Showing papers in "Contributions to Mineralogy and Petrology in 2019"

Application of Ti-in-zircon thermometry to granite studies: problems and possible solutions.

Abstract: The application of the Ti-in-zircon thermometer to granitic rock requires consideration of $$a_{{{\text{TiO}}_{2} }}$$ and $$a_{{{\text{SiO}}_{2} }}$$ during zircon crystallization. Thermodynamic software programs such as rhyolite-MELTS or Perple_X permit the estimation of $$a_{{{\text{TiO}}_{2} }}$$ and $$a_{{{\text{SiO}}_{2} }}$$ values from whole-rock geochemical data as a function of pressure and temperature. Model calculations carried out on a set of 14 different granite types at 2 kbar, 5 kbar, and H2O = 3 wt% show $$a_{{{\text{SiO}}_{2} }}$$ during zircon crystallization close to 1 (0.75–1) and $$a_{{{\text{TiO}}_{2} }}$$ generally far below unity (0.1–0.6). This would suggest that Ti-in-zircon temperatures for granites must be significantly upward corrected relative to the original TiO2- and SiO2-saturated calibration of the thermometer. Both the rhyolite-MELTS and Perple_X calculations indicate that $$a_{{{\text{TiO}}_{2} }}$$ is typically around 0.5 in ilmenite-bearing granites. Thus, for ilmenite-series granites (that is, almost all S-type and many I-type granites), it could be a reasonable first order approximation to apply a constant temperature correction of + 70 °C to the Ti-in-zircon thermometer. Granites lacking the paragenesis zircon–ilmenite, that is, some A-type granites and a few special I-type granites may have even lower $$a_{{{\text{TiO}}_{2} }}$$ (0.1–0.5) and some of them may require a huge upward correction of Ti-in-zircon temperatures on the order of 100–200 °C. Using a set of Ti-in-zircon measurements from a Variscan granite of the Bohemian Massif, we introduce a novel T-dependent $$a_{{{\text{TiO}}_{2} }}$$ and $$a_{{{\text{SiO}}_{2} }}$$ correction of Ti-in-zircon calculated temperatures which is based on $$a_{{{\text{TiO}}_{2} }}$$ -, $$a_{{{\text{SiO}}_{2} }}$$ –T functions modelled with rhyolite-MELTS. This method takes into account that early and late zircons in granitic systems may crystallize at different $$a_{{{\text{SiO}}_{2} }}$$ and $$a_{{{\text{TiO}}_{2} }}$$ . Furthermore, we highlight the usefulness of comparing the corrected results of Ti-in-zircon thermometry with bulk-rock-Zr-based zircon solubility thermometry and ideal zircon crystallization temperature distributions for granites, and we present a graphical method that enables this comparison. In addition, this paper addresses the problem that Ti-in-zircon measurements are commonly collected with only moderate spatial analytical resolution, which leads to an averaging effect and to difficulties in recording accurate crystallization temperatures. Therefore, we propose that Ti-in-zircon thermometry for granites should generally rely on the more representative median-T (Tmed) value of a series of zircon analyses. Peak magma temperatures will be, in general, 35–50 °C above Tmed, as can be modelled using zircon crystallization temperature distributions.

Building Mesoarchaean crust upon Eoarchaean roots: the Akia Terrane, West Greenland

Abstract: Constraining the source, genesis, and evolution of Archaean felsic crust is key to understanding the growth and stabilization of cratons. The Akia Terrane, part of the North Atlantic Craton, West Greenland, is comprised of Meso-to-Neoarchaean orthogneiss, with associated supracrustal rocks. We report zircon U–Pb and Lu–Hf isotope data, and whole-rock geochemistry, from samples of gneiss and supracrustals from the northern Akia Terrane, including from the Finnefjeld Orthogneiss Complex, which has recently been interpreted as an impact structure. Isotope data record two major episodes of continental crust production at ca. 3.2 and 3.0 Ga. Minor ca. 2.7 and 2.5 Ga magmatic events have more evolved eHf, interpreted as reworking of existing crust perhaps linked to terrane assembly. Felsic rocks from the Finnefjeld Orthogneiss Complex were derived from the same source at the same time as the surrounding tonalites, but from shallower melting, requiring any bolide-driven melting event to have occurred almost simultaneously alongside the production of the surrounding crust. A simpler alternative has the Finnefjeld Complex and surrounding tonalite representing the coeval genesis of evolved crust over a substantial lithospheric depth. Hafnium isotope data from the two major Mesoarchaean crust-forming episodes record a contribution from older mafic Eoarchaean crust. Invoking the involvement of an Eoarchaean root in the growth of younger Mesoarchaean crust puts important constraints on geodynamic models of the formation of the discrete terranes that ultimately assembled to form Earth’s cratons.

Zircon and quartz inclusions in garnet used for complementary Raman thermobarometry: application to the Holsnøy eclogite, Bergen Arcs, Western Norway

Abstract: Mineral inclusions are common and have been widely used to investigate complex geological history. When a rock undergoes cooling and decompression after the entrapment of an inclusion into a host mineral, residual pressure may develop within the inclusion because of the differences in thermal expansivity and compressibility between the inclusion and host. By combining laser Raman spectroscopy and experimental data relating hydrostatic pressure and Raman shift, it is possible to estimate the entrapment pressure–temperature (P–T) conditions using an isotropic elastic model. In this study, we report Raman spectroscopic data on both zircon and quartz inclusions in garnet host from the Holsnoy eclogite, Bergen Arcs, Norway. Averaged residual pressures based on different Raman peaks for zircon and quartz inclusions are obtained to be ca. 0.6 GPa and ca. 0.65 GPa respectively. Using the equation of state for zircon and quartz, the entrapment P–T conditions are constrained to be 1.7–1.9 GPa, 680–760 °C, consistent with previous estimates based on phase equilibria. Heating/cooling experiments are performed on an entrapped zircon inclusion. A clear trend is found between the residual zircon inclusion pressure and the externally controlled temperature. We show that the residual zircon inclusion pressure sealed in garnet host is very sensitive to the entrapment temperature, and can be used as a Raman thermometer. The effects of laser heating and the thermo-elastic anisotropy of zircon inclusion are quantified and discussed.

