Showing papers in "Contributions to Mineralogy and Petrology in 2018"

Pyrite textures and compositions from the Zhuangzi Au deposit, southeastern North China Craton: implication for ore-forming processes

Abstract: The Zhuangzi Au deposit in the world-class Jiaodong gold province hosts visible natural gold, and pyrite as the main ore mineral, making it an excellent subject for deciphering the complex hydrothermal processes and mechanisms of gold precipitation. Three types of zoned pyrite crystals were distinguished based on textural and geochemical results from EPMA, SIMS sulfur isotopic analyses and NanoSIMS mapping. Py0 has irregular shapes and abundant silicate inclusions and was contemporaneous with the earliest pyrite–sericite–quartz alteration. It has low concentrations of As (0–0.3 wt.%), Au and Cu. Py1 precipitated with stage I mineralization shows oscillatory zoning with the bright bands having high As (0.4–3.9 wt.%), Au and Cu contents, whereas the dark bands have low contents of As (0–0.4 wt.%), Au and Cu. The oscillatory zoning represents pressure fluctuations and repeated local fluid phase separation around the pyrite crystal. The concentration of invisible gold in Py1 is directly proportional to the arsenic concentration. Py1 is partially replaced by Py2 which occurs with arsenopyrite, chalcopyrite and native gold in stage II. The replacement was likely the result of pseudomorphic dissolution–reprecipitation triggered by a new pulse of Au-rich hydrothermal fluids. The δ34S values for the three types of pyrite are broadly similar ranging from + 7.1 to + 8.8‰, suggesting a common sulfur source. Fluid inclusion microthermometry suggests that extensive phase separation was responsible for the gold deposition during stage II mineralization. Uranium–Pb dating of monazite constrains the age of mineralization to ca. 119 Ma coincident with a short compressional event around 120 Ma linked to an abrupt change in the drift direction of the subducting Pacific plate.

Melt segregation from silicic crystal mushes: a critical appraisal of possible mechanisms and their microstructural record

Abstract: One of the outstanding problems in understanding the behavior of intermediate-to-silicic magmatic systems is the mechanism(s) by which large volumes of crystal-poor rhyolite can be extracted from crystal-rich mushy storage zones in the mid-deep crust. The mechanisms commonly invoked are hindered settling, micro-settling, and compaction. The concept of micro-settling involves extraction of grains from a crystal framework during Ostwald ripening and has been shown to be non-viable in the metallic systems for which it was originally proposed. Micro-settling is also likely to be insignificant in silicic mushes, because ripening rates are slow for quartz and plagioclase, contact areas between grains in a crystal mush are likely to be large, and abundant low-angle grain boundaries promote grain coalescence rather than ripening. Published calculations of melt segregation rates by hindered settling (Stokes settling in a crystal-rich system) neglect all but fluid dynamical interactions between particles. Because tabular silicate minerals are likely to form open, mechanically coherent, frameworks at porosities as high as ~ 75%, settling of single crystals is only likely in very melt-rich systems. Gravitationally-driven viscous compaction requires deformation of crystals by either dissolution–reprecipitation or dislocation creep. There is, as yet, no reported microstructural evidence of extensive, syn-magmatic, internally-generated, viscous deformation in fully solidified silicic plutonic rocks. If subsequent directed searches do not reveal clear evidence for internally-generated buoyancy-driven melt segregation processes, it is likely that other factors, such as rejuvenation by magma replenishment, gas filter-pressing, or externally-imposed stress during regional deformation, are required to segregate large volumes of crystal-poor rhyolitic liquids from crustal mushy zones.

Experimental study of quartz inclusions in garnet at pressures up to 3.0 GPa: evaluating validity of the quartz-in-garnet inclusion elastic thermobarometer

Abstract: Garnet crystals with quartz inclusions were hydrothermally crystallized from oxide starting materials in piston–cylinder apparatuses at pressures from 0.5 to 3 GPa and temperatures ranging from 700 to 800 °C to study how entrapment conditions affect remnant pressures of quartz inclusions used for quartz-in-garnet (QuiG) elastic thermobarometry. Systematic changes of the 128, 206 and 464 cm−1 Raman band frequencies of quartz were used to determine pressures of quartz inclusions in garnet using Raman spectroscopy calibrations that describe the P–T dependencies of Raman band shifts for quartz under hydrostatic pressure. Within analytical uncertainties, inclusion pressures calculated for each of the three Raman band frequencies are equivalent, which suggests that non-hydrostatic stress effects caused by elastic anisotropy in quartz are smaller than measurement errors. The experimental quartz inclusions have pressures ranging from − 0.351 to 1.247 GPa that span the range of values observed for quartz inclusions in garnets from natural rocks. Quartz inclusion pressures were used to model P–T conditions at which the inclusions could have been trapped. The accuracy of QuiG thermobarometry was evaluated by considering the differences between pressures measured during experiments and pressures calculated using published equation of state parameters for quartz and garnet. Our experimental results demonstrate that Raman measurements performed at room temperature can be used without corrections to estimate garnet crystallization pressures. Calculated entrapment pressures for quartz inclusions in garnet are less than ~ 10% different from pressures measured during the experiments. Because the method is simple to apply with reasonable accuracy, we expect widespread usage of QuiG thermobarometry to estimate crystallization conditions for garnet-bearing silicic rocks.

