In-situ monazite Th–U–total Pb dating and zircon LA–ICP–MS depth-profiling was applied to metasedimentary rocks from the Vaimok Lens in the Seve Nappe Complex (SNC), Scandinavian Caledonides. Results of monazite Th–U–total Pb dating, coupled with major and trace element mapping of monazite, revealed 603 ± 16 Ma Neoproterozoic cores surrounded byrims that formed at 498 ± 10 Ma. Monazite rim formation was facilitated via dissolution–reprecipitation of Neoproterozoic monazite. The monazite rims record garnet growth as they are depleted in Y2O3 with respect to the Neoproterozoic cores. Rims are also characterized by relatively high SrO with respect to the cores. Results of the zircon depth-profiling revealed igneous zircon cores with crystallization ages typical for SNC metasediments. Multiple zircon grains also exhibit rims formedby dissolution–reprecipitation that are defined by enrichment of light rare earth elements, U, Th, P, ± Y, and ± Sr. Rims also have subdued Eu anomalies (Eu/Eu* ≈ 0.6–1.2) with respect to the cores. The age of zircon rim formation was calculated from three metasedimentary rocks: 480 ± 22 Ma; 475 ± 26 Ma; and 479 ± 38 Ma. These results show that both monazite and zircon experienced dissolution–reprecipitation under high-pressure conditions. Caledonian monazite formed coeval with garnet growth during subduction of the Vaimok Lens, whereas zircon rim formation coincided with monazite breakdown to apatite, allanite and clinozoisite during initial exhumation.
Iron-bearing oxy-dravite was thermally treated in air and hydrogen atmosphere at 800 °C to study potential changes in Fe, Mg and Al ordering over the octahedrally coordinated Y and Z sites and to explore possible applications to intersite geothermometry based on tourmaline. Overall, the experimental data (structural refinement, Mössbauer, infrared and optical absorption spectroscopy) show that heating Fe-bearing tourmalines results in disordering of Fe over Y and Z balanced by ordering of Mg at Y, whereas Al does not change appreciably. The Fe disorder depends on temperature, but less on redox conditions. The degree of Fe3+–Fe2+ reduction is limited despite strongly reducing conditions, indicating that the fO2 conditions do not exclusively control the Fe oxidation state at the present experimental conditions. Untreated and treated samples have similar short- and long-range crystal structures, which are explained by stable Al-extended clusters around the O1 and O3 sites. In contrast to the stable Al clusters that preclude any temperature-dependent Mg–Al order– disorder, there occurs Mg diffusion linked to temperaturedependent exchange with Fe. Ferric iron mainly resides around O2− at O1 rather than (OH)−, but its intersite disorder induced by thermal treatment indicates that Fe redistribution is the driving force for Mg–Fe exchange and that its diffusion rates are significant at these temperatures. With increasing temperature, Fe progressively disorders over Y and Z, whereas Mg orders at Y according to the order–disorder reaction: YFe + ZMg → ZFe + YMg. The presented findings are important for interpretation of the post-crystallization history of both tourmaline and tourmaline host rocks and imply that successful tourmaline geothermometers may be developed by thermal calibration of the Mg– Fe order–disorder reaction, whereas any thermometers based on Mg–Al disorder will be insensitive and involve large uncertainties.
The Seve Nappe Complex of the Scandinavian Caledonides is thought to be derived from the distal passive margin of Baltica which collided with Laurentia in the Scandian Phase of the Caledonian Orogeny at 430–400 Ma. Parts of the Seve Nappe Complex were affected by pre-Scandian high- and ultrahigh-pressure metamorphism, in a tectonic framework that is still unclear, partly due to uncertainties about the exact timing. Previous age determinations yielded between ~ 505 and ~ 446 Ma, with a general trend of older ages in the North (Norrbotten) than in the South (Jämtland). New age determinations were performed on eclogite and garnet–phengite gneiss at Tjeliken in northern Jämtland. Thermodynamic modelling yielded peak metamorphic conditions of 25–27 kbar/680–760 °C for the garnet–phengite gneiss, similar to published peak metamorphic conditions of the eclogite (25–26 kbar/650–700 °C). Metamorphic rims of zircons from the garnet–phengite gneiss were dated using secondary ion mass spectrometry and yielded a concordia age of 458.9 ± 2.5 Ma. Lu–Hf garnet-whole rock dating yielded 458 ± 1.0 Ma for the eclogite. Garnet in the eclogite shows prograde major-element zoning and concentration of Lu in the cores, indicating that this age is related to garnet growth during pressure increase, i.e. subduction. The identical ages from both rock types, coinciding with published Sm–Nd ages from the eclogite, confirm subduction of the Seve Nappe Complex in Northern Jämtland during the Middle Ordovician in a fast subduction–exhumation cycle.