Clumped-isotope palaeothermometry and LA-ICP-MS U–Pb dating of lava-pile hydrothermal calcite veins

Abstract: Calcite veins are a common product of hydrothermal fluid circulation. Clumped-isotope palaeothermometry is a promising technique for fingerprinting the temperature of hydrothermal fluids, but clumped-isotope systematics can be reset at temperatures of > ca. 100 °C. To model whether the reconstructed temperatures represent calcite precipitation or closed-system resetting, the precipitation age must be known. LA-ICP-MS U–Pb dating of calcite is a recently developed approach to direct dating of calcite and can provide precipitation ages for modelling clumped-isotope systematics in calcite veins. In this study, clumped-isotope and LA-ICP-MS U–Pb calcite analyses were combined in basalt-hosted calcite veins from three settings in Scotland. Samples from all three localities yielded precipitation temperatures of ca. 75–115 °C from clumped-isotope analysis, but veins from only two of the sites were dateable, yielding precipitation ages of 224 ± 8 Ma and 291 ± 33 Ma (2σ). Modelling from the dated samples enabled confident interpretation that no closed-system resetting had occurred in these samples. However, the lack of a precipitation age from the third location meant that a range of possible thermal histories had to be modelled meaning that confidence that resetting had not occurred was lower. This highlights the importance of coupling clumped-isotope thermometry and LA-ICP-MS U–Pb calcite dating in determining the temperature of hydrothermal fluids recorded in calcite veins. This paired approach is shown to be robust in constraining the timing and precipitation temperature of calcite formation, and thus for tracking hydrothermal processes.

Coupled evolution of Neoproterozoic arc mafic magmatism and mantle wedge in the western margin of the South China Craton

Abstract: Subduction of oceanic slabs can physically and chemically modify mantle wedges, but how mantle wedges are temporally evolved is difficult to be constrained. In this study, we use in situ zircon U–Pb ages and Hf–O isotopes of mafic intrusions to examine a coupled evolution of magmas and mantle sources above a subduction zone. Neoproterozoic mafic intrusions in the western margin of the Yangtze Block are mostly composed of gabbros that were formed in an arc system during 870–750 Ma followed by generation of voluminous slab-derived granitoids. The mantle wedge was progressively modified by slab fluids, sediment melts and altered oceanic crust (AOC) melts. Gabbros from the 870-Ma intrusion have normal δ18O (4.79‰ to 6.07‰), high eHf (+ 10.4 to + 15.0) and eNd (+ 4.0 and + 6.4) and were derived from a mantle source enriched by slab fluids. Gabbros from the 860–840-Ma intrusions have overall relatively high δ18O (5.61‰ to 7.42‰), but variable eHf values (− 3.5 to + 15.0) that are decoupled from eNd (+ 1.85 to + 3.87). These features are clearly suggestive of a mantle source modified by sediment melts. However, gabbros from the 820–780-Ma intrusions have relatively low δ18O (4.22‰ to 5.49‰), and constant eHf (+ 4.7 to + 9.6) that are decoupled from eNd (− 0.52 to + 1.92). Such features can be explained by a mantle source contaminated by 18O-depleted AOC melts. The widespread younger TTG-type granitoids were partial melts of the subducted oceanic slab and terminated the mafic magmatism in the region, indicating that slab break-off probably resulted in slab melting after a long period of subduction. Similar Neoproterozoic magmatism also occurred in Greater India and Madagascar, suggesting a giant Andean-type arc system along the western margin of Rodinia. In this arc system, mantle-derived magmas were dominated by an arc affinity in the earlier stage before 820 Ma and became rift-related after that, reflecting regional slab tearing and break-off. Our study also provides evidence for the linkage between the marginal subduction and the internal rifting in Rodinia, and suggest that slab break-off probably triggered its break-up.

Decadal transition from quiescence to supereruption: petrologic investigation of the Lava Creek Tuff, Yellowstone Caldera, WY

Abstract: The magmatic processes responsible for triggering nature’s most destructive eruptions and their associated timescales remain poorly understood. Yellowstone Caldera is a large silicic volcanic system that has had three supereruptions in its 2.1-Ma history, the most recent of which produced the Lava Creek Tuff (LCT) ca. 631 ka. Here we present a petrologic study of the phenocrysts, specifically feldspar and quartz, in LCT ash in order to investigate the timing and potential trigger leading to the LCT eruption. The LCT phenocrysts have resorbed cores, with crystal rims that record slightly elevated temperatures and enrichments in magmaphile elements, such as Ba and Sr in sanidine and Ti in quartz, compared to their crystal cores. Chemical data in conjunction with mineral thermometry, geobarometry, and rhyolite-MELTS modeling suggest the chemical signatures observed in crystal rims were most likely created by the injection of more juvenile silicic magma into the LCT sub-volcanic reservoir, followed by decompression-driven crystal growth. Geothermometry and barometry suggest post-rejuvenation, pre-eruptive temperatures and pressures of 790–815 °C and 80–150 MPa for the LCT magma source. Diffusion modeling utilizing Ba and Sr in sanidine and Ti in quartz in conjunction with crystal growth rates yield conservative estimates of decades to years between rejuvenation and eruption. Thus, we propose rejuvenation as the most likely mechanism to produce the overpressure required to trigger the LCT supereruption in less than a decade.

High-spatial resolution dating of monazite and zircon reveals the timing of subduction–exhumation of the Vaimok Lens in the Seve Nappe Complex (Scandinavian Caledonides)

Abstract: 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 by rims 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 formed by 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.

Phosphorus and aluminum zoning in olivine: contrasting behavior of two nominally incompatible trace elements

Abstract: Phosphorus zoning in olivine is receiving considerable attention for its capacity to preserve key information about rates and mechanisms of crystal growth. Its concentration can vary significantly over sub-micron spatial scales and form intricate, snowflake-like patterns that are generally attributed to fast crystal growth. Ostensibly similar aluminum enrichment patterns have also been observed, suggesting comparable incorporation and partitioning behavior for both elements. We perform 1-atm crystallization experiments on a primitive Kīlauea basalt to examine the formation of P and Al zoning as a function of undercooling − ΔT (− ΔT = Tliquidus − Tcrystallization) during olivine growth. After 24 h spent at Tinitial = 1290 °C (10 °C above olivine stability), charges are rapidly cooled to final temperatures Tfinal = 1220–1270 °C, corresponding to undercoolings − ΔT = 10–60 °C (with Tliquidus = 1280 °C). Compositional X-ray maps of experimental olivine reveal that only a small undercooling (≤ 25 °C) is required to produce the fine-scale enrichments in P and Al associated with skeletal growth. Concentration profiles indicate that despite qualitatively similar enrichment patterns in olivine, P and Al have contrasting apparent crystal/melt mass distribution coefficients of $$K_{\text{P}}^{{{\text{ol}}/{\text{melt}}}}$$ = 0.01‒1 and $$K_{\text{P}}^{{{\text{ol}}/{\text{melt}}}}$$ = 0.002‒0.006. Phosphorus can be enriched by a factor > 40-fold in the same crystal, whereas Al enrichment never exceed factors of 2. Glass in the vicinity of synthetic and natural olivine is usually enriched in Al, but, within analytical uncertainty, not in P. Thus, we find no direct evidence for a compositional boundary layer enriched in P that would suffice to produce P enrichments in natural and synthetic olivine. Numerical models combining growth and diffusion resolve the conditions at which Al-rich boundary layers produce the observed enrichment patterns in olivine. In contrast, the same models fail to reproduce the observed P enrichments, consistent with our observation that P-rich boundary layers are insignificant. If instead, P olivine/melt partitioning is made to depend on growth rate, models adequately reproduce our observations of 40-fold enrichment without boundary layer formation. We surmise that near-partitionless behavior ( $$K_{\text{P}}^{{{\text{ol}}/{\text{melt}}}}$$ close to 1) of P is related to the olivine lattice being perhaps less stiff in accommodating P during rapid crystallization, and/or to enhanced formation of vacancy defects during fast growth. Our results confirm that P is a robust marker of initial rapid growth, but reveal that the undercooling necessary to induce these enrichments is not particularly large. The near-ubiquitous process of magma mixing under volcanoes, for instance, is likely sufficient to induce low-to-moderate degrees of undercooling required for skeletal growth.

