Intracrystalline melt migration in deformed olivine revealed by trace element compositions and polyphase solid inclusions

Melt transport mechanisms have an important impact on the chemical composition of the percolated host rock and the migrating melts. Melt migration is usually assumed to occur at grain boundaries. However, microstructural studies revealed the occurrence of polyphase inclusions along dislocations, subgrain boundaries and microcracks in single mineral grains. The inclusions are interpreted as crystallized melt pockets suggesting that melts can migrate within deformed crystals. Intracrystalline melt migration and diffusive re-equilibration can lead to significant mineral trace element enrichments when associated with dissolution–precipitation reactions. In this contribution, we study a body of replacive troctolites associated with the Erro-Tobbio ophiolitic mantle peridotites (Ligurian Alps, Italy). The replacive formation of the olivine-rich troctolite involved extensive impregnation of a dunitic matrix, i.e. partial dissolution of olivine and concomitant crystallization of interstitial phases. The olivine matrix is characterized by two distinct olivine textures: (i) coarse deformed olivine, representing relicts of the pre-existing mantle dunite matrix (olivine1), and (ii) fine-grained undeformed olivine, a product of the melt–rock interaction process (olivine2). Previous studies documented a decoupling between olivine texture and trace element composition, namely enriched trace element compositions in olivine1 rather than in olivine2, as would be expected from the dissolution–precipitation process. Notably, the trace element enrichments in deformed olivines are correlated with the occurrence of elongated 10 µm size polyphase inclusions (clinopyroxene, Ti-pargasite, chromite) preferentially oriented along olivine crystallographic axes. These inclusions show irregular contacts and have no crystallographic preferred orientation with the host olivine, and the phases composing the inclusions show similar chemical compositions to the vermicular phases formed at the grain boundaries during late-stage reactive crystallization of the troctolite. This suggests that the investigated inclusions did not form as exsolutions of the host olivine but rather by input of metasomatic fluids percolating through the deformed olivine grains during closure of the magmatic system. We infer that strongly fractionated volatile-rich melts were incorporated in oriented microfractures within olivine1 and led to the crystallization of the polyphase inclusions. The presence of intracrystalline melt greatly enhanced diffusive re-equilibration between the evolved melt and the percolated olivine1, in turn acquiring the enriched character expected in neoformed olivine crystals. Intracrystalline melt percolation can have strong geochemical implications and can lead to efficient re-equilibration of percolated minerals and rocks.

Brittle deformation during eclogitization: a perspective from a cold, early Paleozoic subduction zone

<p>The Tsäkkok Lens (northern Scandinavian Caledonides) represents the outermost part of the rifted passive Baltica margin and consists of sediments and pillow basalts of MORB affinity that were metamorphosed under eclogite facies conditions. Fieldwork and further multidisciplinary analytical approach (including e.g. X-ray and EBSD mapping, and μ-CT imaging) revealed that eclogites record brittle deformation on the μm-to-m scale. This deformation is expressed as a set of microfractures (single-grain rupture) and mesofractures (sealed by garnet- and omphacite-veins). Phase equilibrium thermodynamic modeling of phengite-bearing and phengite-free eclogites performed in NCKFMMnASHT and NCFMMnASHT systems predict profuse dehydration related to lawsonite and amphibole breakdown at ~2.35 GPa and ~600°C, close to the peak conditions of ~2.55 GPa and ~640°C. These estimates are in line with conventional thermobarometry and Zr-in-rutile thermometry results. The evidence for dehydration is also provided by the  occurrence of relic glaucophane in matrix and polyphase inclusions in garnet consisting of clinozoisite + quartz ± kyanite ± paragonite that are interpreted as pseudomorphs after lawsonite. Dehydration reactions were responsible for producing fluid, which facilitated brittle fracturing of the eclogites at HP conditions due to increased pore-fluid pressure (also promoted by the volume changes during eclogitization) on the microscale. Altogether, micro- and mesofracturing acted as migration pathways for released fluid, whereas the microfractures are likely precursors of the mesoscale fractures. Garnet-WR Lu-Hf geochronology provided ages of 487.7 ± 4.6, 486.2 ± 3.2, and 484.6 ± 4.5 Ma. LA-ICP-MS trace element profiles of garnet revealed a well-pronounced peak of Lu content in the garnet cores that decreased towards the rims, indicating these dates represent the age of prograde metamorphism. Therefore, the early Paleozoic Tsäkkok Lens eclogites constitute the oldest documented natural example of HP brittle deformation during eclogitization of blueschist.</p><p>Research funded by NCN project no. 2019/33/N/ST10/01479 (M. Bukała) and no. 2014/14/E/ST10/00321 (J. Majka), as well as the Polish National Agency for the Academic Exchange scholarship no. PPN/IWA/2018/1/00046/U/0001 given to M. Bukała.</p>

