Disequilibrium reaction pathways and the twin-mediated growth of tabular forsterite during contact metamorphism of quartz-bearing dolomite.

The forsterite zone of the Ubehebe Peak contact aureole, Death Valley, USA consists of an outer zone of tabular/jack-straw olivine and an inner zone of subequant polyhedral olivine. Subequant polyhedral forsterite crystals close to the intrusion are small and tabular forsterite crystals farther away are larger. To investigate the formation of the two morphologies, forsterite growth experiments were conducted in cold seal pressure vessels in the CaO-MgO-SiO2-CO2-H2O system. Forsterite precipitation follows a disequilibrium reaction pathway made of three reactions: [1] tabular forsterite growth from quartz and dolomite, [2] forsterite growth from tremolite dissolution, and [3] subequant polyhedral forsterite growth from tabular forsterite dissolution. Initially, quartz reacts with dolomite to simultaneously form twinned tabular forsterite and tremolite. As quartz reacts away, forsterite precipitation continues at a slower rate through tremolite dissolution. A second generation of forsterite then precipitates on top of some tabular forsterite but has different habit and tracht. Once all the tremolite reacts away, subequant polyhedral forsterite precipitation continues at an even slower rate through dissolution of tabular forsterite. The tabular morphology of jack-straw olivine is a consequence of twin-mediated unidirectional growth; the abundance of twins being due to rapid nucleation and growth at initially high reaction affinities. Twin junctions are preferential nucleation centers for steps, so faceted growth is enhanced on {100}. This phenomenon is the twin plane re-entrant effect. Subequant polyhedral forsterite in the Ubehebe Peak inner contact aureole recrystallized and ripened from tabular forsterite. In the outer contact aureole, conditions were not conducive to recrystallization and ripening so well-developed tabular forsterite persists.

Identifying crustal contributions in the Patagonian Chon Aike Silicic Large Igneous Province.

The volcanic rocks of the Chon Aike Silicic Large Igneous Province (CASP) are recognized as magmas dominantly produced by crustal anatexis. Investigating the zircon of the CASP provides an opportunity to gain further insight into geochemical and isotopic differences of the potential magmatic sources (i.e., crust versus mantle), to identify crustal reservoirs that contributed to the felsic magmas during anatexis, and to quantify the contributions of the respective sources. We present a combined zircon oxygen and hafnium isotope and trace element dataset for 16 volcanic units of the two youngest volcanic phases in Patagonia, dated here with LA-ICP-MS U-Pb geochronology at ca. 148-153 Ma (El Quemado Complex, EQC) and ca. 159 Ma (western Chon Aike Formation, WCA). The EQC zircon have 18O-enriched values (δ18O from 7 to 9.5‰) with correspondingly negative initial εHf values (- 2.0 to - 8.0). The WCA zircon have δ18O values between 6 and 7‰ and εHf values ranging between - 4.0 and + 1.5. Binary δ18O-εHf mixing models require an average of 70 and 60% melt derived from partial melting of isotopically distinct metasedimentary basements for the EQC and WCA, respectively. Zircon trace element compositions are consistent with anatexis of sedimentary protoliths derived from LIL-depleted upper continental crustal sources. The overlap between a high heat flux environment (i.e., widespread extension and lithospheric thinning) during supercontinental breakup and a fertile metasedimentary crust was key in producing voluminous felsic volcanism via anatexis following the injection and emplacement of basaltic magmas into the lower crust. Supplementary Information: The online version contains supplementary material available at 10.1007/s00410-023-02065-1.

Rapid grain boundary diffusion in foraminifera tests biases paleotemperature records.

The oxygen isotopic compositions of fossil foraminifera tests constitute a continuous proxy record of deep-ocean and sea-surface temperatures spanning the last 120 million years. Here, by incubating foraminifera tests in 18O-enriched artificial seawater analogues, we demonstrate that the oxygen isotopic composition of optically translucent, i.e., glassy, fossil foraminifera calcite tests can be measurably altered at low temperatures through rapid oxygen grain-boundary diffusion without any visible ultrastructural changes. Oxygen grain boundary diffusion occurs sufficiently fast in foraminifera tests that, under normal upper oceanic sediment conditions, their grain boundaries will be in oxygen isotopic equilibrium with the surrounding pore fluids on a time scale of <100 years, resulting in a notable but correctable bias of the paleotemperature record. When applied to paleotemperatures from 38,400 foraminifera tests used in paleoclimate reconstructions, grain boundary diffusion can be shown to bias prior paleotemperature estimates by as much as +0.86 to -0.46 °C. The process is general and grain boundary diffusion corrections can be applied to other polycrystalline biocarbonates composed of small nanocrystallites (<100 nm), such as those produced by corals, brachiopods, belemnites, and molluscs, the fossils of which are all highly susceptible to the effects of grain boundary diffusion.

