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Teichtmeister, Tobias A. ; Paulsen, Christian ; Ambach, Sebastian J. ; Wurst, Klaus ; Bayarjargal, Lkhamsuren ; Schnick, Wolfgang ; Huppertz, Hubert
Herein, the high-pressure/high-temperature synthesis (11 GPa, 650 °C) of Tb3B10O17(OH)5 in a modified Walker-type multianvil device is presented. The structure of this rare-earth borate was determined by single-crystal X-ray diffraction methods and was found to crystallize orthorhombically in the space group Pmn21 (no. 31) with the unit cell parameters a = 16.2527(4), b = 4.4373(1), and c = 8.8174(2) Å. The new compound was further characterized using infrared spectroscopy, energy-dispersive X-ray spectroscopy, second harmonic generation (SHG) measurements, and temperature-dependent X-ray powder diffraction. Tb3B10O17(OH)5 decomposes to β-Tb(BO2)3 at temperatures higher than 460 °C. With increasing temperatures, the formation of μ-TbBO3 was observed, which transforms to π-TbBO3 upon cooling.
High-pressure/high-temperature synthesis of the new boron-rich terbium hydroxyborate Tb3B12O19(OH)7
(2023)
Monoclinic Tb3B12O19(OH)7 was obtained by multianvil high-pressure/high-temperature syntheses at 6 GPa and 650 °C. The crystal structure was investigated by single-crystal X-ray diffraction methods and space group C2 (no. 5) with the unit cell parameters a = 24.2299(5) Å, b = 4.4667(1) Å, c = 7.0964(2) Å, β = 94.58(1)°, and two formula units per cell were revealed. Powder X-ray diffraction, infrared spectroscopy and the investigation of its second harmonic generation properties support the proposed structural model.
Local climate change risk assessments (LCCRAs) are best supported by a quantitative integration of physical hazards, exposures and vulnerabilities that includes the characterization of uncertainties. We propose to use Bayesian Networks (BNs) for this task and show how to integrate freely-available output of multiple global hydrological models (GHMs) into BNs, in order to probabilistically assess risks for water supply. Projected relative changes in hydrological variables computed by three GHMs driven by the output of four global climate models were processed using MATLAB, taking into account local information on water availability and use. A roadmap to set up BNs and apply probability distributions of risk levels under historic and future climate and water use was co-developed with experts from the Maghreb (Tunisia, Algeria, Morocco) who positively evaluated the BN application for LCCRAs. We conclude that the presented approach is suitable for application in the many LCCRAs necessary for successful adaptation to climate change world-wide.
Laniel, Dominique ; Winkler, Björn ; Koemets, Egor ; Fedotenko, Timofey ; Chariton, Stella ; Milman, Victor ; Glazyrin, Konstantin ; Prakapenka, Vitali ; Dubrovinsky, Leonid ; Dubrovinskaia, Natalia
At high pressures, autoionization – along with polymerization and metallization – is one of the responses of simple molecular systems to a rise in electron density. Nitrosonium nitrate (NO+NO3−), known for this property, has attracted a large interest in recent decades and was reported to be synthesized at high pressure and high temperature from a variety of nitrogen–oxygen precursors, such as N2O4, N2O and N2–O2 mixtures. However, its structure has not been determined unambiguously. Here, we present the first structure solution and refinement for nitrosonium nitrate on the basis of single-crystal X-ray diffraction at 7.0 and 37.0 GPa. The structure model (P21/m space group) contains the triple-bonded NO+ cation and the NO3− sp2-trigonal planar anion. Remarkably, crystal-chemical considerations and accompanying density-functional-theory calculations show that the oxygen atom of the NO+ unit is positively charged – a rare occurrence when in the presence of a less-electronegative element.