The 2014–2015 Holuhraun fissure eruption provided a rare opportunity to study in detail the magmatic processes and magma plumbing system dynamics during a 6-month-long, moderate- to large-volume basaltic fissure eruption. In this contribution, we present a comprehensive dataset, including major and trace elements of whole-rock and glassy tephra samples, mineral chemistry, and radiogenic and oxygen isotope analyses from an extensive set of samples (n = 62) that were collected systematically in several field campaigns throughout the entire eruptive period. We also present the first detailed chemical and isotopic characterization of magmatic sulfides from Iceland. In conjunction with a unique set of geophysical data, our approach provides a detailed temporal and spatial resolution of magmatic processes before and during this eruption. The 2014–2015 Holuhraun magma is compositionally indistinguishable from recent basalts erupted from the Bárðarbunga volcanic system, consistent with seismic observations for magma ascent close to the Bárðarbunga central volcano, followed by dyke propagation to the Holuhraun eruption site. Whole-rock elemental and isotopic compositions are remarkably constant throughout the eruption. Moreover, the inferred depth of the magma reservoir tapped during the eruption is consistently 8 ± 5 km, in agreement with geodetic observations and melt inclusion entrapment pressures, but inconsistent with vertically extensive multi-tiered magma storage prior to eruption. The near constancy in the chemical and isotopic composition of the lava is consistent with the efficient homogenization of mantle-derived compositional variability. In contrast, occurrence of different mineral populations, including sulfide globules, which display significant compositional variability, requires a more complex earlier magmatic history. This may include sampling of heterogeneous mantle melts that mixed, crystallized and finally homogenized at mid- to lower-crustal conditions.
Karoo continental flood basalt (CFB) province is known for its highly variable trace element and isotopic composition, often attributed to the involvement of continental lithospheric sources. Here, we report oxygen isotopic compositions measured with secondary ion mass spectrometry for hand-picked olivine phenocrysts from ~ 190 to 180 Ma CFBs and intrusive rocks from Vestfjella, western Dronning Maud Land, that form an Antarctic extension of the Karoo province. The Vestfjella lavas exhibit heterogeneous trace element and radiogenic isotope compositions (e.g., εNd from − 16 to + 2 at 180 Ma) and the involvement of continental lithospheric mantle and/or crust in their petrogenesis has previously been suggested. Importantly, our sample set also includes rare primitive dikes that have been derived from depleted asthenospheric mantle sources (εNd up to + 8 at 180 Ma). The majority of the oxygen isotopic compositions of the olivines from these dike rocks (δ18O = 4.4–5.2‰; Fo = 78–92 mol%) are also compatible with such sources. The olivine phenocrysts in the lavas, however, are characterized by notably higher δ18O (6.2–7.5‰; Fo = 70–88 mol%); and one of the dike samples gives intermediate compositions (5.2‒6.1‰, Fo = 83–87 mol%) between the other dikes and the CFBs. The oxygen isotopic compositions do not correlate with radiogenic isotope compositions susceptible to crustal assimilation (Sr, Nd, and Pb) or with geochemical indicators of pyroxene-rich mantle sources. Instead, δ18O correlates positively with enrichments in large-ion lithophile elements (especially K) and 187Os. We suggest that the oxygen isotopic compositions of the Vestfjella CFB olivines primarily record large-scale subduction-related metasomatism of the sub-Gondwanan mantle (base of the lithosphere or deeper) prior to Karoo magmatism. The overall influence of such sources to Karoo magmatism is not known, but, in addition to continental lithosphere, they may be responsible for some of the geochemical heterogeneity observed in the CFBs.
