Sédimentation organique profonde sur la marge continentale Namibienne (Luderitz, Atlantique Sud-Est) / impacts des variations climatiques sur la paléoproductivité.

L'objectif de cette étude multimarqueurs est de fournir une meilleure compréhension du rôle joué par le système d'upwellings du Benguela vis à vis de la séquestration du carbone au cours des deux derniers cycles climatiques. Les sédiments de la pente continentale namibienne sont riches en matière organique (MO) bien que les processus sédimentaires soient exclusivement hémipélagiques. La première partie de ce travail consiste en la détermination des mécanismes de préservation qui ont participé à la fossilisation de la MO dans la colonne d'eau et le sédiment et leur distribution du haut en bas de pente, au large de Lüderitz (25°6S). Les analyses moléculaires, spectroscopiques, pétrographiques et les pyrolyses révèlent que l'enfouissement de carbone organique était plus efficace pendant les périodes glaciaires du fait de flux de MO accrus vers le sédiment. Ces flux agissent positivement sur l'initiation de mécanismes de fossilisation tels que la sulfuration naturelle. Par ailleurs, des associations organo-minérales dans la colonne d'eau ont probablement été responsables de la protection pendant le transport d'une quantité non négligeable de MO, et assuré son accumulation sur la pente inférieure. Les teneurs en carbone organique varient au rythme des cycles glaciaires-interglaciaires. La deuxième étape de l'étude est donc consacrée à l'estimation des effets des variations climatiques sur la paleoproductivité et les flux exportés. L'étude des signaux d15N, de la taille des particules lithogéniques et des contenus terrigènes et biogènes des sédiments montre que la productivité, soutenue par l'apport de nitrate en surface, n'est que partiellement controllée par la force des alizés. Les advections de masses d'eaux Angolaises, Indiennes et l'utilisation des nutriments en Antarctique conditionnent l'alimentation en nitrate et silicium, le rendement et la nature de la production primaire de l'upwelling à l'échelle des cycles climatiques.The goal of this multi-proxy study is to allow a better understanding of the local role played by the Benguela upwelling system regarding carbon sequestration over the last 2 climatic cycles. Outstandingly high organic matter (OM) accumulation occurs on the Namibian slope albeit sedimentary processes are exclusively hemipelagic. First, we investigate organic matter preservation mechanisms that have acted at the sediment as well as in the water column, and their effectiveness and distribution over the organic-rich slope off Lüderitz (25°6S). Pyrolysis results as well as petrographic, spectroscopic and molecular analyses reveal that OM burial was more effective during glacial periods due to higher OM fluxes to the sediment, which promoted sulphurization processes. In addition, organo-mineral association presumably protected OM during sinking in the water column and ensured its accumulation on the lower slope. Organic carbon contents of the sediment show climatic-related variations. We thus examine the effects of glacial-interglacial changes on paleoproductivity and export fluxes by deciphering the d15N signals, dust grain-size records, biogenic and terrigenous contents of three cores distributed from the upper to the lower slope (from 1000 to 3600m). We suggest that nitratesustained paleoproductivity is only partly controlled by wind-strength. Angola and Indian water mass advection in the Benguela region as well as nutrient utilization in the Souhern Ocean both affect nitrate and silica supplies to the upwellings and hence, the attendant productivity and its rain ratio over climatic cycles

Deglacial Si remobilisation from the deep-ocean reveals biogeochemical and physical controls on glacial atmospheric CO2 levels

