A New Albite Microanalytical Reference Material from Piz Beverin for Na, Al and Si Determination, and the Potential for New K-Feldspar Reference Materials

Determination of alkali elements is important to Earth scientists, yet suitable and reliable microanalytical reference materials are lacking. This paper proposes a new albite reference material and evaluates the potential for future K-feldspar reference materials. The proposed Piz Beverin albite reference material from Switzerland yields a homogeneous composition at the centimetre- to micrometre-scale for Si, Al and Na with \u3c 2000 μg g-1 total trace elements (mostly heterogeneously distributed Ca, K and Sr). EPMA and LA-ICP-MS measurements confirm a composition of 99.5(2)% albite component, which is supported further by bulk XRF measurements. A round robin evaluation involving nine independent EPMA laboratories confirms its composition and homogeneity for Si, Al and Na. In addition, a set of five distinct clear K-feldspar samples was evaluated as possible reference materials. The first two crystals of adular and orthoclase yield unacceptable inhomogeneities with \u3e 2% relative local variations of Na, K and Ba contents. The three other investigated sets of K-feldspar crystals are yellow sanidine crystals from Itrongay (Madagascar). Despite distinct compositions, EPMA confirms they are each homogeneous at the centimetre to micrometre scale for Si, Al and K and have no apparent inclusions; further investigation to find larger amounts of these materials is therefore justified

Protracted hydrothermal alteration recorded at the microscale in the Chenaillet ophicarbonates (Western Alps): Insights from in situ δ<SUP>18</SUP>O thermometry in serpentine, carbonate and magnetite

International audienceThe study of serpentinites and ophicarbonates from ophiolitic terrains provides a three-dimensional perspective on the hydration and carbonation processes affecting modern oceanic lithosphere. The Chenaillet ophiolite (western Alps) is interpreted as a fragment of an oceanic core complex that resembles a modern slow spreading center, and it was weakly affected by Alpine metamorphism. Ophicarbonates from the Chenaillet ophiolite were targeted in this study for in situ analysis by Secondary Ion Mass Spectrometry (SIMS) of oxygen and carbon isotopes in serpentine, calcite, dolomite and magnetite. The high spatial resolution of SIMS allowed us to target different serpentine, carbonate and magnetite generations intergrown at scales ≤ 50 μm, and reveal systematic zoning in δ18O with a range of 5.8‰ in serpentine (from 3.0 to 8.8‰, V-SMOW), 21.2‰ in carbonate (9.4 to 30.6‰), and 5.6‰ in magnetite (-5.0 to -10.6‰). Coupled analysis of oxygen isotopes in seven different touching-pairs of co-crystallized serpentine + carbonate and serpentine + magnetite provides independent constraints on both the temperatures and δ18O(water) values during serpentinization and carbonation responsible for the formation of the Chenaillet ophicarbonates. The new stable isotope data and thermometric estimates can be directly linked to textural and petrographic observations. These new results identify at least four different stages of hydrothermal alteration in the Chenaillet ophicarbonates: (1) peridotite hydration during seafloor exhumation at temperatures down to 200-130 °C and water δ18O values varying from 5 to 2‰, as documented by serpentine + magnetite in mesh textures; (2) carbonation during exhumation near the seafloor at temperatures as low as 10 °C assuming water δ18O values of -1‰, as documented by the highest oxygen isotope ratios in texturally older calcite; (3) serpentinization and carbonation at temperatures up to 240 °C and water δ18O values of 2-3‰, as documented by serpentine + magnetite in veins crosscutting mesh textures (T = 192 ± 66 °C, δ18O(water) = 2 ± 1‰, 2 standard deviation), serpentine + magnetite (T = 182 ± 32 °C, δ18O(water) = 2 ± 1‰) and serpentine + dolomite (T = 243 ± 79 °C, δ18O(water) = 3 ± 2‰) in recrystallized hourglass domains within serpentinite clasts, serpentine + dolomite (T = 229 ± 50 °C, δ18O(water) = 3 ± 1‰) and serpentine + calcite (T = 208 ± 40 °C, δ18O(water) = 2 ± 1‰) within the fine-grained calcite matrix surrounding serpentinite clasts; (4) late stage carbonation at temperatures down to 70-40 °C assuming water δ18O values of 3 to -1‰, as documented by the highest oxygen isotope ratios in a large calcite vein crosscutting both serpentinite clasts and fine-grained carbonate matrix. We suggest that the textural and isotopic observations are consistent with a protracted serpentinization and carbonation of the lithospheric mantle that started during progressive exhumation to the seafloor and continued due to interaction with hot and isotopically shifted seawater, which circulated at depth in the oceanic crust and was then discharged near the seafloor, similar to modern mid-ocean ridge venting systems

