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Caldera-forming volcanic eruptions are low-frequency, high-impact events capable of discharging tens to thousands of cubic kilometres of magma explosively on timescales of hours to days, with devastating effects on local and global scales (1). Because no such eruption has been monitored during its long build-up phase, the precursor phenomena are not well understood. Geophysical signals obtained during recent episodes of unrest at calderas such as Yellowstone, USA, and Campi Flegrei, Italy, are difficult to interpret, and the conditions necessary for large eruptions are poorly constrained (2,3). Here we present a study of pre-eruptive magmatic processes and their timescales using chemically zoned crystals from the 'Minoan' caldera-forming eruption of Santorini volcano, Greece (4), which occurred in the late 1600s bc. The results provide insights into how rapidly large silicic systems may pass from a quiescent state to one on the edge of eruption (5,6). Despite the large volume of erupted magma (4) (40-60 cubic kilometres), and the 18,000-year gestation period between the Minoan eruption and the previous major eruption, most crystals in the Minoan magma record processes that occurred less than about 100 years before the eruption. Recharge of the magma reservoir by large volumes of silicic magma (and some mafic magma) occurred during the century before eruption, and mixing between different silicic magma batches was still taking place during the final months. Final assembly of large silicic magma reservoirs may occur on timescales that are geologically very short by comparison with the preceding repose period, with major growth phases immediately before eruption. These observations have implications for the monitoring of long-dormant, but potentially active, caldera systems., Crystals in volcanic rocks provide records of magma reservoir processes and timescales before eruptions (7). A crystal growing from a magmatic melt incorporates trace elements in quantities governed by thermodynamic [...]

We present in situ microanalyses of [Fe.sup.3]+[summation]Fe in mantle-derived kaersutites as measured by electron probe microanalysis (EMP) based on the 'self absorption induced FeL[alpha] peak shift' method. The EMP results are not in agreement with bulk (wet chemistry) data. The heterogeneities revealed for some kaersutite megacrysts, when comparing bulk and EMP [Fe.sup.3+]/[summation]Fe results, cannot explain the differences with the EMP measurements. It is thus proposed that any EMP overestimation of [Fe.sup.3+]/[summation]Fe results from a beam-induced dehydrogenation and a subsequent oxidation of [Fe.sup.2+] to [Fe.sup.3+] according to the known relation: [Fe.sup.2+] + O[H.sup.-] = [Fe.sup.3+] + [O.sup.2-] + 1/2 [H.sub.2]. To demonstrate this phenomenon, H losses were measured by secondary ion mass spectrometry (SIMS) after EMP irradiation at different beam currents on two amphiboles with 1.1 and 1.7 wt% [H.sub.2]O, respectively. In both amphiboles, H losses were observed under high beam currents (240 and 100 nA). No dehydrogenation is observed under lower beam currents for the 1.1 wt% [H.sub.2]O amphibole, but still occurs, down to at least 50 nA, for the amphibole with the greatest [H.sub.2]O contents. Amphiboles with low [H.sub.2]O contents (below ~0.5 [H.sup.+]) are less affected by beam damage. For amphiboles with higher [H.sub.2]O contents, the electron beam current density should be reduced with consideration given to the resulting high statistical errors. Keywords: [Fe.sup.3+]/[summation]Fe, EMP and SIMS measurements, amphibole, H loss

Detailed electron- and ion-microprobe analysis ofdiopsides extracted from a block of marble collected in the Mt. Marcy anorthosite massif (Adirondack Highlands, New York) shows that single crystals have preserved Al-Si zoning features from early contact metamorphism later modified by regional metamorphism. Diopsides show Al and Si complementary zoning from core to rim; average A1 concentration in rims is constant (0.11 pfu), but values in the cores vary with crystals from 0.06 to 0.14 pfu. A [[delta].sup.18]O profile measured with the ion microprobe shows no zoning. Modeling of the Al-diffusion profiles affected by regional metamorphism of the Grenville orogeny shows that original Al zoning was sharp and corresponds to a rapid change of crystal-growth conditions during early contact metamorphism: (1) diopside cores crystallized with variable Al contents due to restricted fluid circulation or differing sedimentary composition, (2) then pervasive fluid infiltration crystallized the homogeneous rim of diopside, and (3) core to rim Al zoning was later smoothed by granulite-facies metamorphism. Homogeneity of [[delta].sup.18]O in core and mantle (near rim) of diopsides suggests that the crystals were isotopically homogeneous prior to and during regional metamorphism. Values of Al-Si diffusion coefficient deduced from modeling are in agreement with low-temperature extrapolation of experimental data. Keywords: Diopside, zoning, granulite, diffusion, ion probe, oxygen isotopes, Adirondack