An update of the two-energy turbulence scheme is presented, the 2TE + APDF scheme. The original version of the two-energy scheme is able to successfully model shallow convection without the need of an additional parameterization for non-local fluxes. However, the performance of the two-energy scheme is worse in stratocumulus cases, where it tends to overestimate the erosion of the stable layers. We have identified the causes: the non-local stability parameter does not consider local stratification, the scheme lacks an internal parameter that could distinguish between a shallow convection regime and a stratocumulus regime, and it uses an inflexible turbulence length scale formulation. To alleviate this problem, we propose several modifications: an update of the stability parameter, a modified computation of the turbulence length scale, and the introduction of the entropy potential temperature to distinguish between a shallow convection and a stratocumulus regime. In addition, the two-energy scheme is coupled to a simplified assumed probability density function method in order to achieve a more universal representation of the cloudy regimes. The updated turbulence scheme is evaluated for several idealized cases and one selected real case in the ICOsahedral Nonhydrostatic (ICON) modeling framework. The results show that the updated scheme corrects the overmixing problem in the stratocumulus cases. The performance of the updated scheme is comparable to the operational setup, and can be thus used instead of the operational turbulence and shallow convection scheme in ICON. Additionally, the updated scheme improves the coupling with dynamics, which is beneficial for the modeling of coherent flow structures in the atmospheric boundary layer.
The accessories perovskite, pyrochlore, zirconolite, calzirtite and melanite from carbonatites and carbonate-rich foidites from the Kaiserstuhl are variously suited for the in situ determination of their U–Pb ages and Sr, Nd- and Hf-isotope ratios by LA-ICP-MS. The 143Nd/144Nd ratios may be determined precisely in all five phases, the 176Hf/177Hf ratios only in calzirtite and the 87Sr/86Sr ratios in perovskites and pyrochlores. The carbonatites and carbonate-rich foidites belong to one of the three magmatic groups that Schleicher et al. (1990) distinguished in the Kaiserstuhl on the basis of their Sr, Nd and Pb isotope ratios. Tephrites, phonolites and essexites (nepheline monzogabbros) form the second and limburgites (nepheline basanites) and olivine nephelinites the third. Our 87Sr/86Sr isotope data from the accessories overlap with the carbonatite and olivine nephelinite fields defined by Schleicher et al. (1990) but exhibit a much narrower range. These and the εNd and εHf values plot along the mantle array in the field of oceanic island basalts relatively close to mid-ocean ridge basalts. Previously reported K–Ar, Ar–Ar and fission track ages for the Kaiserstuhl lie between 16.2 and 17.8 Ma. They stem entirely from the geologically older tephrites, phonolites and essexites. No ages existed so far for the geologically younger carbonatites and carbonate-rich foidites except for one apatite fission track age (15.8 Ma). We obtained precise U–Pb ages for zirconolites and calzirtites of 15.66, respectively 15.5 Ma (± 0.1 2σ) and for pyrochlores of 15.35 ± 0.24 Ma. Only the perovskites from the Badberg soevite yielded a U–P concordia age of 14.56 ± 0.86 Ma while the perovskites from bergalites (haüyne melilitites) only gave 206Pb/238U and 208Pb/232Th ages of 15.26 ± 0.21, respectively, 15.28 ± 0.48 Ma. The main Kaiserstuhl rock types were emplaced over a time span of 1.6 Ma almost 1 million years before the carbonatites and carbonate-rich foidites. These were emplaced within only 0.32 Ma.
