Nadia Malaspina

The role of C-O-H and oxygen fugacity in subduction-zone garnet peridotites

C-O-H fluids are released by dehydration, partial melting and/or decarbonation of the slab and transferred to the mantle, where they interact with the surrounding rocks, prompting the growth of carbonates, hydrous minerals and C polymorphs. In the pure C-O-H system, C-saturated fluid speciation is a function of the oxygen chemical potential. Therefore, in natural systems, the fluid speciation can be imposed by the redox state of the rock-forming phases. Alternatively, C-O-H fluids may control the bulk oxidation state of the rock system by redox reactions with the mineral phases. We selected three case studies of garnet-bearing ultramafic rocks (Ulten zone, Italy; Sulu, China; Bardane, Norway), which record metasomatic processes driven by C-O-H fluids at the interface between a subducting slab and the overlying mantle wedge. All these rocks contain carbonates (dolomite-only at P , 1.9 GPa at 900 � C, magnesite-only at P. 2.4 GPa at 900 � C, dolomite þ magnesite in between) and hydrous phases (amphibole, phlogopite) equilibrated at some stages in the garnet stability field. The f O2 values, estimated by analysing the Fe 3þ content (skiagite mole fraction) in garnet, indicate that the Ulten and Sulu peridotites record high oxygen fugacities (FMQ to FMQþ2) and a retrograde path with decreasing P and T. The f O2 values obtained for the Bardane garnet websterites, which record a prograde path with increasing T and P, are up to � 2 log units lower than the FMQ. When combined with data for subduction-zone systems (arc lavas and their mantle sources), the studied ultramafic rocks define a trend of decreasing f O2 with increasing pressure. The Bardane websterites contain C-polymorphs in polyphase inclusions, which precipitated from entrapped metasomatic fluids at ultrahigh pressures. The calculated C-O-H fluid phase in equilibrium with the solid phases consists of mixtures of H2O and CO2. Semi-quantitative estimates for the Ulten and Sulu peridotites, in which C-polymorphs have not been found, and petrographic constraints for the Ulten peridotites indicate that the C-O-H component of the fluid could consist of H2OþCO2.

Threshold size for fluid inclusion decrepitation

Fluid inclusions in igneous and metamorphic rocks are equilibrated at pressures reaching a few tens of kilobars at mantle depths. These microsystems experience decompression as a consequence of uplift processes, such as subaerial volcanic eruptions. On decompression, inclusion fluid overpressure is known to bring about the mechanical failure of the crystal matrix through either stretch or decrepitation, depending on ductile or brittle failure mechanism of the matrix, respectively. On the one hand, laboratory experiments performed on synthetic inclusions at one atmosphere show that the decrepitation temperature is strongly size dependent, with the smaller cavities observed to decrepitate at higher temperatures. On the other hand, natural fluid inclusions, which undergo migration through a pressure gradient, are often found intact below a critical size. Here by modeling fluid inclusions as spherical cavities in a continuous elastic medium and by adopting a nonlocal stress approach to fracturing, we demonstrate that the decrepitation phenomenon is predicted to be characterized by a threshold size of the cavity, below which decrepitation would not be allowed. In order to validate our model, two independent experimental data sets relating internal pressure to cavity size are utilized to calculate pertinent model parameters and to evaluate their consistency.

Earthquakes as Precursors of Ductile Shear Zones in the Dry and Strong Lower Crust