Fast ascent rate during the 2017–2018 Plinian eruption of Ambae (Aoba) volcano: a petrological investigation

Abstract: In September 2017, after more than a hundred years of quiescence, Ambae (Aoba), Vanuatu’s largest volcano, entered a new phase of eruptive activity, triggering the evacuation of the island’s 11,000 inhabitants resulting in the largest volcanic disaster in the country’s history. Three subsequent eruptive phases in November 2017, March 2018, and July 2018 expelled some of the largest tropospheric and stratospheric SO2 clouds observed in the last decade. Here, we investigate the mechanisms and dynamics of this eruption. We use major elements, trace elements, and volatiles in olivine and clinopyroxene hosted melt inclusions, embayments, crystals, and matrix glasses together with clinopyroxene geobarometry and olivine, plagioclase, and clinopyroxene geothermometry to reconstruct the physical and chemical evolution of the magma, as it ascends to the surface. Volatile elements in melt inclusions and geobarometry data suggest that the magma originated from depth of ~ 14 km before residing at shallow (~ 0.5 to 3 km) levels. Magma ascent to the surface was likely facilitated by shallow phreatic eruptions that opened a pathway for magma to ascend. Succeeding eruptive phases are characterised by increasingly primitive compositions with evidence of small amounts of mixing having taken place. Mg–Fe exchange diffusion modelling yields olivine residence times in the magma chamber ranging from a few days to a year prior to eruption. Diffusion modelling of volatiles along embayments (melt channels) from the first two phases of activity and microlite number density suggests rapid magma ascent in the range of 15–270 km/h, 4–75 m/s (decompression rates of 0.1 to ~ 2 MPa/s) corresponding to a short travel time between the top of the shallow reservoir and the surface of less than 2 min.

Redox-controlled generation of the giant porphyry Cu–Au deposit at Pulang, southwest China

Abstract: Some porphyry Cu–Au deposits with relatively reduced ore assemblages, characterized by high hydrothermal pyrrhotite contents and a lack of primary hematite and magnetite, are generally considered to be associated with reduced I-type granitoids. However, the role of magmatic oxygen fugacity (fO2) in controlling Cu–Au mineralization in such reduced porphyry deposits is poorly understood. The giant Late Triassic (ca 216 Ma) Pulang porphyry Cu–Au deposit of southwest China shows typical reduced ore assemblages. This study reported the systematical variation of upper crustal magmatic fO2 of Pulang deposit, based on detailed investigations of mineral crystallization sequences and compositional features of the mineralization-related porphyries (early P1 and late P2 porphyry). Results indicate that magma of the mineralization-related porphyries experienced complex fO2 fluctuations during its upper crustal evolution. The early primary magma had very high initial fO2, with ΔFMQ ≥ + 3.0 at depths of > 12 km [ΔFMQ is the deviation of logfO2 from the fayalite–magnetite–quartz (FMQ) buffer]. The fO2 of evolved parental magma subsequently decreased, with ΔFMQ ≤ + 1.9, due to injection of relatively reduced dioritic magmas (ΔFMQ = + 1.4 to + 2.3) from a deeper chamber (17–21 km depth) into the primary magma chamber at 10–12 km depth. Magma mixing had largely ceased at 6–10 km depth. The parental magma then ponded within the reduced Tumugou formation at a depth of ~ 3.7 km where magmatic fO2 decreased to a moderately oxidized state (ΔFMQ = ~ + 1.6), and finally to a moderately reduced state [reflected by log(Fe2O3/FeO) ratios of − 0.5 for P2 porphyry]. Results of this study of magmatic fO2 indicate that porphyry magmas associated with reduced Pulang ore assemblages were initially generated as highly oxidized magma which was subsequently reduced through magma mixing and contamination by reduced sedimentary rocks of the Tumugou Formation. The sharp fO2 decrease at very shallow depth prevented the early loss of Cu and Au because the magma remained oxidized until it was emplaced at ~ 3.7 km depth. Moderately reduced magmas may thus have a genetic association with porphyry Cu–Au mineralization.

Reconsideration of Neo-Tethys evolution constrained from the nature of the Dazhuqu ophiolitic mantle, southern Tibet

Abstract: The nature (i.e., sub-oceanic, sub-arc or sub-continental) of ophiolitic mantle peridotites from the eastern Neo-Tethyan domain in southern Tibet has been hotly debated. This uncertainty limits our understanding of the history and evolution of the eastern Neo-Tethys Ocean. Here we present petrological, geochemical and Re–Os isotopic data for the mantle peridotites from the Dazhuqu ophiolite in the central segment of the Yarlung Zangbo suture zone, southern Tibet. Samples collected include both spinel lherzolites and spinel harzburgites. The lherzolites have spinel Cr# [Cr/(Cr + Al), ~ 0.3–0.4] comparable to those of typical abyssal peridotites. In contrast, the harzburgites have spinel Cr# (~ 0.3–0.7) overlapping with the ranges of both abyssal and fore-arc peridotites; two samples have spinel Cr# higher than 0.6, which is probably ascribed to intense melt–rock interactions. Clinopyroxene trace element modeling indicates that the Dazhuqu mantle peridotites have experienced 0–6% garnet-facies melting followed by 10–18% melting in the spinel stability field. This is similar to the degree of garnet-facies melting inferred for many abyssal peridotites and implies deep initial melting (> 85 km), which distinguishes the Dazhuqu mantle peridotites from fore-arc peridotites (commonly < 80 km in origin). The Dazhuqu peridotites have unradiogenic 187Os/188Os of 0.11836–0.12922, which are commonly lower than the recommended value of primitive upper mantle (PUM). All but one samples yield relatively younger Re depletion ages (TRD = 0.06–0.81 Ga) with respect to the only one sample having an older TRD age of 1.66 Ga. Re–Os isotopes and highly siderophile element (HSE) compositions of the Dazhuqu peridotites are similar to those of abyssal peridotites and the Oman southern massifs but are distinct from non-cratonic sub-continental lithospheric mantle (SCLM) xenoliths and sub-arc mantle. We emphasize the similarity between the Dazhuqu and Oman ophiolites, both representing Neo-Tethyan oceanic lithosphere and implying ridge–trench collision.