Fabric development during exhumation from ultrahigh-pressure in an eclogite-bearing shear zone, Western Gneiss Region, Norway

Petrofabrics and trace-element thermobarometry of deformed quartzofeldspathic gneiss and associated coesite-bearing eclogite in the Salt Mylonite Zone (Western Gneiss Region, Norway) document a pressure–temperature–deformation path from ultrahigh-pressure to amphibolite-facies conditions. The Salt mylonite zone is dominated by quartzofeldspathic gneiss with a strong foliation and lineation. Coesite-bearing eclogite within the shear zone contains a foliation and lineation (defined by elongate omphacite) consistent with that of the host gneiss, suggesting that gneiss and eclogite were deformed in the same kinematic framework. In eclogite, omphacite preserves LS- to L-type crystallographic preferred orientation, and quartz preserves prism fabrics that developed in quartz near coesite–quartz transition conditions. The quartzofeldspathic gneiss in the mylonite zone records prism and rhomb slip in quartz and reverse zoning in plagioclase (higher Ca rims) consistent with re-equilibration during decompression. The Ti concentration in quartz in gneiss is higher than that in quartz in eclogite, suggesting that quartz recrystallized at a lower pressure in the gneiss. Ti-in-quartz thermobarometry of rutile-bearing eclogite and titanite-bearing gneiss indicates equilibration at T > 750 °C and T < 650 °C, respectively. This mylonite zone preserves a discontinuous record of fabric development from incipient stages of exhumation of ultrahigh-pressure rocks to crustal conditions.13 page(s

Oxygen diffusion in garnet: experimental calibration and implications for timescales of metamorphic processes and retention of primary O isotopic signatures

Knowledge of oxygen diffusion in garnet is crucial for a correct interpretation of oxygen isotope signatures in natural samples. A series of experiments was undertaken to determine the diffusivity of oxygen in garnet, which remains poorly constrained. The first suite included high-pressure (HP), nominally dry experiments performed in piston cylinder apparatus at (i) T = 1050- 1600 °C and P = 1.5 GPa and (ii) T = 1500 °C and P = 2.5 GPa using yttrium aluminum garnet (YAG; Y3Al5O12) cubes. Secondly, HP H2O-saturated experiments were conducted at T = 900 °C and P = 1.0-1.5 GPa, wherein YAG crystals were packed into a YAG + Corundum powder, along with 18O-enriched H2O. Thirdly, 1-atm experiments with YAG cubes were performed in a gas-mixing furnace at T = 1500-1600 °C under Ar flux. Finally, an experiment at T = 900 °C and P = 1.0 GPa was done using a pyrope cube embedded into pyrope powder and 18O-enriched H2O. Experiments using grossular were not successful. Profiles of 18O/(18O+16O) in the experimental charges were analyzed with three different Secondary Ion Mass Spectrometers (SIMS): Sensitive High Resolution Ion Microprobe (SHRIMP II and SI), CAMECA IMS-1280 and NanoSIMS. Considering only the measured length of 18O diffusion profiles, similar results were obtained for YAG and pyrope annealed at 900 °C, suggesting limited effects of chemical composition on oxygen diffusivity. However, in both garnet types, a number of profiles deviate from the error function geometry, suggesting that the behavior of O in garnet cannot be fully described as simple concentration-independent diffusion, certainly in YAG and likely in natural pyrope as well. The experimental results are better described by invoking O diffusion via two distinct pathways with an inter-site reaction allowing O to move between these pathways. Modelling this process yields two diffusion coefficients (Ds) for O, one of which is approximately two orders of magnitude higher than the other. Taken together, Arrhenius relationships are: –321(±32)kJmol–1 2.303RT ) –312(±20)kJmol–1 2.303RT ) for the fast pathway. We interpret the two pathways as representing diffusion following vacancy and interstitial mechanisms, respectively. Regardless, our new data suggest that the slow mechanism is prevalent in garnet with natural compositions, thus is likely to control the retentivity of oxygen isotopic signatures in natural samples. The diffusivity of oxygen is similar to Fe-Mn diffusivity in garnet at 1000-1100 °C and Ca diffusivity at 850 °C. However, the activation energy for O diffusion is larger, leading to lower diffusivities at P-T conditions characterizing crustal metamorphism. Therefore, original O isotopic signatures can be retained in garnets showing major element zoning partially re- equilibrated by diffusion, with the uncertainty caveat of extrapolating the experimental data to lower temperature conditions

