Sediment properties, contents and accumulation rates of Hg in cores of Upper Quaternary sediments from the Deryugin Basin, Okhotsk Sea

The Hg distribution and some mineralogical-geochemical features of bottom sediments up to a depth of 10 m in the Deryugin Basin showed that the high and anomalous Hg contents in the Holocene deposits are confined to a spreading riftogenic structure and separate fluid vents within it. The accumulations of Hg in the the sediments were caused by its fluxes from gas and low-temperature hydrothermal vents under favorable oceanological conditions in the Holocene. The two mainly responsible for the high and anomalous Hg contents are infiltration (fluxes of hydrothermal or gas fluids from the sedimentary cover) and plume (Hg precipitation from water plumes with certain hydrochemical conditions forming above endogenous sources). The infiltration anomalies of Hg were revealed in the following environments: (1) near gas vents on the northeastern Sakhalin slope, where high Hg contents are associated only with Se and were caused by the accumulation of gases ascending from beneath the gas hydrate layer; (2) in the area of inferred occasionally operating low-temperature hydrothermal seeps in the central part of the Deryugin Basin, in which massive barite chimneys, hydrothermal Fe-Mn crusts, and anomalous contents of Mn, Ba, Zn, and Ni in sediments develop.

Organic matter composition of Cretaceous sediments of the central Pacific Ocean

Complete records of organic-carbon-rich Cretaceous strata were continuouslycored on the flanks of the Mid-Pacific Mountains and southern Hess Rise in the central North Pacific Ocean during DSDP Leg 62. Organic-carbon-rich laminated silicified limestones were deposited in the western Mid-Pacific Mountains during the early Aptian, a time when that region was south of the equator and considerably shallower than at present. Organic-carbon-rich, laminated limestone on southern Hess Rise overlies volcanic basement and includes 136 m of stratigraphic section of late Albian to early Cenomanian age. This limestone unit was deposited rapidly as Hess Rise was passing under the equatorial high-productivity zone and was subsiding from shallow to intermediate depths. The association of volcanogenic components with organic-carbon-rich strata on Hess Rise in the Mid-Pacific Mountains is striking and suggests that there was a coincidence of mid-plate volcanic activity and the production and accumulation of organic matter at intermediate water depths in the tropical Pacific Ocean during the middle Cretaceous. Pyrolysis assays and analyses of extractable hydrocarbons indicate that the organic matter in the limestone on Hess Rise is composed mainly of lipid-rich kerogen derived from aquatic marine organisms and bacteria. Limestones from the Mid-Pacific Mountains generally contain low ratios of pyrolytic hydrocarbons to organic carbon and low hydrogen indices, suggesting that the organic matter may contain a significant proportion of land-derived material, possibly derived from numerous volcanic islands that must have existed before the area subsided. The organic carbon in all samples analyzed is isotopically light (d13C -24 to -29 per mil) relative to most modern rine organic carbon, and the lightest carbon is also the most lipid-rich. There is a positive linear correlation between sulfur and organic carbon in samples from Hess Rise and from the Mid-Pacific Mountains. The slopes and intercepts of C-S regression lines however, are different for each site and all are different from regression lines for samples from modern anoxic marine sediments and from Black Sea cores. The organic-carbon-rich limestones on Hess Rise, the Mid-Pacific Mountains, and other plateaus and seamounts in the Pacific Ocean are not synchronous but do occur within the same general middle Cretaceous time period as organic-carbon-rich lithofacies elsewhere in the world ocean, particularly in the Atlantic Ocean. Strata of equivalent age in the deep basins of the Pacific Ocean are not rich in organic carbon, and were deposited in oxygenated environments. This observation, together with the evidence that the plateau sites were considerably shallower and closse to the equator during the middle Creataceous suggests that local tectonic and hydrographic conditions may have resulted in high surface-water productivity and the preservation of organic matter in an oxygen-deficient environment where an expanded mid-water oxygen minimum developed and impinged on elevated platforms and seamounts.