Interpreting titanite U–Pb dates and Zr thermobarometry in high-grade rocks: empirical constraints on elemental diffusivities of Pb, Al, Fe, Zr, Nb, and Ce

Abstract: Length scales of compositional heterogeneity in titanite from 750 to 1000 °C metamorphic rocks from southern Madagascar were measured to provide empirical constraints on elemental diffusivities. The calculated Pb diffusivity is comparable to experimental estimates of Sr diffusivity; because of this, U–Pb dates from rocks that reached peak temperatures 900 °C; thus, Zr-in-titanite thermobarometry should not be reset by diffusion in all but the smallest grains in the hottest rocks. Al and Nb diffuse at similar rates to Zr. Ce and Fe diffuse slower than Pb, but faster than Zr. Differences in empirical and experimental estimates of elemental diffusivities might be related to the complexity of most natural titanite solid solutions compared to the near-end-member titanite used in experiments.

Electrical conductivity of OH-bearing omphacite and garnet in eclogite: the quantitative dependence on water content

Abstract: Eclogite is potentially an important constituent in local regions in the deep crust and upper mantle. The electrical conductivity of omphacite and garnet in eclogite has been measured at 1 GPa and 350–800 °C with pre-annealed OH-bearing samples. The conductivities were determined using a piston–cylinder apparatus and a Solartron-1260 Impedance/Gain Phase Analyser in the frequency range of 106–1 Hz. The sample water contents show almost no change before and after the experimental runs. The conductivity of both omphacite and garnet increases with temperature, and the activation enthalpy is ~ 82 kJ/mol for omphacite and 90 kJ/mol for garnet, which is nearly independent of water content in each mineral. The conduction is probably dominated by protons, and for both minerals, the conductivity increases linearly with water content, with a water content exponent of ~ 1. These data are used to model the bulk conductivity of an eclogite with different water contents and modal compositions. In combination with reported data, the conductivity of the eclogite is similar to that of typical granulites above 600 °C, but is much larger than that of olivine, assuming small to moderate water contents. This would mean that the contribution of eclogites, if present, to the electrical structure of the deep continental crust cannot be easily separated from that of granulites, and that the regional enrichments of eclogites in the upper mantle may cause high electrical anomalies. The results also provide information for the electrical property of orogen-related thickened deep crust where eclogites may be locally abundant, e.g., in the Dabieshan region and the Tibet plateau. At mantle depths, eclogitized portions of subducted slabs are usually of very low conductivities as suggested by geophysical observations, implying small water contents in the constitutive omphacite and garnet and the limited ability of these minerals in recycling water into the deep mantle.

The significance of plagioclase textures in mid-ocean ridge basalt (Gakkel Ridge, Arctic Ocean)

Abstract: Textures and compositions of minerals can be used to infer the physiochemical conditions present within magmatic systems. Given that plagioclase is an abundant phase in many magmatic systems, understanding the link between texture and process is vital. Here, we present a database of textural and compositional data for > 1800 plagioclase crystals in mid-ocean ridge basalt from the Gakkel Ridge (Arctic Ocean) to investigate the physiochemical conditions and processes that govern the formation of plagioclase textures and compositions. The Gakkel basalts have high modal crystal contents (up to 50%). The crystal cargo is complex, with both individual plagioclase and glomerocrysts showing large variations in crystal habit, zoning and resorption. The most common types of zoning are reverse and patchy; we attribute patchy zoning to infilling following either skeletal growth or resorption. Resorption is abundant, with multiple resorption events commonly present in a single crystal, and results from both magmatic recharge and decompression. Periods of strong undercooling, distinct to quench crystallisation, are indicated by matured skeletal crystals and thin normally zoned melt inclusion-rich bands following resorption. Individual samples often contain diverse textural and compositional plagioclase groups. Furthermore, most plagioclase is not in equilibrium with its host melt. Finally, the porous open structures of some glomerocrysts suggest that they represent pieces of entrained disaggregated mush. We interpret this to indicate that the crystal cargo is not generally phenocrystic in origin. Instead, plagioclase crystals that formed in different parts of a mush-dominated plumbing system were entrained into ascending melts. The textures of individual crystals are a function of their respective histories of (under)cooling, magma mixing and decompression. The morphologies of melt inclusion trapped in the plagioclase crystals are associated with specific host crystal textures, suggesting a link between plagioclase crystallisation processes and melt inclusion entrapment. The database of plagioclase presented herein may serve as a template for the interpretation of plagioclase textures in magmatic systems elsewhere.

Deep open storage and shallow closed transport system for a continental flood basalt sequence revealed with Magma Chamber Simulator

Abstract: The Magma Chamber Simulator (MCS) quantitatively models the phase equilibria, mineral chemistry, major and trace elements, and radiogenic isotopes in a multicomponent–multiphase magma + wallrock + recharge system by minimization or maximization of the appropriate thermodynamic potential for the given process. In this study, we utilize MCS to decipher the differentiation history of a continental flood basalt sequence from the Antarctic portion of the ~ 180 Ma Karoo large igneous province. Typical of many flood basalts, this suite exhibits geochemical evidence (e.g., negative initial eNd) of interaction with crustal materials. We show that isobaric assimilation-fractional crystallization models fail to produce the observed lava compositions. Instead, we propose two main stages of differentiation: (1) the primitive magmas assimilated Archean crust at depths of ~ 10‒30 km (pressures of 300–700 MPa), while crystallizing olivine and orthopyroxene; (2) subsequent fractional crystallization of olivine, clinopyroxene, and plagioclase took place at lower pressures in upper crustal feeder systems without significant additional assimilation. Such a scenario is corroborated with additional thermophysical considerations of magma transport via a crack network. The proposed two-stage model may be widely applicable to flood basalt plumbing systems: assimilation is more probable in magmas pooled in hotter crust at depth where the formation of wallrock partial melts is more likely compared to rapid passage of magma through shallower fractures next to colder wallrock.