During the last glacial period, the sluggish deep Ocean circulation sequestered carbon into the abyss leading to the lowering of atmospheric CO2. The impact of this redistribution on biologically essential nutrients remains poorly constrained. Using sedimentary δ30 Si of diatoms and biogenic accumulation rates in the Eastern Equatorial Pacific (EEP), we present evidences for the remobilisation of dissolved Silica (DSi) along with carbon from the deep ocean during the Last Deglaciation. Because DSi is essential for diatoms growing in the surface ocean, its concentration in the abyss during the glacial periods amounts to a negative feedback on the oceanic CO2 uptake. However, this effect can be muted by the increased Fe inputs during glacial periods which reduces diatom Si requirements in Fe limited regions such as the EEP. Our results from the EEP suggest that the efficiency of the biological CO2 pump and the size of the local CO2 source is tightly controlled by changes in DSi utilisation driven by Fe availability across the last glacial-interglacial transition.We use a modified PANDORA box model to illustrate that the inventory of DSi in the global ocean surface is controlled by Fe availability in HNLC areas rather than by straightforward Si supply though upwelling. The Holocene is characterised by a fast mode of Si cycling driven by high biological requirement for Si under conditions of iron limitation and efficient overturning, promoting CO2 outgassing and an inefficient biological C pump via the rapid exhaustion of DSi in the surface. The last glacial period saw slower marine Si cycling as a result of decreased DSi biological requirement under Fe-replete conditions in the sea surface and increased Si and CO2 sequestration in the abyssal ocean. The switch between the two modes of Si cycling happened at 15 ka BP, i.e. mid-deglaciation, and resulted in contrasting biological carbon drawdown responses in the EEP and globally between both phases of the deglacial CO2 rise. This illustrates that in addition to deep-sea CO2 storage and overturning, the efficiency of the biological pump also plays a crucial role in determining ocean-atmosphere CO2 exchange and shows the dual controls of ocean circulation and Fe-Si availability in this process.</p

The record of sea water chemistry evolution during the Ediacaran–Cambrian from early marine cements

Abstract The Ediacaran–Cambrian Radiation marks the widespread appearance of metazoans and calcareous biomineralised hard parts. These innovations occurred during an interval of dynamic changes in marine redox and sea water chemistry. Here, changing carbonate mineralogy, Mg/Ca ratios and rare earth element concentrations including the relative abundance of cerium (Ce anomaly: Ceanom) are documented to track sea water oxygen levels, in well‐preserved early marine cements from shallow marine reefs from Cambrian Stages 2–4 (ca 525–512 Ma). First, integrating the mineralogical data with published records, several shifts in dominant carbonate mineralogy are inferred: ‘dolomite‐aragonite seas’ in the late Ediacaran; ‘aragonite/high‐Mg calcite seas’ in Cambrian Stage 2; a temporary shift to a ‘calcite sea’ during early Cambrian Stage 3; an ‘aragonite sea’ between late Cambrian Stage 3 and late Cambrian Stage 4, then a gradual shift from mixed ‘aragonite–calcite seas’ during the middle and upper Cambrian towards a ‘calcite sea’ by the early Ordovician. Second, based on measured mMg/Ca in early marine cements, calculated sea water mMg/Ca at 15 and 35°C ranges from 1.2 to 0.8 in Cambrian Stage 2, 0.7–0.4 in Stage 3 and 1.4–0.9 in Stage 4 respectively. Finally, analysed Ceanom data combined with existing Ceanom data suggest potentially three phases of global oxic expansion. First, a long‐lived phase of progressive oxygenation during the late Ediacaran to Fortunian (ca 550–540 Ma; average Ceanom from 0.99 to 0.41), and possibly two shorter phases during early Cambrian Stage 3 (ca 519 Ma; average Ceanom from 0.91 to 0.40) and Stage 4 (ca 512 Ma; average Ceanom from 1.02 to 0.49), bounded by intervals of more dominant anoxia. Summarising, these data demonstrate that early marine cements offer an underused and high‐resolution archive of shallow marine redox and sea water chemistry through this critical transition in Earth's evolution

Organic matter accumulation and preservation controls in a deep sea modern environment: an example from Namibian slope sediments.

