Evidence for intense REE scavenging at cold seeps from the Niger Delta margin

International audienceFor many trace elements, continental margins are the location of intense exchange processes between sediment and seawater, which control their distribution in the water column, but have yet to be fully understood. In this study, we have investigated the impact of fluid seepage at cold seeps on the marine cycle of neodymium. We determined dissolved and total dissolvable (TD) concentrations for REE and well-established tracers of fluid seepage (CH4, TDFe, TDMn), and Nd isotopic compositions in seawater samples collected above cold seeps and a reference site (i.e. away from any fluid venting area) from the Niger Delta margin. We also analyzed cold seep authigenic phases and various core-top sediment fractions (pore water, detrital component, easily leachable phases, uncleaned foraminifera) recovered near the hydrocast stations. Methane, TDFe and TDMn concentrations clearly indicate active fluid venting at the studied seeps, with plumes rising up to about 100 m above the seafloor. Depth profiles show pronounced REE enrichments in the non-filtered samples (TD concentrations) within plumes, whereas filtered samples (dissolved concentrations) exhibit slight REE depletion in plumes relative to the overlying water column and display typical seawater REE patterns. These results suggest that the net flux of REE emitted into seawater at cold seeps is controlled by the presence of particulate phases, most probably Fe-Mn oxyhydroxides associated to resuspended sediments. At the reference site, however, our data reveal significant enrichment for dissolved REE in bottom waters, that clearly relates to diffusive benthic fluxes from surface sediments. Neodymium isotopic ratios measured in the water column range from εNd ~−15.7 to − 10.4. Evidence that the εNd values for Antarctic Intermediate waters (AAIW) differed from those reported for the same water mass at open ocean settings shows that sediment/water interactions take place in the Gulf of Guinea. At each site, however, the bottom water εNd signature generally differs from that for cold seep minerals, easily leachable sediment phases, and detrital fractions from local sediments, ruling out the possibility that seepage of methane-rich fluids and sediment dissolution act as a substantial source of dissolved Nd to seawater in the Gulf of Guinea. Taken together, our data hence suggest that co-precipitation of Fe-Mn oxyhydroxide phases in sub-surface sediments leads to quantitative scavenging of dissolved REE at cold seeps, preventing their emission into bottom waters. Most probably, it is likely that diffusion from suboxic surface sediments dominates the exchange processes affecting the marine Nd cycle at the Niger Delta margin

Geochronology and stable isotope geochemistry of cold-seep carbonates from the Sea of Marmara

International audienceGeochronology and stable isotope geochemistry of cold-seep carbonates from the Sea of Marmar

The behavior of nickel isotopes at the biogeochemical interface between ultramafic soils and Ni accumulator species

International audienceUltramafic derived soils are characterized by low nutrient soils, a low Ca:Mg ratio, and high metal contents such as Ni, Co and Cr. The vegetation growing on these soils is highly adapted and includes both Ni hyperaccumulator and accumulator species. Today, approximately 530 Ni hyperaccumulator species are listed worldwide and the Ni concentration can be extremely high, e.g. up to 25% in latex from Pycnandra acuminata (Sapotaceae), a tree found in New Caledonia. The aim of this study is to identify the potential role of Ni hyperaccumulator plants in the Ni biogeochemical cycle at the soil surface by using Ni isotopes. A set of Ni hyperaccumulator and Ni accumulator plants as well as topsoils were sampled on the Barro Alto and Niquelândia ultramafic complexes (Goiás State, Brazil). Three Ni hyperaccumulator plants were collected: Justicia lanstyakii, Heliotropium aff. salicoides, Cnidoscolus aff. urens, as well as one Ni accumulator plant, Manihot sp. The isotopic compositions of the whole plants were determined and compared to those of the bulk topsoils and DTPA-extractable Ni. The topsoils exhibited δ60Ni values ranging from −0.30 ± 0.06‰ to 0.16 ± 0.05‰. The DTPA-extractable Ni in the topsoils ranged from 94 to 623 mg kg−1, i.e. 0.9–4.9% of the total soil Ni and was found to be isotopically heavier than the corresponding topsoil (from −0.30 ± 0.05‰ to 0.34 ± 0.08‰). The δ60Ni values for the Ni accumulator plants showed an enrichment in heavy Ni isotopes in the aerial parts of the plant compared to the roots, whereas similar δ60Ni values for the roots, stems and aerial parts suggested that no significant fractionation results from Ni uptake and translocation in Ni hyperaccumulator plants. Moreover, the aerial parts (i.e. leaves and flowers) from all of the plants analyzed showed the highest Ni concentrations and the heaviest δ60Ni values up to 1.21 ± 0.05‰. The enrichment in heavy Ni isotopes in the leaves (0.09 ± 0.06‰ < Δ60Nileaves-soil < 1.06 ± 0.03‰) may result in a heavy Ni input in the litter during organic matter restitution. There is a non-negligible amount of Ni uptake by Ni accumulator and Ni hyperaccumulator plants and this may modify both the Ni isotope composition at the soil-plant interface and the overall cycle of Ni in surface soil