Nanoscale processes of trace element mobility in metamorphosed zircon

Abstract: Several examples of zircon grains from high- to ultrahigh-pressure (UHP) and ultrahigh-temperature (UHT) metapelites exhibit a characteristic, yet atypical, core–rim interface domain < 5-μm wide observed in cathodoluminescence (CL) imaging. The interface domain is located immediately against the magmatic core and is comprised of an irregular, 0–2-μm wide, CL-dark domain that is rimmed by a complex, 0–5-μm wide, CL-bright domain with cuspate margins. The outer margin of the interface domain is rimmed by intermediate-CL zircon with low contrast zoning. To characterize the nature of the interface domain and to identify mechanisms of trace element mobility in metamorphosed zircon, we analyzed several specimens prepared from zircon from the Rhodope Metamorphic Complex (eastern Greece) and the Goshen Dome (western Massachusetts, USA) via atom probe tomography (APT). The data reveal three types of geochemical anomalies, each with a unique morphology. (1) Toroidal clusters with high concentrations of Pb (+ Y, Al) are found exclusively within the core of the Rhodope grain. These clusters are interpreted as decorated dislocation loops that formed during metamorphism and annealing of radiation damage to the lattice. Geochronological and geochemical data support this interpretation. (2) Complex, cross-cutting planar and linear features with anomalous concentrations of Y + P + Yb or U are spatially restricted to the core–rim interface domain; these features do not correlate with inherited geochemical variation (oscillatory zoning) or deformation-induced microstructures. Instead, the planar features likely formed in response to an interface-coupled dissolution–reprecipitation reaction that propagated into the crystal during metamorphism. The observed cross-cutting relationships are the product of either multiple events or complexity of the process that originally formed the domains. (3) Ellipsoidal features with high concentrations of Y + P + Yb (+ Al) are found exclusively within the high-Y + P + Yb planar features. These features are interpreted as the product of spinodal decomposition that occurred during exhumation as the zircon passed the solvus where local equilibria favored nm-scale exsolution to minimize the Gibbs free energy. The presence of multiple types of geochemical features in these examples indicates that trace element mobility in zircon is driven by multiple processes over the course of orogenesis. Given that these atypical domains are apparently restricted to zircon metamorphosed at UHT and (U)HP conditions, their presence may represent a marker of metamorphism at very high-grade conditions.

Unravelling the complexity of magma plumbing at Mount St. Helens: a new trace element partitioning scheme for amphibole

Abstract: Volcanoes at subduction zones reside above complex magma plumbing systems, where individual magmatic components may originate and interact at a range of pressures. Because whole-rock compositions of subduction zone magmas are the integrated result of processes operating throughout the entire plumbing system, processes such as mixing, homogenisation and magma assembly during shallow storage can overprint the chemical signatures of deeper crustal processes. Whereas melt inclusions provide an effective way to study the uppermost 10–15 km of the plumbing system, challenges remain in understanding magma intrusion, fractionation and hybridisation processes in the middle to lower crust (15–30 km depth), which commonly involves amphibole crystallisation. Here, we present new insights into the mid-crustal plumbing system at Mount St. Helens, USA, using multiple regression methods to calculate trace element partition coefficients for amphibole phenocrysts, and thus infer the trace element compositions of their equilibrium melts. The results indicate vertically distributed crystal fractionation, dominated by amphibole at higher pressures and in intermediate melts, and by plagioclase at lower pressures. Variations in Nb, Zr and REE concentrations at intermediate SiO2 contents suggest repeated scavenging of partially remelted intrusive material in the mid-crust, and mixing with material from geochemically diverse sources. Amphibole is an effective probe for deep crustal magmatism worldwide, and this approach offers a new tool to explore the structure and chemistry of arc magmas, including those forming plutonic or cumulate materials that offer no other constraints on melt composition.

Oxygen fugacity at the base of the Talkeetna arc, Alaska

Abstract: The origin of the more oxidized nature of arc magmas as compared to that of mid-ocean ridge basalts (MORB) is debated, considered to be either a feature of their mantle source, or produced during crustal transit and eruption. Fe3+/FeT ratios (Fe3+/[Fe3+ + Fe2+]) in arc volcanic rocks and glasses and thermodynamic oxybarometry on mantle xenoliths from arc lavas indicate elevated magmatic oxygen fugacity ( $$f_{{{\text{O}}_{ 2} }}$$ ), whereas, redox-sensitive trace elements ratios and abundances in arc volcanic rocks have been used to suggest that arcs have source regions with $$f_{{{\text{O}}_{ 2} }}$$ similar to the MORB source. Here, we take an alternative approach by calculating the $$f_{{{\text{O}}_{ 2} }}$$ of the uppermost mantle and lowermost ultramafic cumulates from the accreted Jurassic Talkeetna arc (Alaska). This approach allows us to quantify the $$f_{{{\text{O}}_{ 2} }}$$ of the sub-arc mantle and of primary arc magmas crystallizing at the base of an island arc, which have not been affected by processes during crustal transit and eruption which could affect their $$f_{{{\text{O}}_{ 2} }}$$ . Implementing olivine–spinel oxybarometry, we find that the upper mantle (harzburgites and lherzolites) and ultramafic cumulates (clinopyroxenites and dunites) crystallized between + 0.4 and + 2.3 log units above the fayalite-magnetite-quartz buffer, consistent with previous studies suggesting that the sub-arc mantle is oxidized relative to that of MORB. In addition, the Talkeetna paleo-arc allows us to examine coeval lavas and their redox-sensitive trace element ratios (e.g., V/Sc). The average V/Sc ratios of high MgO (> 6 wt%) lavas are 6.7 ± 1.6 (2σ), similar to that of MORB. However, V/Sc ratios must be interpretted in terms the degree of partial melting, as well as, the initial V/Sc ratio of the mantle source in order to derive information about $$f_{{{\text{O}}_{ 2} }}$$ of their mantle source. The V/Sc ratios of Talkeetna lavas are consistent with the elevated $$f_{{{\text{O}}_{ 2} }}$$ recorded in the sub-arc mantle and primitive cumulates (olivine Mg# [Mg/(Mg + Fe)] × 100 > 82) if a depleted mantle source underwent 15–20% melting. Our results suggest that the arc mantle is, on average, more oxidized than the MORB source and that V/Sc ratios must be interpreted in the context of a partial melting model where all model parameters are appropriate for arc magma genesis. This study reconciles V/Sc ratios in arc volcanic rocks with $$f_{{{\text{O}}_{ 2} }}$$ of primary arc basalts and the sub-arc mantle from the same locality.