The Lüderitz upwelling cell is presently the most productive area of the Benguela current system and abundant organic matter (OM) accumulates on the adjacent slope sediments even at great water depth. OM from two cores taken on the slope and covering the last 280 kyear was analysed in terms of "petroleum quality" (Rock-Eval), chemical features (FTIR, EDS) and petrographic composition (light microscopy and TEM). These data indicate that the OM is more oxidized at 3606 m water depth than on the upper slope sediments (1029 m) although the petroleum quality of the OM throughout the deep-water core remains surprisingly high for hemipelagic deep-sea sediments (HI=200–400 mg/g). The petroleum quality of OM accumulated on the upper slope is consistently high: HI averages 450 mg/g. Two petrographic types of OM are distinguishable from microscopic observation, each ascribed to distinctive preservation mechanisms: (1) ‘Granular' amorphous OM, which dominates in the deep-water core, is formed by organo-mineral aggregates. Aggregation appears to be the primary preservation mode at this depth although is quantitatively limited (maximum TOC value of 4 wt.% of bulk sediment obtained through this process). The ultrastructure of the aggregates highlights an intimate association pattern between sedimentary OM and clays. (2) ‘Gel-like' nannoscopically amorphous OM (NAOM) largely dominates at 1000 m water depth and contains sulfur. Thus, early diagenetic sulfurization was probably involved in the preservation of this OM, but a contribution from the classical degradation–recondensation pathway cannot be ruled out. Moreover, selective preservation occurred at both sites but represents an insignificant part of the OM. Organic fluxes mainly control the occurrence and extent of sulfurisation at both water depths by determining the redox conditions at the sea floor. Aggregate formation is limited by both organic and mineral fluxes at the lower slope whereas OM supply is never limiting on the upper slope. Although consistently operating through time at both depths, preservation by organo-mineral association is limited by mineral availability and thus accounts for a relatively minor portion of the OM accumulated on this organic-rich slope. In the case of large organic fluxes, sulfurisation and/or degradation–recondensation is required to obtain TOC contents above 4 wt.% of bulk sediment in the area

Tracing the role of Arctic shelf processes in Si and N cycling and export through the Fram Strait: insights from combined silicon and nitrate isotopes

Nutrient cycles in the Arctic Ocean are being altered by changing hydrography, increasing riverine inputs, glacial melt and sea-ice loss due to climate change. In this study, combined isotopic measurements of dissolved nitrate (δ15N-NO3 and δ18O-NO3) and silicic acid (δ30Si(OH)4) are used to understand the pathways that major nutrients follow through the Arctic Ocean. Atlantic waters were found to be isotopically lighter (δ30Si(OH)4=+ 1.74 ‰) than their polar counterpart (δ30Si(OH)4=+ 1.85 ‰) owing to partial biological utilisation of dissolved Si (DSi) within the Arctic Ocean. Coupled partial benthic denitrification and nitrification on Eurasian Arctic shelves lead to the enrichment of δ15N-NO3 and lighter δ18O-NO3 in the polar surface waters (δ15N-NO3= 5.44 ‰, δ18O-NO3= 1.22 ‰) relative to Atlantic waters (δ15N-NO3= 5.18 ‰, δ18O-NO3= 2.33 ‰). Using a pan-Arctic DSi isotope dataset, we find that the input of isotopically light δ30Si(OH)4 by Arctic rivers and the subsequent partial biological uptake and biogenic Si burial on Eurasian shelves are the key processes that generate the enriched isotopic signatures of DSi exported through Fram Strait. A similar analysis of δ15N-NO3 highlights the role of N-limitation due to denitrification losses on Arctic shelves in generating the excess dissolved silicon exported through Fram Strait. We estimate that around 40 % of DSi exported in polar surface waters through Fram Strait is of riverine origin. As the Arctic Ocean is broadly N-limited and riverine sources of DSi are increasing faster than nitrogen inputs, a larger silicic acid export through the Fram Strait is expected in the future. Arctic riverine inputs therefore have the potential to modify the North Atlantic DSi budget and are expected to become more important than variable Pacific and glacial DSi sources over the coming decades.</p

North Atlantic temperature control on deoxygenation in the northern tropical Pacific

