Phosphorus geochemistry of eastern equatorial Pacific Ocean sediments

We determined phosphorus (P) concentrations in Leg 138 sediment samples from Sites 844, 846, and 851, using a sequential extraction technique to identify the P associated with five sedimentary components. Total concentrations of P (sum of the five components) ranged from 4 to 35 µmol P/g sediment, with mean values relatively similar between the three sites (11, 14, and 12 for Sites 844,846, and 851, respectively). Authigenic/biogenic P was the most important component in terms of percentage of total P (about 75%), with iron-bound P (13%), adsorbed P (2%-9%), and organic P (4%) of secondary importance; detrital P was a minor P sink (1%) in these sediments. Profiles of adsorbed P and iron-bound P show decreasing concentrations with age, indicating that these components have been affected by diagenesis and reorganization of P. A peak in iron-bound P may reflect higher fluxes of hydrothermally derived Fe to eastern equatorial Pacific Ocean sediments from 11 to 8 Ma. Lower detrital P values for western Site 851 reflect a greater distance of this site from a terrigenous source area, compared to that of Sites 844 and 846. Phosphorus mass accumulation rates (P-MARs; units of µmol P/cm**2/k.y.) were calculated using total P concentrations (not including the minor and oceanically unreactive detrital P component) and sedimentation rates and dry-bulk densities averaged over time intervals of 0.5 m.y. P-MARs generally decrease from 17 Ma to the present. Eastern transect Sites 844 and 846 display a decrease in P-MARs from about 30 to 10 in the interval from 17 to 8 Ma, while western transect Site 851 is highly variable during this interval. P-MARs increase to about 45 and stay relatively high from 8 to 6 Ma, then decrease toward the present to some of the lowest values of the record (about 10). The general trend of high P-MARs at about 6 Ma and decreasing values toward the present is correlated with other geochemical and sedimentary trends through this interval and may reflect (1) a change in net sediment and P burial, (2) a reorganization of fluxes with no change of net burial, or (3) a combination of the two.

(Table 1) Phosphorus and carbon chemistry of ODP Holes 169-1033B and 169-1034B

Uncertainty currently exists about the removal of carbon (C) and phosphorus (P) from the oceanic reservoir, especially in low oxygen settings. In this paper, the cycling of C and P is examined in sediments from the anoxic Saanich Inlet, cored by Ocean Drilling Program (ODP) Leg 169S in 1996 at two sites. Although Corg/Porg ratios are high and increase with depth in the Saanich Inlet, this effect is due largely to a remobilization of P from an organic matter sink to an authigenic sink. Reducible sedimentary components act as temporary shuttles in this process even in this anoxic setting, with the ultimate burial sink for the remobilized P being carbonate fluorapatite. The effective Corg/Preactive molar ratio appears to be about 150-200, indicating some preferential loss of P compared to C during organic matter degradation, but not approaching previously reported values of over 3000 in black shales. Reactive P accumulation rates in this basin range from 10,000-60,000 µmol/cm**2/kyr, greatly exceeding the range of 500-8000 µmol/cm**2/kyr found in most continental-margin settings, including regions of modern phosphogenesis. The initiation of marine sedimentation in the Saanich Inlet occurred after deglaciation, and the high rates of P burial seen here may provide an end-member example of the effects of sea level and margin sedimentation on the distribution of P within the marine P cycle.

Geochemistry of ODP Hole 108-658C sediments

During the African Humid Period (AHP), much of the modern hyperarid Saharan desert was vegetated and covered with numerous lakes. In marine sediments off northwestern Africa, the AHP is represented by markedly reduced siliciclastic sediment flux between ~ 12.3 and 5.5 ka. Changes in the origin of this terrigenous sediment fraction can be constrained by sediment chemistry and radiogenic isotope tracers. At Ocean Drilling Program (ODP) Site 658, Hole C (20°44.95'N, 18°34.85'W, 2263 mbsl), the neodymium (Nd) isotope composition of terrigenous detritus shows little variability throughout the last 25 kyr, indicating that the contributing geological terranes have not changed appreciably since the last glacial period. In contrast, there were large and abrupt changes in strontium (Sr) isotope ratios and chemical compositions associated with the AHP, during which 87Sr/86Sr ratios were markedly less radiogenic, and sediments show higher chemical indices of alteration. We show that sediment geochemical changes during the AHP cannot be attributed to changes in the source terranes, physical sorting, or intensity of chemical weathering. The low 87Sr/86Sr and high Sr concentrations of AHP-age samples also conflict with the interpretation of increased fine-grained, fluvially derived sediments. We propose that the most significant compositional changes at ODP 658C are due to the addition of an aluminosilicate component that has a highly altered major element signature but is enriched in soluble elements like Sr and magnesium (Mg) compared to aluminum (Al) and has low 87Sr/86Sr relative to local terrigenous source areas. We interpret these characteristics to reflect authigenic sediment supply from extensive North African paleolake basins that were prevalent during the AHP.

