Neon isotopic composition of the mantle constrained by single vesicle analyses

© The Author(s), 2016. This is the author's version of the work and is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Earth and Planetary Science Letters 449 (2016): 145-154, doi:10.1016/j.epsl.2016.05.052.The origin of volatiles on Earth is still a matter of debate. Noble gases are an efficient geochemical tool to constrain Earth formation processes due to their inertness. Several studies have focused on the neon isotopic composition of the lower mantle because the 20Ne/22Ne ratio is thought to reflect that of Earth’s primordial components. Two models to explain the origin of light noble gases on Earth have been proposed: either solar wind implantation onto the Earth's solid precursors or dissolution into the mantle of a primordial atmosphere captured from solar nebula gas. In order to test these two models, we analyzed the noble gas compositions (helium, neon and argon) of two submarine oceanic island basalt glasses from Fernandina volcano (Galápagos archipelago), which have among the most primitive/unradiogenic terrestrial helium and neon isotopic compositions. Several sample pieces are studied both by step-crushing and by laser ablation analyses of single vesicles. Results of step-crushing are consistent with those of laser ablation analyses, but the latter results provide new insights into the origin of atmospheric contamination. The single-vesicle laser-ablation measurements overlap with the step crushing results, but have systematically higher 40Ar/36Ar, and 3He/36Ar, suggesting less atmospheric contamination using this method. The single vesicle data therefore suggest that atmospheric contamination is introduced by exposure to the modern atmosphere, after sample collection. 3He/4He values are about 23 times the atmospheric ratio (R/Ra) for the two Fernandina (Galápagos) samples, in agreement with previous studies. We obtain 20Ne/22Ne and 40Ar/36Ar isotopic ratios as high as 12.91 and 9400, respectively, for the mantle source of the Galápagos hotspot. The new data show that step-crushing and laser ablation analyses are complementary methods that should be used together to derive the noble gas ratios in uncontaminated samples. The results of neon compositions are consistent with previous hotspot studies and support the model of solar wind implantation associated with sputtering to explain helium and neon origins on Earth.M.D.K. acknowledges support from NSF OCE in collecting the samples and allowing his participation in this study (OCE-1259218 and OCE-1232985). M.M. acknowledges the financial support from the UnivEarthS Labex program of Sorbonne Paris Cité (ANR-10-LABX-0023 and ANR-11-IDEX-0005-02).2018-06-0

Hydrothermal replacement of biogenic and abiogenic aragonite by Mg-carbonates – Relation between textural control on effective element fluxes and resulting carbonate phase

Dolomitization, i.e., the secondary replacement of calcite or aragonite (CaCO3) by dolomite (CaMg[CO3]2), is one of the most volumetrically important carbonate diagenetic processes. It occurs under near surface and shallow burial conditions and can significantly modify rock properties through changes in porosity and permeability. Dolomitization fronts are directly coupled to fluid pathways, which may be related to the initial porosity/permeability of the precursor limestone, an existing fault network or secondary porosity/permeability created through the replacement reaction. In this study, the textural control on the replacement of biogenic and abiogenic aragonite by Mg-carbonates, that are typical precursor phases in the dolomitization process, was experimentally studied under hydrothermal conditions. Aragonite samples with different textural and microstructural properties exhibiting a compact (inorganic aragonite single crystal), an intermediate (bivalve shell of Arctica islandica) and open porous structure (skeleton of coral Porites sp.) were reacted with a solution of 0.9 M MgCl2 and 0.015 M SrCl2 at 200 °C. The replacement of aragonite by a Ca-bearing magnesite and a Mg-Ca carbonate of non-stoichiometric dolomitic composition takes place via a dissolution-precipitation process and leads to the formation of a porous reaction front that progressively replaces the aragonite precursor. The reaction leads to the development of porosity within the reaction front and distinctive microstructures such as gaps and cavities at the reaction interface. The newly formed reaction rim consists of chemically distinct phases separated by sharp boundaries. It was found that the number of phases and their chemical variation decreases with increasing initial porosity and reactive surface area. This observation is explained by variations in effective element fluxes that result in differential chemical gradients in the fluid within the pore space of the reaction rim. Observed reaction rates are highest for the replacement of the initially highly porous coral and lowest for the compact structure of a single aragonite crystal. Therefore, the reaction progress equally depends on effective element fluxes between the fluid at the reaction interface and the bulk solution surrounding the test material as well as the reactive surface area. This study demonstrates that the textural and microstructural properties of the parent material have a significant influence on the chemical composition of the product phase. Moreover, our data highlight the importance of effective fluid-mediated element exchange between the fluid at the reaction interface and the bulk solution controlled by the local microstructure