Crystallisation and zircon saturation of calc-alkaline tonalite from the Adamello Batholith at upper crustal conditions: an experimental study

Abstract: The understanding of the geochemical and petrophysical evolution of magmas forming intermediate calc-alkaline batholiths at shallow crustal levels critically depends on knowledge of the phase equilibria relations along the liquid line of descent. Here, we present experimental results for a tonalitic system at a pressure of 200 MPa and under water-saturated conditions. Melting experiments were performed at temperatures between 700 and 1000 °C in externally heated HCM pressure vessels, with oxygen fugacity controlled close to the Ni–NiO buffer equilibrium (NNO) employing an argon–methane mixture as pressure medium and Co–Pd redox sensors to verify fO2 conditions. Natural rock powder of a medium-K tonalite from the Adamello Batholith in Northern Italy served as experimental starting material. Based on compositional data of stable phases in the run products and images of entire run charges, mass balance calculations as well as image processing were performed to investigate the evolution of the crystal/melt ratio with respect to temperature. Furthermore, compositional trends of minerals as well as the liquid line of descent of residual melts were obtained. Orthopyroxene, clinopyroxene and plagioclase were identified as near-liquidus phases (below 990 °C). At 900 °C, amphibole joins the solid-phase assemblage at the expense of clinopyroxene, indicating the existence of a peritectic relationship. After an initial near-linear decrease with temperature, residual melt fractions exhibit a plateau of 45–55 vol. % between 750 and 850 °C, followed by a rapid decrease coinciding with quartz saturation at 725 °C. Compositions of residual liquids evolve along a typical calc-alkaline differentiation trend with decreasing temperature (increasing SiO2 and decreasing TiO2, Al2O3, CaO, MgO and FeO contents) and become peraluminous below 900 °C. Intermediate to acidic rocks from the Adamello follow the experimental liquid line of descent indicating that the observed compositional spread of the natural intermediate composition rock record can be explained by low-pressure magma differentiation and liquid extraction. Experimentally determined zircon saturation levels are at low temperatures distinctly lower compared to existing and often used Zr-saturation models, but fully consistent with observed and modelled Zr-evolution trends from the natural rock record of the Southern Adamello Batholith inferring that zircon saturation in these intermediate to felsic plutonic rocks occurred at 800–830 °C corresponding to a melt fraction of about 50 vol. %.

A 2D and 3D nanostructural study of naturally deformed pyrite: assessing the links between trace element mobility and defect structures

Abstract: The links between deformation-induced micro- and nanostructures and trace element mobility in sulphide minerals have recently become a popular subject of research in the Earth sciences due to its connections with metallic ore paragenesis. It has been shown that plastic deformation in pyrite creates diffusion pathways in the form of low-angle grain boundaries that act as traps for base- and precious-metals. However, the plastic behavior of pyrite and the physiochemical processes that concentrate these trace elements in deformation-induced micro- and nanostructures remain poorly understood. In this study, we develop strategies for 2D and 3D analysis of naturally deformed sulphides by combining electron backscatter diffraction, electron channeling contrast imaging and atom probe tomography on pyrite in an attempt to better understand the underlying diffusion processes that mobilize trace elements. The combined results reveal structures associated with crystal-plastic deformation in the form of dislocations, stacking faults, and low-angle grain boundaries that are decorated by As and Co. Although our data support a dislocation-impurity pair diffusion model, we have evidence that multiple diffusion mechanisms may have acted simultaneously. In this study, we applied new data processing techniques that allow for orientation measurement of nanostructural crystal defects from atom probe tomography data. Dislocations within our studied sample occur along the (110) planes suggesting glide on {110}.

Geochemical and petrological diversity of mafic magmas from Mount St. Helens

Abstract: Quaternary eruptive products in the Cascade arc include a variety of different basalt types. At Mount St. Helens (MSH), the most active volcano in the Cascades throughout the last 35 ka, three different mafic endmembers erupted at the end of the Castle Creek period (1900–1700 years B.P.): (1) high-field strength element (HFSE)-rich basalt enriched in K, Ti, P, and incompatible trace elements; (2) low-K olivine tholeiite (LKOT) with lower amounts of incompatible trace elements; and (3) calc-alkaline (arc-type) basaltic andesite with a typical subduction signature, i.e., enrichment in fluid-mobile large ion lithophile elements (LILE) relative to immobile high-field strength elements (HFSE). Each type has compositions projecting backwards to more primitive endmembers in the Cascades. Single units encompassing basaltic-to-basaltic andesitic compositions with intermediate trace-element abundances form two almost continuous trends towards basaltic andesite. These trends are interpreted to result from assimilation of pre-existing, more evolved, calc-alkaline material (and in one case mixing of different mafic magma types) during migration of the magmas through the crust. Most of the erupted basalts are porphyritic (10–30%) with an assemblage dominated by olivine and plagioclase and show disequilibrium textures preventing detailed reconstruction of mantle melting processes. Although typical hydrous arc basalt produced by flux melting in the mantle is absent in the eruptive products of MSH, arc-type basaltic andesite suggests its presence at depth. LKOT magmas are interpreted as decompression melts from the upper mantle, whereas HFSE-rich basalts are likely derived from the water-poor periphery of the main flux melting regime, potentially tapping a trace-element-enriched source. Primitive spinel compositions and whole-rock trace-element variations indicate at least two distinct, relatively fertile lherzolite sources for these two basalt types. Weak crustal zones associated with an old fracture system beneath MSH likely provide conduits for fast and isolated ascent of distinct batches of magma, bypassing the lower crustal mush zone. The eruption of the basalts through the upper crustal magma system and main edifice is consistent with an offset plumbing system suggested by geophysical data.

The genesis of arc dacites: the case of Mount St. Helens, WA

Abstract: Throughout the last 35 ka, Mount St. Helens has been the most active volcano in the Cascade arc, but the origin of its voluminous dacites remains controversial. These dacites were traditionally interpreted as a result of melting metabasaltic lower crust. Yet, recent studies have challenged this view and suggested an origin dominated by differentiation of mafic magmas through assimilation-fractional crystallization (AFC) processes. To address this discrepancy on the origin of dacites at Mount St. Helens, we conduct an interdisciplinary study using a combination of thermal and geochemical modeling. Our results show that ~ 45% crystallization of a basaltic andesite parent reproduces the compositions of the dacites with a maximum of ~ 20–30% assimilation of lower crustal lithologies. Amphibole textures and compositions support such a differentiation trend in a polybaric mush system. Combined with recent geophysical imaging and experimental data, we suggest that Mount St. Helens dacites are generated by (1) mantle-derived arc magma evolving by AFC to intermediate compositions in a lower crustal magma reservoir and (2) ascent of these magmas to a mid to upper crustal reservoir, where they reach high crystallinity without significant further chemical differentiation, and are subject to frequent recharge that leave a clear mixing/mingling overprint.