Determination of Uranium, Thorium, and Ionium in sediment cores of the Caribbean and Ionian Sea

A rapid procedure for Io (Th230) dating of sediments with accumulation rates in the range of several cm/1000 years is described. Studying of large sample populations with very small Io-excess activity is possible as the counting time (around 1500 min/sample) are 2 to 5 times shorter than with the standard Io-excess method. Improved sensitivity of the Io-excess measurement is achieved by: 1) extraction ( ~90 %) of the authigenic Io-excess with EDTA, with minor leaching ( ~30 %) of the allogenic Th232 and Io-supported, 2) processing samples as large as 10 g or more. The procedure was applied to sediments from the Caribbean (V 12-122) and from the Ionian Sea (M22_48 and M17_17). In the case of the standard core V 12-122 our results are in good agreement with previous time-consuming Io determinations. The resulting average accumulation rates of 2.0 ± 0.3 cm/1000 years for the Ionian Sea cores are close to the average derived from magnetic reversal studies of a nearby core.

High-resolution pore-water and solid-phase analyses of sediment cores GeoB6520-3 (Hydrate Hole) and GeoB6521-2 (Worm Hole) of the northern Congo Fan

The geochemical cycling of barium was investigated in sediments of pockmarks of the northern Congo Fan, characterized by surface and subsurface gas hydrates, chemosynthetic fauna, and authigenic carbonates. Two gravity cores retrieved from the so-called Hydrate Hole and Worm Hole pockmarks were examined using high-resolution pore-water and solid-phase analyses. The results indicate that, although gas hydrates in the study area are stable with respect to pressure and temperature, they are and have been subject to dissolution due to methane-undersaturated pore waters. The process significantly driving dissolution is the anaerobic oxidation of methane (AOM) above the shallowest hydrate-bearing sediment layer. It is suggested that episodic seep events temporarily increase the upward flux of methane, and induce hydrate formation close to the sediment surface. AOM establishes at a sediment depth where the upward flux of methane from the uppermost hydrate layer counterbalances the downward flux of seawater sulfate. After seepage ceases, AOM continues to consume methane at the sulfate/methane transition (SMT) above the hydrates, thereby driving the progressive dissolution of the hydrates "from above". As a result the SMT migrates downward, leaving behind enrichments of authigenic barite and carbonates that typically precipitate at this biogeochemical reaction front. Calculation of the time needed to produce the observed solid-phase barium enrichments above the present-day depths of the SMT served to track the net downward migration of the SMT and to estimate the total time of hydrate dissolution in the recovered sediments. Methane fluxes were higher, and the SMT was located closer to the sediment surface in the past at both sites. Active seepage and hydrate formation are inferred to have occurred only a few thousands of years ago at the Hydrate Hole site. By contrast, AOM-driven hydrate dissolution as a consequence of an overall net decrease in upward methane flux seems to have persisted for a considerably longer time at the Worm Hole site, amounting to a few tens of thousands of years.

Magnetic extracts of three gravity cores located at the Ceará Rise, the Mid-Atlantic Ridge and the Sierra Leone Rise