Formation of chromitite seams and associated anorthosites in layered intrusion by reactive volatile-rich fluid infiltration

Drilling related to development of the platinum-group element deposit of the J-M Reef of the Stillwater Complex returned samples of a rare chromitite seam between anorthosite and norite in a discordant anorthositic body. Plagioclase core An concentrations are marginally higher and modestly reversely zoned on the norite side (average Ancore = 83.8; average Ancore-Anrim = -1.1) as compared with the anorthosite side (Average Ancore 82.5; Average Ancore-Anrim = +1.0). The anorthosites are also characterized by a slightly smaller average plagioclase grain size than plagioclase in the norite (1.41 mm and 1.54 mm, respectively). The chromite can contain single and polyphase inclusions of orthopyroxene, plagioclase, amphibole, biotite and Cl-rich apatite. These and other compositional and textural features, as well as inference from other discordant anorthositic bodies in the Banded series, are all consistent with a chromatographic model of chromite precipitation at a reaction front as a norite protolith reacts with a Cl-rich aqueous fluid saturated in plagioclase alone. Chromitite seam formation is modeled using an infiltration metasomatic model, in which a fluid becomes progressively undersaturated in pyroxene as it rises into the hotter part of the crystal pile. As this pyroxene-undersaturated fluid moves through a noritic protolith, it dissolves the Cr-bearing orthopyroxene to produce an anorthosite. Chromite precipitates at the reaction front between the anorthosite and the norite owing to liberation of Mg and Cr from pyroxene. Continuous redissolution and reprecipitation of chromite occurs as the pyroxene dissolution front moves in direction of fluid flow, collecting the Cr lost from the anorthosite. Owing to Cr dissolved mainly as a neutral divalent cation complex, (CrCl(OH)0, in the solution, but incorporated as a trivalent cation in chromite, the required redox reaction can involve concurrent precipitation of sulfide with chromite. This mechanism differs from some recent models in that the anorthosites are themselves replacement bodies and are not original precipitates from a magma nor formed by loss of mafic material by partial melting. The results show the need for experimental mineral solubility data at T and P conditions appropriate to upper crustal mafic/ultramafic intrusions.

Brittle Deformation During Eclogitization of Early Paleozoic Blueschist

The Tsäkkok Lens of the Scandinavian Caledonides represents the outermost Baltican margin that was subducted in late Cambrian/Early Ordovician time during closure of the Iapetus Ocean. The lens predominantly consists of metasedimentary rocks hosting eclogite bodies that preserve brittle deformation on the μm-to-m scale. Here, we present a multidisciplinary approach that reveals fracturing related to dehydration and eclogitization of blueschists. Evidence for dehydration is provided by relic glaucophane and polyphase inclusions in garnet consisting of clinozoisite + quartz ± kyanite ± paragonite that are interpreted as lawsonite pseudomorphs. X-Ray chemical mapping of garnet shows a network of microchannels that propagate outward from polyphase inclusions. These microchannels are healed by garnet with elevated Mg relative to the surrounding garnet. Electron backscatter diffraction mapping revealed that Mg-rich microchannels are also delimited by low angle (<3°) boundaries. X-ray computed microtomography demonstrates that some garnet is transected by up to 300 μm wide microfractures that are sealed by omphacite ± quartz ± phengite. Locally, mesofractures sealed either by garnet- or omphacite-dominated veins transect through the eclogites. The interstices within the garnet veins are filled with omphacite + quartz + rutile + glaucophane ± phengite. In contrast, omphacite veins are predominantly composed of omphacite with minor apatite + quartz. Omphacite grains are elongated along [001] crystal axis and are preferably oriented orthogonal to the vein walls, indicating crystallization during fracture dilation. Conventional geothermobarometry using omphacite, phengite and garnet adjacent to fractures, provides pressure-temperature conditions of 2.47 ± 0.32 GPa and 620 ± 60°C for eclogites. The same method applied to a mesoscale garnet vein yields 2.42 ± 0.32 GPa at 635 ± 60°C. Zirconium-in-rutile thermometry applied to the same garnet vein provides a temperature of ∼620°C. Altogether, the microchannels, microfractures and mesofractures represent migration pathways for fluids that were produced during glaucophane and lawsonite breakdown. The microfractures are likely precursors of the mesoscale fractures. These dehydration reactions indicate that high pore-fluid pressure was a crucial factor for fracturing. Brittle failure of the eclogites thus represents a mechanism for fluid-escape in high-pressure conditions. These features may be directly associated with seismic events in a cold subduction regime.

