Trace-element-rich brines in eclogitic veins: implications for fluid composition and transport during subduction

Primary and pseudosecondary fluid inclusions occur in oscillatory-and sector-zoned omphacite in eclogitic veins from the Monviso ophiolitic complex in the Western Alps. The inclusions contain aqueous brines and daughter crystals of halite, sylvite, calcite, dolomite, albite, anhydrite and/or gypsum, barite, baddeleyite, rutile, sphene, Fe oxides, pyrite and monazite. This daughter mineral suite indicates high solubilites of Na, K, Ca, Mg, Fe, Zr, Ti, P, Ba, Ce, La, Th, and S species and provides direct evidence for transport of high-fieldstrenght, large-ion-lithophile, and light-rare-earth elements as dissolved species during subduction. Fluid-inclusion heterogeneities preserved within and between adjacent grains in the veins, however, suggest that the scale of fluid equilibration was small. A crack-seal geometry in some of the veins implies that fluid release in pulses rather than steady flow controlled mineral deposition and growth in the veins. From these observations, we develop a model of fluid release and entrapment in which pulses of fluid are associated in time with increments of shear and tensile failure; the rate of fluid release and the reduction in porosity both depend on the rate of plastic flow. Vein fluids may initially be derived from decreptitation of early fluid inclusions in the host eclogites, Small-scale fluid heterogeneities implied by the fluid inclusions in the veins are best interpreted in terms of limited fluid flow, and hence limited metasomatism. We conclude that element recycling into the mantle wedge during subduction will depend at least as strongly on fluid transport mechanisms as on element solubilities in the fluid phase. At Monviso, despite evidence for high trace element solubilities in saline brines, the elements were not removed from the downgoing slab prior to teaching depths of 40 km.     

Oxygen and nitrogen isotopes as tracers of fluid activities in serpentinites and metasediments during subduction

Summary N and O isotope systematics of a suite of high-pressure (HP) and ultrahigh-pressure (UHP) metasediments of the Schistes Lustrés nappe and metaperidotites of the Erro Tobbio Massif from the Alpine-Appennine system are compared with their unmetamorphosed or hydrothermally-altered equivalent from the same localities and from the South West Indian Ridge (SWIR). The HP and UHP rocks studied represent a sequence of pelagic sediments and altered ultramafic rocks subducted to different depths of down to 90 km along a cold geothermal gradient (8 °C/km). Unmetamorphosed and HP metasediments show the same range in δ¹⁵N values irrespective of their metamorphic grade and bulk nitrogen concentrations. Together with several other geochemical features (K, Rb and Cs contents, δD), this indicates that δ¹⁵N values were unaffected by metamorphism and N was not released during subduction. N isotope analysis of serpentinites coupled with δ¹⁸O systematics suggests the involvement of a mafic (crustal) component during partial deserpentinization of the subducted oceanic mantle at the depth locus of island arc magmatism. This does not imply large-scale fluxes as the metagabbros are spatially associated with the analyzed serpentinites. It rather indicates preservation of presubduction chemical and isotopic heterogeneities on a local scale as documented for the metasediments.     

Fluid composition and evolution in coesite-bearing rocks (Dora-Maira massif,Western Alps): implications for element recycling during subduction