Nanogeochemistry of hydrothermal magnetite

Abstract: Magnetite from hydrothermal ore deposits can contain up to tens of thousands of parts per million (ppm) of elements such as Ti, Si, V, Al, Ca, Mg, Na, which tend to either structurally incorporate into growth and sector zones or form mineral micro- to nano-sized particles. Here, we report micro- to nano-structural and chemical data of hydrothermal magnetite from the Los Colorados iron oxide–apatite deposit in Chile, where magnetite displays both types of trace element incorporation. Three generations of magnetites (X–Z) were identified with concentrations of minor and trace elements that vary significantly: SiO2, from below detection limit (bdl) to 3.1 wt%; Al2O3, 0.3–2.3 wt%; CaO, bdl–0.9 wt%; MgO, 0.02–2.5 wt%; TiO2, 0.1–0.4 wt%; MnO, 0.04–0.2 wt%; Na2O, bdl–0.4 wt%; and K2O, bdl–0.4 wt%. An exception is V2O3, which is remarkably constant, ranging from 0.3 to 0.4 wt%. Six types of crystalline nanoparticles (NPs) were identified by means of transmission electron microscopy in the trace element-rich zones, which are each a few micrometres wide: (1) diopside, (2) clinoenstatite; (3) amphibole, (4) mica, (5) ulvospinel, and (6) Ti-rich magnetite. In addition, Al-rich nanodomains, which contain 2–3 wt% of Al, occur within a single crystal of magnetite. The accumulation of NPs in the trace element-rich zones suggest that they form owing to supersaturation from a hydrothermal fluid, followed by entrapment during continuous growth of the magnetite surface. It is also concluded that mineral NPs promote exsolution of new phases from the mineral host, otherwise preserved as structurally bound trace elements. The presence of abundant mineral NPs in magnetite points to a complex incorporation of trace elements during growth, and provides a cautionary note on the interpretation of micron-scale chemical data of magnetite.

Zircon ages in granulite facies rocks: decoupling from geochemistry above 850 °C?

Abstract: Granulite facies rocks frequently show a large spread in their zircon ages, the interpretation of which raises questions: Has the isotopic system been disturbed? By what process(es) and conditions did the alteration occur? Can the dates be regarded as real ages, reflecting several growth episodes? Furthermore, under some circumstances of (ultra-)high-temperature metamorphism, decoupling of zircon U–Pb dates from their trace element geochemistry has been reported. Understanding these processes is crucial to help interpret such dates in the context of the P–T history. Our study presents evidence for decoupling in zircon from the highest grade metapelites (> 850 °C) taken along a continuous high-temperature metamorphic field gradient in the Ivrea Zone (NW Italy). These rocks represent a well-characterised segment of Permian lower continental crust with a protracted high-temperature history. Cathodoluminescence images reveal that zircons in the mid-amphibolite facies preserve mainly detrital cores with narrow overgrowths. In the upper amphibolite and granulite facies, preserved detrital cores decrease and metamorphic zircon increases in quantity. Across all samples we document a sequence of four rim generations based on textures. U–Pb dates, Th/U ratios and Ti-in-zircon concentrations show an essentially continuous evolution with increasing metamorphic grade, except in the samples from the granulite facies, which display significant scatter in age and chemistry. We associate the observed decoupling of zircon systematics in high-grade non-metamict zircon with disturbance processes related to differences in behaviour of non-formula elements (i.e. Pb, Th, U, Ti) at high-temperature conditions, notably differences in compatibility within the crystal structure.

The role of trace elements in controlling H incorporation in San Carlos olivine

Abstract: We conducted a series of hydroxylation experiments using mm-sized cuboids cut from six different crystals of San Carlos olivine with a range of trace-element concentrations. The cuboids were pre-annealed and then hydroxylated under identical conditions, ensuring that variation in the amounts of H incorporated depended only on the compositional variables. The pre-anneal was at 1400 °C, atmospheric pressure and an oxygen fugacity equivalent to Δlog FMQ + 1, with the subsequent hydroxylation at 800 °C and 1.5 GPa, for 3 days. Hydrogen was incorporated into all six crystals by the four main substitution mechanisms [Si], [Mg], [Ti] and [triv], with homogeneous H contents in the cores of the crystals, indicating H diffusion rates faster than 10− 11 m2/s. Total H as H2O in the homogeneous cores calculated by summing all the infrared absorbance bands ranges from 13 to 27 wt. ppm. The total H2O in the six pre-annealed crystals is poorly correlated with any measured compositional variable. However, when the H2O associated with individual infrared bands is compared, clear trends emerge. The intensity of absorption bands at 3572 and 3525 cm− 1 are strongly correlated with Ti concentrations, whose range in the six crystals exceeds an order of magnitude. Bands between 3400 and 3300 cm− 1, correlate negatively with Na+, but are positively correlated with the difference between molar Cr3+ and Na+. This highlights a previously unrecognised role for Na in suppressing H incorporation in natural olivines. The results confirm the important role that the trace constituents of olivine play in H incorporation. Two of these trace elements, Na and Ti, tend to be similarly enriched or depleted by partial melting or metasomatism of the mantle, but have opposite effects on H incorporation, with Ti enhancing it but Na suppressing it. Models estimating the effect of H in olivine on mantle rheology must, therefore, consider carefully the availability of these trace elements.

Melt inclusion constraints on petrogenesis of the 2014–2015 Holuhraun eruption, Iceland

Abstract: The 2014–2015 Holuhraun eruption, on the Barðarbunga volcanic system in central Iceland, was one of the best-monitored basaltic fissure eruptions that has ever occurred, and presents a unique opportunity to link petrological and geochemical data with geophysical observations during a major rifting episode. We present major and trace element analyses of melt inclusions and matrix glasses from a suite of ten samples collected over the course of the Holuhraun eruption. The diversity of trace element ratios such as La/Yb in Holuhraun melt inclusions reveals that the magma evolved via concurrent mixing and crystallization of diverse primary melts in the mid-crust. Using olivine–plagioclase–augite–melt (OPAM) barometry, we calculate that the Holuhraun carrier melt equilibrated at 2.1 ± 0.7 kbar (7.5 ± 2.5 km), which is in agreement with the depths of earthquakes (6 ± 1 km) between Barðarbunga central volcano and the eruption site in the days preceding eruption onset. Using the same approach, melt inclusions equilibrated at pressures between 0.5 and 8.0 kbar, with the most probable pressure being 3.2 kbar. Diffusion chronometry reveals minimum residence timescales of 1–12 days for melt inclusion-bearing macrocrysts in the Holuhraun carrier melt. By combining timescales of diffusive dehydration of melt inclusions with the calculated pressure of H2O saturation for the Holuhraun magma, we calculate indicative magma ascent rates of 0.12–0.29 m s−1. Our petrological and geochemical data are consistent with lateral magma transport from Barðarbunga volcano to the eruption site in a shallow- to mid-crustal dyke, as has been suggested on the basis of seismic and geodetic datasets. This result is a significant step forward in reconciling petrological and geophysical interpretations of magma transport during volcano-tectonic episodes, and provides a critical framework for the interpretation of premonitory seismic and geodetic data in volcanically active regions.