Halogen composition of replaced apatite formed during a regional metasomatic event (Bamble Sector, SE Norway) reveals information about the composition and evolution of the hydrothermal fluid. Infiltration and pervasive fluid flow of highly saline fluids into gabbroic bodies lead to scapolitization and amphibolitization, where magmatic Cl-rich apatite reacts with the hydrothermal fluid to form OH- and/or F-rich apatite. Apatite from highly altered samples adjacent to the shear zone has highest F (up to 15,000 µg/g) and lowest Br (4–25 µg/g) concentrations, whereas apatite from least altered samples has very low F (30–200 µg/g) and high Br (30–85 µg/g). In addition, individual replaced apatite grains show a zonation in F with high concentrations along rims and cracks and low F in core regions. Iodine concentrations remain rather constant as low values of 0.18–0.70 µg/g. We interpret all observed compositional features of replaced apatite to be the result of a continuous evolution of the fluid during fluid–rock interaction. Due to its high compatibility, F from the infiltrating fluid is incorporated early into recrystallized apatite (close to shear zone and rims of individual apatite grains). In contrast, Br as an incompatible halogen becomes enriched in the fluid and is highest in the most evolved fluid. Using experimental partition data between replaced apatite and fluid, we calculated F concentrations of the evolving fluid to decrease from 60 to <1 µg/g and Br to increase from ~1200 to ~5000 µg/g; I concentrations of the fluid are constant in the order of 370 µg/g. Although Cl is expected to show a similar behavior as Br, replaced apatite has constant Cl concentrations throughout the alteration sequence (~1 wt.%), which is likely the result of a rather constant Cl activity in the fluid. Chlorine stable isotope values of individual apatite grains are heterogeneous and range from −1.2 to +3.7 ‰. High δ 37Cl values are generally correlated with OH-rich zones of replaced apatite, whereas low δ 37Cl values are measured in F-rich zones of replaced apatite and in Cl-apatite of probably magmatic origin. Though apatite δ 37Cl values follow the general bulk trend, the individual δ 37Cl signature seems to reflect the highly localized composition of interfacial fluid at the reaction front. Our observations suggest that apatite can be used as a fluid probe for F, Br, and I to detect a compositional evolution of the fluid, which can be quantified by using experimentally derived partition coefficients. Partitioning of Cl and Cl stable isotopes between highly saline fluids and apatite is complex and likely controlled by more unknown factors than just the Cl concentration.
This contribution evaluates the relation between protracted zircon geochronological signal and protracted crustal melting in the course of polyphase high to ultrahigh temperature (UHT; T > 900 °C) granulite facies metamorphism. New U–Pb, oxygen isotope, trace element, ion imaging and cathodoluminescence (CL) imaging data in zircon are reported from five samples from Rogaland, South Norway. The data reveal that the spread of apparent age captured by zircon, between 1040 and 930 Ma, results both from open-system growth and closed-system post-crystallization disturbance. Post-crystallization disturbance is evidenced by inverse age zoning induced by solid-state recrystallization of metamict cores that received an alpha dose above 35 × 1017 α g−1. Zircon neocrystallization is documented by CL-dark domains displaying O isotope open-system behaviour. In UHT samples, O isotopic ratios are homogenous (δ18O = 8.91 ± 0.08‰), pointing to high-temperature diffusion. Scanning ion imaging of these CL-dark domains did not reveal unsupported radiogenic Pb. The continuous geochronological signal retrieved from the CL-dark zircon in UHT samples is similar to that of monazite for the two recognized metamorphic phases (M1: 1040–990 Ma; M2: 940–930 Ma). A specific zircon-forming event is identified in the orthopyroxene and UHT zone with a probability peak at ca. 975 Ma, lasting until ca. 955 Ma. Coupling U–Pb geochronology and Ti-in-zircon thermometry provides firm evidence of protracted melting lasting up to 110 My (1040–930 Ma) in the UHT zone, 85 My (ca. 1040–955 Ma) in the orthopyroxene zone and some 40 My (ca. 1040–1000 Ma) in the regional basement. These results demonstrate the persistence of melt over long timescales in the crust, punctuated by two UHT incursions.