Assessing magmatic volatile equilibria through FTIR spectroscopy of unexposed melt inclusions and their host quartz: a new technique and application to the Mesa Falls Tuff, Yellowstone

Abstract: Fourier transform infrared spectroscopy (FTIR) is a precise, non-destructive, and highly sensitive means of measuring volatile species in melt inclusions. Existing methods of applying FTIR to quartz-hosted melt inclusions, however, require challenging physical manipulation of the host quartz crystals, which can present a significant limitation. Here, we describe a technique for measuring the H2O and CO2 concentrations of melt inclusions fully enclosed in quartz crystals using transmission FTIR, where melt inclusion thickness is calculated using the host quartz silicate overtones. The greater thickness of quartz crystals permitted by this technique allows an additional assessment of volatile equilibrium by measuring structural OH− within the quartz host itself. To demonstrate the advantages of this technique, we applied it to quartz crystals from the Mesa Falls Tuff, Yellowstone. The majority of melt inclusions consist of transparent or brown glassy melt inclusions and record concentrations of 2.9–3.3 wt% H2O and 181–561 ppm CO2, with precision similar to that obtained by standard double-exposed FTIR. Based on volatile saturation models, such concentrations reflect a largely un-degassed magma body equilibrated at pre-eruptive pressures of 100–150 MPa. These H2O concentrations and equilibrium conditions are supported by independent assessments using mineral–mineral and mineral-melt thermohygrometry and thermodynamic modelling using rhyolite-MELTS. The preservation of pre-eruptive volatile concentrations is further corroborated by measurements of OH− in the quartz hosts. A clear decrease in hydroxyl concentrations from core to rim matches closely the zoning in Al, which, combined with the position of quartz infrared bands, most likely reflects variations in Al-moderated OH− solubility rather than diffusive loss. The outermost 200 µm rims, however, show a sharper decline in OH− and corresponding increase in Li+ which is interpreted to record minor diffusive H+ loss and incorporation of Li+ to maintain charge balance. Our FTIR-based technique is simple, effective, and widely applicable to other quartz-bearing magmatic systems, opening up new possibilities to trace pre- syn- and post-eruptive volatile behaviour.

Recycled oceanic crust in the form of pyroxenite contributing to the Cenozoic continental basalts in central Asia: new perspectives from olivine chemistry and whole-rock B–Mo isotopes

Abstract: Cenozoic continental basalts are widespread in central Asia. To explore their source nature and petrogenesis, this study presents an integrated study of olivine chemistry, bulk-rock 40Ar/39Ar age and geochemistry as well as Sr–Nd–Pb–B–Mo isotopes for the Miocene (ca. 15.5 Ma) Halaqiaola basalts in the Chinese Altai, central Asia. The Halaqiaola basalts mostly have basanite compositions with high total alkali (Na2O + K2O = 6.89–8.01 wt%) contents and high K2O/Na2O (0.87–1.39) ratios. Compared with partial melting products of mantle peridotite, the basaltic samples possess lower CaO and CaO/Al2O3 but higher TiO2, Zn/Mn and Zn/Fe values. Meanwhile, olivine phenocrysts from these basalts are characterized by lower Ca, Ni and Mn contents but higher Fe/Mn ratios than their counterparts in the peridotitic melts, suggesting a pyroxenite-rich source. Moreover, these rocks show OIB-like trace element patterns (e.g., spikes of Ba, Sr, Nb and Ta and troughs of Th and U), and constant Nd but variable Sr and EM1-like Pb isotopic compositions, and yield light δ11B (– 11.0 to – 8.1‰) and δ98Mo (– 0.40 to – 0.06‰) values. The above geochemical data suggest that secondary pyroxenite was likely produced by reaction of recycled oceanic crust with its ambient peridotite and subsequently became the main source for the basanite. Furthermore, their light and variable δ98Mo values probably reflect that recycled oceanic crust involved in such pyroxenite was altered with different degrees. In combination with available data from adjacent regions, we propose that the far-field effect of India–Eurasia collision was the first-order factor for the upwelling of dispersive asthenospheric mantle beneath central Asia, subsequent melting of which gave rise to the widespread Cenozoic volcanism.

Djerfisherite in kimberlites and their xenoliths: implications for kimberlite melt evolution

Abstract: Djerfisherite (K6(Fe,Ni,Cu)25S26Cl) occurs as an accessory phase in the groundmass of many kimberlites, kimberlite-hosted mantle xenoliths, and as a daughter inclusion phase in diamonds and kimberlitic minerals. Djerfisherite typically occurs as replacement of pre-existing Fe–Ni–Cu sulphides (i.e. pyrrhotite, pentlandite and chalcopyrite), but can also occur as individual grains, or as poikilitic phase in the groundmass of kimberlites. In this study, we present new constraints on the origin and genesis of djerfisherite in kimberlites and their entrained xenoliths. Djerfisherite has extremely heterogeneous compositions in terms of Fe, Ni and Cu ratios. However, there appears to be no distinct compositional range of djerfisherite indicative of a particular setting (i.e. kimberlites, xenoliths or diamonds), rather this compositional diversity reflects the composition of the host kimberlite melt and/or interacting metasomatic medium. In addition, djerfisherite may contain K and Cl contents less than the ideal formula unit. Raman spectroscopy and electron backscatter diffraction (EBSD) revealed that these K–Cl poor sulphides still maintain the same djerfisherite crystal structure. Two potential mechanisms for djerfisherite formation are considered: (1) replacement of pre-existing Fe–Ni–Cu sulphides by djerfisherite, which is attributed to precursor sulphides reacting with metasomatic K–Cl bearing melts/fluids in the mantle or the transporting kimberlite melt; (2) direct crystallisation of djerfisherite from the kimberlite melt in groundmass or due to kimberlite melt infiltration into xenoliths. The occurrence of djerfisherite in kimberlites and its mantle cargo from localities worldwide provides strong evidence that the metasomatising/infiltrating kimberlite melt/fluid was enriched in K and Cl. We suggest that kimberlites originated from melts that were more enriched in alkalis and halogens relative to their whole-rock compositions.

Microstructural evolution of silicate immiscible liquids in ferrobasalts

Abstract: An experimental study of the microstructural evolution of an immiscible basaltic emulsion shows that the Fe-rich liquid forms homogeneously nucleated droplets dispersed in a continuous Si-rich liquid, together with droplets heterogeneously nucleated on plagioclase, magnetite, and pyroxene. Heterogeneous nucleation is likely promoted by localised compositional heterogeneities around growing crystals. The wetting angle of Fe-rich droplets on both plagioclase and magnetite increases with decreasing temperature. Droplet coarsening occurs by a combination of diffusion-controlled growth and Ostwald ripening, with an insignificant contribution from coalescence. Characteristic microstructures resulting from the interaction of immiscible Fe-rich liquid with crystal grains during crystal growth can potentially be used as an indicator of liquid unmixing in fully crystallised natural samples. In magma bodies < ~ 10 m in size, gravitationally driven segregation of immiscible Fe-rich droplets is unlikely to be significant.