Chemical and Sr isotopic compositions of 3 step leachates and residues of bulk samples, zeolites, and smectites from Lower Miocene sediments at ODP Site 166-1007

Massive clinoptilolite authigenesis was observed at about 1105 meters below sea floor (mbsf) in lower Miocene wellcompacted carbonate periplatform sediments from the Great Bahama Bank [Ocean Drilling Program, ODP Leg 166, Site 1007]. The diagenetic assemblage comprises abundant zeolite crystallized within foraminifer tests and sedimentary matrix, as well as Mg smectites. In carbonate-rich deposits, the formation of the zeolite requires a supply of silica. Thus, the objective of the study is to determine the origin of the silica supply, its diagenetic evolution, and consequently the related implications on interpretation of the sedimentary record, in terms of local or global paleoceanographic change. For lack of evidence for any volcaniclastic input or traces of Si-enriched deep fluids circulation, an in situ biogenic source of silica is validated by isotopic data and chemical modeling for the formation of such secondary minerals in shallow-water carbonate sequences. Geochemical and strontium isotopic data clearly establish the marine signature of the diagenetic zeolite, as well as its contemporaneous formation with the carbonate deposition (Sr model ages of 19.6-23.2 Ma). The test of saturation for the pore fluids specifies the equilibrium state of the present mineralogical assemblage. Seawater-rock modeling specifies that clinoptilolite precipitates from the dissolution of biogenic silica, which reacts with clay minerals. The amount of silica (opal-A) involved in the reaction has to be significant enough, at least 10 wt.%, to account for the observed content of clinoptilolite occurring at the most zeolite-rich level. Modeling also shows that the observed amount of clinoptilolite (~19%) reflects an in situ and short-term reaction due to the high reactivity of primary biogenic silica (opal-A) until its complete depletion. The episodic occurrence of these well-lithified zeolite-rich levels is consistent with the occurrence of seismic reflectors, particularly the P2 seismic sequence boundary located at 1115 mbsf depth and dated as 23.2 Ma. The age range of most zeolitic sedimentary levels (biostratigraphic ages of 21.5-22 Ma) correlates well with that of the early Miocene glaciation Mi-1 and Mi-1a global events. Thus, the clinoptilolite occurrence in the shallow carbonate platform environment far from volcanogenic supply, or in other sensitive marine areas, is potentially a significant new proxy for paleoproductivity and oceanic global events, such as the Miocene events, which are usually recognized in deep-sea pelagic sediments and high latitude deposits.

Geochemical composition of sediments from ODP Site 164-997, Blake Ridge

Twenty-two trace elements in 355 sediment samples from Site 997 on the Blake Ridge were examined by inductively coupled plasma-optical emission spectrometry and inductively coupled plasma-mass spectrometry, for respective fractions of acid-soluble and insoluble compositions. Downhole profiles of these elements exhibit complicated fluctuations throughout late Miocene to Pleistocene, principally due to the variations in the acid-soluble fraction. Noncarbonate composition is given from the acid-insoluble residues, which permits us to recognize secular feature of selected element variance for four intervals. These intervals (I: 0-183 mbsf; II: 183- 440 mbsf; III: 440-618 mbsf; and IV: 618-750 mbsf) are interpreted to have originated from changes in the suite of sediments of particular sources and chemical composition, sedimentation rate, dilution of biogenic carbonate abundance, and possibly the current system that controlled deposition and reworking of the terrigenous materials.