Raddatz, Jacek ; Liebetrau, Volker ; Rüggeberg, Andres ; Foubert, Anneleen ; Flögel, Sascha ; Nürnberg, Dirk ; Hissmann, Karen ; Musiol, Johannes ; Goepfert, Tyler Jay ; Eisenhauer, Anton ; Dullo, Wolf-Christian
Living on the edge: environmental variability of a shallow late Holocene cold-water coral mound
(2022)
Raddatz, Jacek ; Liebetrau, Volker ; Rüggeberg, Andres ; Foubert, Anneleen ; Flögel, Sascha ; Nürnberg, Dirk ; Hissmann, Karen ; Musiol, Johannes ; Goepfert, Tyler Jay ; Eisenhauer, Anton ; Dullo, Wolf-Christian
Similar to their tropical counterparts, cold-water corals (CWCs) are able to build large three-dimensional reef structures. These unique ecosystems are at risk due to ongoing climate change. In particular, ocean warming, ocean acidification and changes in the hydrological cycle may jeopardize the existence of CWCs. In order to predict how CWCs and their reefs or mounds will develop in the near future one important strategy is to study past fossil CWC mounds and especially shallow CWC ecosystems as they experience a greater environmental variability compared to other deep-water CWC ecosystems. We present results from a CWC mound off southern Norway. A sediment core drilled from this relatively shallow (~ 100 m) CWC mound exposes in full detail hydrographical changes during the late Holocene, which were crucial for mound build-up. We applied computed tomography, 230Th/U dating, and foraminiferal geochemical proxy reconstructions of bottom-water-temperature (Mg/Ca-based BWT), δ18O for seawater density, and the combination of both to infer salinity changes. Our results demonstrate that the CWC mound formed in the late Holocene between 4 kiloannum (ka) and 1.5 ka with an average aggradation rate of 104 cm/kiloyears (kyr), which is significantly lower than other Holocene Norwegian mounds. The reconstructed BWTMg/Ca and seawater density exhibit large variations throughout the entire period of mound formation, but are strikingly similar to modern in situ observations in the nearby Tisler Reef. We argue that BWT does not exert a primary control on CWC mound formation. Instead, strong salinity and seawater density variation throughout the entire mound sequence appears to be controlled by the interplay between the Atlantic Water (AW) inflow and the overlying, outflowing Baltic-Sea water. CWC growth and mound formation in the NE Skagerrak was supported by strong current flow, oxygen replenishment, the presence of a strong boundary layer and larval dispersal through the AW, but possibly inhibited by the influence of fresh Baltic Water during the late Holocene. Our study therefore highlights that modern shallow Norwegian CWC reefs may be particularly endangered due to changes in water-column stratification associated with increasing net precipitation caused by climate change.
Spahr, Dominik ; Koch, Tamara ; Merges, David ; Bayarjargal, Lkhamsuren ; Genzel, Philomena-Theresa ; Christ, Oliver ; Wilde, Fabian ; Brenker, Frank E. ; Winkler, Björn
We performed an experiment under long-term microgravity conditions aboard the International Space Station (ISS) to obtain information on the energetics and experimental constraints required for the formation of chondrules in the solar nebula by ’nebular lightning’. As a simplified model system, we exposed porous forsterite (Mg2 SiO4) dust particles to high-energetic arc discharges. The characterization of the samples after their return by synchrotron microtomography and scanning electron microscopy revealed that aggregates had formed, consisting of several fused Mg2SiO4 particles. The partial melting and fusing of Mg2SiO4 dust particles under microgravity conditions leads to a strong reduction of their porosity. The experimental outcomes vary strongly in their appearance from small spherical melt-droplets (∅≈90 µm) to bigger and irregularly shaped aggregates (∅≈350 µm). Our results provided new constraints with respect to energetic aspects of chondrule formation and a roadmap for future and more complex experiments on Earth and in microgravity conditions.
Several past summer floods in Central Europe were associated with so-called Vb‑cyclones propagating from the Mediterranean Sea north-eastward to Central Europe. This study illustrates the usefulness of the parametric transfer entropy measure TE‑linear in investigating heavy Vb‑cyclone precipitation events in the Odra catchment (Poland). With the application of the TE‑linear approach, we confirm the impact of the Mediterranean Sea on precipitation intensification. Moreover, we also detect significant information exchange to Vb‑cyclone precipitation from evaporation over the European continent along the typical Vb‑cyclone pathway. Thus, the Mediterranean Sea could enhance the Vb‑cyclone precipitation by pre-moistening continental moisture source regions that contribute to precipitation downstream in the investigated catchments. Overall, the transfer entropy approach with the measure TE‑linear proved to be computationally effective and complementary to traditional methods such as Lagrangian and Eulerian diagnostics.