Magmatic platinum nanoparticles in metasomatic silicate glasses and sulfides from Patagonian mantle xenoliths

Abstract: Platinum-rich nanonuggets (s.l., nanoparticles) are commonly produced in experiments attempting to quantify the solubility or partitioning of noble metals in silicate and sulfide melts. However, it has been thought that these represent artifacts produced during quenching of the experimental runs. Here, we document nanoparticles (~ 20–80 nm) of Pt-rich alloys and arsenides dispersed in high-temperature metasomatic silicate glasses and in base-metal sulfides (BMS) entrained in them, found interstitially between minerals of mantle peridotite xenoliths from southern Patagonia. Pt-rich nanoparticles found in the interstitial silicate glasses are frequently attached to, or in the proximities of, oxides (ilmenite or Cr-spinel) suggesting a close link between the formation of the oxides and the Pt-rich nanoparticles. The interstitial glasses in the studied xenoliths correspond to quenched alkaline basaltic melts that infiltrated the subcontinental lithospheric mantle (SCLM) at > 1000 °C at an oxygen fugacity (fO2) near the fayalite–magnetite–quartz (FMQ) buffer. Experimental works indicate that at these conditions the crystallization of oxides such as ilmenite or Cr-spinel may lower fO2 to promote the precipitation of Pt-rich nanoparticles. The investigation of four Pt-rich nanoparticles hosted in two different pentlandite grains using a combination of focused ion beam and high-resolution transmission electron microscopy (FIB/HRTEM) show that these nanoparticles consists of polycrystalline aggregates < 10 nm that are randomly oriented relative to their sulfide host matrices. These observations suggest that these nanoparticles could be segregated either directly from the infiltrating alkaline basaltic melt prior to sulfur saturation in the silicate melt, or from droplets of immiscible sulfide melt once sulfur saturation was achieved. The formation of Pt-rich nanoparticles in high-temperature melts, either silicate or sulfide, provides new clues on the processes of fractionation, transport and concentration of Pt in the mantle.

Bulk rock and zircon geochemistry of granitoids from the Chotanagpur Granite Gneissic Complex (CGGC): implications for the late Paleoproterozoic continental arc magmatism in the East Indian Shield

Abstract: The north-eastern part of the Chotanagpur Granite Gneissic Complex (CGGC) exposes a vast expanse of felsic orthogneisses (~ 1450 Ma magmatic crystallization age) containing a variety of metamorphosed supracrustal rocks and augen gneiss. However, origin and timing of emplacement of the protolith of the augen gneiss are not well constrained. Owing to lack of detailed study and paucity of exposures, the antiquity of the basements of the CGGC also remains poorly understood. To address this issue, we present bulk rock geochemical data and the U–Pb and Lu–Hf isotope composition of zircon from augen gneisses from two adjoining areas within the CGGC. Our obtained data suggest that the augen gneiss have been derived from hybrid source involving older crustal rocks and metasomatised mantle. The bulk rock and zircon geochemistry also suggest that the protolith of the augen gneiss was emplaced in an early Paleoproterozoic basement in a continental arc setting. U–Pb ages of the magmatic zircon grains constrain the age of intrusion at ca. 1710 Ma and ca. 1635 Ma. The timing of this late Paleoproterozoic felsic magmatism overlaps with the timing of the regional high-to-ultrahigh-temperature granulite facies metamorphism in the CGGC.

Experimental study of trace element distribution between calcite, fluorite and carbonatitic melt in the system CaCO 3 + CaF 2 + Na 2 CO 3 ± Ca 3 (PO 4 ) 2 at 100 MPa

Abstract: Here we present an experimental study of the distribution of a broad range of trace elements between carbonatite melt, calcite and fluorite. The experiments were performed in the CaCO3 + CaF2 + Na2CO3 ± Ca3(PO4)2 synthetic system at 650–900 °C and 100 MPa using rapid-quench cold-seal pressure vessels. Starting mixtures were composed of reagent-grade oxides, carbonates, Ca3(PO4)2 and CaF2 doped with 1 wt% REE–HFSE mixture. The results show that the distribution coefficients of all the analyzed trace elements for calcite and fluorite are below 1, with the highest values observed for Sr (0.48–0.8 for calcite and 0.14–0.3 for fluorite) and Y (0.18–0.3). The partition coefficients of REE gradually increase with increasing atomic number from La to Lu. The solubility of Zr, Hf, Nb and Ta in the synthetic F-rich carbonatitic melts, which were used in our experiments, is low and limited by crystallization of baddeleyite and Nb-bearing perovskite.

New shock microstructures in titanite (CaTiSiO5) from the peak ring of the Chicxulub impact structure, Mexico

Abstract: Accessory mineral geochronometers such as apatite, baddeleyite, monazite, xenotime and zircon are increasingly being recognized for their ability to preserve diagnostic microstructural evidence of hypervelocity-impact processes. To date, little is known about the response of titanite to shock metamorphism, even though it is a widespread accessory phase and a U–Pb geochronometer. Here we report two new mechanical twin modes in titanite within shocked granitoid from the Chicxulub impact structure, Mexico. Titanite grains in the newly acquired core from the International Ocean Discovery Program Hole M0077A preserve multiple sets of polysynthetic twins, most commonly with composition planes (K1) = ~ {1¯11}, and shear direction (η1) = , and less commonly with the mode K1 = {130}, η1 = ~ . In some grains, {130} deformation bands have formed concurrently with the deformation twins, indicating dislocation slip with Burgers vector b = can be active during impact metamorphism. Titanite twins in the modes described here have not been reported from endogenically deformed rocks; we, therefore, propose this newly identified twin form as a result of shock deformation. Formation conditions of the twins have not been experimentally calibrated, and are here empirically constrained by the presence of planar deformation features in quartz (12 ± 5 and ~ 17 ± 5 GPa) and the absence of shock twins in zircon (< 20 GPa). While the lower threshold of titanite twin formation remains poorly constrained, identification of these twins highlight the utility of titanite as a shock indicator over the pressure range between 12 and 17 GPa. Given the challenges to find diagnostic indicators of shock metamorphism to identify both ancient and recent impact evidence on Earth, microstructural analysis of titanite is here demonstrated to provide a new tool for recognizing impact deformation in rocks where other impact evidence may be erased, altered, or did not manifest due to generally low (< 20 GPa) shock pressure.