Formation of carbonate chimneys in the Mediterranean Sea linked to deep-water oxygen depletion

Marine sediments at ocean margins vent substantial amounts of methane1, 2. Microbial oxidation of the methane released can trigger the precipitation of carbonate within sediments and support a broad diversity of seafloor ecosystems3, 4. The factors controlling microbial activity and carbonate precipitation associated with the seepage of submarine fluid over geological time remain poorly constrained. Here, we characterize the petrology and geochemistry of rocks sampled from metre-size build-ups of methane-derived carbonate chimneys located at the Amon mud volcano on the Nile deep-sea fan. We find that these carbonates comprise porous structures composed of aggregated spherules of aragonite, and closely resemble microbial carbonate reefs forming at present in the anoxic bottom waters of the Black Sea5. Using U-series dating, we show that the Amon carbonate build-ups formed between 12 and 7 thousand years ago, contemporaneous with the deposition of organic-rich sediments in the eastern Mediterranean, the so-called sapropel layer S1. We propose that the onset of deep-water suboxic or anoxic conditions associated with sapropel formation resulted in the development of intense anaerobic microbial activity at the sea floor, and thus the formation of carbonate chimneys

Hf and Nd isotopes in marine sediments: Constraints on global silicate weathering

The combined use of Lu–Hf and Sm–Nd isotope systems potentially offers a unique perspective for investigating continental erosion, but little is known about whether, and to what extent, the Hf–Nd isotope composition of sediments is related to silicate weathering intensity. In this study, Hf and Nd elemental and isotope data are reported for marine muds, leached Fe-oxide fractions and zircon-rich turbidite sands collected off the Congo River mouth, and from other parts of the SE Atlantic Ocean. All studied samples from the Congo fan (muds, Fe-hydroxides, sands) exhibit indistinguishable Nd isotopic composition (?Nd ~ ? 16), indicating that Fe-hydroxides leached from these sediments correspond to continental oxides precipitated within the Congo basin. In marked contrast, Hf isotope compositions for the same samples exhibit significant variations. Leached Fe-hydroxide fractions are characterized by ?Hf values (from ? 1.1 to + 1.3) far more radiogenic than associated sediments (from ? 7.1 to ? 12.0) and turbidite sands (from ? 27.2 to ? 31.6). ?Hf values for Congo fan sediments correlate very well with Al/K (i.e. a well-known index for the intensity of chemical weathering in Central Africa). Taken together, these results indicate that (1) silicate weathering on continents leads to erosion products having very distinctive Hf isotope signatures, and (2) a direct relationship exists between ?Hf of secondary clay minerals and chemical weathering intensity.These results combined with data from the literature have global implications for understanding the Hf–Nd isotope variability in marine precipitates and sediments. Leached Fe-hydroxides from Congo fan sediments plot remarkably well on an extension of the ‘seawater array’ (i.e. the correlation defined by deep-sea Fe–Mn precipitates), providing additional support to the suggestion that the ocean Hf budget is dominated by continental inputs. Fine-grained sediments define a diffuse trend, between that for igneous rocks and the ‘seawater array’, which we refer to as the ‘zircon-free sediment array’ (?Hf = 0.91 ?Nd + 3.10). Finally, we show that the Hf–Nd arrays for seawater, unweathered igneous rocks, zircon-free and zircon-bearing sediments (?Hf = 1.80 ?Nd + 2.35) can all be reconciled, using Monte Carlo simulations, with a simple weathering model of the continental crust.<br/

Hf and Nd isotopes in marine sediments: Constraints on global silicate weathering

