Zircon coronas around Fe–Ti oxides: a physical reference frame for metamorphic and metasomatic reactions

Ilmenite in coronitic gabbros from the Bamble and Kongsberg sectors, southern Norway, is surrounded by zircons ranging in diameters from a fraction of a micrometer to 10 μm across. The zircons are inert during subsequent metamorphism (amphibolite- to pumpellyite–prehnite facies) and metasomatism (scapolitization and albitization) and can be found as trails in silicates (phlogopite, talc, chlorite, amphibole, albite, and tourmaline) in the altered rocks. The trails link up to form polygons outlining the former oxide grain boundary. This 3-dimensional framework of zircons is used to (a) recognize metasomatic origin of rocks, (b) quantify the mobility of elements during mineral replacement, (c) establish the growth direction of reaction fronts and to identify the reaction mechanism as dissolution–reprecipitation. Zircon coronas on Fe–Ti oxides have been described from a number of terrains and appear to be common in mafic rocks (gabbros and granulites) providing a tool for a better understanding of metasomatic and metamorphic reactions.     

Complex replacement patterns in garnets from Bergen Arcs eclogites: A combined EBSD and analytical TEM study

Eclogite-facies rocks within the Bergen Arcs, western Norway, have formed from granulites along shear zones and fluid pathways. Garnets that were inherited from granulite facies protoliths show different types of replacement patterns due to an incomplete eclogitisation process including concentric rim zoning, zoning along vein fillings and inclusion trails, and zoning bands without inclusions. The interfacial part between the granulitic core and the eclogitic rim of garnet as well as the microstructure of other relevant minerals (omphacite, plagioclase) has been analysed using analytical transmission electron microscopy (ATEM). In garnet, the interface is characterised by gradual changes in composition from X_alm=0.31, X_pyr=0.50 to X_alm=0.54, and X_pyr=0.25 within ≈20 μm and exhibits no distinct change in microstructure. Granulitic plagioclase shows exsolution lamellae of the Bøggild intergrowth. In omphacite, anti-phase domains (APDs) which potentially record the temperature of cation ordering after mineral growth have been observed and their size suggest eclogitisation at 600–700 °C. The electron backscatter diffraction (EBSD) analysis revealed that the lattice orientation of the granulitic feldspar is basically unrelated to tectonic axes whereas newly formed eclogitic minerals omphacite and kyanite show a crystallographic relation to the foliation. In garnet, no change in the basic crystallographic orientation between the eclogitic and granulitic garnet composition was confirmed. However, misorientation analysis suggests a cellular microstructure not more than 1° misorientation in the core of the garnets, which is missing in the eclogitic rim indicating textural equilibration of the latter. The heterogeneous replacement patterns are characteristic for dissolution and re-precipitation reactions in an open system limited to fluid availability. The appearance of the compositional profile in garnet is interpreted as a diffusional re-equilibration step after the time-limited, fluid-mediated eclogitisation event that apparently obscured the initially sharp interface within the further retrograde metamorphic history.     

Retrograde fluid infiltration in the high-grade Modum Complex South Norway: evidence for age,source and REE mobility

The high-grade metamorphic basement of the Modum Complex, South Norway,exhibits retrogradation and alteration due to late stage fluid infiltration.Extensive alteration zones of albite-and calcite-rich veining occur especiallywithin and around numerous metagabbros. The gabbros, intruded at 1224±15Ma, are now partly altered to amphibolites due to the subsequent high-grade metamorphism.Two generations of albite-rich rocks have been recognized: (1) a fine-grained, foliated type;(2) a coarse-grained, crosscutting type. Both types show a typical greenschist facies mineralassemblage; albite ± actinolite ± chlorite ± talc. The calcite veins/dykesrepresent a younger generation of veins than both albite-rich types. U–Pb data for spheneof type (1) yielded an age of 1080±3 Ma, determining a point on the retrogradeP-T-t path of the Modum Complex. Increasing albitisation of themetagabbros leads to a decrease in(¹⁴³ND/¹⁴⁴Nd)_oand an increase in (⁸⁷Sr/⁸⁶)_o.Albite- and calcite-rich samples show negative _Nd and positive _Sr, suggesting that fluids which interacted with the metagabbros originated from a crustal reservoir. The Nd and Sr isotopic data show disequilibrium at the microscale as well as at the macroscale. Negative Sm–Nd model ages of the albite-rich rocks demonstrate that rare-earth elements (REEs) were mobile and fractionated during albitisation.     