The magnetic microparticle and nanoparticle inventories of marine sediments from equatorial Atlantic sites were investigated by scanning and transmission electron microscopy to classify all present detrital and authigenic magnetic mineral species and to investigate their regional distribution, origin, transport, and preservation. This information is used to establish source-to-sink relations and to constrain environmental magnetic proxy interpretations for this area. Magnetic extracts were prepared from sediments of three supralysoclinal open ocean gravity cores located at the Ceará Rise (GeoB 1523-1; 3°49.9'N/41°37.3'W), the Mid-Atlantic Ridge (GeoB 4313-2; 4°02.8'N/33°26.3'W), and the Sierra Leone Rise (GeoB 2910-1; 4°50.7'N/21°03.2'W). Sediments from two depths corresponding to marine isotope stages 4 and 5.5 were processed. This selection represents glacial and interglacial conditions of sedimentation for the western, central, and eastern equatorial Atlantic and avoids interferences from subsurface and anoxic processes. Crystallographic, elemental, morphological, and granulometric data of more than 2000 magnetic particles were collected by scanning and transmission electron microscopy. On basis of these properties, nine particle classes could be defined: detrital magnetite, titanomagnetite (fragmental and euhedral), titanomagnetite-hemoilmentite intergrowths, silicates with magnetic inclusions, microcrystalline hematite, magnetite spherules, bacterial magnetite, goethite needles, and nanoparticle clusters. Each class can be associated with fluvial, eolian, subaeric, and submarine volcanic, biogenic, or chemogenic sources. Large-scale sedimentation patterns are delineated as well: detrital magnetite is typical of Amazon discharge, fragmental titanomagnetite is a submarine weathering product of mid-ocean ridge basalts, and titanomagnetite-hemoilmenite intergrowths are common magnetic particles in West African dust. This clear regionalization underlines that magnetic petrology is an excellent indicator of source-to-sink relations. Hematite encrustations, magnetic spherules, and nanoparticle clusters were found at all investigated sites, while bacterial magnetite and authigenic hematite were only detected at the more oxic western site. At the eastern site, surface pits and crevices were seen on the crystal faces indicating subtle early diagenetic reductive dissolution. It was observed that paleoclimatic signatures of magnetogranulometric parameters such as the ratio of anhysteretic and isothermal remanent magnetizations can be formed either by mixing of multiple sources with separate, relatively narrow grain size ranges (western site) or by variable sorting of a single source with a broad grain size distribution (eastern site). Hematite, goethite, and possibly ferrihydrite nanoparticles occur in all sediment cores studied and have either high-coercive or superparamagnetic properties depending on their partly ultrafine grain sizes. These two magnetic fractions are generally discussed as separate fractions, but we suggest that they could actually be genetically linked.

Grain size effects on excess Thorium-230 of sediment cores from the Southern Ocean and the South East Atlantic

Excess Thorium-230 (230Thxs) as a constant flux tracer is an essential tool for paleoceanographic studies, but its limitations for flux normalization are still a matter of debate. In regions of rapid sediment accumulation, it has been an open question if 230Thxs-normalized fluxes are biased by particle sorting effects during sediment redistribution. In order to study the sorting effect of sediment transport on 230Thxs, we analyzed the specific activity of 230Thxs in different particle size classes of carbonate-rich sediments from the South East Atlantic, and of opal-rich sediments from the Atlantic sector of the Southern Ocean. At both sites, we compare the 230Thxs distribution in neighboring high vs. low accumulation settings. Two grain-size fractionation methods are explored. We find that the 230Thxs distribution is strongly grain size dependent, and 50-90% of the total 230Thxs inventory is concentrated in fine material smaller than 10 µm, which is preferentially deposited at the high accumulation sites. This leads to an overestimation of the focusing factor Psi, and consequently to an underestimation of the vertical flux rate at such sites. The distribution of authigenic uranium indicates that fine organic-rich material has also been re-deposited from lateral sources. If the particle sorting effect is considered in the flux calculations, it reduces the estimated extent of sediment focusing. In order to assess the maximum effect of particle sorting on Psi, we present an extreme scenario, in which we assume a lateral sediment supply of only fine material (< 10 µm). In this case, the focusing factor of the opal-rich core would be reduced from Psi = 5.9 to Psi = 3.2. In a more likely scenario, allowing silt-sized material to be transported, Psi is reduced from 5.9 to 5.0 if particle sorting is taken into consideration. The bias introduced by particle sorting is most important for strongly focused sediments. Comparing 230Thxs-normalized mass fluxes biased by sorting effects with uncorrected mass fluxes, we suggest that 230Thxs-normalization is still a valid tool to correct for lateral sediment redistribution. However, differences in focusing factors between core locations have to be evaluated carefully, taking the grain size distributions into consideration.