Fast and pervasive diagenetic isotope exchange in foraminifera tests is species-dependent.

Oxygen isotope compositions of fossil foraminifera tests are commonly used proxies for ocean paleotemperatures, with reconstructions spanning the last 112 million years. However, the isotopic composition of these calcitic tests can be substantially altered during diagenesis without discernible textural changes. Here, we investigate fluid-mediated isotopic exchange in pristine tests of three modern benthic foraminifera species (Ammonia sp., Haynesina germanica, and Amphistegina lessonii) following immersion into an 18O-enriched artificial seawater at 90 °C for hours to days. Reacted tests remain texturally pristine but their bulk oxygen isotope compositions reveal rapid and species-dependent isotopic exchange with the water. NanoSIMS imaging reveals the 3-dimensional intra-test distributions of 18O-enrichment that correlates with test ultra-structure and associated organic matter. Image analysis is used to quantify species level differences in test ultrastructure, which explains the observed species-dependent rates of isotopic exchange. Consequently, even tests considered texturally pristine for paleo-climatic reconstruction purposes may have experienced substantial isotopic exchange; critical paleo-temperature record re-examination is warranted.

Alpine peak pressure and tectono-metamorphic history of the Monte Rosa nappe: evidence from the cirque du Véraz, upper Ayas valley, Italy.

The Monte Rosa nappe consists of a wide range of lithologies that record conditions associated with peak Alpine metamorphism. While peak temperature conditions inferred from previous studies largely agree, variable peak pressures have been estimated for the Alpine high-pressure metamorphic event. Small volumes of whiteschist lithologies with the assemblage chloritoid + phengite + talc + quartz record peak pressures up to 0.6 GPa higher compared to associated metapelitic and metagranitic lithologies, which yield a peak pressure of ca. 1.6 GPa. The reason for this pressure difference is disputed, and proposed explanations include tectonic mixing of rocks from different burial depths (mélange) or local deviations of the pressure from the lithostatic value caused by heterogeneous stress conditions between rocks of contrasting mechanical properties. We present results of detailed field mapping, structural analysis and a new geological map for a part of the Monte Rosa nappe exposed at the cirque du Véraz field area (head of the Ayas valley, Italy). Results of the geological mapping and structural analysis shows the structural coherency within the western portions of the Monte Rosa nappe. This structural coherency falsifies the hypothesis of a tectonic mélange as reason for peak pressure variations. Structural analysis indicates two major Alpine deformation events, in agreement with earlier studies: (1) north-directed nappe emplacement, and (2) south-directed backfolding. We also analyze a newly discovered whiteschist body, which is located at the intrusive contact between Monte Rosa metagranite and surrounding metapelites. This location is different to previous whiteschist occurrences, which were entirely embedded within metagranite. Thermodynamic calculations using metamorphic assemblage diagrams resulted in 2.1 ± 0.2 GPa and 560 ± 20 °C for peak Alpine metamorphic conditions. These results agree with metamorphic conditions inferred for previously investigated nearby whiteschist outcrops embedded in metagranite. The new results, hence, confirm the peak pressure differences between whiteschists and the metagranite and metapelite. To better constrain the prograde pressure-temperature history of the whiteschist, we compare measured Mg zoning in chloritoid with Mg zoning predicted by fractional crystallization pseudo-section modelling for several hypothetical pressure-temperature paths. In order to reach a ca. 0.6 GPa higher peak pressure compared to the metapelite and metagranite, our results suggest that the whiteschist likely deviated from the prograde burial path recorded in metapelite and metagranite lithologies. However, the exact conditions at which the whiteschist pressure deviated are still contentious due to the strong temperature dependency of Mg partitioning in whiteschist assemblages. Our pseudo-section results suggest at least that there was no dramatic isothermal pressure increase recorded in the whiteschist.

The role of the antigorite + brucite to olivine reaction in subducted serpentinites (Zermatt, Switzerland).

