The Grønnedal-Ika Carbonatite-Syenite Complex, South Greenland: Carbonatite Formation by Liquid Immiscibility

The Grønnedal-Ika complex is dominated by layered nepheline syenites which were intruded by a xenolithic syenite and a central plug of calcite to calcite-siderite carbonatite. Aegirine-augite, alkali feldspar and nepheline are the major mineral phases in the syenites, along with rare calcite. Temperatures of 680-910°C and silica activities of 0·28-0·43 were determined for the crystallization of the syenites on the basis of mineral equilibria. Oxygen fugacities, estimated using titanomagnetite compositions, were between 2 and 5 log units above the fayalite-magnetite-quartz buffer during the magmatic stage. Chondrite-normalized REE patterns of magmatic calcite in both carbonatites and syenites are characterized by REE enrichment (LaCN-YbCN = 10-70). Calcite from the carbonatites has higher Ba (∼5490 ppm) and lower HREE concentrations than calcite from the syenites (54-106 ppm Ba). This is consistent with the behavior of these elements during separation of immiscible silicate-carbonate liquid pairs. εNd(T = 1·30 Ga) values of clinopyroxenes from the syenites vary between +1·8 and +2·8, and εNd(T) values of whole-rock carbonatites range from +2·4 to +2·8. Calcite from the carbonatites has δ18O values of 7·8 to 8·6‰ and δ13C values of −3·9 to −4·6‰. δ18O values of clinopyroxene separates from the nepheline syenites range between 4·2 and 4·9‰. The average oxygen isotopic composition of the nepheline syenitic melt was calculated based on known rock-water and mineral-water isotope fractionation to be 5·7 ± 0·4‰. Nd and C-O isotope compositions are typical for mantle-derived rocks and do not indicate significant crustal assimilation for either syenite or carbonatite magmas. The difference in δ18O between calculated syenitic melts and carbonatites, and the overlap in εNd values between carbonatites and syenites, are consistent with derivation of the carbonatites from the syenites via liquid immiscibilit

Fluid-induced breakdown of white mica controls nitrogen transfer during fluid–rock interaction in subduction zones

Author Posting. © The Author(s), 2016. This is the author's version of the work. It is posted here by permission of Taylor & Francis for personal use, not for redistribution. The definitive version was published in International Geology Review 59 (2017): 702-720, doi:10.1080/00206814.2016.1233834.In order to determine the effects of fluid–rock interaction on nitrogen elemental and isotopic systematics in high-pressure metamorphic rocks, we investigated three different profiles representing three distinct scenarios of metasomatic overprinting. A profile from the Chinese Tianshan (ultra)high-pressure–low-temperature metamorphic belt represents a prograde, fluid-induced blueschist–eclogite transformation. This profile shows a systematic decrease in N concentrations from the host blueschist (~26 μg/g) via a blueschist–eclogite transition zone (19–23 μg/g) and an eclogitic selvage (12–16 μg/g) towards the former fluid pathway. Eclogites and blueschists show only a small variation in δ15Nair (+2.1 ± 0.3‰), but the systematic trend with distance is consistent with a batch devolatilization process. A second profile from the Tianshan represents a retrograde eclogite–blueschist transition. It shows increasing, but more scattered, N concentrations from the eclogite towards the blueschist and an unsystematic variation in δ15N values (δ15N = + 1.0 to +5.4‰). A third profile from the high-P/T metamorphic basement complex of the Southern Armorican Massif (Vendée, France) comprises a sequence from an eclogite lens via retrogressed eclogite and amphibolite into metasedimentary country rock gneisses. Metasedimentary gneisses have high N contents (14–52 μg/g) and positive δ15N values (+2.9 to +5.8‰), and N concentrations become lower away from the contact with 11–24 μg/g for the amphibolites, 10–14 μg/g for the retrogressed eclogite, and 2.1–3.6 μg/g for the pristine eclogite, which also has the lightest N isotopic compositions (δ15N = + 2.1 to +3.6‰). Overall, geochemical correlations demonstrate that phengitic white mica is the major host of N in metamorphosed mafic rocks. During fluid-induced metamorphic overprint, both abundances and isotopic composition of N are controlled by the stability and presence of white mica. Phengite breakdown in high-P/T metamorphic rocks can liberate significant amounts of N into the fluid. Due to the sensitivity of the N isotope system to a sedimentary signature, it can be used to trace the extent of N transport during metasomatic processes. The Vendée profile demonstrates that this process occurs over several tens of metres and affects both N concentrations and N isotopic compositions.Support of this project was partly provided by National Science Foundation grant EAR-0711355 to GEB.2017-10-1

