial-interglacial contrasts in iron deposition, which we infer reflects strongly changing Patagonian conditions. During glacial terminations, changes in Patagonia apparently preceded sea-ice reduction, indicating that multiple mechanisms may be responsible for different phases of CO2 increase during glacial terminations. We observe no changes in internal climatic feedbacks that could have caused the change in amplitude of Antarctic temperature variations observed 440,000 years ago.

Chemical and Sr isotopic compositions and timing of carbonate mineral precipitation, ODP Leg 115

The strontium isotope ratios of authigenic carbonates from Indian Ocean sea-floor basalts have been used to determine the timing of carbonate mineral precipitation and fluid flow. The samples include calcites from 57.2 Ma crust from Ocean Drilling Project (ODP) Site 715, and calcites, aragonites, and siderites from 63.7 Ma crust from ODP Site 707. At Site 715, calcite precipitation may have begun at any time after the basalts cooled, and it continued until approximately 31 Ma, or 26 m.y. after basalt eruption. At Site 707, aragonite and siderite did not begin to precipitate until about 36 Ma, almost 30 m.y. after basalt eruption, and continued to precipitate until at least 30 and 28 Ma, respectively. Calcite precipitation began at approximately 32 Ma and continued until 22 Ma. These ages suggest that vein mineral deposition and low-temperature fluid circulation in the ocean crust may continue for much longer periods of time than previously observed.

Chemical and Sr isotopic compositions of pore fluids and marine carbonates from ODP Hole 130-807A

The 87Sr/86Sr ratios and Sr concentrations in sediment and pore fluids are used to evaluate the rates of calcite recrystallization at ODP Site 807A on the Ontong Java Plateau, an 800-meter thick section of carbonate ooze and chalk. A numerical model is used to evaluate the pore fluid chemistry and Sr isotopes in an accumulating section. The deduced calcite recrystallization rate is 2% per million years (%/Myr) near the top of the section and decreases systematically in older parts of the section such that the rate is close to 0.1/age (in years). The deduced recrystallization rates have important implications for the interpretation of Ca and Mg concentration profiles in the pore fluids. The effect of calcite recrystallization on pore fluid chemistry is described by the reaction length, L, which varies by element, and depends on the concentration in pore fluid and solid. When L is small compared to the thickness of the sedimentary section, the pore fluid concentration is controlled by equilibrium or steady-state exchange with the solid phase, except within a distance L of the sediment-water interface. When L is large relative to the thickness of sediment, the pore fluid concentration is mostly controlled by the boundary conditions and diffusion. The values of L for Ca, Sr, and Mg are of order 15, 150, and 1500 meters, respectively. L_Sr is derived from isotopic data and modeling, and allows us to infer the values of L_Ca and L_Mg. The small value for L_Ca indicates that pore fluid Ca concentrations, which gradually increase down section, must be equilibrium values that are maintained by solution-precipitation exchange with calcite and do not reflect Ca sources within or below the sediment column. The pore fluid Ca measurements and measured alkalinity allow us to calculate the in situ pH in the pore fluids, which decreases from 7.6 near the sediment-water interface to 7.1+/-0.1 at 400-800 mbsf. While the calculated pH values are in agreement with some of the values measured during ODP Leg 130, most of the measurements are artifacts. The large value for L_Mg indicates that the pore fluid Mg concentrations at 807A are not controlled by calcite-fluid equilibrium but instead are determined by the changing Mg concentration of seawater during deposition, modified by aqueous diffusion in the pore fluids. We use the pore fluid Mg concentration profile at Site 807A to retrieve a global record for seawater Mg over the past 35 Myr, which shows that seawater Mg has increased rapidly over the past 10 Myr, rather than gradually over the past 60 Myr. This observation suggests that the Cenozoic rise in seawater Mg is controlled by continental weathering inputs rather than by exchange with oceanic crust. The relationship determined between reaction rate and age in silicates and carbonates is strikingly similar, which suggests that reaction affinity is not the primary determinant of silicate dissolution rates in nature.