Oxygen diffusion in garnet: Experimental calibration and implications for timescales of metamorphic processes and retention of primary O isotopic signatures

Knowledge of oxygen diffusion in garnet is crucial for a correct interpretation of oxygen isotope signatures in natural samples. A series of experiments was undertaken to determine the diffusivity of oxygen in garnet, which remains poorly constrained. The first suite included high-pressure (HP), nominally dry experiments performed in piston-cylinder apparatus at: (1) T = 1050-1600 degrees C and P = 1.5 GPa and (2) T = 1500 degrees C and P = 2.5 GPa using yttrium aluminum garnet (YAG; Y3Al5O12) cubes. Second, HP H2O-saturated experiments were conducted at T = 900 degrees C and P = 1.0-1.5 GPa, wherein YAG crystals were packed into a YAG + Corundum powder, along with O-18-enriched H2O. Third, 1 atm experiments with YAG cubes were performed in a gas-mixing furnace at T = 1500-1600 degrees C under Ar flux. Finally, an experiment at T = 900 degrees C and P = 1.0 GPa was done using a pyrope cube embedded into pyrope powder and O-18-enriched H2O. Experiments using grossular were not successful.Profiles of O-18/(O-18+O-16) in the experimental charges were analyzed with three different secondary ion mass spectrometers (SIMS): sensitive high-resolution ion microprobe (SHRIMP II and SI), CAMECA IMS-1280, and NanoSIMS. Considering only the measured length of O-18 diffusion profiles, similar results were obtained for YAG and pyrope annealed at 900 degrees C, suggesting limited effects of chemical composition on oxygen diffusivity. However, in both garnet types, several profiles deviate from the error function geometry, suggesting that the behavior of O in garnet cannot be fully described as simple concentration-independent diffusion, certainly in YAG and likely in natural pyrope as well. The experimental results are better described by invoking O diffusion via two distinct pathways with an inter-site reaction allowing O to move between these pathways. Modeling this process yields two diffusion coefficients (D values) for O, one of which is approximately two orders of magnitude higher than the other. Taken together, Arrhenius relationships are:logDm(2)s(-1) = -7.2(+/- 1.3)+(-321(+/- 32)kJ mol(-1))/2.303RT)for the slow pathway, andlogDm(2)s(-1) = -5.4(+/- 0.7)+(-312(+/- 20)kJ mol(-1)/2.303RT)for the fast pathway. We interpret the two pathways as representing diffusion following vacancy and interstitial mechanisms, respectively. Regardless, our new data suggest that the slow mechanism is prevalent in garnet with natural compositions, and thus is likely to control the retentivity of oxygen isotopic signatures in natural samples.The diffusivity of oxygen is similar to Fe-Mn diffusivity in garnet at 1000-1100 degrees C and Ca diffusivity at 850 degrees C. However, the activation energy for 0 diffusion is larger, leading to lower diffusivities at P-T conditions characterizing crustal metamorphism. Therefore, original O isotopic signatures can be retained in garnets showing major element zoning partially re-equilibrated by diffusion, with the uncertainty caveat of extrapolating the experimental data to lower temperature conditions