On the fluid-mobility of molybdenum, tungsten, and antimony in subduction systems

Molybdenum (Mo) and tungsten (W) have long been regarded as being more or less immobile during slab fluid-induced arc magma generation. Here we characterize about 180 samples of young, predominantly mafic to intermediate tephras and lavas for their Mo, W, and antimony (Sb) concentrations, to examine the fluid-mobility of these elements in subduction systems. Samples were taken along the active arcs of the Chilean Southern Volcanic Zone (SVZ) and the Central American Volcanic Arc (CAVA). When relating Mo, W, and Sb to trace element ratios typically used to constrain the involvement of subduction fluids in magma formation, such as Ba/La or U/Th, Mo, W, and Sb are enriched in the most fluid-influenced, highest-degree melts. W/Mo ratios correlate positively with Pb/Ce, which is established to reflect a recent subduction signal or assimilation of crustal material with an ancient subduction signature, suggesting that subduction processes promote enrichment of W over Mo. This is well expressed at the SVZ and most of the CAVA; while few OIB-type rocks from Central Costa Rica form an opposite trend. Moreover, Mo/W ratios co-vary with Cl contents derived from melt inclusions, indicating that the relative degree of mobilization responds to the composition of the subduction fluid. To evaluate the mobility of Mo, W, and Sb during metamorphism in the slab, eclogites with no or minor metasomatic overprint and a fluid-induced overprint in an eclogite-blueschist sequence were investigated. None of the three elements shows a systematic variability related to metasomatism and the minor variations are interpreted to reflect protolith heterogeneity. This suggests that Mo, W and Sb remain relatively immobile up to depths of 70 km in the subduction zone

Boron isotope record of peak metamorphic ultrahigh-pressure and retrograde fluid–rock interaction in white mica (Lago di Cignana, Western Alps)

This study presents boron (B) concentration and isotope data for white mica from (ultra)high-pressure (UHP), subduction-related metamorphic rocks from Lago di Cignana (Western Alps, Italy). These rocks are of specific geological interest, because they comprise the most deeply subducted rocks of oceanic origin worldwide. Boron geochemistry can track fluid–rock interaction during their metamorphic evolution and provide important insights into mass transfer processes in subduction zones. The highest B contents (up to 345 μg/g B) occur in peak metamorphic phengite from a garnet–phengite quartzite. The B isotopic composition is variable (δ11B = − 10.3 to − 3.6%) and correlates positively with B concentrations. Based on similar textures and major element mica composition, neither textural differences, prograde growth zoning, diffusion nor a retrograde overprint can explain this correlation. Modelling shows that B devolatilization during metamorphism can explain the general trend, but fails to account for the wide compositional and isotopic variability in a single, well-equilibrated sample. We, therefore, argue that this trend represents fluid–rock interaction during peak metamorphic conditions. This interpretation is supported by fluid–rock interaction modelling of boron leaching and boron addition that can successfully reproduce the observed spread in δ11B and [B]. Taking into account the local availability of serpentinites as potential source rocks of the fluids, the temperatures reached during peak metamorphism that allow for serpentine dehydration, and the high positive δ11B values (δ11B = 20 ± 5) modelled for the fluids, an influx of serpentinite-derived fluid appears likely. Paragonite in lawsonite pseudomorphs in an eclogite and phengite from a retrogressed metabasite have B contents between 12 and 68 μg/g and δ11B values that cluster around 0% (δ11B = − 5.0 to + 3.5). White mica in both samples is related to distinct stages of retrograde metamorphism during exhumation of the rocks. The variable B geochemistry can be successfully modelled as fluid–rock interaction with low-to-moderate (< 3) fluid/rock ratios, where mica equilibrates with a fluid into which B preferentially partitions, causing leaching of B from the rock. The metamorphic rocks from Lago di Cignana show variable retention of B in white mica during subduction-related metamorphism and exhumation. The variability in the B geochemical signature in white mica is significant and enhances our understanding of metamorphic processes and their role in element transfer in subduction zones

Insights into Li and Li isotope cycling and sub-arc metasomatism from veined mantle xenoliths, Kamchatka