The rheology and the conditions for viscous flow of the dry granulite facies lower crust are still poorly understood. Viscous shearing in the dry and strong lower crust commonly localizes in pseudotachylyte veins, but the deformation mechanisms responsible for the weakening and viscous shear localization in pseudotachylytes are yet to be explored. We investigated examples of pristine and mylonitized pseudotachylytes in anorthosites from Nusfjord (Lofoten, Norway). Mutual overprinting relationships indicate that pristine- and mylonitized pseudotachylytes are coeval and resulted from the cyclical interplay between brittle and viscous deformation. The stable mineral assemblage in the mylonitized pseudotachylytes consists of plagioclase, amphibole, clinopyroxene, quartz, biotite, ± garnet ± K-feldspar. Amphibole-plagioclase geothermobarometry and thermodynamic modelling indicate that pristine- and mylonitized pseudotachylytes formed at 650-750°C and 0.7-0.8 GPa. Thermodynamic modelling indicates that a limited amount of H2O infiltration (0.20-0.40 wt%) was necessary to stabilize the mineral assemblage in the mylonite. Diffusion creep is identified as the main deformation mechanisms in the mylonitized pseudotachylytes based on the lack of crystallographic preferred orientation in plagioclase, the high degree of phase mixing, and the synkinematic nucleation of amphiboles in dilatant sites. Extrapolation of flow laws to natural conditions indicates that mylonitized pseudotachylytes are up to 3 orders of magnitude weaker than anorthosites deforming by dislocation creep, thus highlighting the fundamental role of lower crustal earthquakes as agents of weakening in strong granulites.

Fluid-induced plastic deformation in the crustal Austroalpine system (Western Italian Alps): a petrologic and fluid inclusion analysis

This work investigates the interplay between fluids and metamorphic recrystallisation in the Austroalpine Dent Blanche Nappe (Western Alps, Italy). This nappe consists of the Arolla and Valpelline Units, respectively dominated by metagranitoids and paraschists with Pre-Alpine to Alpine polymetamorphic history. In the Arolla Unit the Alpine tectonitic to mylonitic foliation anastomoses around weakly deformed bodies preserving the pre-Alpine igneous textures. In the Valpelline Unit, the Alpine structures are concentrated within a narrow shear horizon at the contact with the Arolla Unit, which parallels the pre-Alpine foliation. This contrast in the Alpine deformation between the Arolla and the Valpelline Units suggests heterogeneous fluid distribution in the Dent Blanche system during the Alpine orogeny. The relict (meta)igneous Arolla rocks record a post-magmatic, pre-Alpine stage of amphibolite-facies hydration at relatively low pressure. A deeper crustal origin of the Valpelline Unit than the Arolla Unit can be envisaged due to the presence of high temperature and pressure assemblages (clinopyroxene, garnet, plagioclase, amphibole) in the mafic rocks. In Arolla granitoids igneous plagioclase records two hydration events recorded by aggregates of: (i) pre-Alpine amphibolite-facies andesine + epidote, and (ii) Alpine greenschist-facies albite + epidote. The quartz crystals associated with the altered magmatic plagioclase contain two-phase (liquid + vapour) and three-phase (liquid + vapour + chloride daughter crystals) inclusions. Isochores of the salt-saturated inclusions plot in the andesine + epidote stability field, pointing to pre-Alpine plagioclase alteration in response to infiltration of saline aqueous solutions at amphibolite-facies conditions. Most isochores of the liquid + vapour inclusions plot in the albite + epidote stability field, suggesting entrapment during the lower temperature greenschist-facies hydration of plagioclase. Preferential fluids influx in the Arolla Unit during pre-Alpine amphibolite-facies metamorphism enhanced the reaction softening of plagioclase. Alteration of plagioclase played a major role in promoting the deformation of granitoids during Alpine tectonics.

Redox processes and the role of carbon-bearing volatiles from the slab–mantle interface to the mantle wedge

The valence of carbon is governed by the oxidation state of the host system. The subducted oceanic lithosphere contains considerable amounts of iron so that Fe3+/Fe2+ equilibria in mineral assemblages are able to buffer the (intensive) fO2 and the valence of carbon. Alternatively, carbon itself can be a carrier of (extensive) ‘excess oxygen’ when transferred from the slab to the mantle, prompting the oxidation of the sub-arc mantle. Therefore, the correct use of intensive and extensive variables to define the slab-to-mantle oxidation by C-bearing fluids is of primary importance when considering different fluid/rock ratios. Fluid-mediated processes at the slab–mantle interface can also be investigated experimentally. The presence of CO2 (or CH4 at highly reduced conditions) in aqueous COH fluids in peridotitic systems affects the positions of carbonation or decarbonation reactions and of the solidus. Some methods to produce and analyse COH fluid-saturated experiments in model systems are introduced, together with the measurement of experimental COH fluids composition in terms of volatiles and dissolved solutes. The role of COH fluids in the stability of hydrous and carbonate minerals is discussed comparing experimental results with thermodynamic models and the message of nature.