Age model and chemistry of sediment core STK7 from Steisslinger See

Stable isotope records for carbon and oxygen in bulk carbonates, carbon in bulk organic matter, and for total and chromium-reducible sulfur in a lacustrine sediment core from Lake Steisslingen (Southwest Germany) show several distinct and abrupt shifts during the last 15,000 years. Variations in the isotopic composition of authigenic carbonates indicate two major phases in the lake history. In the pre-Holocene, the hydrological budget of the lake was apparently stable. Variations of delta18O values of authigenic carbonates were, therefore, dominantly controlled by temperature changes. A decrease in the delta18Ocarb values of about 2 per mil at the Allerød/Younger Dryas transition is interpreted as a drop in mean annual air temperatures of approximately 5°C. An abrupt temperature increase of a similar magnitude is inferred at the Younger Dryas/Preboreal boundary. Throughout most of the Holocene, the isotopic composition of authigenic carbonates was influenced by marked changes in the hydrological budget of the lake. A major positive excursion in the delta13Ccarb and delta18Ocarb values at the beginning of the Atlantic and a smaller one in the Preboreal were related to evaporation effects, which indicate that dry climatic conditions must have prevailed at that time. A simultaneous increase in delta13C values of bulk organic matter at the beginning of the Atlantic suggests a high level of productivity in the lake. As a consequence, aqueous sulfate became limited as indicated by variations in the delta34S values of total and chromium-reducible sedimentary sulfur. Therefore, we conclude that the beginning of the Atlantic was characterized not only by dry but also by warm climatic conditions, which triggered a higher productivity in the lake. In the Subatlantic sediments, large variations in carbon, oxygen, and sulfur isotope ratios were observed as a result of human activities, causing considerable perturbations in the biogeochemical element cycling of Lake Steisslingen. Results obtained by the study of the continuous 15 ka record of Lake Steisslingen document clearly that isotopic proxy data from lacustrine sediments can provide useful information on environmental and climatic changes of local, regional, and in the case of the Younger Dryas event, of even hemispherical significance.

Sedimentology and geochemistry of surface sediments from the Pagassitikos Gulf

Volos city and its port are situated in the northern part of Pagassitikos Gulf, a shallow, semi-enclosed marine area in central Greece. A wastewater treatment plant (WWTP) and pipeline operate in the same area. Muddy sediments with low carbonate contents cover most of the seabed, except for the Volos embayment and the western part of the gulf where sandy carbonates prevail. Bulk organic carbon contents and the organic carbon contents of the clay fractions are high in the vicinity of Volos embayment. High element (Pb, Cu, and Zn) contents and Igeo (geoaccumulation index) values were found for the clay fractions in the northern part of Pagassitikos Gulf. This enrichment is attributed to the discharge of raw domestic and industrial effluents of Volos city and port before the WWTP was installed. The dispersal of pollutants is essentially controlled by diffusion from point sources (city, port and WWTP) and is limited to Volos Bay. Relatively high Mn levels are ascribed to diagenetic formation of manganese carbonates (authigenic phase), whereas Cr and Ni are elevated due to weathering of ultrabasic formations on land.

(Table 1) Chemical and isotopic composition of pore fluids in cores TGC-1 and TGC-6

The role of sediment diagenesis in the marine cycles of Li and B is poorly understood. Because Li and B are easily mobilized during burial and are consumed in authigenic clay mineral formation, their abundance in marine pore waters varies considerably. Exchange with the overlying ocean through diffusive fluxes should thus be common. Nevertheless, only a minor Li sink associated with the low-temperature alteration of volcanic ash has been observed. We describe a low-temperature diagenetic environment in the Black Sea dominated by the alteration of detrital plagioclase feldspars. Fluids expelled from the Odessa mud volcano in the Sorokin Trough originate from shallow (~100-400 m deep) sediments which are poor in volcanic materials but rich in anorthite. These fluids are depleted in Na+, K+, Li+, B, and 18O and enriched in Ca2+ and Sr2+, indicating that anorthite is dissolving and authigenic clays are forming. Using a simple chemical model, we calculate the pH and the partial pressure of CO2 (PCO2) in fluids associated with this alteration process. Our results show that the pH of these fluids is up to 1.5 pH units lower than in most deep marine sediments and that PCO2 levels are up to several hundred times higher than in the atmosphere. These conditions are similar to those which favor the weathering of silicate minerals in subaerial soil environments. We propose that in Black Sea sediments enhanced organic matter preservation favors CO2 production through methanogenesis and results in a low pore water pH, compared to most deep sea sediments. As a result, silicate mineral weathering, which is a sluggish process in most marine diagenetic environments, proceeds rapidly in Black Sea sediments. There is a potential for organic matter-rich continental shelf environments to host this type of diagenesis. Should such environments be widespread, this new Li and B sink could help balance the marine Li and Li isotope budgets but would imply an apparent imbalance in the B cycle.