Nannofossil datums and abundance in sediments from ODP Leg 164 sites

Twenty routinely used nannofossil datums in the late Neogene and Quaternary were identified at three Blake Ridge sites drilled during Leg 164. The quantitative investigation of the nannofossil assemblages in 236 samples selected from Hole 994C provide new biostratigraphic and paleoceanographic information. Although mostly overlooked previously, Umbilicosphaera aequiscutum is an abundant component of the late Neogene flora, and its last occurrence at ~2.3 Ma is a useful new biostratigraphic event. Small Gephyrocapsa evolved within the upper part of Subzone CN11a (~4.3 Ma), and after an initial acme, it temporarily disappeared for 400 k.y., between 2.9 and 2.5 Ma. Medium-sized Gephyrocapsa evolved in the latest Pliocene ~2.2 Ma), and after two short temporary disappearances, common specimens occurred continuously just above the Pliocene/Pleistocene boundary. The base of Subzone CN13b should be recognized as the beginning of the continuous occurrence of medium-sized (>4 µm) Gephyrocapsa. Stratigraphic variation in abundance of the very small placoliths and Florisphaera profunda alternated, indicating potential of the former as a proxy for the paleoproductivity. At this site, it is likely that upwelling took place during three time periods in the late Neogene (6.0-4.6 Ma, 2.3-2.1 Ma, and 2.0-1.8 Ma) and also in the early Pleistocene (1.4-0.9 Ma). Weak upwelling is also likely to have occurred intermittently through the late Pliocene. Due to the sharp and abrupt turnover of the nannofossils, which resulted from an evolution of very competitive species, the paleoproductivity of the late Pleistocene is not clear. The site was mostly in an oligotrophic central gyre setting during the 4.6- to 2.3-Ma interval, intermittently between 2.1 and 1.4 Ma, and continuously for the last several tens of thousand years.

Geotechnical engineering characterization of sediments at DSDP Leg 72 Holes

The hydraulic piston coring device (HPC-15) allows recovery of deep ocean sediments with minimal disturbance. The device was used during Leg 72 of the Deep Sea Drilling Project (DSDP) aboard the Glomar Challenger. Core samples were recovered from bore holes in the Rio Grande Rise in the southwest Atlantic Ocean. Relatively undisturbed sediment cores were obtained from Holes 515A, 516, 517, and 518. The results of shipboard physical property measurements and on-shore geotechnical laboratory tests on these cores are presented in this chapter. A limited number of 0.3 m cores were obtained and used in a series of geotechnical tests, including one-dimensional consolidation, direct shear, Atterburg limit, particle size analysis, and specific gravity tests. Throughout the testing program, attention was focused on assessment of sample disturbance associated with the HPC-15 coring device. The HPC-15 device limits sample disturbance reasonably well in terrigenous muds (clays). However, sample disturbance associated with coring calcareous sediments (nannofossil-foraminifer oozes) is severe. The noncohesive, granular behavior of the calcareous sediments is vulnerable to severe disturbance, because of the design of the sampling head on the device at the time of Leg 72. A number of modifications to the sampling head design are recommended and discussed in this chapter. The modifications will improve sample quality for testing purposes and provide longer unbroken core samples by reducing friction between the sediment column and the sampling tool.

Sulfur and iron speciations in bottom sediments from the southwest Caspian Sea

Speciations of sulfur (sulfide S, pyrite S, sulfate S) and of reactive iron (Fe3+, Fe2+, sulfide Fe) in bottom sediments have been studied in gravity cores and drill cores collected on the shelf of the southwest Caspian Sea. It has been shown that intensity of reduction processes, in particular sulfate reduction, as well as speciations of S and reactive Fe reflect the change of transgressive and regressive stages of the Caspian basin. Characteristic features for the investigated area are high sedimentation rate and high reactivity of organic matter entering bottom sediments.