Metastability of granulites and processes of eclogitisation in the UHP region of western Norway

The Flatraket Complex, a granulite facies low strain enclave within the Western Gneiss Region, provides an excellent example of metastability of plagioclase‐bearing assemblages under eclogite facies conditions. Coesite eclogites are found <200 m structurally above and <1 km below the Flatraket Complex, and are separated from it by amphibolite facies gneisses related to pervasive late‐orogenic deformation and overprinting. Granulites within the Flatraket Complex equilibrated at 9–11 kbar, 700–800°C. These predate eclogite facies metamorphism and were preserved metastably in dry undeformed zones under eclogite facies conditions. Approximately 5% of the complex was transformed to eclogite in zones of fluid infiltration and deformation, which were focused along lithological contacts in the margin of the complex. Eclogitisation proceeded by domainal re‐equilibration and disequilibrium breakdown of plagioclase by predominantly hydration reactions. Both hydration and anhydrous plagioclase breakdown reactions were kinetically linked to input of fluid. More pervasive hydration of the complex occurred during exhumation, with fluid infiltration linked to dehydration of external gneisses. Eclogite facies shear zones within the complex equilibrated at 20–23 kbar, 650–800°C, consistent with the lack of coesite and with the equilibration conditions of external HP eclogites. If the complex experienced pressures equivalent to those of nearby coesite eclogites (> 28 kbar), unprecedented metastability of plagioclase and quartz is implied. Alternatively, a tectonic break exists between the Flatraket Complex and UHP eclogites, supporting the concept of a tectonic boundary to the UHP zone of the Western Gneiss Region. The distribution of eclogite and amphibolite facies metamorphic overprints demonstrates that the reactivity of the crust during deep burial and exhumation is strongly controlled by fluid availability, and is a function of the protolith.     

Late Devonian rifting in the central North Sea: Evidence from altered felsic volcanic rocks in the Embla oil field

In the Embla oil field on the northern flank of the Mid North Sea High, the central North Sea, multiple quartz porphyric volcanic beds at ca. 4600 m depth form part of a volcano-sedimentary interval above the Caledonian basement as interpreted from seismic data. Zircon U–Pb laser ablation ICPMS date one bed to 374 ± 3 Ma, indicating that the volcanic rocks and interbedded sediments are early Famennian and correlate to the Buchan Formation. The volcanic rocks have been extensively clay and carbonate altered in a near-surface environment, but high field strength element data show that the protoliths were alkali rhyolites, yielding intra-plate signatures in tectonic discrimination diagrams. Famennian quartz porphyric volcanic rocks have also been reported from well A17-1 on the southern flank of the Mid North Sea High. The Famennian volcanism on the northern and southern flanks testify to an active magmatic environment in the central North Sea in the early Famennian, supporting the existence of a late Devonian proto-Central Graben rift extending northwards into the central North Sea. The rift is likely an early example of strain localisation to a zone of reduced crustal strength along the Caledonian suture between Avalonia and Baltica.     