Climatic and biogeographical drivers of functional diversity in the flora of the Canary Islands
(2022)
Hanz, Dagmar Martina ; Cutts, Vanessa ; Barajas-Barbosa, Martha Paola ; Algar, Adam C. ; Beierkuhnlein, Carl ; Fernández-Palacios, José María ; Field, Richard ; Kreft, Holger ; Steinbauer, Manuel J. ; Weigelt, Patrick ; Irl, Severin
Aim: Functional traits can help us to elucidate biogeographical and ecological processes driving assemblage structure. We analysed the functional diversity of plant species of different evolutionary origins across an island archipelago, along environmental gradients and across geological age, to assess functional aspects of island biogeographical theory.
Location: Canary Islands, Spain.
Major taxa studied: Spermatophytes.
Time period: Present day.
Methods: We collected data for four traits (plant height, leaf length, flower length and fruit length) associated with resource acquisition, competitive ability, reproduction and dispersal ability of 893 endemic, non-endemic native and alien plant species (c. 43% of the Canary Island flora) from the literature. Linking these traits to species occurrences and composition across a 500 m × 500 m grid, we calculated functional diversity for endemic, non-endemic native and alien assemblages using multidimensional functional hypervolumes and related the resulting patterns to climatic (humidity) and island biogeographical (geographical isolation, topographic complexity and geological age) gradients.
Results: Trait space of endemic and non-endemic native species overlapped considerably, and alien species added novel trait combinations, expanding the overall functional space of the Canary Islands. We found that functional diversity of endemic plant assemblages was highest in geographically isolated and humid grid cells. Functional diversity of non-endemic native assemblages was highest in less isolated and humid grid cells. In contrast, functional diversity of alien assemblages was highest in arid ecosystems. Topographic complexity and geological age had only a subordinate effect on functional diversity across floristic groups.
Main conclusions: We found that endemic and non-endemic native island species possess similar traits, whereas alien species tend to expand functional space in ecosystems where they have been introduced. The spatial distribution of the functional diversity of floristic groups is very distinct across environmental gradients, indicating that species assemblages of different evolutionary origins thrive functionally in dissimilar habitats.
Koch, Tamara ; Spahr, Dominik ; Tkalcec, Beverley J. ; Christ, Oliver ; Genzel, Philomena-Theresa ; Lindner, Miles ; Merges, David ; Wilde, Fabian ; Winkler, Björn ; Brenker, Frank E.
In order to gain further insights into early solar system aggregation processes, we carried out an experiment on board the International Space Station, which allowed us to study the behavior of dust particles exposed to electric arc discharges under long-term microgravity. The experiment led to the formation of robust, elongated, fluffy aggregates, which were studied by scanning electron microscopy, electron backscatter diffraction, and synchrotron micro-computed tomography. The morphologies of these aggregates strongly resemble the typical shapes of fractal fluffy-type calcium-aluminum-rich inclusions (CAIs). We conclude that a small amount of melting could have supplied the required stability for such fractal structures to have survived transportation and aggregation to and compaction within planetesimals. Other aggregates produced in our experiment have a massy morphology and contain relict grains, likely resulting from the collision of grains with different degrees of melting, also observed in some natural CAIs. Some particles are surrounded by igneous rims, which remind in thickness and crystal orientation of Wark–Lovering rims; another aggregate shows similarities to disk-shaped CAIs. These results imply that a (flash-)heating event with subsequent aggregation could have been involved in the formation of different morphological CAI characteristics.