Fluid Evolution of the Čukaru Peki Cu-Au Porphyry System (East Serbia) inferred from a fluid inclusion study

Čukaru Peki is a recently discovered copper-gold deposit in the Bor metallogenic zone in east Serbia. Three types of mineralization can be distinguished in this ore deposit: porphyry, high-sulphidation, and transitional epithermal type. This research was focused on fluid inclusion analysis of genetically different veins from the porphyry and the transitional zones of Čukaru Peki with an aim of better understanding the fluid evolution and mineralization processes in this system. Seven types of veins were identified in the porphyry zone of Čukaru Peki and four of these veins contained transparent minerals which were suitable for fluid inclusion analysis. Eight types of inclusion assemblages were distinguished in these veins: type 1 – primary inclusions with homogenization temperatures above 550°C and high salinity, type 2a- scattered polyphase inclusions two salt crystals, type 2b-polyphase inclusions with two salt crystals in crystal growth zones, type 3- brine inclusions with one salt crystal in crystal growth zones, type 4- vapour-rich inclusions, type 5- primary inclusions in anhydrite, and types 6 and 7- secondary low-temperature inclusions This research suggests that saline fluids (30-40% wt.% NaCl eq.) were the most important ones for the formation of porphyry-type mineralization and that the mineralization was formed at temperatures between 350 and 450°C and pressures between 100 and 500 bars. The epithermal stage was characterized by cooler low-salinity fluids with temperatures between 150-350°C, and salinity between 0 and 7 wt.% NaCl eq.

How to disclose local equilibrium in subducted metapelites from the Cima Lunga Unit (Central Alps)

<p>Subducted metapelites are more prone to re-equilibrate during exhumation than mafic or ultramafic rocks to the point that recognizing high-pressure (HP) relicts is often very challenging. Geologic evidence from the Cima Lunga Unit (Central Alps) show this apparent discrepancy between high to ultra-high pressure metamorphism (28 kbar and 780 °C) recorded in mafic/ultramafic lenses, and Barrovian metamorphism (<10 kbar, 650°C) in the adjacent metapelitic rocks. We collected a white mica – garnet – biotite – plagioclase – kyanite (+ quartz, + zircon, + rutile) bearing metapelite adjacent to the garnet metaperidotite lens that displays an apparently well equilibrated Barrovian mineral assemblage (garnet + plagioclase + biotite), with no macroscopic or microtextural indication of a HP and/or HT metamorphic event (e.g. omphacite crystals; migmatitic texture; polyphase inclusions). Nevertheless, microstructures like atoll-like garnet or large white mica flakes surrounded by biotite and ilmenite replacing rutile suggest incomplete re-equilibration. We investigated garnet and phengite crystals by electron probe and laser ablation-ICP-MS mapping. Major and trace element mapping reveals very complex mineral zoning in both minerals. In particular, high Ti content in phengite and increasing P and Zr contents in pyrope-rich garnet indicate that the studied rock underwent a HP-HT event. This is also supported by Zr in rutile thermometry that indicates temperatures well above the Barrovian metamorphism (T > 700 °C). We combined detailed textural analysis with petrological-geochemical data and thermodynamic modelling to reconstruct the metamorphic evolution of the studied rock. We show that, thank to incomplete re-equilibration, the rock documents an evolution from prograde to UHP-HT peak (27 kbar and 800 °C) to retrograde (Barrovian) conditions (10 kbar and 620 °C). Noteworthy, peak metamorphic conditions of metapelite coincide with peak metamorphic conditions of the garnet metaperidotite. Lastly, geochemical evidence for minor wet melting of the studied metapelite at HP-HT conditions was recognized and is likely linked to the dehydration of chlorite to form garnet peridotite in the adjacent ultramafic body. We propose that metapelites and ultramafic rocks were coupled before subduction or at least in its early stage. This finding opens new scenarios for the geodynamic interpretation of the Cima Lunga unit. We propose that the ultramafic lenses at Cima di Gagnone were parts of the exhumed and serpentinised mantle emplaced at the hyper-extended European continental margin of the Piemont-Ligurian ocean. Slices of the margin were detached and tectonically mixed in the subduction channel. These new constraints call for re-evaluation of the paleogeographic position of the Adula-Cima Lunga nappe.</p>