Harzburgitic xenoliths cut by pyroxenite veins from Avachinsky volcano, Kamchatka, are derived from the sub-arc mantle and record element transfer from the slab to the arc. Olivine and orthopyroxene in the harzburgites have Li isotopic compositions (δ7Li = +2.8 to +5.6) comparable to estimates of the upper mantle (δ7Li ~ +4 ± 2). The pyroxenite veins, which represent modal metasomatism and may therefore provide information about the metasomatic agent, have mantle-normalized trace element characteristics that suggest overprinting of their mantle source by an aqueous, slab-derived fluid. These include relative enrichments of Pb over Ce, U over Th and Sr over Nd. Li is enriched relative to the HREE, and ortho- and clinopyroxene from the veins are in Li elemental and isotopic equilibrium with each other and the surrounding harzburgite. Vein samples (δ7Li = +3.0 to +5.0) do not record a significant slab-derived δ7Li signature. These observations can be reconciled if slab Li diffusively re-equilibrates in the mantle wedge. Modeling demonstrates that Li equilibration of small (1–2 cm width) veins or melt conduits is achieved at mantle wedge temperatures within 101–105 years. We conclude that strongly fractionated Li isotopic signatures cannot be sustained for long periods in the sub-arc mantle, at least at shallow (<70 km) depths

Effects of fluid-rock interaction on 40Ar/39Ar geochronology in high-pressure rocks (Sesia-Lanzo Zone, Western Alps)

Author Posting. © The Author(s), 2013. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 126 (2014):475-494, doi:10.1016/j.gca.2013.10.023.in situ UV laser spot 40Ar/39Ar analyses of distinct phengite types in eclogite-facies rocks from the Sesia-Lanzo Zone (Western Alps, Italy) were combined with SIMS boron isotope analyses as well as boron (B) and lithium (Li) concentration data to link geochronological information with constraints on fluid-rock interaction. In weakly deformed samples, apparent 40Ar/39Ar ages of phengite cores span a range of ∼20 Ma, but inverse isochrons define two distinct main high-pressure (HP) phengite core crystallization periods of 88-82 Ma and 77-74 Ma, respectively. The younger cores have on average lower B contents (∼36 mg/g) than the older ones (∼43-48 mg/g), suggesting that loss of B and resetting of the Ar isotopic system were related. Phengite cores have variable d11B values (-18 to -10 ‰), indicating the lack of km scale B homogenization during HP crystallization. Overprinted phengite rims in the weakly deformed samples generally yield younger apparent 40Ar/39Ar ages than the respective cores. They also show variable effects of heterogeneous excess 40Ar incorporation and Ar loss. One acceptable inverse isochron age of 77.1 ±1.1 Ma for rims surrounding older cores (82.6 ±0.6 Ma) overlaps with the second period of core crystallization. Compared to the phengite cores, all rims have lower B and Li abundances but similar d11B values (-15 to -9 ‰), reflecting internal redistribution of B and Li and internal fluid buffering of the B isotopic composition during rim growth. The combined observation of younger 40Ar/39Ar ages and boron loss, yielding comparable values of both parameters only in cores and rims of different samples, is best explained by a selective metasomatic overprint. In low permeability samples, this overprint caused recrystallization of phengite rims, whereas higher permeability in other samples led to complete recrystallization of phengite grains. Strongly deformed samples from a several km long, blueschist-facies shear zone contain mylonitic phengite that forms a tightly clustered group of relatively young apparent 40Ar/39Ar ages (64.7 to 68.8 Ma), yielding an inverse isochron age of 65.0 ±3.0 Ma. Almost complete B and Li removal in mylonitic phengite is due to leaching into a fluid. The B isotopic composition is significantly heavier than in phengites from the weakly deformed samples, indicating an external control by a high-d11B fluid (d11B = +7 ±4 ‰). We interpret this result as reflecting phengite recrystallization related to deformation and associated fluid flow in the shear zone. This event also caused partial resetting of the Ar isotope system and further B loss in more permeable rocks of the adjacent unit. We conclude that geochemical evidence for pervasive or limited fluid flow is crucial for the interpretation of 40Ar/39Ar data in partially metasomatized rocks.Funding of this work by the Deutsche Forschungsgemeinschaft (grant KO-3750/2-1) is gratefully acknowledged

Multi-stage subduction-related metasomatism recorded in whiteschists from the Dora-Maira Massif, Western Alps