The legacy of crystal-plastic deformation in olivine: high-diffusivity pathways during serpentinization

Crystal-plastic olivine deformation to produce subgrain boundaries composed of edge dislocations is an inevitable consequence of asthenospheric mantle flow. Although crystal-plastic deformation and serpentinization are spatio-temporally decoupled, we identified compositional readjustments expressed on the micrometric level as a striped Fe-enriched ( [`(X)]<sub>\textFe</sub> \bar{X}_{\text{Fe}}  = 0.24 ± 0.02 (zones); 0.12 ± 0.02 (bulk)) or Fe-depleted ( [`(X)]_\textFe \bar{X}_{\text{Fe}}  = 0.10 ± 0.01 (zones); 0.13 ± 0.01 (bulk)) zoning in partly serpentinized olivine grains from two upper mantle sections in Norway. Focused ion beam sample preparation combined with transmission electron microscopy (TEM) and aberration-corrected scanning TEM, enabling atomic-level resolved electron energy-loss spectroscopic line profiling, reveals that every zone is immediately associated with a subgrain boundary. We infer that the zonings are a result of the environmental Fe²⁺Mg₋₁ exchange potential during antigorite serpentinization of olivine and the drive toward element exchange equilibrium. This is facilitated by enhanced solid-state diffusion along subgrain boundaries in a system, which otherwise re-equilibrates via dissolution-reprecipitation. Fe enrichment or depletion is controlled by the silica activity imposed on the system by the local olivine/orthopyroxene mass ratio, temperature and the effect of magnetite stability. The Fe-Mg exchange coefficients K_\textD^{\textAtg/\textOl} K_{\text{D}}^{{{\text{Atg}}/{\text{Ol}}}} between both types of zoning and antigorite display coalescence toward exchange equilibrium. With both types of zoning, Mn is enriched and Ni depleted compared with the unaffected bulk composition. Nanometer-sized, heterogeneously distributed antigorite precipitates along olivine subgrain boundaries suggest that water was able to ingress along them. Crystallographic orientation relationships gained via electron backscatter diffraction between olivine grain domains and different serpentine vein generations support the hypothesis that serpentinization was initiated along olivine subgrain boundaries.     

Experimental study of the carbonation of partially serpentinized and weathered peridotites

Carbonation of partially serpentinized and weathered peridotites was studied experimentally under hydrothermal conditions (T: 200 °C, P_CO2: 130-180 bars). Experiments were performed in a closed system using whole rock drill core samples (height: 1 cm, diameter: 1 cm) as starting material. The initial samples were composed mainly of meshwork serpentine, relicts of primary olivine and an olivine weathering product (deweylite assemblage). Two types of solutions, each with a total salt content corresponding to that of average seawater (35 g/L dissolved salts), were used: (1) a Na-Ca-Cl solution (12.5 g/L CaCl₂ + 22.5 g/L NaCl) and (2) a NaCl solution (35 g/L NaCl). After 15-25 days of experimental treatment, the samples were partly covered with carbonates. In addition, noticeable carbonation reactions had occurred below the sample surfaces within zones with thicknesses up to 250 μm. In the Na-Ca-Cl solution, both the olivine relicts and the deweylite assemblage were partly replaced by calcite along the surrounding serpentine veins. However, the extent of calcitization was found to be considerably larger for the deweylite assemblage than for the olivine. Bulk fluid analyses show an increase in the Mg and Si concentrations with reaction time. In the NaCl solution, the deweylite assemblage was partly dissolved resulting in large voids within the reaction zone. In contrast, the olivine was replaced by magnesite. Under the conditions of our experiments, the meshwork serpentine was not reactive, but aided fluid infiltration into the rock samples. The experimentally produced microtextures closely resemble those found in natural examples. Our study elucidates the mechanisms by which carbonates form in ultramafic rocks under relatively high P_CO2-T conditions and particularly in the presence of Ca-bearing aqueous solutions. The existence of a serpentine meshtexture and the presence of weathering products formed from primary Mg-silicates may have significant beneficial effects on in situ CO₂ mineral sequestration in ultramafic rocks.     