Introduction: High pressure minerals from meteoritic shock melt veins are key to understand the collisional history of the Solar System. The L chondrites, the most shocked meteorites [1], present abundant shock melt veins from which we can retrace their history. To this day, their family of origin is still debated. The shock timescale of 7 chondrites was measured to deduce their parent body diameters. Moreover, we use tuite, a high pressure phosphate mineral to perform U-Pb datation by SIMS. We find a bimodal distribution of ages, which match closely the ages previously obtained for Creston and Novato, two other shocked L6 chondrites [2]. Samples and Methods: Seven samples were first studied by optical microscopy and Raman spectroscopy to identify high pressure (HP) polymorphs. Scanning Transmission Electron Microscopy (STEM) was then used to study microstructures and transformation/growth mechanisms. The EDX was used to locate eligible minerals for datation (phosphates). Combined STEM-EDX (UMET, Lille, France) and NanoSIMS (MNHN, Paris, France) chemical maps were finally collected on the same FIB sections in order to compare these two analytical approaches and produce chemical maps. The U and Pb isotope concentrations where then measured on the identified tuite grains with the help of a Cameca IMS 1280 LG SIMS (CRPG, Nancy France) for datation. Results: Multiple high pressure textures were observed in all seven samples. Polycristalline assemblages of ringwoodite are typically the dominant texture, but more exotic textures were also found. Some meteorites present ringwoodite as lamellae inside olivine crystals, whereas others seem to present an assemblage of MgSiO3 glass with akimotoite crystallites. Both these textures allowed us to investigate elemental diffusion induced by structural changes. We therefore calculated shock timescales following the methods described in [3,4]. For all our samples, assuming a temperature of 2400K [5], shock timescales ranging between 0.5 and 20 seconds were derived. The meteorites that do not contain ringwoodite lamellae have significantly higher shock timescales, between 11 and 16 seconds. These larger shock timescales were caused by an impact between larger bolides, including a parent body of at least 150km wide. This is significantly higher than parent-bodies with diameters around 70km required by the other group. In almost all meteorites, we find tuites inside the shock melt veins. The meteorites that do not contain tuite have at least shocked apatites and whitlockites, with shifted Raman spectra indicating a change in structure. We date both the host rock apatites and the shock vein phosphates. This allows us to obtain conclusive collision ages from a normal concordia diagram for two of our samples, one of each group. The tuites record collisions ages of 461+-57Ma for the group with the largest parent body, and 650+-160Ma for the group with the smaller parent body. The host rock minerals record upper intercepts of 4481Ma in both meteorites. Conclusion: Shocked L chondrites seem to define two groups, which are texturally different and appear to have a completely different history. A smaller, 70km-wide parent body exploded first (650 Ma ago) and yielded most of the shocked meteorites, and a larger one exploded in the cataclysmic collision known today as the "L chondrite parent body breakup" 470Ma ago. The upper intercept of 4481Ma could date the early separation of the original L chondrite parent body into different families. [ABSTRACT FROM AUTHOR]