Fluid inclusions and F, Cl concentration of hydrous minerals were analysed in the coesite-pyrope quartzite, the interlayered jadeite quartzite and their country-rock gneiss from the Dora-Maira massif using a combination of microthermometry, Raman spectrometry, synchrotron X-ray microfiuorescence and electron microprobe analysis. Three populations of fluid inclusions were recognized texturally and can be related to distinct metamorphic stages. A low-salinity aqueous fluid occurs in the retrogressed country gneiss and as late secondary inclusions in jadeite quartzite and chloritized pyrope. An earlier secondary population is found in matrix quartz of the jadeite- and pyro-pe-quartzites. This population can be related to the early decompression and so to incipient breakdown of garnet into phlogopite-bearing assemblages. The inclusion fluid is highly saline (up to 84 wt% equivalent NaCl) and contains Na, Ca, Fe, Cu and Zn as major cations. In pyrope quartzite, additional K was found in these brines, which locally coexist with CO₂-rich inclusions. The oldest fluid inclusions are preserved in kyanite grains included in fresh pyrope and in pyrope itself. In pyrope, all inclusions have decrepitated and contain magnesite, an Mg-phosphate, sheet-silicate(s), a chloride and an opaque phase, with no fluid preser ved. In contrast, the kyanite inclusions in pyrope preserve primary H₂O-CO₂ low-salinity fluid inclusions, probably owing to the low compressibility of the kyanite inclusions and host garnet. In spite of in-situ re-equilibration, these inclusions can be interpreted as relics of the dehydration fluid that attended pyrope growth. These correlations between textural and chemical fluid inclusion data and metamorphic stages are consistent with the fluid composition calculated from the halogen content of different generations of phlogopite and biotite. The preservation of different fluid compositions, both in time and space, is evidence for local control and possibly origin of the fluids, in agreement with isotopic data. These results, in particular the absence of CO₂ in the jadeite quartzite, are best interpreted in terms of a fluid-melt system evolution. With increasing metamorphism, partitioning of H₂O, Na, Ca, Fe and heavy metals into melt (jadeite quartzite) and Mg, Na/K, F, CO₂ and P(?) into a residual aqueous fluid can account for depletion in Na, Ca and Fe of the pyrope quartzite. During the retrograde path, a _{H 2 O} rose as melt crystallized, generating the two populations of hypersaline and water-rich fluids that were highly reactive to pyrope. The process of fluid-melt interaction envisioned here coupled with models of melt extraction in subduction zones provides an attractive opportunity for the instantaneous ( < 1 Ma) and selective transport of elements between a downgoing slab and the overlying mantle wedge.     

Chemical composition of Luna 20 soil and rock fragments

Abundances of 22 elements, including 9 rare earth elements (REE), have been determined by ‘monostandard’ instrumental neutron activation analysis of samples from the Luna 20 soil and in 6 rock fragments, including a crystalline rock of highland origin, a breccia of similar composition, a glass and a feldspar grain. The soil appears to have been contaminated with W and Mo. The REE content of the soil is very low, being close to 2.3 times below the level in the Luna 16 soil. Sampling errors, for most elements, are negligible in the case of analyses performed on one or several tens of mg of soil, but they become significant on crystalline rock fragments in the 1–2 mg range.     

Chlorine isotopic composition in seafloor serpentinites and high-pressure metaperidotites. Insights into oceanic serpentinization and subduction processes

Bulk-rock chlorine content and isotopic composition (δ³⁷Cl) were determined in oceanic serpentinites, high-pressure metaperidotites and metasediments in order to gain constraints on the global chlorine cycle associated with hydrothermal alteration and subduction of oceanic lithosphere. The distribution of insoluble chlorine in oceanic serpentinites was also investigated by electron microprobe. The hydrothermally-altered ultramafic samples were dredged along the South West Indian Ridge and the Mid-Atlantic Ridge. The high-pressure metamorphic samples were collected in the Western Alps: metaperidotites in the Erro-Tobbio unit and metasediments in the Schistes Lustrés nappe.Oceanic serpentinites show relatively large variations of bulk-rock Cl contents and δ³⁷Cl values with mean values of 1105 ± 596 ppm and −0.7 ± 0.4‰, respectively (n = 8; 1σ). Serpentines formed after olivine (meshes) show lower Cl content than those formed after orthopyroxene (bastites). In bastites of two different samples, Cl is positively correlated with Al₂O₃ and negatively correlated with SiO₂. These relationships are interpreted as reflecting preferential Cl-incorporation into the bastite structure distorted by Al (substituted for Si) rather than different alteration conditions between olivine and orthopyroxene minerals. High-pressure metaperidotites display relatively homogeneous Cl contents and δ³⁷Cl values with mean values of 467 ± 88 ppm and −1.4 ± 0.1‰, respectively (n = 7; 1σ). A macroscopic high-pressure olivine-bearing vein, formed from partial devolatilization of serpentinites at ∼2.5 GPa and 500-600 °C, shows a Cl content and a δ³⁷Cl value of 603 ppm and −1.6‰, respectively. Metasediments (n = 2) show low whole-rock Cl contents (<15 ppm Cl) that did not allow Cl isotope analyses to be obtained.The range of negative δ³⁷Cl values observed in oceanic serpentinites is likely to result from water-rock interaction with fluids that have negative δ³⁷Cl values. The homogeneity of δ³⁷Cl values from the high-pressure olivine-bearing vein and the metaperidotite samples implies that progressive loss of Cl inherited from oceanic alteration throughout subduction did not significantly fractionate Cl isotopes. Chlorine recycled in subduction zones via metaperidotites should thus show a range of δ³⁷Cl values similar to the range found in oceanic serpentinized peridotites.     