Geochemical constraints on the link between volcanism and plutonism at the Yunshan caldera complex, SE China

Abstract: The Yunshan caldera complex is part of a larger scale, ca. 2000-km-long volcanic–plutonic complex belt in the coastal region of SE China. The volcanic rocks in the caldera complex are characterized by high-silica peraluminous and peralkaline rhyolites associated with an intracaldera porphyritic quartz monzonite pluton. In this study, we present zircon U–Pb, Hf and stable O isotopes along with geochemical data of both volcanic and plutonic rocks to evaluate the potential petrogenetic link between volcanism and plutonism in the Yunshan caldera complex. SHRIMP zircon U–Pb geochronology of both volcanic and plutonic rocks yields almost identical ages ranging from 95.6 to 93.1 Ma. The peraluminous and peralkaline rhyolites show negative anomalies of Sr, P, Ti and Ba and to a lesser extent negative Nb and Ta anomalies, along with positive Rb anomalies and ‘seagull-like’ rare earth element (REE) patterns with negative Eu anomalies and low (La/Yb)N ratios. The intracaldera porphyritic quartz monzonite displays minor negative Rb, Nb, Ta, Sr, P and Ti anomalies and a positive Ba anomaly with REE patterns characterized by relatively high (La/Yb)N ratios and lack significant Eu anomalies. The peraluminous and peralkaline rhyolites and the porphyritic quartz monzonite exhibit consistent e Nd(t) of − 3.7 to − 2.2 and display zircon e Hf(t) values of − 2.1 to 3.7. They further have similar, mantle-like, zircon oxygen isotopic compositions (δ18OVSMOW mainly = 4.63 to 5.76‰). We interpret these observations to be in agreement with a crystal mush model in which the parental magma of the volcanic and plutonic rocks of the Yunshan caldera complex was likely produced by interaction of asthenosphere melts with subduction-influenced enriched mantle wedge. The peralkaline rhyolites are interpreted to represent the most differentiated magma that has subsequently experienced significant fluid–melt interactions, whereas the porphyritic quartz monzonite may be representative of the residual crystal mush. The Yunshan rhyolites typically match the geochemical characteristics of ‘hot-dry-reduced’ rhyolites indicating that, during the late Cretaceous, the tectonic setting of SE China changed from a compressional environment to an extensional environment, i.e., from an arc into a back-arc setting. Our results imply that volcanic and plutonic rocks in caldera systems may provide unique constraints on the evolution of the magmatic system in which both the erupting melt and the residual crystalline material are being preserved.

Ferric/ferrous ratio in silicate melts: a new model for 1 atm data with special emphasis on the effects of melt composition

Abstract: The effect of MgO and total FeO on ferric/ferrous ratio in model multicomponent silicate melts was investigated experimentally in the temperature range 1300–1500 °C at 1 atm total pressure in air. We demonstrate that the addition of these weak network modifier cations results in an increase of Fe3+/Fe2+ ratio in both mafic and silicic melts. Based on present and published experimental data, a new empirical equation is proposed to predict the ferric/ferrous ratio as a function of oxygen fugacity, temperature and melt composition. In contrast to previous equations, the compositional effect of melts on the Fe3+/Fe2+ ratio is not only modeled by the sum of the molar fraction of the individual oxide components. Additional interactions terms have also been incorporated. The main advantage of the proposed model is its applicability for a wide compositional range. However, its application to felsic melts (> 68 wt% SiO2) is not recommended. Other advantages of this equation and differences when compared with previous models are discussed.

Exhumation rates in the Gran Paradiso Massif (Western Alps) constrained by in situ U–Th–Pb dating of accessory phases (monazite, allanite and xenotime)

Abstract: Exhumation rates for high-pressure metamorphic rocks need to be carefully estimated to decipher tectonic processes in subduction/collision belts. In the Gran Paradiso Massif (Western Alps), the Money Unit crops out as a tectonic window below the Gran Paradiso Unit. According to previous studies, the Gran Paradiso and Money Units reached peak pressure conditions at ~ 18 to 20 kbar, 480–520 °C and ~ 17 to 18 kbar, 500–550 °C, respectively. This yields a maximum difference of ~ 9 to 10 km in the subduction depth reached by these two units during the Alpine history. Thrusting of the Gran Paradiso Unit over the Money Unit led to the simultaneous development of the main foliation under the same metamorphic conditions (~ 12.5 to 14.5 kbar and 530–560 °C) in both units. The thrust contact was subsequently folded and then both units were exhumed together. The relative timing of the growth and dissolution of the accessory phases was assessed by combining thermodynamic modelling with inclusion, textural and chemical (major and trace element) data from both major and accessory phases. The age of monazite constrained the high-pressure metamorphism in both the Gran Paradiso Unit and the Money Unit at 41.5 ± 0.3 and 42.0 ± 0.6 Ma, respectively. Allanite replacing monazite in the matrix has been dated at 32.7 ± 4.2 Ma. The late growth of xenotime associated with the crystallization of biotite pseudomorphs at the expense of garnet (at about 10 kbar) was dated at 32.3 ± 1.0 Ma. Our petrochronological data indicate about 10 m.y. between the peak pressure conditions and the crystallization of xenotime leading to an exhumation rate of the order of 2.2–5 mm/year. The new ages allow to better constrain the timing of the displacement of the thrust defining the lower boundary of the extruding wedge of eclogite-facies rocks.

Decoding a protracted zircon geochronological record in ultrahigh temperature granulite, and persistence of partial melting in the crust, Rogaland, Norway

Abstract: 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.

