Éditeur(s) : Gauthier-Villars
Résumé : The analysis of humic compounds by elemental analysis, PY-GC-MS and HPLC techniques permitted determination of the origin of organic inputs, essentially terrestrial, and the effects of environmental conditions in the deposits along a north-south transect through the Rhone delta, from the river mouth to the open sea. In the prodelta the sedimentation of fine particles enriches the sediments in organic matter. The humic compound contents were relatively low in sediments, perhaps due to a rapid burying of organic matter which leads to anoxic conditions. In sediments fulvic acids are more abundant than humic acids. Elemental analysis indicated that fulvic acids were enriched in hydrogen and nitrogen as compared to humic acids. Furthermore, H/C and N/C ratios increased in the fulvic and humic acids towards the open sea, related to a more marine character. Pyrolysis analysis showed some differences between the chemical composition of fulvic acids which correspond to low molecular weights enriched in carbohydrates, and that of humic acids, high molecular weight compounds which are enriched in phenols and aromatic hydrocarbons. The pyrolysis-derived phenols were abundant near the river mouth, decreasing towards the open sea as nitrogen-containing-compounds increased. Near the river mouth, the abundance of phenolic aldehydes demonstrated by HPLC emphasized the existence of fresh organic matter. On the other hand, off the mouth, an increase in phenolic acids could indicate a more degraded organic material. The fractionation of humic acids in various classes of molecular weight species using ultrafiltration (Amicon membranes) and their analysis showed that, close to the river mouth, the large proportion of the high molecular weight humic compounds observed was enriched in phenols and carbohydrates, probably inherited from the terrestrial ligno-cellulosic complex. This process seemed to be superimposed on the increase of molecular weights which is usually observed as the environment becomes purely marine. These humic compounds would derived either from organic matter from terrestrial soils swept along by the river flow, after deposition on its bed or, more probably, from high molecular weight compounds which, associated with the mineral phase, flocculated when reaching the fluvio-marine front. Generally, the low molecular weight fractions were enriched in hydrogen and nitrogen. Near the river mouth, nitrogen-containing compounds were concentrated in the low molecular weight classes which correspond to organic molecules regarded as humic precursors. Off the mouth, they were incorporated into the high molecular weight complexes, certainly of marine origin.
Oceanologica Acta (0399-1784) (Gauthier-Villars), 1992 , Vol. 15 , N. 1 , P. 61-74

Droits : info:eu-repo/semantics/openAccess
http://archimer.ifremer.fr/doc/00101/21187/18804.pdf
http://archimer.ifremer.fr/doc/00101/21187/

Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
LA-ICP-MS analysis of the chemical composition of biogenic carbonate has many applications in the environmental sciences but the characteristics of the material produced by the ablation process are largely unknown. To fill this gap, we have undertaken a study of the chemical and physical nature of particles produced by laser ablation of biogenic carbonates. SEM imaging suggests that laser ablation produces two distinct particle populations, one consisting of microsize particles and the other of nanosize particles. A 213 nm laser gives rise to a higher proportion of microsize particles than a 193 nm laser, probably because the 213 nm laser couples less completely with carbonate material. The microsize particles appear to form by photomechanical fracturing along lines of cleavage or weakness, rather than by hydrodynamic sputtering (as is generally observed for silicates). Chemical analysis of the carbonate particles suggests that little chemical fractionation of biogenic carbonates occurs during the ablation process or during transport to the plasma. This is supported by the constancy of the fractionation factor ([X/Ca](measured)/[X/Ca] true) during the course of an ablation of a carbonate standard. In contrast, changes in the fractionation factor during the first few seconds of ablation of the NIST 612 are observed for some elements. This difference in fractionation is likely to result from the different formation mechanisms of the microsize particles.
ISSN: 0267-9477

hal-00411933
https://hal.archives-ouvertes.fr/hal-00411933
DOI : 10.1039/b706727e

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Highly siderophile element concentrations (HSE: Re and platinum-group elements (PGE)) are presented for gabbros, gabbroic eclogites and basaltic eclogites from the high-pressure Zermatt-Saas ophiolite terrain, Switzerland. Rhenium and PGE (Os, Ir, Ru, Rh, Pt, Pd) abundances in gabbro- and eclogite-hosted sulphides, and Re-Os isotopes and elemental concentrations in silicate phases are also reported. This work, therefore, provides whole rock and mineral-scale insights into the PGE budget of gabbroic oceanic crust and the effects of subduction metamorphism on gabbroic and basaltic crust. Chondrite-normalised PGE patterns for the gabbros are similar to published mid-ocean ridge basalts (MORB), but show less inter-element fractionation. Mean Pt and Pd contents of 360 and 530 pg/g, respectively, are broadly comparable to MORB, but gabbros have somewhat higher abundances of Os, Ir and Ru (mean: 64, 57 and 108 pg/g). Transformation to eclogite has not significantly changed the concentrations of the PGE, except Pd which is severely depleted in gabbroic eclogites relative to gabbros (similar to 75% loss). In contrast, basaltic eclogites display significant depletion of Pt (>= 60%), Pd (>85%) and Re (50-60%) compared with published MORB, while Os, Ir and Ru abundances are broadly comparable. Thus, these data suggest that only Pt, Pd and Re, and not Os, Ir and Ru, may be significantly fluxed into the mantle wedge from mafic oceanic crust. Re-Os model ages for gabbroic and gabbroic eclogite minerals are close to age estimates for igneous crystallisation and high-pressure metamorphism, respectively, hence the HSE budgets can be related to both igneous and metamorphic behaviour. The gabbroic budget of Os, Ir, Ru and Pd (but not Pt) is dominated by sulphide, which typically hosts >90% of the Os, whereas silicates account for most of the Re (with up to 75% in plagioclase alone). Sulphides in gabbroic eclogites tend to host a smaller proportion of the total Os (10-90%) while silicates are important hosts, probably reflecting Os inheritance from precursor phases. Garnet contains very high Re concentrations and may account for >50% of Re in some samples. The depletion of Pd in gabbroic eclogites appears linked, at least in part, to the loss of Ni-rich sulphide. Both basaltic and gabbroic oceanic crust have elevated Pt/Os ratios, but Pt/Re ratios are not sufficiently high to generate the coupled Os-186-Os-187 enrichments observed in some mantle melts, even without Pt loss from basaltic crust. However, the apparent mobility of Pt and Re in slab fluids provides an alternative mechanism for the generation of Pt- and Re-rich mantle material, recently proposed as a potential source of Os-187-Os-186 enrichment.
ISSN: 0016-7037