Nitrogen isotopes in ophiolitic metagabbros: A re-evaluation of modern nitrogen fluxes in subduction zones and implication for the early Earth atmosphere

Nitrogen contents and isotope compositions together with major and trace element concentrations were determined in a sequence of metagabbros from the western Alps (Europe) in order to constrain the evolution and behavior of N during hydrothermal alteration on the seafloor and progressive dehydration during subduction in a cold slab environment (8 °C/km). The rocks investigated include: (i) low-strain metagabbros that equilibrated under greenschist to amphibolite facies (Chenaillet Massif), blueschist facies (Queyras region) and eclogite facies (Monviso massif) conditions and (ii) highly-strained mylonites and associated eclogitic veins from the Monviso Massif. In all samples, nitrogen (2.6-55 ppm) occurs as bound ammonium () substituting for K or Na-Ca in minerals. Cu concentrations show a large variation, from 73.2 to 6.4 ppm, and are used as an index of hydrothermal alteration on the seafloor because of Cu fluid-mobility at relatively high temperature (>300 °C). In low-strain metagabbros, δ¹⁵N values of +0.8‰ to +8.1‰ are negatively correlated with Cu concentrations. Eclogitic mylonites and veins display Cu concentrations lower than 11 ppm and show a δ¹⁵N-Cu relationship that does not match the δ¹⁵N-Cu correlation found in low-strain rocks. This δ¹⁵N-Cu correlation preserved in low-strain rocks is best interpreted by leaching of Cu-N compounds, possibly of the form Cu(NH₃)₂²⁺, during hydrothermal alteration. Recognition that the different types of low-strain metagabbros show the same δ¹⁵N-Cu correlation indicates that fluid release during subduction zone metamorphism did not modify the original N and Cu contents of the parent hydrothermally-altered metagabbros. In contrast, the low Cu content present in eclogitic veins and mylonites implies that ductile deformation and veining were accompanied either by a loss of copper or that externally-derived nitrogen was added to the system.We estimate the global annual flux of N subducted by metagabbros as 4.2 (±2.0) × 10¹¹ g/yr. This value is about half that of sedimentary rocks, which suggests that gabbros carry a significant portion of the subducted nitrogen. The net budget between subducted N and that outgassed at volcanic arcs indicates that ∼80% of the subducted N is not recycled to the surface. On a global scale, the total amount of N buried to the mantle via subduction zones is estimated to be three times higher than that released from the mantle via mid-ocean ridges, arc and intraplate volcanoes and back-arc basins. This implies that N contained in Earth surface reservoirs, mainly in the atmosphere, is progressively transferred and sequestered into the mantle, with a net flux of ∼9.6 × 10¹¹ g/yr. Assuming a constant flux of subducted N over the Earth’s history indicates that an amount equivalent to the present atmospheric N may have been sequestered into the silicate Earth over a period of 4 billion years.     

X-ray imaging of uranium in individual fluid inclusions

The spatial distribution of major (K, Ca, Mn, Fe) and trace elements (Ti, Cr, Cu, As, Br, Rb, Sr, Zr, Pb, Th, U) were determined in individual fluid inclusions from quartz veins of the Streltsov uranium deposit, Russia, using synchrotron radiation X-ray fluorescence (SXRF). The analyses were performed on the beamline ID-22 Micro-FID (Fluorescence, Imaging, Diffraction) of the European Synchrotron Research Facility (ESRF, Grenoble, France). Fluorescence X-ray maps of single fluid inclusions show a relatively homogeneous distribution of most elements throughout the inclusion, whereas Fe and, to a lesser extent, Sr display highly localized count rates. This observation argues for the presence of minute, optically invisible, compounds that are precipitated inside the inclusion. Simple model calculations indicate that relatively diluted solutions (10–100 ppm U) trapped at geologically relevant temperatures (e.g. 250 °C) would precipitate submicron sized particles. These particles would be highly reactive to the photon flux but not necessarily visible under the microscope. These results indicate that third-generation synchrotron light source can be a powerful technique to study the physical processes undergone by the fluid. When combined with chemical data, this technique can help to clarify fluid transport properties in natural systems.     