Granitic magmas with I-type affinities, from mainly metasedimentary sources: the Harcourt batholith of southeastern Australia

Abstract: The high-K, calcalkaline granitic rocks of the 370 Ma, post-orogenic Harcourt batholith in southeastern Australia have I-type affinities but are mildly peraluminous and have remarkably radiogenic isotope characteristics, with 87Sr/86Srt in the range 0.70807 to 0.714121 and eNdt in the range − 5.6 to − 4.3. This batholith appears to be a good example of magmas that were derived through partial melting of distinctly heterogeneous source rocks that vary from intermediate meta-igneous to mildly aluminous metasedimentary rocks, with the balance between the two rock types on the metasedimentary side. Such transitional S-I-type magmas, formed from mainly metasedimentary source rocks, may be more common than is generally realised. The Harcourt batholith also contains mainly granodioritic igneous microgranular enclaves (IMEs). Like their host rocks, the IMEs are peraluminous and have rather radiogenic isotope signatures (87Sr/86Srt of 0.71257–0.71435 and eNdt of − 7.3 to − 4.3), though some are hornblende-bearing. Origins of these IMEs by mixing a putative mantle end member with the host granitic magma can be excluded because of the variability in whole-rock isotope ratios and, for the same reason, the IME magmas cannot represent quench cumulates (autoliths) from the host magmas. Less abundant monzonitic to monzosyenitic IMEs cannot represent accumulations of magmatic biotite and/or alkali feldspar because K-feldspar is absent, and there is no co-enrichment of K2O and FeO + MgO, nor can they be mixtures of anything plausible with the host-rock magma. The granodioritic IMEs probably originated through high degrees of assimilation of a range of crustal materials (partial melts?) by basaltic magmas in the deep crust, and the monzonitic IMEs as melts of enriched subcontinental mantle. Such enclave suites provide little or no information on the chemical evolution of their host granitic rocks.

Ti K-edge XANES study on the coordination number and oxidation state of Titanium in pyroxene, olivine, armalcolite, ilmenite, and silicate glass during mare basalt petrogenesis

Abstract: Lunar mare basalts are a product of partial melting of the lunar mantle under more reducing conditions when compared to those expected for the Earth’s upper mantle. Alongside Fe, Ti can be a major redox sensitive element in lunar magmas, and it can be enriched by up to a factor of ten in lunar basaltic glasses when compared to their terrestrial counterparts. Therefore, to better constrain the oxidation state of Ti and its coordination chemistry during lunar magmatic processes, we report new X-ray absorption near edge structure (XANES) spectroscopy measurements for a wide range of minerals (pyroxene, olivine, Fe–Ti oxides) and basaltic melt compositions involved in partial melting of the lunar mantle. Experiments were conducted in 1 bar gas-mixing furnaces at temperatures between 1100 and 1300 °C and oxygen fugacities (fO2) that ranged from air to two orders of magnitude below the Fe–FeO redox equilibrium. Run products were analysed via electron microprobe and XANES Ti K-edge. Typical run products had large (> 100 µm) crystals in equilibrium with quenched silicate glass. Ti K-edge XANES spectra show a clear shift in energy of the absorption edge features from oxidizing to reducing conditions and yield an average valence for Fe–Ti oxides (armalcolite and ilmenite) of 3.6, i.e., a 40% of the overall Ti is Ti3+ under fO2 conditions relevant to lunar magmatism (IW − 1.5 to − 1.8). Pyroxenes and olivine have average Ti valence of 3.75 (i.e., 25% of the overall Ti is trivalent), while in silicate glasses Ti is exclusively tetravalent. Pre-edge peak intensities also indicate that the coordination number of Ti varies from an average V-fold in silicate glass to VI-fold in the Fe–Ti oxides and a mixture between IV and VI-fold coordination in the pyroxenes and olivine, with up to 82% [IV]Ti4+ in the pyroxene. In addition, our results can help to better constrain the Ti3+/∑Ti of the lunar mantle phases during magmatic processes and are applied to provide first insights into the mechanisms that may control Ti mass-dependent equilibrium isotope fractionation in lunar mare basalts.

Constraints on the source of Cu in a submarine magmatic-hydrothermal system, Brothers volcano, Kermadec island arc

Abstract: Most magmatic-hydrothermal Cu deposits are genetically linked to arc magmas. However, most continental or oceanic arc magmas are barren, and hence new methods have to be developed to distinguish between barren and mineralised arc systems. Source composition, melting conditions, the timing of S saturation and an initial chalcophile element-enrichment represent important parameters that control the potential of a subduction setting to host an economically valuable deposit. Brothers volcano in the Kermadec island arc is one of the best-studied examples of arc-related submarine magmatic-hydrothermal activity. This study, for the first time, compares the chemical and mineralogical composition of the Brothers seafloor massive sulphides and the associated dacitic to rhyolitic lavas that host the hydrothermal system. Incompatible trace element ratios, such as La/Sm and Ce/Pb, indicate that the basaltic melts from L’Esperance volcano may represent a parental analogue to the more evolved Brothers lavas. Copper-rich magmatic sulphides (Cu > 2 wt%) identified in fresh volcanic glass and phenocryst phases, such as clinopyroxene, plagioclase and Fe–Ti oxide suggest that the surrounding lavas that host the Brothers hydrothermal system represent a potential Cu source for the sulphide ores at the seafloor. Thermodynamic calculations reveal that the Brothers melts reached volatile saturation during their evolution. Melt inclusion data and the occurrence of sulphides along vesicle margins indicate that an exsolving volatile phase extracted Cu from the silicate melt and probably contributed it to the overlying hydrothermal system. Hence, the formation of the Cu-rich seafloor massive sulphides (up to 35.6 wt%) is probably due to the contribution of Cu from a bimodal source including wall rock leaching and magmatic degassing, in a mineralisation style that is hybrid between Cyprus-type volcanic-hosted massive sulphide and subaerial epithermal–porphyry deposits.

The role of magma mixing/mingling and cumulate melting in the Neapolitan Yellow Tuff caldera-forming eruption (Campi Flegrei, Southern Italy)

Abstract: Understanding the mechanisms responsible for the generation of chemical gradients in high-volume ignimbrites is key to retrieve information on the processes that control the maturation and eruption of large silicic magmatic reservoirs. Over the last 60 ky, two large ignimbrites showing remarkable zoning were emplaced during caldera-forming eruptions at Campi Flegrei (i.e., Campanian Ignimbrite, CI, ~ 39 ka and Neapolitan Yellow Tuff, NYT, ~ 15 ka). While the CI displays linear compositional, thermal and crystallinity gradients, the NYT is a more complex ignimbrite characterized by crystal-poor magmas ranging in composition from trachy-andesites to phonolites. By combining major and trace element compositions of matrix glasses and mineral phases from juvenile clasts located at different stratigraphic heights along the NYT pyroclastic sequence, we interpret such compositional gradients as the result of mixing/mingling between three different magmas: (1) a resident evolved magma showing geochemical characteristics of a melt extracted from a cumulate mush dominated by clinopyroxene, plagioclase and oxides with minor sanidine and biotite; (2) a hotter and more mafic magma from recharge providing high-An plagioclase and high-Mg clinopyroxene crystals and (3) a compositionally intermediate magma derived from remelting of low temperature mineral phases (i.e., sanidine and biotite) within the cumulate crystal mush. We suggest that the presence of a refractory crystal mush, as documented by the occurrence of abundant crystal clots containing clinopyroxene, plagioclase and oxides, is the main reason for the lack of erupted crystal-rich material in the NYT. A comparison between the NYT and the CI, characterized by both crystal-poor extracted melts and crystal-rich magmas representing remobilized portions of a “mature” (i.e., sanidine dominated) cumulate residue, allows evaluation of the capability of crystal mushes of becoming eruptible upon recharge.