Whiteschists from the Dora-Maira massif (Western Alps, Italy) are Mg and K-rich metasomatised granites which experienced ultra-high pressure metamorphism and fluid-rock interaction during Alpine continental subduction. The sources and timing of fluid infiltration are a source of significant debate. In this study we present boron (B) isotopes and other fluid-mobile trace element (FME) concentrations in various generations of phengite from whiteschists and their country rock protoliths to investigate the sources and timing of metasomatic fluid influx. Reconstructed bulk rock concentrations based on modal data and mineral compositions indicate that significant amounts B and other FME were added to the rock during prograde metamorphism, but that this fluid influx postdates the main Mg metasomatic event. High B concentrations (150–350 µg/g) and light δ11B values (-16 to -4 ‰) recorded in phengite point to a B-rich sediment-derived fluid as the main source of B in the whiteschists. Further redistribution of FME during metamorphism was associated with breakdown of hydrous minerals such as talc, phlogopite and ellenbergerite. The source of the Mg-rich fluids cannot be constrained based on the B data in phengite, since its signature was overprinted by the later main B metasomatic event. Rare tourmaline-bearing whiteschists record additional information about B processes. Tourmaline δ11B values (-6 to +1 ‰) are in isotopic equilibrium with similar fluids to those recorded in most phengite, but phengites in tourmaline-bearing samples records anomalous B isotope compositions that reflect later redistribution of B. This study demonstrates the utility of in situ analyses in unravelling complex fluid-rock interaction histories, where whole rock analyses make it difficult to distinguish between different stages of fluid-rock interaction. Polymetasomatism may result in decoupling of different isotopic systems, thus complicating their interpretation. The Dora-Maira whiteschists interacted with multiple generations of fluids during subduction and therefore may represent a long-lived fluid pathway

A stable (Li, O) and radiogenic (Sr, Nd) isotope perspective on metasomatic processes in a subducting slab

Two distinct types of eclogites from the Raspas Complex (Ecuador), which can be distinguished based on petrography and trace element geochemistry, were analyzed for their stable (Li, O) and radiogenic (Sr, Nd) isotope signature to constrain metasomatic changes due to fluid-overprinting in metabasaltic rocks at high-pressure conditions and to identify fluid sources. MORB-type eclogites are characterized by a relative LREE depletion similar to MORB. High-pressure (HP) minerals from this type of eclogite have highly variable oxygen isotope compositions (garnet: + 4.1 to + 9.8 ‰; omphacite: + 6.1 to + 11.0 ‰; phengite: 8.7 to 10.4 ‰; amphibole: 6.2 to 10.1 ‰) and generally show equilibrium oxygen isotope fractionation. Initial 87Sr/86Sr isotope ratios are also variable (0.7037-0.7063), whereas εNd130Ma values (+ 8.3 to + 11.0) are relatively similar. Sr and O isotopic compositional differences among rocks on outcrop scale, the preservation of O isotopic compositions of low-temperature altered oceanic crust, and Sr-Nd isotopic trends typical for seafloor alteration suggest inheritance from variably altered oceanic crust. However, decreasing δ7Li values (-0.5 to -12.9 ‰) with increasing Li concentrations (11-94 ppm) indicate Li isotope fractionation by diffusion related to fluid-rock interaction. Li isotopes prove to be a very sensitive tracer of metasomatism, although the small effects on the Sr-Nd-O isotope systems suggest that the fluid-induced metasomatic event in the MORB-type eclogites was small-scale at low-water/rock ratios. This metasomatic fluid is thought to predominantly derive from in situ dehydration of MORB-type rocks. Zoisite eclogites, the second eclogite type from the Raspas Complex, are characterized by the presence of zoisite and enrichment in many incompatible trace elements compared to the MORB-type eclogites. The zoisite eclogites have a homogenous Sr-Nd isotopic signature (Initial 87Sr/86Sr = 0.7075-0.7081, εNd130Ma = -6.7 to -8.7), interpreted to reflect a metasomatic overprint. The isotopic signature can be attributed to the metasomatic formation of zoisite because associated zoisite veins are isotopically similar. Relatively homogenous O isotope values for garnet (10.9-12.3 ‰) omphacite (9.4 to 10.8 ‰), amphibole (10.0-10.1 ‰) and zoisite (10.5-11.9 ‰) and inter-mineral O isotopic disequilibria are consistent with a metasomatic overprint via open-system fluid input. Li concentrations (46-76 ppm) and δ7Li values of the zoisite eclogites overlap the range of the MORB-type eclogites. The large amount of fluid required for isotopic homogenization, combined with the results from fluid inclusion studies, suggests that deserpentinization played a major role in generating the metasomatic fluid that altered the zoisite eclogites. However, influence of a (meta)sedimentary source is required based on Sr-Nd isotope data and trace element enrichments. The significant geochemical variation in the various eclogites generated by interaction with metasomatic fluids has to be considered in attempts to constrain recycling at convergent margins