Mineralogy and geochemistry of the inclusion-bearing Cr-pyropes from the Chompolo lamprophyres, Aldan shield, Siberian сraton

<p>Inclusion assemblages within Cr-pyrope xenocrysts from the Aldanskaya and Ogonek lamprophyres (Chompolo field, Aldan shield of Siberian craton, Yakutia) are characterized by the wide list of minerals. Partially the inclusion assemblages with graphite within Cr-pyropes in Chompolo lamprophyres were previously described (Nikolenko et al., 2017).</p><p>Here we present the results of a trace-elements study of 54 pyrope grains with Cr-spinel inclusions. The majority of studied pyropes are lherzolitic with small amount of wherlitic and harzburgitic ones, according to the classification schemes (Sobolev et al 1973; Grutter et al., 2004). The concentration of Cr<sub>2</sub>O<sub>3</sub> ranges from 1.58 to 7.56 wt% at Mg # = 69.6-84.4 and Ca # = [100Ca / (Ca + Mg + Fe + Mn)] = 8.6-26.3. The TiO<sub>2</sub> content does not exceed 0.36 wt%. The MnO contents in the pyropes studied is in the range of 0.35–0.69 wt%, which indicates rather low temperature conditions (Grutter at al., 2004).</p><p>Studied mineral inclusions can be divided in two groups by their morphology and position within the host pyrope grain. Majority of the studied Cr-spinels within pyropes are represented by the single-mineral inclusions (CrSp-I), which have clear octahedral morphology but some of them can be described by more complex morphology that looks as irregular or rounded. Single Cr-spinel inclusions are commonly large and range in size from 100 to 500 µm. Another inclusions type represents joint associations of Cr-spinels (CrSp-II) with silicates, carbonates, sulphides, graphite, volatile-bearing minerals and series of Ti-oxides. Size of Cr-spinels II in this samples is usually 10-50 µm and rarely reaches 100 µm.</p><p>The distribution of the rare earth elements (REE) for pyropes containing CrSp-I inclusions in chondrite-normalized REE-diagram has a sinusoidal pattern and is characterized by the chondrite-normalized ratio Sm<sub>N</sub>/Er<sub>N </sub>> 1 at low Ti/Eu values, which is a sign of carbonatite metasomatism (Shchukina et al., 2017). Pyropes containing complex polyphase inclusions with CrSp-II carry signs of silicate (melt) metasomatism, expressed in elevated contents of Y (up to 20.5 ppm) and Zr (9.5–44.6 ppm) and an increased Ti impurity. Pyropes with CrSp-II inclusions have typical for lherzolites distribution of REE with  Sm<sub>N</sub>/Er<sub>N</sub> ratio in the range of 0.5-1.</p><p>Cr-spinel inclusions within pyropes were also studied in detail and revealed some differences in the chemical composition between two groups.</p><p>Temperatures estimated for the pyropes containing mineral inclusions using Ni-in-garnet thermometer ranges from 640-910 °C. Temperatures were also estimated for Cr-spinel inclusions by use the Zn-in-spinel thermometer (Ryan et al., 1996). The temperature distribution for CrSp-I and CrSp-II groups shows different values with maximum frequency at 650-700 and 750-800 °C respectively.</p><p>The geochemical features, the composition of inclusions and the results of thermometry of the two described pyrope populations with Cr-spinel inclusions indicate different metasomatic processes associated with their formation.</p><p>Complex studies of mineral inclusions in Cr-pyropes and major element analyses of Cr-pyropes and Cr-spinels were supported by the Russian Science Foundation, grant No 18-77-10062. Trace-elements studies of Cr-pyropes were supported by the Russian Science Foundation, grant No 18-17-00249.</p>