Mean chemical characteristics and volcano signatures of ice cores from Belukha, the Everest and three Svalbard sites

Ice cores from outside the Greenland and Antarctic ice sheets are difficult to date because of seasonal melting and multiple sources (terrestrial, marine, biogenic and anthropogenic) of sulfates deposited onto the ice. Here we present a method of volcanic sulfate extraction that relies on fitting sulfate profiles to other ion species measured along the cores in moving windows in log space. We verify the method with a well dated section of the Belukha ice core from central Eurasia. There are excellent matches to volcanoes in the preindustrial, and clear extraction of volcanic peaks in the post-1940 period when a simple method based on calcium as a proxy for terrestrial sulfate fails due to anthropogenic sulfate deposition. We then attempt to use the same statistical scheme to locate volcanic sulfate horizons within three ice cores from Svalbard and a core from Mount Everest. Volcanic sulfate is <5% of the sulfate budget in every core, and differences in eruption signals extracted reflect the large differences in environment between western, northern and central regions of Svalbard. The Lomonosovfonna and Vestfonna cores span about the last 1000 years, with good extraction of volcanic signals, while Holtedahlfonna which extends to about AD1700 appears to lack a clear record. The Mount Everest core allows clean volcanic signal extraction and the core extends back to about AD700, slightly older than a previous flow model has suggested. The method may thus be used to extract historical volcanic records from a more diverse geographical range than hitherto.

Physical and chemical investigations on ice cores from the Filchner-Ronne Ice Shelf

The accumulation and distribution of the 2H content of near-surface layers in the eastern part of the Ronne Ice Shelf were determined from 16 firn cores drilled to about 10 m depth during the Filchner IIIa and IV campaigns in 1990 and 1992, respectively. The cores were dated stratigraphically by seasonal d2H variations in the firn. In addition, 3H and high-resolution chemical profiles were used to assist in dating. Both the accumulation rate and the stable-isotope content decrease with increasing distance from the ice edge: the d2H values range from about -195 per mil at the ice edge to -250 per mil at BAS sites 5 and 6, south of Henry Ice Rise, and the accumulation rates from about 210 to 90 kg/m**2/a. The d2H values of the near-surface firn and the 10 m firn temperatures (Theta) at individual sites are very well correlated: ddelta2H/dTheta=(10.3±0.6)per mil /K; r = 0.97. The d2H profiles of the two ice cores B13 and B15 drilled in 1990 and 1992 to 215 and 320 m depth, respectively, reflect the gradual depletion in 2H in the firn upstream of the drill sites. Comparison with tlie surface data indicates that the ice above 142 m in core B15 and above 137 m in core B13 was deposited on the ice shelf, whereas the deeper ice, down to 152.8 m depth, most probably originated from the margin of the Antarctic ice sheet.

Chemical composition and dated ages of detrital smectites in sediments at DSDP Legs 43, 48 and 50

Mineralogical, morphological and isotopic (Rb-Sr and K-Ar) determinations were made on some detrital smectites of Palaeocene and Cenomanian ages from DSDP. drillings in the Atlantic Ocean. These minerals are not inert in their depositional environment; authigenic laths grow on detrital sheets with sharp borders. This authigenesis could occur slightly after deposition in a closed system, for some of these smectites. It has been tentatively quantified by the Rb-Sr and K-Ar isotopic methods, which seem also well suited to evaluate the chemical extent of this authigenesis. At least, no preferential loss of 40Ar vs. 87Sr could be detected in the minerals, even in those which are smaller than 0.2 ?m.

Physical and chemical analysis of firn cores from Ronne Ice Shelf, Antarctica

This data on the distribution of the accumulation rate and 18O content of near-surface layers in the eastern part of the Ronne Ice Shelf, Antarctica, were derived from an analysis of 16 firn cores. The firn cores were drilled along the traverse route of the Filchner-V-Campaign in 1995. The traverse followed an ice flowline of the Foundation Ice Stream and reached the margin of the inland ice, an area which has not yet been investigated. On the ice shelf the accumulation rates decrease with distance from the coast. Ascending to the inland ice the accumulation rates again reach almost coastal values. This regional distribution is in agreement with the temperature gradient along the traverse. The 18O content of the near-surface layers is closely related to the 10 m firn temperature. They strongly decrease from the grounding line towards the inland ice. At the southernmost site at 1100 m a.s.l., the mean d18O value of the firn decreases to -40?. Ice with that isotopic signature was found in cores from the central part of the Ronne Ice Shelf just above the marine ice layer, indicating that it originates from this area. All ice deposited as snow further south was melted beneath the ice shelf after passing the grounding-line area. The time series of accumulation rate and 18O content reveal no climatic trend during the last 30-50 years.

Contents of radioactive elements, main chemical composition, and sedimentation rates of bottom sediments from some stations in the Southeast Pacific

Gamma-spectrometric analysis was used for six sediment cores from the area occupied by metalliferous sediments in the Southeast Pacific. In five of these cores vertical distribution curves of 230Th enabled positions of equilibrium points to be determined and sediments to be dated. The ionium curve was normalized for one core. Vertical distribution of 230Th in metalliferous sediments resembles its distribution in normal ocean-floor sediments beyond the area of influence of active ridges. Sedimentation rates lay within the range 0.7-12.3 mm/ky.