hal-00420072
https://hal.archives-ouvertes.fr/hal-00420072
DOI : 10.1016/j.gca.2008.11.036

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Several recent studies have documented that reactions between melt and crystal mush in primitive gabbroic rocks (via reactive porous flow) have an important control in the formation of the lower oceanic crust and the evolution of MORBs. In this context, olivine-rich rocks can form either by fractional crystallization of primitive melts or by open system reactive percolation of pre-existing (possibly mantle-derived) olivine matrix. To address this question, we performed in-situ trace element analyses (by LA-ICP-MS) of olivine from the Erro-Tobbio ophiolite Unit (Ligurian Alps), where mantle peridotites show gradational contacts with an hectometer-scale body of troctolites and plagioclase wehrlites, and both are cut by later decameter-wide lenses and dykes of olivine gabbros. Previous studies inferred that troctolites and olivine gabbros represent variably differentiated crystallization products from primitive MORB-type melts. Olivines in the three rock types (mantle peridotites, troctolites, olivine gabbros) exhibit distinct geochemical signature and well-defined elemental correlations. As expected, compatible elements (e.g. Ni) show the highest concentrations in peridotites (2580–2730 ppm), intermediate in troctolites (2050–2230 ppm) and lowest in gabbros (1355–1420 ppm), whereas moderate incompatible elements (e.g. Mn, Zn) show the opposite behaviour. By contrast, highly incompatible elements like Zr, Hf, Ti, HREE are variably enriched in olivines of troctolites, and the enrichment in absolute concentrations is coupled to development of significant HFSE/REE fractionation (ZrN/NdN up to 80). AFC modelling shows that such large ZrN/NdN ratios in olivines are consistent with a process of olivine assimilation and plagioclase crystallization at decreasing melt mass, in agreement with textural observations. In-situ trace element geochemistry of olivine, combined with microstructural investigations, thus appears a powerful tool to investigate reactive percolation and the origin of olivine-rich rocks in the lower oceanic crust.
ISSN: 0016-7037

hal-01419938
https://hal.archives-ouvertes.fr/hal-01419938
DOI : 10.1016/j.gca.2016.06.029

Éditeur(s) : HAL CCSD Elsevier
Résumé : In situ analysis of major elements, platinum-group elements and Os isotope composition data for 170 grains of Ru–Os–Ir alloys from podiform chromitites in the Luobusa and Dongqiao ophiolites, Tibet, provide new constraints on the sources of the alloy grains, the Os-isotope composition of the Neo-Tethyan oceanic upper mantle, and the timing of melt–rock reactions in the ultramafic peridotites of the host ophiolites. Most alloy grains are osmiridium and iridosmine. Based on elemental and isotopic compositions, two populations can be identified. Group I, found in both ophiolite bodies, has fractionated PGE patterns typical of alloys and homogeneous 187Os/188Os 0.12645 ± 4 (2s; n = 145). Group II alloys from the Dongqiao ophiolites show smooth PGE patterns and 187Os/188Os ranges from 0.12003 to 0.12194 (yielding Re-depletion ages ≥ 1.1 Ga). Both the PGE patterns and the Os isotopic compositions of Group II resemble those of sulfides residual after melting. Group I alloys represent an early cumulate phase during the crystallization of magmas and are interpreted as derived from an asthenospheric melt. In contrast, Group II alloys are inferred to derive from the breakdown of residual sulfides from the mantle section of the ophiolite, which may represent relics of a sub-continental lithospheric mantle. The coexistence of the two groups of alloys in Dongqiao samples reflects interaction between asthenosphere-derived melts and old depleted lithospheric mantle and suggests that the chromitites originated through melt–rock reactions. The data on the Group I alloys support the hypothesis that the Re–Os evolution of the convective oceanic mantle resembles that of enstatite chondrites.
ISSN: 0012-821X

hal-00404967
https://hal.archives-ouvertes.fr/hal-00404967
DOI : 10.1016/j.epsl.2007.05.044