Table 1. Radiocarbon ages of sediment core LDB01-I

Magnetic susceptibility (MS) was measured with high resolution (5 mm) on a 9 m long, 14C dated core from Lake Le Bourget (Savoie, France), spanning the last 7200 years. The strong correlation (R=0.85) of the MS with the silicate-borne suite of elements (Si, Al, Fe, Mg, K) and anti-correlation with the carbonate content (R =-0.87) allows it to be used as a proxy for the fluctuations of the abundance of riverborne clastic fraction versus authigenic carbonates in sediment. As the Rhône is the only river bringing a significant amount of silicate minerals to the coring site, the MS downstream is interpreted as a proxy of the Rhône suspended load discharge in Lake Le Bourget. This is confirmed over the last 3000 years by the good match with the evolution of hydrological activity of the Rhône as it is known through geomorphological studies of well-dated archaeological sites. Over the last 7200 years, the record is consistent with the regional record of lake water-level fluctuations. While the intensity of the MS signal might be widely affected by the human impact on soil stability, the timing of the period of enhanced hydrological activity appears to be mostly climate-related, and should thus constitute a first step toward a high-resolution (< 8 yr) continuous history of hydrological conditions in the NW Alps.

Methane fluxes and carbonate deposits at eastern Mediterranean cold seeps

High acoustic seafloor-backscatter signals characterize hundreds of patches of methane-derived authigenic carbonates and chemosynthetic communities associated with hydrocarbon seepage on the Nile Deep Sea Fan (NDSF) in the Eastern Mediterranean Sea. During a high-resolution ship-based multibeam survey covering a ~ 225 km**2 large seafloor area in the Central Province of the NDSF we identified 163 high-backscatter patches at water depths between 1500 and 1800 m, and investigated the source, composition, turnover, flux and fate of emitted hydrocarbons. Systematic Parasound single beam echosounder surveys of the water column showed hydroacoustic anomalies (flares), indicative of gas bubble streams, above 8% of the high-backscatter patches. In echosounder records flares disappeared in the water column close to the upper limit of the gas hydrate stability zone located at about 1350 m water depth due to decomposition of gas hydrate skins and subsequent gas dissolution. Visual inspection of three high-backscatter patches demonstrated that sediment cementation has led to the formation of continuous flat pavements of authigenic carbonates typically 100 to 300 m in diameter. Volume estimates, considering results from high-resolution autonomous underwater vehicle (AUV)-based multibeam mapping, were used to calculate the amount of carbonate-bound carbon stored in these slabs. Additionally, the flux of methane bubbles emitted at one high-backscatter patch was estimated (0.23 to 2.3 × 10**6 mol a**-1) by combined AUV flare mapping with visual observations by remotely operated vehicle (ROV). Another high-backscatter patch characterized by single carbonate pieces, which were widely distributed and interspaced with sediments inhabited by thiotrophic, chemosynthetic organisms, was investigated using in situ measurements with a benthic chamber and ex situ sediment core incubation and allowed for estimates of the methane consumption (0.1 to 1 × 10**6 mol a**-1) and dissolved methane flux (2 to 48 × 10**6 mol a**-1). Our comparison of dissolved and gaseous methane fluxes as well as methane-derived carbonate reservoirs demonstrates the need for quantitative assessment of these different methane escape routes and their interaction with the geo-, bio-, and hydrosphere at cold seeps.

Chemical composition of samples from DSDP Holes 16-163 and 17-164

Considerable postsedimentational alteration of fine dispersed minerals in Cretaceous sedimentary sequences was found in three deep-sea drillholes (163, 164, 169). Original Fe-montmorillonites formed from basalts were converted during lithification to mixed-layer montmorillonite-hydromicas and then to pure hydromicas (celadonites). An assumption that the minerals were originally of authigenic-diagenetic composition is based on a broad spectrum of other diagenetic minerals present: silica group from opal A to opal CT and quartz, clinoptilolite and palygorskite. In addition, quartz-hydromica ratio is strikingly atypical of aeolian transport.