Xenon in Archean barite: Weak decay of Ba, mass-dependent isotopic fractionation and implication for barite formation

In order to investigate radioactive decay of ¹³⁰Ba and ¹³²Ba which have half-lives on the order 10²⁰-10²¹ a, the isotopic composition of xenon has been measured in 3.5 Ga barite of the Dresser Formation, Pilbara, Western Australia. The analyzed samples were collected at about 86 m depth from a diamond drill core (Pilbara Drilling Project). The fact that the sample has been shielded from modern cosmic ray exposure reduces the number of potentially interfering production pathways, simplifying interpretation of the Xe isotope spectrum. This spectrum is clearly distinct from that of either modern or ancient atmospheric Xe. A strong excess of ¹³⁰Xe is identified, as well as other isotopic excursions which are attributed to mass-dependent isotopic fractionation and contributions from products of uranium fission. The mass-dependent fractionation, estimated at 2.1 ± 0.3% amu⁻¹, can be accounted for by mutual diffusion and Rayleigh distillation during barite formation that is consistent with geological constraints. After correction for mass-dependent fractionation, the concentrations of fissiogenic Xe isotopes demonstrate that the U-Xe isotope system has remained closed over 3.5 Ga. From the excess of ¹³⁰Xe, the two successive electron capture half life of this isotope is estimated at 6.0 ± 1.1 × 10²⁰ a, which is 3.4 times faster than previously estimated (Meshik et al., 2001). We could not find evidence of ¹³²Ba decay within our Xe isotope spectra.     

Radioactivité artificielle de l'air

Summary The author summarizes the various results concerning the total -radioactivity of the samples taken either at the level of the earth or at different altitudes. Furthermore, in the first paragraph, the difficulties encountered during these measurements as well as the observations made after the French explosions, are indicated. The results, in the second paragraph are discussed either under the form of radioactivity curves dependant on the altitude, or through employing the notion of the speed of the fall out.     

High-resolution imaging of sulfur oxidation states, trace elements, and organic molecules distribution in individual microfossils and contempo rary microbial filaments

Owing to the delicate nature of fossil microorganisms and inherent difficulties for discriminating true fossils from artifacts, an important challenge is to extract unequivocal biogenic information from individual microfossils using high-resolution, nondestructive and sensitive techniques. Here, we use combined synchrotron (X-ray microfluorescence, X-ray absorption near-edge structure and infrared microspectroscopies) and particle-induced X-ray emission analyses to image the spatial distribution at a μm-scale of a variety of potential biogenic markers (major and trace elements, C-H bonds, and sulfur-oxidation states) in individual prokaryotic microfossils. In particular, we analyzed iron-oxide fossil filaments of putative biogenic origin encapsulated with amorphous silica from a fragment of an inactive hydrothermal chimney of the East Pacific Rise. In order to test the biogenic origin of the markers studied, we performed the same analyses on filamentous bacteria corresponding most likely to the ?-Proteobacteria, and collected from substrates exposed to a hydrothermal fluid vent at the Mid-Atlantic Ridge. In both types of fossil and contemporary filaments, the occurrence of CH₂ groups and of three sulfur species (sulfate, sulfite, organic S) showing heterogeneous distribution that underline the cytoplasm of individual cells in the case of the present-day filament, suggests that the original microorganisms were actively metabolizing sulfur. These results show the large potential of combining high-resolution synchrotron techniques to analyze individual microfossils for extracting unequivocal biogenic information. Furthermore, they also suggest that cooccurrence of different sulfur oxidation states within single microfossils could constitute a biogenic metabolic marker indicating S-metabolizing activities.