Diffusion versus recrystallization processes in Rb-Sr geochronology: Isotopic relics in eclogite facies rocks, Western Gneiss Region, Norway

Rb-Sr and U-Pb isotopic data for granulite facies rocks, forming textural relics with respect to eclogite facies metamorphism in the Western Gneiss Region (WGR) of Norway, highlight the importance of textures and mineral reaction kinetics for the interpretation of geochronological data. Studied rocks from Bårdsholmen, southern WGR, were subjected to granulite facies metamorphism at 955 ± 3 Ma (U-Pb, zircon). Later on, they experienced a subduction-related, kinetically stranded eclogitization (T > 650 °C at ∼20 kbar) at 404 ± 2 Ma (Rb-Sr multimineral internal isochron data), followed by exhumation through amphibolite facies conditions. Full conversion of granulite to eclogite was restricted to zones of fluid infiltration and deformation. Despite the fact that metamorphic temperatures vastly exceeded the commonly assumed ‘closure temperature’ for Rb-Sr in submillimeter-sized biotite for several Ma during eclogite facies overprint, Sr-isotopic signatures of relic biotite have not been fully reset. Large biotite crystals nearly record their Sveconorwegian (Grenvillian) crystallization age. Sr signatures of other granulite facies phases (feldspar, pyroxenes, amphibole) remained unchanged, with the exception of apatite. The results imply that isotopic signatures much closer correspond to the P, T conditions of formation recorded by a dated phase and its paragenesis, than to a temperature history. In texturally well-equilibrated high-grade rocks which experienced no mineral reactions and remained devoid of free fluids during exhumation, like granulites or eclogites, isotopic resetting during cooling is either kinetically locked, or restricted to sluggish intermineral diffusion which demonstrably does not lead to full isotopic homogenization. In texturally unequilibrated rocks, textural relics are likely to represent isotopic relics. It is shown that for both high-grade rocks and for rocks with textural disequilibria, geologically meaningful isotopic ages based on isochron methods can only be derived from sub-assemblages in isotopic equilibrium, which have to be defined by analysis of all rock-forming minerals. Conventional two-point ‘mica ages’ for such rocks are a priori geochronologically uninterpretable, and valid multimineral isochron ages a priori do not record cooling but instead date recrystallization-inducing processes like fluid-rock interaction.     

CO2 sequestration and extreme Mg depletion in serpentinized peridotite clasts from the Devonian Solund basin, SW-Norway

The conglomerates of the Solund Devonian basin of SW-Norway contain numerous (locally up to 20 vol.%) peridotitic clasts with concentric mm- to 10-cm thick zones of varying red to black color. The peridotite clasts show a clear, alteration-related textural evolution. The least-altered rocks are partly serpentinized peridotites, showing a typical mesh texture with veins of serpentine, magnesite and Ni-rich magnetite surrounding olivine (Fo₉₁) relicts and its Mg-depleted, clay-like alteration product (deweylite assemblage). In the more advanced ophicarbonate stage, the mesh cells contain calcite, silica and are surrounded by talc. In the final stage, quartz, calcite, and hematite dominate the mineralogy and occur together with minor amounts of chromite, talc, Cr-chlorite, and Cr-hydroandradite. In tandem with this textural evolution is a decrease in MgO from 40 to 2.5 wt% and a CaO increase from 1 to 35 wt%. All peridotite clasts are characterized by high Cr and Ni concentrations. The chemistry and the textural evolution show that the clasts formed by an extreme Mg-mobilization from the peridotite, with development of secondary porosity and subsequent precipitation of calcite. MgO removed from the clasts after burial is in part consumed by replacement reactions in the sediment matrix around the clasts where Mg-free minerals (e.g., almandine) are replaced by Mg-bearing minerals (e.g., talc). Calculated apparent ⁸⁷Sr/⁸⁶Sr ratios of the clasts at 385 Ma (0.7124-0.7139), corresponding to the inferred age of sediment deposition and incipient clast alteration, indicate interaction with diagenetic basinal fluids. We explain the reaction history as a three stage process involving (a) partial serpentinization of olivine in an oceanic environment (b) breakdown of olivine relicts to the deweylite assemblage resulting in mobilization of MgO under (near-) surface conditions in a tropical Devonian climate and (c) further Mg-mobilization and replacement of the deweylite assemblage by calcite and quartz after diagenesis. Sedimentary basins with abundant weathered peridotite represent potential sites for a permanent CO₂ storage by formation of calcite in a low-temperature environment.