The combined use of Lu-Hf and Sm-Nd isotope systems potentially offers a unique perspective for investigating continental erosion, but little is known about whether, and to what extent, the Hf-Nd isotope composition of sediments is related to silicate weathering intensity. In this study, Hf and Nd elemental and isotope data are reported for marine muds, leached Fe-oxide fractions and zircon-rich turbidite sands collected off the Congo River mouth, and from other parts of the SE Atlantic Ocean. All studied samples from the Congo fan (muds, Fe-hydroxides, sands) exhibit indistinguishable Nd isotopic composition (εNd ~ - 16), indicating that Fe-hydroxides leached from these sediments correspond to continental oxides precipitated within the Congo basin. In marked contrast, Hf isotope compositions for the same samples exhibit significant variations. Leached Fe-hydroxide fractions are characterized by εHf values (from - 1.1 to + 1.3) far more radiogenic than associated sediments (from - 7.1 to - 12.0) and turbidite sands (from - 27.2 to - 31.6). εHf values for Congo fan sediments correlate very well with Al/K (i.e. a well-known index for the intensity of chemical weathering in Central Africa). Taken together, these results indicate that (1) silicate weathering on continents leads to erosion products having very distinctive Hf isotope signatures, and (2) a direct relationship exists between εHf of secondary clay minerals and chemical weathering intensity. These results combined with data from the literature have global implications for understanding the Hf-Nd isotope variability in marine precipitates and sediments. Leached Fe-hydroxides from Congo fan sediments plot remarkably well on an extension of the 'seawater array' (i.e. the correlation defined by deep-sea Fe-Mn precipitates), providing additional support to the suggestion that the ocean Hf budget is dominated by continental inputs. Fine-grained sediments define a diffuse trend, between that for igneous rocks and the 'seawater array', which we refer to as the 'zircon-free sediment array' (εHf = 0.91 εNd + 3.10). Finally, we show that the Hf-Nd arrays for seawater, unweathered igneous rocks, zircon-free and zircon-bearing sediments (εHf = 1.80 εNd + 2.35) can all be reconciled, using Monte Carlo simulations, with a simple weathering model of the continental crust. © 2008 Elsevier B.V. All rights reserved

Nickel distribution and isotopic fractionation in a Brazilian lateritic regolith: coupling Ni isotopes and Ni K-edge XANES.

Ultramafic (UM) rocks are known to be nickel (Ni) rich and to weather quickly, which makes them a good candidate to look at the Ni isotope systematics during weathering processes at the Earth’s surface. The present study aims at identifying the Ni solid speciation and discussing the weathering processes that produce Ni isotope fractionation in two deep laterite profiles under tropical conditions (Barro Alto, Goiás State, Brazil). While phyllosilicates and to a lower extent goethite are the main Ni-bearing phases in the saprolitic part of the profile, iron (Fe) oxides dominate the Ni budget in the lateritic unit. Nickel isotopic composition (δ60Ni values) has been measured in each unit of the regolith, i.e., rock, saprock, saprolite and laterite (n=52). δ60Ni varies widely within the two laterite profiles, from -0.10 ± 0.05‰ to 1.43 ± 0.05‰, showing that significant Ni isotope fractionation occurs during the weathering of UM rocks. Overall, our results show that during weathering, the solid phase is depleted in heavy Ni isotopes due to the preferential sorption and incorporation of light Ni isotopes into Fe oxides; the same mechanisms likely apply to the incorporation of Ni into phyllosilicates (type 2:1). However, an isotopically heavy Ni pool is observed in the solid phase at the bottom of the saprolitic unit. This feature can be explained by two hypotheses that are not mutually exclusive: i) a depletion in light Ni isotopes during the first stage of weathering due to the preferential dissolution of light Ni-containing minerals, and ii) the sorption or incorporation of isotopically heavy Ni carried by percolating waters (groundwater samples have δ60Ni of 2.20 and 2.27‰), that were enriched in heavy Ni isotopes due to successive weathering processes in the overlying soil and laterite units

Abrupt drainage cycles of the Fennoscandian Ice Sheet

Continental ice sheets are a key component of the Earth’s climate system, but their internal dynamics need to be further studied. Since the last deglaciation, the northern Eurasian Fennoscandian Ice Sheet (FIS) has been connected to the Black Sea (BS) watershed, making this basin a suitable location to investigate former ice-sheet dynamics. Here, from a core retrieved in the BS, we combine the use of neodymium isotopes, high-resolution elemental analysis, and biomarkers to trace changes in sediment provenance and river runoff. We reveal cyclic releases of meltwater originating from Lake Disna, a proglacial lake linked to the FIS during Heinrich Stadial 1. Regional interactions within the climate–lake–FIS system, linked to changes in the availability of subglacial water, led to abrupt drainage cycles of the FIS into the BS watershed. This phenomenon raised the BS water level by ∼100 m until the sill of the Bosphorus Strait was reached, flooding the vast northwestern BS shelf and deeply affecting the hydrology and circulation of the BS and, probably, of the Marmara and Aegean Seas