Intergrowths of baddeleyite have been found in zircon grain interiors from amphibolite- and granulite-facies felsic rocks from southwest Greenland. The zircon grains are either close to or in direct contact with quartz. A series of experiments has been conducted using natural, unaltered zircon grains ± SiO2 in H2O–CaCl2, and H2O–Ca(OH)2 solutions with varying molar proportions of Ca to Si at 900 °C; 1000 MPa and 600 °C; 400 MPa for 4–50 days. Experimental results indicate that baddeleyite formed in the reacted zircon if the molar amount of Ca was close to or greater than Si in the system. The baddeleyite primarily takes the form of bead-like trails along the reaction front between the altered and unaltered zircon. Uranium, Th, and Y + REE were detected in both the newly formed baddeleyite and in the altered zircon, while Pb was effectively absent in both phases. Formation of baddeleyite from zircon in the silica-saturated rocks only appears to be possible when Ca saturates the system, such that the Si is tied up as CaSiO3 lowering the silica activity to < 1. This highly localized (µm to nm scale) effect in natural quartz-bearing rocks, where baddeleyite forms in the interiors of zircon grains in contact with quartz, implies that metastability in natural rock-forming systems can occur on a very small scale. Non-incorporation of Pb in the newly formed baddeleyite, or in areas of the zircon altered by fluids, implies that either could be used to date the metasomatic event responsible for their formation.
The discovery of Hadean to Paleoarchean zircons in a metaconglomerate from Jack Hills, Western Australia, has catalyzed intensive study of these zircons and their mineral inclusions, as they represent unique geochemical archives that can be used to unravel the geological evolution of early Earth. Here, we report the occurrence and physical properties of previously undetected CO2 inclusions that were identified in 3.36–3.47 Ga and 3.80–4.13 Ga zircon grains by confocal micro-Raman spectroscopy. Minimum P–T conditions of zircon formation were determined from the highest density of the inclusions, determined from the density-dependence of the Fermi diad splitting in the Raman spectrum and Ti-in-zircon thermometry. For both age periods, the CO2 densities and Ti-in-zircon temperatures correspond to high-grade metamorphic conditions (≥5 to ≥7 kbar/~670 to 770 °C) that are typical of mid-crustal regional metamorphism throughout Earth’s history. In addition, fully enclosed, highly disordered graphitic carbon inclusions were identified in two zircon grains from the older population that also contained CO2 inclusions. Transmission electron microscopy on one of these inclusions revealed that carbon forms a thin amorphous film on the inclusion wall, whereas the rest of the volume was probably occupied by CO2 prior to analysis. This indicates a close relationship between CO2 and the reduced carbon inclusions and, in particular that the carbon precipitated from a CO2-rich fluid, which is inconsistent with the recently proposed biogenic origin of carbon inclusions found in Hadean zircons from Jack Hills.
Zircon crystals from a locally charnockitizedPaleoproterozoic high-K metagranite from the KeralaKhondalite Belt (KKB) of southern India have been investigatedby high-spatial resolution secondary ion mass spectrometryanalysis of U–Th–Pb and rare earth elements(REE), together with scanning ion imaging and scanningion tomography (depth-profiled ion imaging). The spotanalyses constrain the magmatic crystallization age of themetagranite to ca. 1,850 Ma, with ultrahigh-temperature(UHT) metamorphism occurring at ca. 570 Ma and superimposedcharnockite formation at ca. 520–510 Ma, whilethe ion imaging reveals a patchy distribution of radiogenicPb throughout the zircon cores. Middle- to heavy-REEdepletion in ca. 570 Ma zircon rims suggests that thesegrew in equilibrium with garnet and therefore date theUHT metamorphism in the KKB. The maximum apparent207Pb/206Pb age obtained from the unsupported radiogenicPb concentrations is also consistent with formationof the Pb patches during this event. The superimposed charnockitization event appears to have caused additionalPb-loss in the cores and recrystallization of the rims. Theresults of depth-profiling of the scanning ion tomographyimage stack show that the Pb-rich domains range in sizefrom <5 nm to several 10 nm (diameter if assumed to bespherical). The occurrence of such patchy Pb has previouslybeen documented only from UHT metamorphiczircon, where it likely results from annealing of radiation-damaged zircon. The formation of a discrete, heterogeneouslydistributed and subsequently immobile Pb phaseeffectively arrests the normal Pb-loss process seen at lowergrades of metamorphism.