Metamorphic olivine formed by the reaction of antigorite + brucite is widespread in serpentinites that crop out in glacier-polished outcrops at the Unterer Theodulglacier, Zermatt. Olivine overgrows a relic magnetite mesh texture formed during ocean floor serpentinization. Serpentinization is associated with rodingitisation of mafic dykes. Metamorphic olivine coexists with magnetite, shows high Mg# of 94-97 and low trace element contents. A notable exception is 4 µg/g Boron (> 10 times primitive mantle), introduced during seafloor alteration and retained in metamorphic olivine. Olivine incorporated 100-140 µg/g H2O in Si-vacancies, providing evidence for low SiO2-activity imposed by brucite during olivine growth. No signs for hydrogen loss or major and minor element diffusional equilibration are observed. The occurrence of olivine in patches within the serpentinite mimics the former heterogeneous distribution of brucite, whereas the network of olivine-bearing veins and shear zones document the pathways of the escaping fluid produced by the olivine forming reaction. Relic Cr-spinels have a high Cr# of 0.5 and the serpentinites display little or no clinopyroxene, indicating that they derive from hydrated harzburgitic mantle that underwent significant melt depletion. The enrichment of Mg and depletion of Si results in the formation of brucite during seafloor alteration, a pre-requisite for later subduction-related olivine formation and fluid liberation. The comparison of calculated bulk rock brucite contents in the Zermatt-Saas with average IODP serpentinites suggests a large variation in fluid release during olivine formation. Between 3.4 and 7.2 wt% H2O is released depending on the magnetite content in fully serpentinized harzburgites (average oceanic serpentinites). Thermodynamic modelling indicates that the fluid release in Zermatt occurred between 480 °C and 550 °C at 2-2.5 GPa with the Mg# of olivine varying from 68 to 95. However, the majority of the fluid released from this reaction was produced within a narrow temperature field of < 30 °C, at higher pressures 2.5 GPa and temperatures 550-600 °C than commonly thought. Fluids derived from the antigorite + brucite reaction might thus trigger eclogite facies equilibration in associated metabasalts, meta-gabbros, meta-rodingites and meta-sediments in the area. This focused fluid release has the potential to trigger intermediate depths earthquakes at 60-80 km in subducted oceanic lithosphere.

Source and fractionation controls on subduction-related plutons and dike swarms in southern Patagonia (Torres del Paine area) and the low Nb/Ta of upper crustal igneous rocks.

The subduction system in southern Patagonia provides direct evidence for the variability of the position of an active continental arc with respect to the subducting plate through time, but the consequences on the arc magmatic record are less well studied. Here we present a geochemical and geochronological study on small plutons and dykes from the upper crust of the southern Patagonian Andes at ~ 51°S, which formed as a result of the subduction of the Nazca and Antarctic plates beneath the South American continent. In situ U-Pb geochronology on zircons and bulk rock geochemical data of plutonic and dyke rocks are used to constrain the magmatic evolution of the retro-arc over the last 30 Ma. We demonstrate that these combined U-Pb and geochemical data for magmatic rocks track the temporal and spatial migration of the active arc, and associated retro-arc magmatism. Our dataset indicates that the rear-arc area is characterized by small volumes of alkaline basaltic magmas at 29-30 Ma that are characterized by low La/Nb and Th/Nb ratios with negligible arc signatures. Subsequent progressive eastward migration of the active arc culminated with the emplacement of calc-alkaline plutons and dikes ~ 17-16 Ma with elevated La/Nb and Th/Nb ratios and typical subduction signatures constraining the easternmost position of the southern Patagonian batholith at that time. Geochemical data on the post-16 Ma igneous rocks including the Torres del Paine laccolith indicate an evolution to transitional K-rich calc-alkaline magmatism at 12.5 ± 0.2 Ma. We show that trace element ratios such as Nb/Ta and Dy/Yb systematically decrease with increasing SiO2, for both the 17-16 Ma calc-alkaline and the 12-13 Ma K-rich transitional magmatism. In contrast, Th/Nb and La/Nb monitor the changes in the source composition of these magmas. We suggest that the transition from the common calc-alkaline to K-rich transitional magmatism involves a change in the source component, while the trace element ratios, such as Nb/Ta and Dy/Yb, of derivative higher silica content liquids are controlled by similar fractionating mineral assemblages. Analysis of a global compilation of Nb/Ta ratios of arc magmatic rocks and simple geochemical models indicate that amphibole and variable amounts of biotite exert a major control on the low Dy/Yb and Nb/Ta of derivative granitic liquids. Lastly, we suggest that the low Nb/Ta ratio of silica-rich magmas is a natural consequence of biotite fractionation and that alternative models such as amphibolite melting in subduction zones and diffusive fractionation are not required to explain the Nb/Ta ratio of the upper continental crust.