Petrology and geochemistry of the 2014-2015 Holuhraun eruption, central Iceland: compositional and mineralogical characteristics, temporal variability and magma storage

Abstract: 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 Barðarbunga volcanic system, consistent with seismic observations for magma ascent close to the Barðarbunga 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.

Multiple timescale constraints for high-flux magma chamber assembly prior to the Late Bronze Age eruption of Santorini (Greece)

Abstract: The rhyodacitic magma discharged during the 30–80 km3 DRE (dense rock equivalent) Late Bronze Age (LBA; also called ‘Minoan’) eruption of Santorini caldera is known from previous studies to have had a complex history of polybaric ascent and storage prior to eruption. We refine the timescales of these processes by modelling Mg–Fe diffusion profiles in orthopyroxene and clinopyroxene crystals. The data are integrated with previously published information on the LBA eruption (phase equilibria studies, melt inclusion volatile barometry, Mg-in-plagioclase diffusion chronometry), as well as new plagioclase crystal size distributions and the established pre-LBA history of the volcano, to reconstruct the events that led up to the assembly and discharge of the LBA magma chamber. Orthopyroxene, clinopyroxene and plagioclase crystals in the rhyodacite have compositionally distinct rims, overgrowing relict, probably source-derived, more magnesian (or calcic) cores, and record one or more crystallization (plag ≫ opx > cpx) events during the few centuries to years prior to eruption. The crystallization event(s) can be explained by the rapid transfer of rhyodacitic melt from a dioritic/gabbroic region of the subcaldera pluton (mostly in the 8–12 km depth range), followed by injection, cooling and mixing in a large melt lens at 4–6 km depth (the pre-eruptive magma chamber). Since crystals from all eruptive phases yield similar timescales, the melt transfer event(s), the last of which took place less than 2 years before the eruption, must have involved most of the magma that subsequently erupted. The data are consistent with a model in which prolonged generation, storage and segregation of silicic melts were followed by gravitational instability in the subcaldera pluton, causing the rapid interconnection and amalgamation of melt-rich domains. The melts then drained to the top of the pluton, at fluxes of up to 0.1–1 km3 year− 1, where steep vertical gradients of density and rheology probably caused them to inject laterally, forming a short-lived holding chamber prior to eruption. This interpretation is consistent with growing evidence that some large silicic magma chambers are transient features on geological timescales. A similar process preceded at least one earlier caldera-forming eruption on Santorini, suggesting that it may be a general feature of this rift-hosted magmatic system.

Experimental determination of magnesia and silica solubilities in graphite-saturated and redox-buffered high-pressure COH fluids in equilibrium with forsterite + enstatite and magnesite + enstatite

Abstract: We experimentally investigated the dissolution of forsterite, enstatite and magnesite in graphite-saturated COH fluids, synthesized using a rocking piston cylinder apparatus at pressures from 1.0 to 2.1 GPa and temperatures from 700 to 1200 °C. Synthetic forsterite, enstatite, and nearly pure natural magnesite were used as starting materials. Redox conditions were buffered by Ni–NiO–H2O (ΔFMQ = − 0.21 to − 1.01), employing a double-capsule setting. Fluids, binary H2O–CO2 mixtures at the P, T, and fO2 conditions investigated, were generated from graphite, oxalic acid anhydrous (H2C2O4) and water. Their dissolved solute loads were analyzed through an improved version of the cryogenic technique, which takes into account the complexities associated with the presence of CO2-bearing fluids. The experimental data show that forsterite + enstatite solubility in H2O–CO2 fluids is higher compared to pure water, both in terms of dissolved silica (mSiO2 = 1.24 mol/kgH2O versus mSiO2 = 0.22 mol/kgH2O at P = 1 GPa, T = 800 °C) and magnesia (mMgO = 1.08 mol/kgH2O versus mMgO = 0.28 mol/kgH2O) probably due to the formation of organic C–Mg–Si complexes. Our experimental results show that at low temperature conditions, a graphite-saturated H2O–CO2 fluid interacting with a simplified model mantle composition, characterized by low MgO/SiO2 ratios, would lead to the formation of significant amounts of enstatite if solute concentrations are equal, while at higher temperatures these fluid, characterized by MgO/SiO2 ratios comparable with that of olivine, would be less effective in metasomatizing the surrounding rocks. However, the molality of COH fluids increases with pressure and temperature, and quintuplicates with respect to the carbon-free aqueous fluids. Therefore, the amount of fluid required to metasomatize the mantle decreases in the presence of carbon at high P–T conditions. COH fluids are thus effective carriers of C, Mg and Si in the mantle wedge up to the shallowest level of the upper mantle.

Divergent T–ƒO 2 paths during crystallisation of H 2 O-rich and H 2 O-poor magmas as recorded by Ce and U in zircon, with implications for TitaniQ and TitaniZ geothermometry

Abstract: In the original article, the Eq. 1 and email address of the co-author are published incorrectly. The correct Eq. 1 and email address of the co-author are given below.