Ocean oxygen content is decreasing with global change. A major challenge for modelling future declines in oxygen concentration is our lack of knowledge of the natural variability associated with marine oxygen inventory on interannual and multidecadal timescales. Here, we present 10 annually resolved 200 year-long records of denitrification, a marker of deoxygenation, from a varved sedimentary archive in the North Pacific oxygen minimum zone covering key periods over the last glacial–interglacial cycle. Spectral analyses on these records reveal strong signals at periodicities typical of today’s Atlantic multidecadal oscillation. Modern subsurface circulation reanalyses regressed on the positive Atlantic and Pacific Climatic Oscillation indices further confirm that North Atlantic temperature patterns are the main control on the subsurface zonal circulation and therefore the most likely dominant driver of oxygen variability in the tropical Pacific. With currently increasing temperatures in the Northern Hemisphere high latitudes and North Atlantic, we suggest deoxygenation will intensify in the region

Silicic acid biogeochemistry in the Gulf of California: Insights from sedimentary Si isotopes

Iron is considered to play a large role in the cycling of Si in Fe-limited regions of the ocean, but little is known about its role in Si biogeochemistry outside these areas. Here, we present published sediment trap data, new nutrient profiles and high resolution sedimentary records (Si isotopes, Biogenic silica%, N% and C%) from the Gulf of California, a non-Fe-limited region, to investigate the history of Si cycling in this highly productive basin. Modern nutrient profiles show that silicic acid in subsurface waters is in excess relative to nitrate and is therefore incompletely utilized during moderate winter upwelling events. Modern data, however, suggest that during intense upwelling episodes, silicic acid is preferentially utilized relative to nitrate by the biota, which we suggest reflects transient iron limitation. Our new delta Si-30 record from the Guaymas Basin shows dramatic variations at millennial timescales. Low delta Si-30 values synchronous with Heinrich events are interpreted as resulting from the decline in Si(OH)(4) utilization at times of decreased upwelling strength, while nearly complete Si(OH)(4) utilization was observed at times of invigorated upwelling and increased opal burial during the Holocene, the Bolling-Allerod and the last glacial period. We attribute the complete utilization of Si(OH)(4) to the occurrence of transient Fe limitation at these times. Our study highlights the importance of Fe limitation on Si and C cycling in coastal upwelling regions and suggests that upwelling dynamics, in combination with Fe availability, have the potential to modulate marine Si distribution and opal burial even at short timescales.KEYWORDS: North Pacific, Coastal upwelling regimes, Climate change, Marine diatoms, Biogenic silica, Guaymas basin, Equatorial Pacific, Iron, Late quaternary, Southern ocea

Recent sedimentation of organic matter along the SE Atlantic Margin : A key for understanding deep offshore petroleum source rocks.

Classical views for the deposition of organic-rich sediments in deep-sea environments invoke two principal types of oceanographic and sedimentologic settings. The first is confined basins in which stratified oxygen depleted waters lead to anoxic preservation of organic matter in the water column and in underlying sediments (Demaison and Moore, 1980). The second is an open ocean setting where the episodic mass transfers due to slope sediment instability lead to the rapid burial of outer-shelf and upper slope-derived organic matter and its consequent preservation due to limited oxic or anoxic degradation (Stow, 1987). Other studies have shown, however, that organic matter in modern deep-sea sediments may occur in high amounts where oxygen is not significantly depleted (Pedersen and Calvert, 1990). Recent studies have demonstrated that highly biological productive areas, such as the upwelling zones associated to the Benguela Current in S-E Atlantic, may deliver sufficient quantity of organic material to (1) outbalance the degradative capacity of the water column and (2) sustain the formation of organic-rich sediments even in deep and oxygenated conditions (Bertrand et al., 2003). It appears that the S-E Atlantic margins provide a good example for revisiting the sedimentology of organic matter in deep water environments in the frame of the GDR Marges Continentales. This may have important implications for a better understanding of the distribution of ancient source rocks in deep offshore petroleum systems (Huc et al., 2001; Bertrand et al., 2003)