Radiochemical analyses and contents of organic carbon and CaCO3 in equatorial Pacific Ocean sediments

Uranium series nuclide concentrations have been measured on sediments from five box cores from an equatorial Pacific transect. 230Thexcess activities show discontinuities at the Holocene-glacial boundary as dated by 14C. The glacial sedimentation rates determined by 230Th and 14C are 2.5-3.0 cm/kyr. The Holocene rates from 230Th are much lower than those dated by 14C (1.9-2.3 cm/kyr) because of carbonate dissolution. 230Th sedimentation fluxes exceed water column supply by factors of 1.2-1.8 in the Holocene and 1.8-3.0 in the glacial sections. A number of models have been applied to calculate carbonate dissolution rates. The results show that carbonate dissolution rates in the Holocene (in g/cm**2 kyr) equal 1.5 * 10**-3 exp (1.4D) where D is water depth in kilometers. A point-by- point estimation of sediment fluxes through time show that clay accumulation rates in the area have been near constant at 0.1-0.2 g/cm**2 kyr over the past 20 kyr whereas carbonate accumulation rates have decreased dramatically from 0.6-1.0 g/cm**2 kyr in the glacial sections of the cores to 0.2-0.6 g/cm**2 kyr in the Holocene. The errors caused by the uncertainties in the age of the termination of the last glacial period have been investigated and results show that a range of 11-14 kyr leads to an error upper limit of about 30% in the estimation of CaCO3 dissolution rates. The response time of CaCO3 and 230Thex concentrations in the mixed layer of sediments due to an impulse of change in CaCO3 dissolution rate has also been discussed, showing that the observed changes in carbonate dissolution may be explained in terms of a single or a continuous change, depending upon the thickness of the mixed layer.

Biomass and bioturbation in surface sediments of the Arctic Ocean

Little is known about the benthic communities of the Arctic Ocean's slope and abyssal plains. Here we report on benthic data collected from box cores along a transect from Alaska to the Barents Abyssal Plain during the Arctic Ocean Section of 1994. We determined: (1) density and biomass of the polychaetes, foraminifera and total infauna; (2) concentrations of potential sources of food (pigment concentration and percent organic carbon) in the sediments; (3) surficial particle mixing depths and rates using downcore 210Pb profiles; and (4) surficial porewater irrigation using NaBr as an inert tracer. Metazoan density and biomass vary by almost three orders of magnitude from the shelf to the deep basins (e.g. 47 403 individuals m**-2 on the Chukchi Shelf to 95 individuals m**-2 in the Barents Abyssal Plain). Water depth is the primary determinant of infaunal density, explaining 39% of the total variability. Potential food concentration varies by almost two orders of magnitude during the late summer season (e.g. the phaeopigment concentration integrated to 10 cm varies from 36.16 mg m**-2 on the Chukchi Shelf to 0.94 mg m**-2 in the Siberia Abyssal Plain) but is not significantly correlated with density or biomass of the metazoa. Most stations show evidence of particle mixing, with mixing limited to <=3 cm below the sediment-water interface, and enhanced pore water irrigation occurs at seven of the nine stations examined. Particle mixing depths may be related to metazoan biomass, while enhanced pore water irrigation (beyond what is expected from diffusion alone) appears to be related to total phaeopigment concentration. The data presented here indicate that Arctic benthic ecosystems are quite variable, but all stations sampled contained infauna and most stations had indications of active processing of the sediment by the associated infauna.

Benthic foraminifera in surface sediments of the Gulf of Lions

Surface sediment was sampled at two bathyal sites in the southwestern Gulf of Lions in the western Mediterranean Sea in February and August 1997 to study the distribution and microhabitat of living (Rose Bengal stained) deep sea benthic foraminifera. Both standing stock and diversity of the faunas, and the microhabitat of distinct species mirror the trophic situation and the depth of the oxidised layer at the different sites. Our results suggest that the faunas do not comprise highly opportunistic species and are adapted to rather stable environments. In the axial channel of the Lacaze-Duthiers Canyon, organic matter fluxes are enhanced due to advective transport of organic matter resulting in elevated oxygen consumption rates in the surface sediment and a rather thin oxidised layer. The corresponding benthic foraminiferal fauna is characterised by rather high standing stock and diversity, and a well-developed deep infauna. In addition to freshly deposited phytodetritus, more degraded organic matter seems to be an important food source. In contrast, at the open slope, organic matter fluxes and oxygen consumption rates in the surface sediment are lower and the oxidised layer is much thicker than inside the canyon. The corresponding benthic foraminiferal fauna comprises mainly epifaunal and shallow-infaunal species with much lower standing stocks and clear differences between February and August. In August standing stocks are higher and the average living depths of most species shift towards the sediment surface. These differences can be attributed to patchiness or represent a seasonal trophic signal.