New Reference Materials and Assessment of Matrix Effects for SIMS Measurements of Oxygen Isotopes in Garnet

Accurate ion microprobe analysis of oxygen isotope ratios in garnet requires appropriate reference materials to correct for instrumental mass fractionation that partly depends on the garnet chemistry (matrix effect). The matrix effect correlated with grossular, spessartine and andradite components was characterised for the Cameca IMS 1280HR at the SwissSIMS laboratory based on seventeen reference garnet samples. The correlations fit a second-degree polynomial with maximum bias of ca. 4‰, 2‰ and 8‰ respectively. While the grossular composition range 0–25% is adequately covered by available reference materials, there is a paucity of them for intermediate compositions. We characterise three new garnet reference materials GRS2, GRS-JH2 and CAP02 with a grossular content of 88.3 ± 1.2% (2s), 83.3 ± 0.8% and 32.5 ± 3.0% respectively. Their micro scale homogeneity in oxygen isotope composition was evaluated by multiple SIMS sessions. The reference δ18O value was determined by CO2 laser fluorination (δ18OLF). GRS2 has δ18OLF = 8.01 ± 0.10‰ (2s) and repeatability within each SIMS session of 0.30–0.60‰ (2s), GRS-JH2 has δ18OLF = 18.70 ± 0.08‰ and repeatability of 0.24–0.42‰ and CAP02 has δ18OLF = 4.64 ± 0.16‰ and repeatability of 0.40–0.46‰

Whiteschist genesis through metasomatism and metamorphism in the Monte Rosa nappe (Western Alps)

International audienceWhiteschists from the Monte Rosa Nappe were examined in the field as well as with petrographic, geochemical, and isotopic methods to constrain the controversial origin of these rocks in their Alpine metamorphic context. Whiteschists occur as ellipsoidal-shaped, decametric-sized bodies, within a Permian metagranite, and consist mainly of chloritoid, talc, phengite, and quartz. The transition from whiteschist to metagranite is marked by multiple sharp mineralogical boundaries defining concentric zones unrelated to Alpine deformation. The development of reaction zones, as well as the geometry of the whiteschist suggest a pervasive fluid infiltration, facilitated and canalized by reaction fingering. Whole-rock compositions of whiteschists and metagranites indicate an enrichment in MgO and H2O and depletion of Na2O, CaO, Ba, Sr, Pb, and Zn in the whiteschist relative to the metagranite. Trace- and rare-earth elements, together with all other major elements, notably K2O and SiO2, were within uncertainty not mobile. Such a K and Si saturated, Na undersaturated fluid is not compatible with previous interpretations of fluids derived from ultramafic rocks, evaporites, or Mg-enriched seawater due to mantle interactions. Together with the large variations in δD and δ18O values, this indicates large fluid fluxes during metasomatism. Calculated δD and δ18O values of fluids in equilibrium with the whiteschist support a magmatic–hydrothermal fluid source, as does the chemical alteration pattern. Bulk rock 87Sr/86Sr ratios in whiteschists confirm a pre-Alpine age of fluid infiltration. The 87Sr/86Sr ratios in whiteschists were subsequently partially homogenized in a closed system during Alpine metamorphism. In conclusion, the granite was locally affected by late magmatic–hydrothermal alteration, which resulted in sericite–chlorite alteration zones in the granite. The entire nappe underwent high-pressure metamorphism during the Alpine orogeny and the mineralogy of the whiteschist was produced during dehydration of the metasomatic assemblage under otherwise closed-system metamorphism. While each whiteschist locality needs to be studied in detail, this in-depth study suggests that many whiteschists found in granitic bodies in the Alps might be of similar origin

Interplay between fluid circulation and Alpine metamorphism in the Monte Rosa whiteschist from white mica and quartz in situ oxygen isotope analysis by SIMS

In situ oxygen isotope compositions of white mica and quartz have been used to characterize the interplay of metamorphism and fluid events between a metasomatic whiteschist and its granite protolith in the Monte Rosa nappe, Western Alps. New natural muscovite and phengite reference materials were calibrated for in situ Secondary Ion Mass Spectrometry (SIMS) oxygen isotope measurement. White mica and quartz oxygen isotope compositions were measured in situ in one whiteschist and two metagranites. Based on microtextural observation, phengite composition of white mica, and phase petrology modeling, it is possible to identify two events of fluid infiltration and one event of fluid expulsion, all of which were responsible for forming this unique whiteschist occurrence and for tracing its metamorphic evolution from late Permian intrusion to Alpine subduction and finally to the present day, exhumed whiteschist