Convective rain cell properties and the resulting precipitation scaling in a warm-temperate climate
(2022)
Convective precipitation events have been shown to intensify at rates exceeding the Clausius–Clapeyron rate (CC rate) of ca. 7% K−1 under current climate conditions. In this study, we relate atmospheric variables (low-level dew point temperature, convective available potential energy, and vertical wind shear), which are regarded as ingredients for severe deep convection, to properties of convective rain cells (cell area, maximum precipitation intensity, lifetime, precipitation sum, and cell speed). The rain cell properties are obtained from a rain gauge-adjusted radar dataset in a mid-latitude region, which is characterized by a temperate climate with warm summers (Germany). Different Lagrangian cell properties scale with dew point temperature at varying rates. While the maximum precipitation intensity of cells scales consistently at the CC rate, the area and precipitation sum per cell scale at varying rates above the CC rate. We show that this super-CC scaling is caused by a covarying increase of convective available potential energy with dew point temperature. Wind shear increases the precipitation sum per cell mainly by increasing the spatial cell extent. From a Eulerian point of view, this increase is partly compensated by a higher cell velocity, which leads to Eulerian precipitation scaling rates close to and slightly above the CC rate. Thus, Eulerian scaling rates of convective precipitation are modulated by convective available potential energy and vertical wind shear, making it unlikely that present scaling rates can be applied to future climate conditions. Furthermore, we show that cells that cause heavy precipitation at fixed locations occur at low vertical wind shear and, thus, move relatively slowly compared to typical cells.
Moisture sources of heavy precipitation in Central Europe in synoptic situations with Vb-cyclones
(2022)
During the past century, several extreme summer floods in Central Europe were associated with so-called Vb-cyclones propagating from the Mediterranean Sea north-eastward to Central Europe. The processes intensifying the precipitation in synoptic situations with Vb-cyclones in the Danube, Elbe, and Odra catchments are only partially understood. Our study aims to investigate these processes with Lagrangian moisture-source diagnostics for 16 selected Vb-events. Moreover, we analyse the characteristics of typical moisture source regions during 1107 Vb-events from 1901 to 2010 based on ERA-20C reanalysis dynamically downscaled with COSMO-CLM+NEMO. We observe moisture contributions by various source regions highlighting the complex dynamical interplay of different air masses leading to moisture convergence in synoptic situations with Vb-cyclones. Overall, up to 80% of the precipitation originates from the European continent, indicating the importance of continental moisture recycling, especially within the respective river catchment. Other major moisture uptake regions are the North Sea, the Baltic Sea, the North Atlantic, and for a few events the Black Sea. Remarkably, anomalies in these oceanic source regions show no connection to precipitation amounts in synoptic situations with Vb-cyclones. In contrast, the Vb-cyclones with the highest precipitation are associated with anomalously high evaporation in the Mediterranean Sea, even though the Mediterranean Sea is only a minor moisture source region on average. Interestingly, the evaporation anomalies are not connected with sea-surface temperature but with wind-speed anomalies (Spearman’s rank correlation coefficient R≈0.7, significant with p<0.01) indicating mainly dynamically driven evaporation. The particular role of the Mediterranean Sea hints towards possible importance of Mediterranean moisture for the early-stage intensification of Vb-cyclones and the pre-moistening of the continental uptake regions upstream of the target catchments.
The Yacoraite Formation (Salta rift, Argentina) consists of Maastrichtian–Danian lacustrine carbonate and siliciclastic deposits with interbedded volcanic ash layers, organized in four third-order stratigraphic sequences. It offers the exceptional opportunity to jointly apply in situ zircon and carbonate U-Pb geochronology that resulted in two distinct depositional age depth models. Ages of the youngest zircon population from ash layers were linearly interpolated to derive a zircon depositional age depth model. A carbonate depositional age depth model was instead obtained from dated carbonate phases including microbialites, ooids, oncoids of calcitic and dolomitic mineralogy as well as early lacustrine calcite cements. Mean ages were defined from different carbonate phases belonging to the same layer and then linearly interpolated. Sedimentation rates were calculated from both depth models between pairs of dated samples and used to estimate the age of sequence boundaries, as well as the duration of the four stratigraphic sequences. The zircon and carbonate depositional age depth models agree with biostratigraphic constraints and exhibit excellent consistency. The onset and end of sedimentation were estimated at 68.2 ± 0.9 Ma and 62.3 ± 0.6 Ma (duration ca 5.7 Ma) via zircon geochronology and at 67.9 ± 1.7 Ma and 61.9 ± 1.3 Ma (duration ca 6.0 Ma) via carbonate geochronology. Results from this study show that with suitable samples and a newly implemented working strategy, in situ U-Pb dating of depositional and early diagenetic carbonates represent a valuable chronostratigraphic tool for estimating sedimentation rate and duration in poorly time-framed depositional systems.