Carbon and Lead chemistry of sediments from the Middle Atlantic Bight

A mass budget was constructed for organic carbon on the upper slope of the Middle Atlantic Bight, a region thought to serve as a depocenter for fine-grained material exported from the adjacent shelf. Various components of the budget are internally consistent, and observed differences can be attributed to natural spatial variability or to the different time scales over which measurements were made. The flux of organic carbon to the sediments in the core of the depocenter zone, at a water depth of 1000 m, was measured with sediment traps to be 65 mg C m**-2 day**-1, of which 6-24 mg C m**-2 day**-1 is buried. Oxygen fluxes into the sediments, measured with incubation chambers attached to a free vehicle lander, correspond to total carbon remineralization rates of 49-70 mg C m**-2 day**-1. Carbon remineralization rates estimated from gradients of Corg within the mixed layer, and from gradients of dissolved ammonia and phosphate in pore waters, sum to only 4-6 mg C m**-2 day**-1. Most of the Corg remineralization in slope sediments is mediated by bacteria and takes place within a few mm of the sediment-water interface. Most of the Corg deposited on the upper slope sediments is supplied by lateral transport from other regions, but even if all of this material were derived from the adjacent shelf, it represents <2% of the mean annual shelf productivity. This value is further lowered by recognizing that as much as half of the Corg deposited on the slope is refractory, having originated by reworking from older deposits. Refractory Corg arrives at the sea bed with an average 14C age 600-900 years older than the pre-bomb 14C age of DIC in seawater, and has a mean life in the sediments with respect to biological remineralization of at least 1000 years. Labile carbon supplied to the slope, on the other hand, is rapidly and (virtually) completely remineralized, with a mean life of < 1 year. Carbon-14 ages of fine-grained carbonate and organic carbon present within the interstices of shelf sands are consistent with this material acting as a source for the old carbon supplied to the slope. Winnowing and export of reworked carbon may contribute to the often-described relationship between organic carbon preservation and accumulation rate of marine sediments.

Dinoflagellate cysts abundance and events of ODP Hole 189-1168A sediments

Palynomorphs were studied in samples from Ocean Drilling Program (ODP) Leg 189, Hole 1168A (slope of the western margin of Tasmania; 2463 m water depth). Besides organic-walled dinoflagellate cysts (dinocysts), broad categories of other palynomorphs were quantified in terms of relative abundance. In this contribution, we provide an overview of the early late Eocene-Quaternary dinocyst distribution and illustrate main trends in palynomorph distribution. Dinocyst species throughout Hole 1168A are largely cosmopolitan with important contributions of typical low-latitude taxa and virtual absence of endemic Antarctic taxa. Dinocyst stratigraphic distribution broadly matches that known from the Northern Hemisphere and equatorial regions, although significant differences are noted. Selected potentially biochronostratigraphically useful events are summarized. The distribution of dinocysts in the middle-upper Miocene interval is rather patchy, probably due to prolonged exposure to oxygen. An important general aspect in the dinocyst assemblages is the near absence of Antarctic endemic species and the apparent influence of relatively warm waters throughout the succession at Site 1168. General palynomorph distribution indicates continued deepening from an initial shallow, even restricted, marine setting from late Eocene-Quaternary times. A curious massive influx of small skolochorate acritarchs is recorded throughout the late early-early middle Miocene; the significance of this signal is not yet understood. A general long-term oligotrophic nature of the surface waters influencing Site 1168 is suggested from the low abundance of (proto) peridinioid, presumably heterotrophic, species. The overall dinocyst distribution pattern corresponds to the long-term existence of a Leeuwin-like current influencing the region, including Site 1168, confirming results of earlier studies on other microfossil groups. The occasional influence of colder surface water conditions is, however, also apparent, notably during the late Pliocene-Quaternary, indicating the potential of high-resolution dinocyst analysis for future paleoceanographic studies.

