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The study area is located at the transition between the northern end of the Tonga Trench and the North Fiji fracture zone, where tectonic movements are reputed to be the fastest in the world. To the southeast of Futuna Island, a broad area of volcanism occurs within a region characterized by a change in the tectonic fabric between a NE-SW oriented volcanic graben and the N-S oriented Alofi ridge. In 2010, the active volcano Kulo Lasi, which represents the most recent volcanic episode in the Futuna area, was discovered in the center of this extensive volcanic zone. Kulo Lasi is a 20 km diameter shield volcano that rises 400 m above the seafloor. It is composed of basaltic to trachy-andesitic lava with no obvious geochemical affinity with the Tonga subduction that occurs 500 km to the east. The central caldera is 5 km in diameter and 300 m deep and is located at a water depth of 1500 m. Diving operations with the submersible Nautile and high-resolution AUV mapping, have revealed the presence of numerous active and inactive hydrothermal fields on the floor and the walls of the caldera. Four tectono-volcanic stages can be distinguished at Kulo Lasi caldera. In stage 1, the shield volcano is built. Annular reverse faults develop at the summit and control circulation of water/rock-dominated hydrothermal fluids and high-temperature alteration of rocks along the nascent normal faults. Mixing of hydrothermal fluids with seawater is favored along normal superficial faults, leading to the formation of low-temperature Fe/Mn mineralization at the summit of the volcano. During stage 2, the caldera collapse, gradually revealing outcrops of the altered and mineralized zones formed during Stage 1. As the magma chamber cools and collapses, less heat is available. As a result, medium to low-temperature (<100 °C) Fe/Si deposits form on the floor of the caldera. In stage 3, refilling and ascent of the magma chamber at depth promote the uplift of a central resurgent dome devoid of recent

Ferromanganese (Fe-Mn) deposits constitute a ubiquitous mineral type in oceanic settings, with metal (Cu, Ni, Zn, Co, Pt) and rare earth elements (REE) enrichments of potential economic interest. Routine analysis of trace elements by ICP-MS has advanced our understanding of the impact of hydrogenetic, diagenetic and hydrothermal processes on the mobility and interaction of high field strength elements (HFSE: Zr, Ti) and REE and yttrium (REY) with Fe-Mn oxyhydroxides. Recent discoveries in the French exclusive economic zone (EEZ) of Wallis and Futuna (southwest Pacific Ocean) have brought new insight to the formation of low temperature (LT) hydrothermal Mn deposits and lead us to reconsider the classification and discrimination diagrams for of Fe-Mn deposits and ore-forming processes. Using a suite of LT hydrothermal Fe-Mn crusts from Wallis and Futuna, we investigate how contrasting genetic processes influence the distribution of metals (Mn, Fe, Cu, Ni, Co), HFSE and REY in hydrogenetic, diagenetic, hydrothermal and mixed-type deposits from different environments in the global ocean. The interaction of the different metal oxide-forming processes indicates that: (i) enrichment of Co, HFSE and REY is favored by hydrogenetic precipitation, (ii) diagenetic processes produce higher Mn, Cu, and Ni concentrations with oxic remobilization in the sedimentary column, while suboxic conditions promote greater Mn and Fe remobilization that competes with the incorporation of Cu and Ni ions in nodules. HFSE and REY derived from seawater are usually low in diagenetic precipitates, which discriminate between hydrogenetic and diagenetic inputs within nodules, (iii) hydrothermal Fe-Mn deposits show strong depletion in HFSE and REY due to rapid formation and high contents of either Fe or Mn oxides. We present a new discrimination scheme for the genetic types of Fe-Mn deposits using a 10*(Cu + Ni + Co) – 100*(Zr + Y + Ce) – (Fe + Mn)/4 ternary diagram. The use of HFSE and REY in the cla

The aim of this study is to investigate the information provided by sulfur count rates obtained by X-ray fluorescence core scanner (XRF-CS) along sedimentary records. The analysis of two marine sediment cores from the Niger Delta margin shows that XRF-CS sulfur count rates obtained at the surface of split core sections with XRF-CS correlate with both direct quantitative pyrite concentrations, as inferred from X-ray powder diffraction (XRD) and sulfur determination by wavelength dispersive X-ray fluorescence (WD-XRF) spectrometry, and total dissolved sulfide (TDS) contents in the sediment pore water. These findings demonstrate the potential of XRF-CS for providing continuous profiles of pyrite distribution along split sections of sediment cores. The potential of XRF-CS to detect TDS pore water enrichments in marine sediment records, even a long time after sediment recovery, will be further discussed.