Physico-chemical parameters of sediment core PG1975-1 (09-Tik-05) from a Tundra Lake, Northeastern Siberia

The relationships between thermokarst activity, limnogeological processes and climate change in the Siberian Arctic are not well understood. The objective of this paper is to identify the factors controlling the patterns of deposition, using grain size distribution, organic content, elemental composition and mineralogical composition of a 137-cm long sediment core with a maximum age of ~10.9 cal. kyr BP from Lake El'gene-Kyuele in the tundra of northeastern Siberia. Eight fine sand layers are attributed to depositional events associated with thaw slump activity acting upon orthogonally oriented patterns of ice-wedge networks in the ice-rich permafrost on the NW margin of the lake catchment. Sr/Rb ratios, which correspond to the total feldspar and illite content, serve as high-resolution grain size proxies. The Br content relates to the total organic carbon content, and the Fe/Mn ratio reflects the degree of oxidisation. Our results indicate a relationship between repeated phases of fine sand input and retrogressive thaw slumping dependent on hydroclimate variability and orthogonally oriented ice-wedge networks within the catchment.

Chemical and isotope compositions of sediments from DSDP Hole 86-576A and Core LL44-GPC-3

A record of changes in Pb and Sr isotopic composition of two cores (DSDP 86-576A and LL44- GPC-3) from the red clay region of the central North Pacific has been determined for the past 60-65 million years. The isotope records of the eolian silicate fraction of the red clays reflect the change in source area as the core sites migrated under different wind systems. The Sr isotope compositions of eolian silicate material are consistent with Asian loess and North American arc volcanism that has been recognized from mineralogical studies. The silicate-bound eolian Pb isotopic compositions similarly reflect Asian loess and arc volcanism. The isotope records of three ferromanganese crusts from similar locations in the central Pacific are similar to the eolian component of red clays, but offset to less radiogenic values. This may be due to two mechanisms: (1) Pb that can be removed from eolian material by seawater is much less radiogenic, or less likely (2) hydrothermal Pb can be transported further away from venting sites through particle exchange with seawater, despite hydrothermal venting acting as a net sink of oceanic Pb. The temporal changes in Pb isotopes in the ferromanganese crusts, bulk red clays and eolian silicates are similar although offset from each other suggesting that eolian deposition is an important source of Pb to seawater and to ferromanganese crusts. This contrasts with the Atlantic and Southern Ocean where more intense deep water flow leads to isotopic gradients in FeMn crusts that do not reflect surface water conditions immediately above the crust. A mechanism is proposed which accounts for Pacific deepwater Pb being isotopically influenced by eolian deposition.

Chemical composition of DSDP and ODP cherts

Rare earth element (REE), major, and trace element abundances and relative fractionations in forty nodular cherts sampled by the Deep Sea Drilling Project (DSDP) and Ocean Drilling Program (ODP) indicate that the REE composition of chert records the interplay between terrigenous sources and scavenging from the local seawater. Major and (non-REE) trace element ratios indicate that the aluminosilicate fraction within the chert is similar to NASC (North American Shale Composite), with average Pacific chert including ~7% NASC-like particles, Indian chert ~11% NASC, Atlantic chert ~17% NASC, and southern high latitude (SHL) chert 53% NASC. Using La as a proxy for sum REE, approximations of excessive La (the amount of La in excess of that supplied by the detrital aluminosilicate fraction) indicate that Pacific chert contains the greatest excessive La (85% of total La) and SHL chert the least (38% of total La). As shown by interelement associations, this excessive La is most likely an adsorbed component onto aluminosilicate and phosphatic phases. Accordingly, chert from the large Pacific Ocean, where deposition occurs relatively removed from significant terrigenous input, records a depositional REE signal dominated by adsorption of dissolved REEs from seawater. Pacific chert Ce/Ce* <<1 and normative La/Yb ~ 0.8-1, resulting from adsorption of local Ce-depleted seawater and preferential adsorption of LREEs from seawater (e.g., normative La/Yb ~0.4), which increases the normative La/Yb ratio recorded in chert. Chert from the Atlantic basin, a moderately sized ocean basin lined by passive margins and with more terrigenous input than the Pacific, records a mix of adsorptive and terrigenous REE signals, with moderately negative Ce anomalies and normative La/Yb ratios intermediate to those of the Pacific and those of terrigenous input. Chert from the SHL region is dominated by the large terrigenous input on the Antarctic passive margin, with inherited Ce/Ce* ~1 and inherited normative La/Yb values of ~1.2-1.4. Ce/Ce* does not vary with age, either throughout the entire data base or within a particular basin. Overall, Ce/Ce* does not correlate with P2O5 concentrations, even though phosphatic phases may be an important REE carrier.