Diamond formation during metasomatism of mantle eclogite by chloride-carbonate melt

Abstract: A xenolith of bimineralic eclogite from the Udachnaya kimberlite pipe provides a snapshot of interaction between mantle rocks and diamond-forming fluids/melts The major-element composition of the eclogite is similar to that of N-MORB and/or oceanic gabbros, but its trace-element pattern shows the effects of mantle metasomatism, which resulted in diamond formation The diamonds are clustered in alteration veins that crosscut primary garnet and clinopyroxene The diamonds contain microinclusions of a fluid/melt dominated by carbonate and KCl Compared to the worldwide dataset, the microinclusions in these diamonds fall in middle of the range between saline fluids and low-Mg carbonatitic melts The fluid/melt acted as a metasomatic agent that percolated through ancient eclogitic rocks stored in the mantle This interaction is consistent with calculated partition coefficients between the rock-forming minerals and diamond-forming fluid/melt, which are similar to experimentally-determined values Some differences between the calculated and experimental values may be due to the low contents of water and silicates in the chloride-carbonate melt observed in this study, and in particular its high contents of K and LILE The lack of nitrogen aggregation in the diamonds implies that the diamond-forming metasomatism took place shortly before the eruption of the kimberlite, and that the microinclusions thus represent saline carbonate-rich fluids circulating in the basement of lithospheric mantle (150–170 km depth)

How deceptive are microstructures in granitic rocks? Answers from integrated physical theory, phase equilibrium, and direct observations.

Abstract: In this contribution, we address the vexed question of the extent to which microstructures in granitic rocks reflect their igneous histories or have been masked by later events. The previous works have tended to address the problem either using theoretical or modelling considerations, or by interpretation of observed microstructures. Here, we use an approach that integrates the theory of microstructural development and the results of experimental phase-equilibrium studies with direct observation of natural examples on a variety of scales. We show that the predictions of the theoretical and experimental approaches agree perfectly with the mesoscopic and microscopic evidence from granitic rocks themselves. Our conclusion is that although, in many cases, granitic rock microstructures have been modified by near-solidus reactions and crystallisation, in the absence of tectonic deformation the fundamental elements of their igneous heritage remain intact. This means that it is perfectly in order to infer aspects of crystallisation sequences, magmatic reactions, and magma flow through careful microstructural observations. Thus, our answer to the question of how deceptive granitic textures are is, in most instances, ‘not very’. However, some undeformed plutons have undergone fluid-driven alteration, and others have been affected by contact metamorphism. Thus, each case should be examined on its own merits.

Near-solidus melts of MORB + 4 wt% H 2 O at 0.8–2.8 GPa applied to issues of subduction magmatism and continent formation

Abstract: Experiments on MORB + 4 wt% H2O at 0.8–2.8 GPa and 700–950 °C (Liu in High pressure phase equilibria involving the amphibolite–eclogite transformation. PhD dissertation, Stanford University, Stanford, California, 1997; Liu et al. in Earth Planet Sci Lett 143:161–171, 1996) were reexamined for their major and trace element melt compositions and melting relations. Degree of melting diminishes at greater pressures, with corresponding evolution of melt from andesitic at the lowest pressures and hottest temperatures to high-silica rhyolitic at the greatest pressure and coolest temperature. Quartz contributes greatly to the production of near-solidus melts of basaltic eclogite, with the result that melt productivity falls markedly following quartz exhaustion. This limits the extent of melting attainable in the basaltic eclogite portions of sub-arc subducting plates to no more than ~ 2 × the modal wt% quartz in the mafic eclogite protolith. Synthesized residual mineral assemblages lack an epidote-series mineral at temperatures > 750 °C, and as a result, melts from the rutile eclogite and rutile-amphibole eclogite facies have elevated concentrations of light rare earth elements, U, Th, have elevated Ba, K, and Sr, high Sr/Y, and are strongly depleted in Nb, Y, and the heavy rare earth elements. Models of eclogite partial melt reacting with peridotite of the mantle wedge reproduce major and trace element characteristics of parental arc magmas so long as the proportions of infiltrating melt to peridotite are relatively high, consistent with channelized ascent. Melt mass is estimated to increase roughly three- to ten-fold, consistent with H2O concentrations of 3–7 wt% in the magmas produced by reaction. Partial melts of subducting basaltic eclogite are predicted to have positive Sr concentration anomalies, relative to Ce and Nd, that persist through melt-peridotite reactions. Primitive arc magmas commonly have positive Sr anomalies, whereas such anomalies are smaller in estimates of the bulk continental crust. Overall, Sr anomalies diminish passing from primitive to more evolved arc volcanic rocks, consistent with extensive mineral-melt differentiation (crystallization, partial remelting) involving plagioclase. On the order of 50 wt% differentiation would be necessary to eliminate Sr positive anomalies, based on geochemical variations in the Cascade and western Aleutian magmatic arcs. Loss to the mantle of cumulates and restites with high Sr anomalies, in abundances broadly equal to the mass of the preserved crust, would be required to form the continents via processes similar to present-day subduction magmatism.

Melt inclusion constraints on volatile systematics and degassing history of the 2014–2015 Holuhraun eruption, Iceland

Abstract: The mass of volatiles emitted during volcanic eruptions is often estimated by comparing the volatile contents of undegassed melt inclusions, trapped in crystals at an early stage of magmatic evolution, with that of the degassed matrix glass. Here we present detailed characterisation of magmatic volatiles (H2O, CO2, S, Fl and Cl) of crystal-hosted melt and fluid inclusions from the 2014–2015 Holuhraun eruption of the Barðarbunga volcanic system, Iceland. Based on the ratios of magmatic volatiles to similarly incompatible trace elements, the undegassed primary volatile contents of the Holuhraun parental melt are estimated at 1500–1700 ppm CO2, 0.13–0.16 wt% H2O, 60–80 ppm Cl, 130–240 ppm F and 500–800 ppm S. High-density fluid inclusions indicate onset of crystallisation at pressures ≥ 0.4 GPa (~ 12 km depth) promoting deep degassing of CO2. Prior to the onset of degassing, the melt CO2 content may have reached 3000–4000 ppm, with the total magmatic CO2 budget estimated at 23–55 Mt. SO2 release commenced at 0.12 GPa (~ 3.6 km depth), eventually leading to entrapment of SO2 vapour in low-density fluid inclusions. We calculate the syn-eruptive volatile release as 22.2 Mt of magmatic H2O, 5.9–7.7 Mt CO2, and 11.3 Mt of SO2 over the course of the eruption; F and Cl release were insignificant. Melt inclusion constraints on syn-eruptive volatile release are similar to estimates made during in situ field monitoring, with the exception of H2O, where field measurements may be heavily biased by the incorporation of meteoric water.