We present in situ microanalyses of Fe3+/ΣFe in mantle-derived kaersutites as measured by electron probe microanalysis (EMP) based on the "self absorption induced FeLα peak shift" method. The EMP results are not in agreement with bulk (wet chemistry) data. The heterogeneities revealed for some kaersutite megacrysts, when comparing bulk and EMP Fe3+/ΣFe results, cannot explain the differences with the EMP measurements. It is thus proposed that any EMP overestimation of Fe3+/ΣFe results from a beam-induced dehydrogenation and a subsequent oxidation of Fe2+ to Fe3+ according to the known relation: Fe2+ + OH- = Fe3+ + O2- + 1/2 H2. To demonstrate this phenomenon, H losses were measured by secondary ion mass spectrometry (SIMS) after EMP irradiation at different beam currents on two amphiboles with 1.1 and 1.7 wt% H2O, respectively. In both amphiboles, H losses were observed under high beam currents (240 and 100 nA). No dehydrogenation is observed under lower beam currents for the 1.1 wt% H2O amphibole, but still occurs, down to at least 50 nA, for the amphibole with the greatest H2O contents. Amphiboles with low H2O contents (below ~0.5 H+) are less affected by beam damage. For amphiboles with higher H2O contents, the electron beam current density should be reduced with consideration given to the resulting high statistical errors. [ABSTRACT FROM AUTHOR]

Detailed electron- and ion-microprobe analysis of diopsides extracted from a block of marble collected in the Mt. Marcy anorthosite massif (Adirondack Highlands, New York) shows that single crystals have preserved Al-Si zoning features from early contact metamorphism later modified by regional metamorphism. Diopsides show Al and Si complementary zoning from core to rim; average Al concentration in rims is constant (0.11 pfu), but values in the cores vary with crystals from 0.06 to 0.14 pfu. A δ18O profile measured with the ion microprobe shows no zoning. Modeling of the Al-diffusion profiles affected by regional metamorphism of the Grenville orogeny shows that original Al zoning was sharp and corresponds to a rapid change of crystal-growth conditions during early contact metamorphism: (1) diopside cores crystallized with variable Al contents due to restricted fluid circulation or differing sedimentary composition, (2) then pervasive fluid infiltration crystallized the homogeneous rim of diopside, and (3) core to rim Al zoning was later smoothed by granulite-facies metamorphism. Homogeneity of δ18O in core and mantle (near rim) of diopsides suggests that the crystals were isotopically homogeneous prior to and during regional metamorphism. Values of Al-Si diffusion coefficient deduced from modeling are in agreement with low-temperature extrapolation of experimental data. [ABSTRACT FROM AUTHOR]

The occurrence of rhyolite melts in the mantle has been predicted by high pressure-high temperature experiments but never observed in nature. Here we report natural quartz-bearing rhyolitic melt inclusions and interstitial glass within peridotite xenoliths. The oxygen isotope composition of quartz crystals shows the unequivocal continental crustal derivation of these melts, which approximate the minimum composition in the quartz-albite-orthoclase system. Thermodynamic modelling suggests rhyolite was originated from partial melting of near-anhydrous garnet-bearing metapelites at temperatures ~1000 °C and interacted with peridotite at pressure ~1 GPa. Reaction of rhyolite with olivine converted lherzolite rocks into orthopyroxene-domains and orthopyroxene + plagioclase veins. The recognition of rhyolitic melts in the mantle provides direct evidence for element cycling through earth's reservoirs, accommodated by dehydration and melting of crustal material, brought into the mantle by subduction, chemically modifying the mantle source, and ultimately returning to surface by arc magmatism., (© 2022. The Author(s).)

Lithium elemental and isotopic compositions of olivines in peridotite xenoliths from Hebi in the North China Craton provide direct evidence for the highly variable δ(7)Li in Archean lithospheric mantle. The δ(7)Li in the cores of olivines from the Hebi high-Mg# peridotites (Fo > 91) show extreme variation from -27 to +21, in marked deviation from the δ(7)Li range of fresh MORB (+1.6 to +5.6) although the Li abundances of the olivines are within the range of normal mantle (1-2 ppm). The Li abundances and δ(7)Li characteristics of the Hebi olivines could not have been produced by recent diffusive-driven isotopic fractionation of Li and therefore the δ(7)Li in the cores of these olivines record the isotopic signature of the subcontinental lithospheric mantle. Our data demonstrate that abnormal δ(7)Li may be preserved in the ancient lithospheric mantle as observed in our study from the central North China Craton, which suggest that the subcontinental lithospheric mantle has experienced modification of fluid/melt derived from recycled oceanic crust.