Granulite facies overprint in garnet peridotites and kyanite eclogites of Monte Duria (Central Alps, Italy): clues from srilankite- and sapphirine-bearing symplectites

Peridotites and different types of eclogites occurring in the Monte Duria area (Adula–Cima Lunga unit, Central Alps, Italy) share a common eclogite-facies peak at P1⁄42 6–3 0 GPa and T1⁄4 710–750 C, constrained by conventional thermobarometry and thermodynamic modelling. High-pressure minerals are replaced both in peridotites and in eclogites by lower-P and high-T assemblages. In peridotites, the zirconium titanate srilankite occurs as micrometre-sized crystals in textural equilibrium with spinel, clinopyroxene and orthopyroxene in kelyphites developed between garnet and olivine. By using a new ZrO2–TiO2 solid-solution model, we provide evidence that srilankite is stable in peridotites relative to zirconþ rutile for T>810 C at an assumed P 0 9 GPa, consistent with estimates of T 850 C (at assumed P1⁄4 0 9 GPa) determined for symplectites made of sapphirineþspinelþAl-rich orthopyroxeneþ amphibole found in fractures within garnet. In eclogites, kyanite is replaced by symplectites made of anorthite-rich plagioclaseþ spinel6 sapphirine6 corundum, formed at T 850 C and P1⁄40 8–1 0 GPa, conditions that are coincident with the high-T overprint observed in the peridotites. Thermodynamic modelling coupled with a material-transfer study provides constraints for these sapphirine-bearing symplectites. In these micro-domains, the ‘inert’ components could not fully equilibrate with the surrounding rock, and the locally high Al content promoted the stability of the Al-rich phases (i.e. mosaic equilibrium). This is the first report from the Alps of eclogite-facies rocks of supposed Alpine age showing a granulite-facies metamorphic overprint, which is, in contrast, well documented in the Variscan belt. On these grounds, although the age of the high-pressure and hightemperature stages in the Monte Duria rocks is still not constrained, the possibility that they reached eclogitic and granulitic conditions in pre-Alpine times should be taken into account.

Contrasting subduction–exhumation paths in the blueschists of the Anarak Metamorphic Complex (Central Iran)

The Anarak Metamorphic Complex, localized in Central Iran, is a fossil accretionary wedge composed of several tectonometamorphic units. Some of these, the Chah Gorbeh, the Morghab and the Ophiolitic complexes, contain mafic rocks that have been metamorphosed at high-pressure–low-temperature conditions. Such units have been stacked together and later refolded during the final stages of exhumation. Structural analysis at the mesoscale recognized at least three deformation events. Microstructural analyses, mineral chemistry and thermodynamic modelling reveal that the mafic schists followed contrasting P–T paths during their tectonometamorphic evolutions. In the schists of the Chah Gorbeh and Ophiolitic complexes an early greenschist-facies stage was later overprinted by blueschist-facies phase assemblages with suggested peak conditions of 390–440°C at 0.6–0.9 GPa for the meta-basalt within the Ophiolitic Complex and 320–380°C at 0.6–0.9 GPa for the blueschists of the Chah Gorbeh Complex. P–T conditions at metamorphic peak were 410–450°C at 0.78–0.9 GPa for the Morghab blueschists, but they are reached before a greenschist-facies re-equilibration. Compositional zoning of amphiboles and epidotes of this greenschist-facies stage suggests a renewed pressure increase at the end of this metamorphic stage. Based on these data we reconstructed a clockwise P–T path for the Morghab mafic schists and a counter-clockwise path for the Chah Gorbeh blueschists and ophiolitic meta-basalts. Such contrasting metamorphic evolutions of tectonic units that were later accreted to the same wedge are indicative of the complex tectonic dynamics that occur within accretionary–subduction complexes.