Olivine in ultramafic lamprophyres: chemistry, crystallisation, and melt sources of Siberian Pre- and post-trap aillikites

Abstract: We studied olivines from the Devonian pre-trap (the Ilbokich occurrence) and the Triassic post-trap (the Chadobets occurrence) carbonate-rich ultramafic lamprophyres (UMLs) in the southwestern portion of the Siberian craton. On the basis of detailed investigations of major, minor, and trace-element distributions, we have reconstructed the main processes that control the origins of these olivines. These include fractional crystallisation from melt, assimilation, and fractional crystallisation processes with orthopyroxene assimilation, melt-reaction diffusive re-equilibration, alkali enrichment, and CO2 degassing of the melt. Furthermore, we inferred the composition of the sources of the primary UML melt and their possible correlations with proto-kimberlitic melts, as well as the influence of the Triassic Siberian plume on the composition of the lithospheric mantle. The main differences between olivines from the Ilbokich and the Chadobets aillikites were that the olivines from the former had more magnesium-rich cores (Mg# = 89.2 ± 0.2), had Mg- and Cr-rich transition zones (Mg# = 89.7 ± 0.2 and 300–500 ppm Cr), had lower Ni (up to 3100 ppm) and Li (1.4–1.5 ppm), and had higher B (0.8–2.6 ppm) contents, all at higher Fo values (90–86), relative to the olivines from the latter (Mg# = 88–75; 200–300 ppm Cr; up to 3400 ppm Ni; 1.4–2.4 ppm Li; 0.4–2.2 ppm B). The Siberian aillikite sources contained a significant amount of metasomatic material. Phlogopite-rich MARID-type veins provided the likely metasomatic component in the pre-trap Devonian Ilbokich aillikite source, whereas the Triassic Chadobets aillikitic post-trap melts were derived from a source with a significant carbonate component. A comparison of UML olivines with olivines from the pre-trap and post-trap Siberian kimberlites shows a striking similarity. This suggests that the carbonate component in the aillikitic source could have been produced by evolved kimberlite melts. The differences in the lithospheric metasomatic component that contributed to pre-trap and post-trap aillikitic melts can be interpreted as reflections of the thermal impact of the Siberian Traps, which reduced phlogopite-bearing metasomes within the southwestern Siberian sub-continental lithospheric mantle.

Transport properties of olivine grain boundaries from electrical conductivity experiments

Abstract: Grain boundary processes contribute significantly to electronic and ionic transports in materials within Earth’s interior. We report a novel experimental study of grain boundary conductivity in highly strained olivine aggregates that demonstrates the importance of misorientation angle between adjacent grains on aggregate transport properties. We performed electrical conductivity measurements of melt-free polycrystalline olivine (Fo90) samples that had been previously deformed at 1200 °C and 0.3 GPa to shear strains up to γ = 7.3. The electrical conductivity and anisotropy were measured at 2.8 GPa over the temperature range 700–1400 °C. We observed that (1) the electrical conductivity of samples with a small grain size (3–6 µm) and strong crystallographic preferred orientation produced by dynamic recrystallization during large-strain shear deformation is a factor of 10 or more larger than that measured on coarse-grained samples, (2) the sample deformed to the highest strain is the most conductive even though it does not have the smallest grain size, and (3) conductivity is up to a factor of ~ 4 larger in the direction of shear than normal to the shear plane. Based on these results combined with electrical conductivity data for coarse-grained, polycrystalline olivine and for single crystals, we propose that the electrical conductivity of our fine-grained samples is dominated by grain boundary paths. In addition, the electrical anisotropy results from preferential alignment of higher-conductivity grain boundaries associated with the development of a strong crystallographic preferred orientation of the grains.

Evacuation of multiple magma bodies and the onset of caldera collapse in a supereruption, captured in glass and mineral compositions

Abstract: Complexities in the nature of large-scale silicic eruptions and their magmatic systems can be discerned through micro-analytical geochemical studies. We present high-resolution, stratigraphically constrained compositional data on glassy matrix material and feldspar crystals from the initial fall deposits and earliest ignimbrite (base of member A) of the 2.08 Ma, ~ 2500 km3 Huckleberry Ridge Tuff (HRT), Yellowstone. We use these data to document the nature of the magmatic system and compositional changes related to the transition from fall to widespread ignimbrite deposition, inferred to mark the onset of caldera collapse. Although major element glass compositions are relatively uniform, trace elements span a large range (e.g. Ba 10–900 ppm, Sr/Rb = 0.005–0.09), with highly evolved glasses dominating in the fall deposits. Several trace elements (e.g. Ba and light rare earth elements) in the glass samples serve to define statistically significant compositional clustering in the fall deposits and basal ignimbrite. These clusters are inferred to reflect melt compositions controlled by fractional crystallisation processes and are interpreted to represent multiple, discrete melt-dominant domains that were tapped by multiple vents. The onset of widespread ignimbrite deposition is marked by an increase in the number of erupted melt compositional clusters from four in the fall deposits to eight, representing nine melt-dominant domains. There is an absence of geographical variation of glass compositions within the basal ignimbrite, with samples from proximal to distal localities north, west and south of the HRT caldera exhibiting similar variability. Pairing of glass analyses with sanidine major and minor element compositional data suggests that the nine melt compositional domains converged at depth into two compositionally distinct upper-crustal magmatic lineages that were both active during these early stages of the eruption. Our data collectively indicate the evacuation of an exceptionally complex and heterogeneous magma system. The onset of widespread ignimbrite deposition, inferred to relate to caldera collapse, occurred after ~ 50 km3 of magma had been discharged. Although external controls were important as an eruption trigger, depressurisation of the system led to caldera collapse with the eruption of numerous discrete melt-dominant domains.