Thulium is a heavy rare earth element (REE) whose geochemical behavior is intermediate between Er and Yb, and that is not expected to be decoupled from these elements during accretion of planetary bodies and geological processes. However, irregularities in REE volatilities at higher temperature could have decoupled the REEs relative to one another during the early stages of condensation of the solar nebula. Indeed, positive Tm anomalies are found in some refractory inclusions from carbonaceous chondrites, and it is possible that large scale nebular reservoirs displaying positive or negative Tm anomalies were formed during the early history of the solar system. We analyzed a series of meteorites and terrestrial rocks in order to evaluate the existence of Tm anomalies in planetary materials. Relative to CIs (Ivuna-type carbonaceous chondrites), carbonaceous chondrites display unresolved or positive Tm anomalies, while most of the noncarbonaceous chondrites show slightly negative Tm anomalies. Quantification of these anomalies in terrestrial samples is complicated when samples display fractionated heavy REE patterns. Taking this effect into account, we show that the Earth, Mars, Vesta, the aubrite and ureilite parent bodies display small negative anomalies (Tm/Tm∗≈0.975), very similar to those found in ordinary and enstatite chondrites. We suggest that a slight negative Tm anomaly relative to CI is a widespread feature of the materials from the inner solar system. This finding suggests that CI chondrites may not be appropriate for normalizing REE abundance patterns of most planetary materials as they may be enriched in a high-temperature refractory component with non-solar composition. The presence of Tm anomalies at a bulk planetary scale is, to this day, the strongest piece of evidence that refractory lithophile elements are not present in constant proportions in planetary bodies.

Dolomite nodules are widespread within the Tortonian marls of Fortuna and Lorca basins in southern Spain. They occur as large bodies of various forms (round, ovoid, tabular) that are parallel or secant relative to the stratification. They are massive and present sometimes internal conduits that are considered as drains used for the migration of fluids. This study brings new results on the mineralogy and elemental and isotopic geochemistry of these dolomite nodules to better describe the processes that were occurring during their formation. The diagenetic reactions that have driven authigenic dolomite precipitation within the sediments involved on the one hand methanogenesis that produced 13C-poor CH4 and 13C-rich CO2, on the other hand carbonate and silicate weathering by the CO2-rich solutions, that released respectively alkalinity and cations in pore solutions. Moreover, the distribution of the major elements (Si, Al, K, Na, Ca, Mg, Fe) in the marls and dolomite nodules indicates that these elements were redistributed within the sedimentary formation during the diagenetic reactions without external inputs by the circulating fluids. These observations thus confirm the link between authigenic dolomite formation and clay minerals diagenesis in sediments where methanogenesis was active.

Marine sediments at ocean margins vent substantial amounts of methane(1,2). Microbial oxidation of the methane released can trigger the precipitation of carbonate within sediments and support a broad diversity of seafloor ecosystems(3,4). 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 Sea(5). 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.

A joint industrial project with IFREMER and Total provides insights into the tectonic setting and the geochemistry of a large active pockmark offshore W-Africa in the Niger Delta. The study combines both geophysical (seismic) and geochemical data to infer the dynamics of a 300 m wide pockmark located at 667 m water depth. Two Calypso cores, one at the centre and one outside the pockmark, along with three box-cores, two inside the pockmark and one outside, were collected to study the geochemistry of gas hydrates, carbonates and pore waters. Two seismic lines, a 3D high resolution random line and a 2D high resolution seismic line, provide a good description of the plumbing of the system. The integrated results depict a very active pockmark characterized by several gas charged-bodies, a well identified BSR marking a hydrate accumulation zone, charged from deeper sources via a network of faults. Hydrates and carbonate concretions have been detected inside the pockmark while only the latter has been found outside. The hydrate analyses show that the hydrate-forming gases are of thermogenic origin, albeit overwhelmingly composed of methane. Pore-water analyses reveal the occurrence of anaerobic oxidation of methane coupled with sulphate reduction at shallow depth (∼200 cm). The chloride concentration profile exhibits both values lower than that of seawater which is inherent to hydrate dissociation after core recovery and positive anomalies (values 7% higher than that of seawater background) at the lowermost part of the core. The latter evidence suggests current or recent hydrate formation at this area. The carbonate dating provides additional temporal information and indicates that this pockmark has been active since ∼21 kyr.