Chemical composition of basalts from DSDP Hole 46-396B

Samples of crystalline basalt from Site 396 B are all more or less altered, usually in strongly zoned patterns. Evidence has been found for several related or independent alteration stages, including (1) minor localized deuteric (amphibole and mixed clay minerals in miarolitic voids); (2) minor widespread nonoxidizing (pyrite on walls of vugs and cracks); (3) localized diffusion-controlled rug filling ("glauconite" in black halos); (4) pervasive low level oxidizing (transformation of titanomagnetite to cation-deficient titanomaghemite); (5) localized diffusion-controlled strongly oxidizing (breakdown of olivine and titanomaghemite in brown zones). Plagioclase and pyroxene are essentially unaltered. Detailed analyses of gray and brown zones in pillow basalts show that low temperature oxidation has proceeded in a step-wise fashion, with the relative stabilities of the igneous minerals controlling the steps. Secondary minerals that crystallized from pore fluids on to the walls of vugs may or may not be related to local alteration of primary phases. During the most intense stage of alteration, brown oxidation zones grew into basalt fragments behind diffusion controlled fronts. The specific reactions and products of this stage differ among the lithologic units at the site. A model is proposed whereby efficient seawater circulation through the pillow units maintains the pH and the concentrations of Mg2+ and SiO2 dissolved at low levels in pore fluids, so that olivine is replaced by hydrous ferric oxides, and Mg and SiO2 are removed from the system. In the massive basalt unit, circulation is somewhat less effective and Mg and SiO2 are retained in smectites. Deposition of authigenic minerals in the sequence saponite/Fe-Mn oxides/phillipsite/calcite in vugs and cracks may reflect the gradual closing of the systems and probably signals the end of localized oxidation in parts of the core. Mineral compositions indicate that most of these deposits formed from seawater at very low temperature.

Mineralogical-sedimentological and chemical investigation of sediments from Cross Bank off Florida

The sediments of a core of.1.55 m length taken on the windward side of the Cross Bank, Florida Bay, are clearly subdivided into two portions, as shown by grain size analysis: silt-sized particles predominate in the relatively homogeneous lower two thirds of the core. This is succeeded abruptly by a thin layer of sand, containing fragments of Halimeda. They indicate a catastrophic event in the Florida Bay region, because Halimeda does not grow within Florida Bay. Above this layer, the amount of sand decreases at first and then continuously increases right to the present sediment-water-interface. The median and skewness increase simultaneously with the increase in the sand and granule portion. We assume that the changing grain size distribution was determined chiefly by the density of the marine flora: during the deposition of the lower two thirds of the core a dense grass cover acted as a sediment catcher for the fine-grained detritus washed out of the shallow basins of the Florida Bay, and simultaneously prohibited renewed reworking. Similar processes go on today on the surface of most mud banks of Florida Bay. The catastrophic event indicated by the sand layer probably changed the morphology of the bank to such an extent that the sampling point was shifted more to the windward side of the bank. This side is characterized by less dense plant growth. Therefore, less detritus could be caught and the material deposited could be reworked. The pronounced increase in skewness in the upper third of the core certainly indicates a strong washing out of the smaller-sized particles. The sediments are predominantly made up of carbonates, averagely 88.14 percent. The average CaCO3-content is 83.87 percent and the average MgCO3-content amounts to 4.27 percent. The chief carbonate mineral is aragonite making up 60.1 percent of the carbonate portion in the average, followed by high-magnesian calcite (33.8 percent) and calcite (6.1 percent). With increasing grain size the aragonite clearly increases at the cost of high-magnesian calcite in the upper third of the core. Chemically, this is shown by an increase of the CaCO3 : MgCO3-ratio. This increase is mainly caused by the more common occurrence of aragonitic fragments of mollusks in the coarse grain fractions. The bulk of the carbonates is made up of mollusks, foraminifera, ostracods, and - to a much lesser extent - of corals, worm-tubes, coccolithophorids, and calcareous algae, as shown by microscopic investigations. The total amount of the carbonate in the sediments is biogenic detritus with the possible exception of a very small amount of aragonite needles in the clay and fine silt fraction. The individual carbonate components of the gravel and sand fraction can be relatively easy identified as members of a particular animal or plant group. This becomes very difficult in the silt and clay fraction. Brownish aggregates are very common in the coarse and medium silt fraction. It was not always possible to clarify their origin (biogenic detritus, faecal pellets or carbonate particles cemented by carbonates or organic slime, etc.). Organic matter (plant fragments, rootlets), quartz, opal (siliceous sponge needles), and feldspar also occur in the sediments, besides carbonates. The lowermost part of the core has an age of 1365 +/- 90 years, as shown by 14C analysis.