Concentration of C2-C6 hydrocarbon gases in dry sediments of ODP Sites 180-1109 and 180-1115

Low molecular weight hydrocarbon (LMWH) distributions were examined in sediments from Sites 1109 and 1115 in the western Woodlark Basin using purge-trap thermal adsorption/desorption gas analysis. A number of different hydrocarbon components >C1, which were not detected during shipboard gas analysis, were detected at both sites using the purge-trap procedure. Concentrations of ethane, propane, and butane remained relatively low (<100 pmol/g) throughout Site 1109 and had no consistent trend with depth. In contrast, the longer-chain components increased in concentration with depth. Hexane concentrations rose to 716 pmol/g at the base of the site with a concomitant increase in both 2-methyl- and 3-methylpentane. At Site 1115, concentrations of ethane, propane, butane, and isobutylene + 1-butene remained low (<60 pmol/g) throughout the site and again had no consistent trend with depth. 2-Methylpentane, 3-methylpentane, and hexane concentrations had a subsurface maximum that coincided with sediments containing abundant plant-rich material. The LMWH downhole profiles plus low in situ temperatures suggest that the LMWH components were formed in situ by low-temperature biological processes. Purge-trap analysis has indicated the presence of some unexpected deep low-temperature bacterial reactions, which demonstrates that further analysis of LMWH may provide valuable information at future Ocean Drilling Program sites.

Trace metals in sediments of the Var Canyon turbidite system at the DYFAMED station in the Ligurian Sea

The magnitude and the chronology of anthropogenic impregnation by Hg and other trace metals of environmental concern (V, Cr, Ni, Cu, Zn, Ag, Cd and Pb, including its stable isotopes) in the sediments are determined at the DYFAMED station, a site in the Ligurian Sea (Northwestern Mediterranean) chosen for its supposed open-sea characteristics. The DYFAMED site (VD) is located on the right levee of the Var Canyon turbidite system, at the end of the Middle Valley. In order to trace the influence of the gravity current coming from the canyon on trace metal distribution in the sediment, we studied an additional sediment core (VA) from a terrace of the Var Canyon, and material collected in sediment traps at the both sites at 20 m above sea bottom. The patterns of Hg and other trace element distribution profiles are interpreted using stable Pb isotope ratios as proxies for its sources, taking into account the sedimentary context (turbidites, redox conditions, and sedimentation rates). Major element distributions, coupled with the stratigraphic examination of the sediment cores point out the high heterogeneity of the deposits at VA, and major turbiditic events at both sites. At the DYFAMED site, we observed direct anthropogenic influence in the upper sediment layer (<2 cm), while on the Var Canyon site (VA), the anthropization concerns the whole sedimentary column sampled (19 cm). Turbiditic events superimpose their specific signature on trace metal distributions. According to the 210Pbxs-derived sedimentation rate at the DYFAMED site (0.4 mm yr-1), the Hg-enriched layer of the top core corresponds to the sediment accumulation of the last 50 years, which is the period of the highest increase in Hg deposition on a global scale. With the hypothesis of the absence of significant post-depositional redistribution of Hg, the Hg/C-org ratio changes between the surface and below are used to estimate the anthropogenic contribution to the Hg flux accumulated in the sediment. The Hg enrichment, from pre-industrial to the present time is calculated to be around 60%, consistent with estimations of global Hg models. However, based on the chemical composition of the trapped material collected in sediment traps, we calculated that epibenthic mobilization of Hg would reach 73%. Conversely, the Cd/C-org ratio decreases in the upper 5 cm, which may reflect the recent decrease of atmospheric Cd inputs or losses due to diagenetic processes.