Diamonds growing in the Earth’s mantle often trap inclusions of fluids that are highly saline in composition. These fluids are thought to emerge from deep in subduction zones and may also be involved in the generation of some of the kimberlite magmas. However, the source of these fluids and the mechanism of their transport into the mantle lithosphere are unresolved. Here, we present experimental results showing that alkali chlorides are stable solid phases in the mantle lithosphere below 110 km. These alkali chlorides are formed by the reaction of subducted marine sediments with peridotite and show identical K/Na ratios to fluid inclusions in diamond. At temperatures >1100°C and low pressures, the chlorides are unstable; here, potassium is accommodated in mica and melt. The reaction of subducted sediments with peridotite explains the occurrence of Mg carbonates and the highly saline fluids found in diamonds and in chlorine-enriched kimberlite magmas.
Codillo, Emmanuel A. ; Klein, Frieder ; Dragovic, Besim ; Marschall, Horst R. ; Baxter, Ethan ; Scambelluri, Marco ; Schwarzenbach, Esther
Metasomatic reaction zones between mafic and ultramafic rocks exhumed from subduction zones provide a window into mass-transfer processes at high pressure. However, accurate interpretation of the rock record requires distinguishing high-pressure metasomatic processes from inherited oceanic signatures prior to subduction. We integrated constraints from bulk-rock geochemical compositions and petrophysical properties, mineral chemistry, and thermodynamic modeling to understand the formation of reaction zones between juxtaposed metagabbro and serpentinite as exemplified by the Voltri Massif (Ligurian Alps, Italy). Distinct zones of variably metasomatized metagabbro are dominated by chlorite, amphibole, clinopyroxene, epidote, rutile, ilmenite, and titanite between serpentinite and eclogitic metagabbro. Whereas the precursor serpentinite and oxide gabbro formed and were likely already in contact in an oceanic setting, the reaction zones formed by diffusional Mg-metasomatism between the two rocks from prograde to peak, to retrograde conditions in a subduction zone. Metasomatism of mafic rocks by Mg-rich fluids that previously equilibrated with serpentinite could be widespread along the subduction interface, within the subducted slab, and the mantle wedge. Furthermore, the models predict that talc formation by Si-metasomatism of serpentinite in subduction zones is limited by pressure-dependent increase in the silica activity buffered by the serpentine-talc equilibrium. Elevated activities of aqueous Ca and Al species would also favor the formation of chlorite and garnet. Accordingly, unusual conditions or processes would be required to stabilize abundant talc at high P-T conditions. Alternatively, a different set of mineral assemblages, such as serpentine- or chlorite-rich rocks, may be controlling the coupling-decoupling transition of the plate interface.
Talc formation via silica-metasomatism of ultramafic rocks is believed to play key roles in subduction zone processes. Yet, the conditions of talc formation remain poorly constrained. We used thermodynamic reaction-path models to assess the formation of talc at the slab-mantle interface and show that it is restricted to a limited set of pressure–temperature conditions, protolith, and fluid compositions. In contrast, our models predict that chlorite formation is ubiquitous at conditions relevant to the slab-mantle interface of subduction zones. The scarcity of talc and abundance of chlorite is evident in the rock record of exhumed subduction zone terranes. Talc formation during Si-metasomatism may thus play a more limited role in volatile cycling, strain localization, and in controlling the decoupling-coupling transition of the plate interface. Conversely, the observed and predicted ubiquity of chlorite corroborates its prominent role in slab-mantle interface processes that previous studies attributed to talc.