Population-wide garnet growth zoning revealed by LA-ICP-MS mapping: implications for trace element equilibration and syn-kinematic deformation during crystallisation

Abstract: The strong partitioning of many trace elements into garnet and their slow diffusivities in both garnet and the rock matrix means that their distribution may record valuable petrogenetic information not documented by major elements in metamorphic rocks. Complex trace element growth zoning in garnet porphyroblasts from a garnet-grade metapelite from the Barrovian sequence of the Sikkim Himalaya is assessed using quantified LA-ICP-MS raster mapping coupled with X-ray micro-computed tomography. The data document systematic changes in the zoning patterns from early- to late-nucleated crystals, and also suggest that the REE+Y chemistry incorporated into garnet is dependent on persistent disequilibrium in the rock volume. There is evidence for HREE+Y diffusion haloes surrounding growing garnets and a heterogeneous HREE+Y distribution in the rock matrix. Annuli superimposed on oscillatory zoning are not consistent with formation during some rock-wide event, but are dependent on the spatial disposition of the garnet. Annuli are interpreted to reflect an integrated history of varying growth rates and the incorporation of pre-existing heterogeneities due to relatively slow matrix diffusivities. Conversely, smooth zoning of many transition metals indicate that their distribution in garnet may be controlled by equilibrium partitioning between garnet and the rock matrix. Significant rotation of garnet porphyroblasts during growth is revealed due to immobility of Cr over the duration of the crystallisation interval and overprinting of the heterogenous precursor Cr distribution. Strain rate estimates derived from this zoning are on the order of $$10^{-11}$$ – $$10^{-12}\, \hbox {s}^{-1}$$ .

Apatite-hosted melt inclusions from the Panzhihua gabbroic-layered intrusion associated with a giant Fe–Ti oxide deposit in SW China: insights for magma unmixing within a crystal mush

Abstract: The ∼ 2-km-thick Panzhihua gabbroic-layered intrusion in SW China is unusual because it hosts a giant Fe–Ti oxide deposit in its lower zone. The deposit consists of laterally extensive net-textured and massive Fe–Ti oxide ore layers, the thickest of which is ∼ 60 m. To examine the magmatic processes that resulted in the Fe enrichment of parental high-Ti basaltic magma and the formation of thick, Fe–Ti oxide ore layers, we carried out a detailed study of melt inclusions in apatite from a ∼ 500-m-thick profile of apatite-bearing leucogabbro in the middle zone of the intrusion. The apatite-hosted melt inclusions are light to dark brown in color and appear as polygonal, rounded, oval and negative crystal shapes, which range from ∼ 5 to ∼ 50 µm in width and from ∼ 5 to ∼ 100 µm in length. They have highly variable compositions and show a large and continuous range of SiO2 and FeOt with contrasting end-members; one end-member being Fe-rich and Si-poor (40.2 wt% FeOt and 17.7 wt% SiO2) and the other being Si-rich and Fe-poor (74.0 wt% SiO2 and 1.20 wt% FeOt). This range in composition may be attributed to entrapment of the melt inclusions over a range of temperature and may reflect the presence of µm-scale and immiscible Fe-rich and Si-rich components in different proportions. Simulating results for the motion of Si-rich droplets within a crystal mush indicate that Si-rich droplets would be separated from Fe-rich melt and migrate upward due to density differences in the interstitial liquid when the magma unmixed. Migration of the Si-rich, immiscible liquid component from the interstitial liquid caused the remaining Fe-rich melt in the lower part to react with plagioclase primocrysts (An59–60), as evidenced by fine-grained lamellar intergrowth of An-rich plagioclase (An79–84) + clinopyroxene in the oxide gabbro of the lower zone. Therefore, magma unmixing within a crystal mush, combined with gravitationally driven loss of the Si-rich component, resulted in the formation of Fe-rich, melagabbro and major Fe–Ti oxide ores in the lower part and Si-rich, leucogabbro in the upper part of the intrusion.

Experimental constraints on hydrogen diffusion in garnet

Abstract: The incorporation mechanisms and diffusional loss of hydrogen in garnet have been experimentally investigated. A suite of gem-quality hydrous spessartine- and grossular-rich garnets were analysed by Fourier transform infrared spectroscopy (FTIR) and by ion microprobe (SHRIMP-SI) to determine the calibration coefficients for quantification of FTIR data. The excellent agreement between measured absorption and OH/O indicates that the same molar extinction coefficient can be used for spessartine and grossular. The coefficient of 14400 l mol− 1 cm− 2 proposed by Maldener et al. (Phys Chem Miner 30:337–344, 2003) seems the most appropriate for both minerals. A grossular with 6.4% andradite and 1.6% almandine containing 834 ppm H2O, and an almost pure spessartine with 282 ppm H2O, were selected for diffusion experiments. 1.5-mm cubes of garnets were heated between 12 h and 10 days at 1 atm under various temperature (750–1050 °C) and oxygen fugacity ( $${f_{{{\text{O}}_2}}}$$ ) conditions, (ΔQFM + 15.2 to − 3.0). Diffusion profiles were acquired from sections through the cubes using FTIR, with a deconvolution algorithm developed to assess peak-specific behaviour. Different families of peaks have been identified based on their diffusive behaviour, representing hydrogen incorporated in different H-bearing defects. A dominant, fast, strongly $${f_{{{\text{O}}_2}}}$$ -dependent oxidation-related diffusion mechanism is proposed $$\left( {\{ {{\text{M}}^{2+}}+{{\text{H}}^+}\} +\frac{1}{4}{{\text{O}}_2}={{\text{M}}^{3+}}+\frac{1}{2}{{\text{H}}_2}{\text{O}}} \right)$$ (M=Fe, Mn) with a relatively low activation energy (158 ± 19 kJ mol− 1). This diffusion mechanism is likely restricted by availability of ferrous iron in grossular. At low oxygen fugacity, this diffusion mechanism is shut off and the diffusivity decreased by more than three orders of magnitude. A second, slower hydrogen diffusion mechanism has been observed in minor bands, where charge balance might be maintained by diffusion of cation vacancies, with much higher activation energy (≈ 200–270 kJ mol− 1). Spessartine shows clear differences in peak retentivity suggesting that up to four different H sites might exist. This opens exciting opportunities to use hydrogen diffusion in garnet as speedometer. However, it is essential to constrain the main diffusion mechanisms and the oxygen fugacity in the rocks investigated to obtain timescales for metamorphic or igneous processes.

Enrichment of 18O in the mantle sources of the Antarctic portion of the Karoo large igneous province

Abstract: 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., eNd 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 (eNd 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.