Geophysical data and sampling of the Golo Basin (East Corsica margin) provide the opportunity to study mass balance in a single drainage system over the last 130 kyr, by comparing deposited sediments in the sink and the maximum eroded volume in the source using total denudation proxies. Evaluation of the solid sediments deposited offshore and careful integration of uncertainties from the age model and physical properties allow us to constrain three periods of sedimentation during the last climatic cycle. The peak of sedimentation initiated during Marine Isotopic Stage (MIS) 3 (ca. 45 ka) and lasted until late in MIS 2 (ca. 18 ka). This correlates with Mediterranean Sea palaeoclimatic records and the glaciation in high altitude Corsica. The yield of solid sediment into the Golo Basin drops in the observed present day Mediterranean basins (gauging stations), whereas the palaeo-denudation estimate derived from the sediments over the last glacial period is one to ten times higher than that predicted using cosmogenic or thermochronometer estimates of exhumation. The catchment-wide denudation rate calculated from deposited solid sediment ranges from 47 to 219 mm kyr−1, which is higher than the estimate from palaeosurface ablation in the proximal part of the source (9–140 mm kyr−1) and lower than the distal, narrow, incised channel of the Golo River (160–475 mm kyr−1). This mismatch raises questions about the investigation of denudation at millennial-time scale (kyr) and at higher integrating times (Myr) as a reliable tool for determining the effect of climate change on mountain building and on sedimentary basin models.

An interdisciplinary study was conducted to evaluate the relationship between geological and paleoenvironmental parameters and the bacterial and archaeal community structure of two contrasting subseafloor sites in the Western Mediterranean Sea (Ligurian Sea and Gulf of Lion). Both depositional environments in this area are well-documented from paleoclimatic and paleooceanographic point of views. Available data sets allowed us to calibrate the investigated cores with reference and dated cores previously collected in the same area, and notably correlated to Quaternary climate variations. DNA-based fingerprints showed that the archaeal diversity was composed by one group, Miscellaneous Crenarchaeotic Group (MCG), within the Gulf of Lion sediments and of nine different lineages (dominated by MCG, South African Gold Mine Euryarchaeotal Group (SAGMEG) and Halobacteria) within the Ligurian Sea sediments. Bacterial molecular diversity at both sites revealed mostly the presence of the classes Alphaproteobacteria, Betaproteobacteria and Gammaproteobacteria within Proteobacteria phylum, and also members of Bacteroidetes phylum. The second most abundant lineages were Actinobacteria and Firmicutes at the Gulf of Lion site and Chloroflexi at the Ligurian Sea site. Various substrates and cultivation conditions allowed us to isolate 75 strains belonging to four lineages: Alpha-, Gammaproteobacteria, Firmicutes and Actinobacteria. In molecular surveys, the Betaproteobacteria group was consistently detected in the Ligurian Sea sediments, characterized by a heterolithic facies with numerous turbidites from a deep-sea levee. Analysis of relative betaproteobacterial abundances and turbidite frequency suggested that the microbial diversity was a result of main climatic changes occurring during the last 20 ka. Statistical direct multivariate canonical correspondence analyses (CCA) showed that the availability of electron acceptors and the quality of electron donors (indicated by age) stro

We report on a multidisciplinary study of cold seeps explored in the Central Nile deep-sea fan of the Egyptian margin. Our approach combines in situ seafloor observation, geophysics, sedimentological data, measurement of bottom-water methane anomalies, pore-water and sediment geochemistry, and Th-230/U dating of authigenic carbonates. Two areas were investigated, which correspond to different sedimentary provinces. The lower slope, at similar to 2100 m water depth, indicates deformation of sediments by gravitational processes, exhibiting slope-parallel elongated ridges and seafloor depressions. In contrast, the middle slope, at similar to 1650 m water depth, exhibits a series of debris-flow deposits not remobilized by post-depositional gravity processes. Significant differences exist between fluid-escape structures from the two studied areas. At the lower slope, methane anomalies were detected in bottom-waters above the depressions, whereas the adjacent ridges show a frequent coverage of fractured carbonate pavements associated with chemosynthetic vent communities. Carbonate U/Th age dates (similar to 8 kyr BP), pore-water sulphate and solid phase sediment data suggest that seepage activity at those carbonate ridges has decreased over the recent past. In contrast, large (similar to 1 km(2)) carbonate-paved areas were discovered in the middle slope, with U/Th isotope evidence for ongoing carbonate precipitation during the Late Holocene (since similar to 5 kyr BP at least). Our results suggest that fluid venting is closely related to sediment deformation in the Central Nile margin. It is proposed that slope instability leads to focused fluid flow in the lower slope and exposure of 'fossil' carbonate ridges, whereas pervasive diffuse flow prevails at the unfailed middle slope.