Key Points:
Limited talc formation by Si-metasomatism of ultramafic rocks in subduction zones
Chlorite formation is likely pervasive at the slab-mantle interface
Preferential formation of chlorite has wide-ranging chemical and physical implications for subduction zone processes
Plain Language Summary: In subduction zones, talc can form during chemical reactions of mantle rocks with silica-enriched fluids at the interface between descending oceanic plates and the overriding mantle. Its formation and distribution in subduction zones are believed to affect the volatile budget, rheological properties, and the down-dip limit of the decoupling of the slab-mantle interface. Therefore, illuminating the conditions that facilitate talc formation at high pressure-temperature conditions is key in assessing its roles in fundamental subduction zone processes. Using thermodynamic reaction-path models, we show that the formation of talc at the slab-mantle interface is restricted to a limited set of environmental conditions, because its formation is highly sensitive to the compositions of the mantle rocks and reactant fluids. Contrary to common belief, talc is unlikely to form in high abundance in ultramafic rocks metasomatized by Si-rich slab-derived fluids. Rather, our models predict the ubiquitous formation of chlorite along with other silicate minerals during Si-metasomatism due to the competing effects from other dissolved components that favor their formation over talc. This study calls into question the importance of talc during Si-metasomatism in subduction zones but highlights the more predominant role of chlorite.
Fossil records of early solar irradiation and cosmolocation of the CAI factory: a reappraisal
(2021)
Bekaert, David V. ; Auro, Maureen ; Shollenberger, Quinn R. ; Liu, Ming-Chang ; Marschall, Horst ; Burton, Kevin W. ; Jacobsen, Benjamin ; Brennecka, Gregory A. ; MacPherson, Glenn J. ; Mutius, Richard von ; Sarafian, Adam ; Nielsen, Sune G.
Calcium-aluminum–rich inclusions (CAIs) in meteorites carry crucial information about the environmental conditions of the nascent Solar System prior to planet formation. Based on models of 50V–10Be co-production by in-situ irradiation, CAIs are considered to have formed within ~0.1 AU from the proto-Sun. Here, we present vanadium (V) and strontium (Sr) isotopic co-variations in fine- and coarse-grained CAIs and demonstrate that kinetic isotope effects during partial condensation and evaporation best explain V isotope anomalies previously attributed to solar particle irradiation. We also report initial excesses of 10Be and argue that CV CAIs possess essentially a homogeneous level of 10Be, inherited during their formation. Based on numerical modeling of 50V–10Be co-production by irradiation, we show that CAI formation during protoplanetary disk build-up likely occurred at greater heliocentric distances than previously considered, up to planet-forming regions (~1AU), where solar particle fluxes were sufficiently low to avoid substantial in-situ irradiation of CAIs.
Chloritoid and kyanite coexist in metapelites from the high-pressure/low-temperature Massa Unit in the Alpi Apuane metamorphic complex (Northern Apennines, Italy). The composition of chloritoid is extremely variable throughout the Massa Unit. Fe-chloritoid occurs in association with hematite-free, graphite-bearing schists, whereas strongly zoned Fe-Mg chloritoid is found with hematite and kyanite. We investigated the effect of different bulk Fe2O3 contents in controlling chloritoid composition through phase equilibria modelling of four selected samples, representative of the different chloritoid-bearing parageneses found in the Massa Unit. The ferric iron content, measured through wet chemical titration, ranges from 0 (graphite-chloritoid schist) to 73% of the total iron (hematite-chloritoid schist). We show that Mg-rich chloritoid compositions and stability of kyanite at greenschist to blueschist facies conditions can be reproduced in the MnO–Na2O–K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–O (MnNKFMASHTO) chemical system only considering the presence of significant amounts of ferric iron as part of the bulk composition. The stabilization of kyanite at lower grade is directly linked to the presence of Fe2O3, which renders the reactive bulk rock composition effectively enriched in Al2O3 with respect to Fe and Mg. We also document that high Fe2O3 contents exacerbate the effect of chloritoid fractionation, producing strongly zoned Fe-Mg-chloritoid grains. Finally, the P–T modelling of the Massa Units performed in this study allows, for the first time, the recognition of a two-stage evolution at peak conditions, with an earlier pressure peak (1.2–1.3 GPa at 350–400°C), and a later thermal peak (0.7–1.1 GPa at 440–480°C), compatible with subduction, underthrusting and exhumation of the Adria continental margin during growth of the Northern Apennine orogenic wedge.