Éditeur(s) : Elsevier Science Bv
Résumé : For 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 epsilon(Nd) similar to-15.7 to -10.4. Evidence that the epsilon(Nd) 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 epsilon(Nd) 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. (C) 2011 Elsevier B.V. All rights reserved.
Earth And Planetary Science Letters (0012-821X) (Elsevier Science Bv), 2011-12 , Vol. 312 , N. 3-4 , P. 443-452

Droits : 2011 Elsevier B.V. All rights reserved.
http://archimer.ifremer.fr/doc/00066/17754/15571.pdf
DOI:10.1016/j.epsl.2011.10.008
http://archimer.ifremer.fr/doc/00066/17754/

Éditeur(s) : Pergamon-elsevier Science Ltd
Résumé : We report rare earth element (REE) and neodymium (Nd) isotope data for the organic fraction of sediments collected from various depositional environments, i.e. rivers (n=25), estuaries (n=18), open-ocean settings (n=15), and cold seeps (n=12). Sedimentary Organic Matter (SOM) was extracted using a mixed hydrogen peroxide/nitric acid solution (20%-H2O2 – 0.02M-HNO3), after removal of carbonate and oxy-hydroxide phases with dilute hydrochloric acid (0.25M-HCl). A series of experimental tests indicate that extraction of sedimentary organic compounds using H202 may be complicated occasionally by partial dissolution of sulphide minerals and residual carbonates. However, this contamination is expected to be minor for REE because measured concentrations in H2O2 leachates are about two-orders of magnitude higher than in the above mentioned phases. The mean REE concentrations determined in the H2O2 leachates for samples from rivers, estuaries, coastal seas and open-ocean settings yield relatively similar levels, with ΣREE = 109 ± 86 ppm (mean ± s; n=58). The organic fractions leached from cold seep sediments display even higher concentration levels (285 ± 150 ppm; mean ± s; n=12). The H2O2 leachates for most sediments exhibit remarkably similar shale-normalized REE patterns, all characterized by a mid-REE enrichment compared to the other REE. This suggests that the distribution of REE in leached sedimentary organic phases is controlled primarily by biogeochemical processes, rather than by the composition of the source from which they derive (e.g. pore, river or sea- water). The Nd isotopic compositions for organic phases leached from river sediments are very similar to those for the corresponding detrital fractions. In contrast, the SOM extracted from marine sediments display εNd values that typically range between the εNd signatures for terrestrial organic matter (inferred from the analysis of the sedimentary detrital fractions) and marine organic matter (inferred from the analysis of local surface seawater). A notable exception is the case of organic matter (OM) fractions leached from cold seep sediment samples, which sometimes exhibit εNd values markedly different from both terrigenous and surface seawater signatures. This suggests that a significant fraction of organic compounds in these sediments may be derived from chemosynthetic processes, recycling pore water REE characterized by a distinct isotopic composition. Overall, our results confirm that organic matter probably plays an important role in the oceanic REE budget, through direct scavenging and remineralization within the water column. Both the high REE abundances and the shape of shale-normalized patterns for leached SOM also suggest that OM degradation in sub-surface marine sediments during early diagenesis could control, to a large extent, the distribution of REE in pore waters. Benthic fluxes of organic-bound REE could hence substantially contribute to the exchange processes between particulates and seawater that take place at ocean margins. Neodymium isotopes could provide useful information for tracing the origin (terrestrial versus marine) and geographical provenance of organic matter, with potential applications in paleoceanography. In particular, future studies should further investigate the potential of Nd isotopes in organic compounds preserved in sedimentary records for reconstructing past variations of surface ocean circulation.
Geochimica Et Cosmochimica Acta (0016-7037) (Pergamon-elsevier Science Ltd), 2014-09 , Vol. 140 , P. 177-198

Droits : 2014 Elsevier Ltd. All rights reserved.
http://archimer.ifremer.fr/doc/00191/30250/28682.pdf
DOI:10.1016/j.gca.2014.05.016
http://archimer.ifremer.fr/doc/00191/30250/

Éditeur(s) : Elsevier
Résumé : 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, between that for igneous rocks and the,seawater array', which we refer to as the 'zircon-free sediment array' (epsilon(Hf)=0-91 epsilon(Nd)+3.10). Finally, we show that the Hf-Nd arrays for seawater, unweathered igneous rocks, zircon-free and zircon-bearing sediments (epsilon(Hf)= 1.80 epsilon(Nd)+2.35) can all be reconciled, using Monte Carlo simulations, with a simple weathering model of the continental crust. (C) 2008 Elsevier B.V. All rights reserved.
Earth and Planetary Science Letters (0012-821X) (Elsevier), 2009 , Vol. 277 , N. 3-4 , P. 318-326

Droits : 2009 Elsevier B.V. All rights reserved.
http://archimer.ifremer.fr/doc/2009/publication-6451.pdf
DOI:10.1016/j.epsl.2008.10.028
http://archimer.ifremer.fr/doc/00000/6451/