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 (epsilon(Nd)similar to - 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 epsilon(Hf) values (from -1.1 to +13) far more radiogenic than associated sediments (from -7.1 to -12.0) and turbidite sands (from -27.2 to -31.6). epsilon(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 epsilon(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, betw

We present a revised method for the determination of concentrations of rare earth (REE) and other trace elements (Y, Sc, Zr, Ba, Hf, Th) in geological samples. Our analytical procedure involves sample digestion using alkaline fusion (NaOH-Na2O2) after addition of a Tm spike, co-precipitation on iron hydroxides, and measurement by sector field-inductively coupled plasma-mass spectrometry (SF-ICP-MS). The procedure was tested successfully for various rock types (i.e., basalt, ultramafic rock, sediment, soil, granite), including rocks with low trace element abundances (sub ng g(-1)). Results obtained for a series of nine geological reference materials (BIR-1, BCR-2, UB-N, JP-1, AC-E, MA-N, MAG-1, GSMS-2, GSS-4) are in reasonable agreement with published working values.Nous prEsentons une mEthode rEvisEe pour la dEtermination des teneurs en Terres Rares et autres ElEments traces (Y, Sc, Zr, Ba, Hf, Th) dans les Echantillons gEologiques. Notre procEdure analytique implique la digestion des Echantillons par fusion alcaline (NaOH-Na2O2) apres ajout d'un spike de Tm, la co-prEcipitation avec des oxydes de Fer, et la mesure par spectromEtrie de masse a secteur magnEtique couplEe a une source a plasma induit (SF-ICP-MS). La procEdure a EtE testEe avec succes pour plusieurs types de roches (basalte, roche ultramafique, sEdiment, sol, granite), y compris des roches caractErisEes par de faibles teneurs en ElEments traces (sub ng g(-1)). Les rEsultats obtenus pour une sErie de neuf matEriaux de rEfErences gEologiques (BIR-1, BCR-2, UB-N, JP-1, AC-E, MA-N, MAG-1, GSMS-2, GSS-4) sont en accord avec les valeurs de travail publiEes dans la littErature.

The poorly known ferromanganese nodule fauna is a widespread hard substratum community in the deep sea that will be considerably impacted by large-scale nodule mining operations. The objective of this study was to analyze the spatial distribution of the fauna attached to nodules in the Clarion-Clipperton Fracture Zone at two scales; a regional scale that includes the east (14 degrees N, 130 degrees W) and the west (9 degrees N, 150 degrees W) zones and a local scale in which different geological facies (A, B, C and west) are recognizable. The fauna associated with 235 nodules was quantitatively described: 104 nodules from the east zone (15 of facies A, 50 of facies B and 39 of facies C) and 131 nodules from the west zone. Percent cover was used to quantify the extent of colonization at the time of sampling, for 42 species out of the 62 live species observed. Fauna covered up to 18% of exposed nodule surface with an average of about 3%. While species richness increased with exposed nodule surface, both at the regional and at the facies scales (except for facies A), total species density decreased (again except for facies A). When all nodules were included in the statistical analysis, there was no relation between faunal cover and exposed nodule surface. Nevertheless, faunal cover did decrease with exposed nodule surface for the east zone in general and for both facies B and C in particular. Species distributions among facies were significantly different but explained only a very small portion of the variance (similar to 5%). We identified two groups of associated species: a first group of two species and a second group of six species. The other species (34) were independently distributed.. suggesting that species interactions play only a minor role in the spatial distribution of nodule fauna. The flux of particulate organic carbon to the bottom is the only major environmental factor considered to vary between the two zones within this study. We conclude that the high

We report on a reconnaissance analysis of the geochemical composition of authigenic carbonates and sediment samples collected from various seepage sites on the Niger deep-sea fan. Our aim has been to investigate whether evidence for the presence of authigenic carbonates and gas hydrates within sediments is discernible from solid-phase sediment geochemistry. We show that sedimentary Sr/Ca and Mg/Ca ratios can be used to infer the presence of authigenic aragonite (Sr-rich) and Mg-rich carbonate phases (high-Mg calcite, dolomite) in cold seep settings. Using Sr/Ca and Mg/Ca ratios, the proportion (wt.%) of authigenic carbonates in Niger Fan sediments can be calculated from a mixing model between sediment fractions of terrigenous material, biogenic calcite, aragonite and high-Mg calcite. This approach was applied to high-resolution geochemical profiles along sediment cores recovered from various cold seep settings (mud volcano, diapirs, pockmarks, gas-hydrate bearing sediments). Our data reveal that authigenic carbonates occur as discrete phases in sediments from gas-hydrate-bearing areas, suggesting that such carbonate-rich sediment layers may represent paleo-indicators for ancient methane seepage in marine sediments, possibly associated to gas-hydrate reservoirs. (C) 2007 Elsevier B.V. All rights reserved.

A range of X-ray analytical techniques contributes particularly well to the mineralogical and geochemical characterisations of cobalt-rich iron and manganese oxides crusts. X-ray diffraction is used to identify the weak crystallinity of the material. Bulk geochemical characterisation of the crusts is done by X-ray fluorescence for the precise determination of ca. thirty major and trace elements. Fine scale analysis is carried out by electron microprobe to quantitatively map the distribution of elements in oxide phases within the crusts. Microprobe work is essential to obtain the chemical composition of the embedded metallic micro-meteorites.