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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.
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)
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.
In subduction zones, sediments and hydrothermally altered oceanic crust, which together form part of the subducting slab, contribute to the chemical composition of lavas erupted at the surface to form volcanic arcs. Transport of this material from the slab to the overlying mantle wedge is thought to involve discreet melts and fluids that are released from various portions of the slab. We use a meta-analysis of geochemical data from eight globally representative arcs to show that melts and fluids from individual slab components cannot be responsible for the formation of arc lavas. Instead, the data are compatible with models that first invoke physical mixing of slab components and the mantle wedge, widely referred to as high-pressure mélange, before arc magmas are generated.
Titanite is a potentially powerful U–Pb petrochronometer that may record metamorphism, metasomatism, and deformation. Titanite may also incorporate significant inherited Pb, which may lead to inaccurate and geologically ambiguous U–Pb dates if a proper correction is not or cannot be applied. Here, we present laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)-derived titanite U–Pb dates and trace element concentrations for two banded calcsilicate gneisses from south-central Maine, USA (SSP18-1A and SSP18-1B). Single spot common Pb-corrected dates range from 400 to 280 Ma with ±12–20 Ma propagated 2SE. Titanite grains in sample SSP18-1B exhibit regular core-to-rim variations in texture, composition, and date. We identify four titanite populations: (1) 397 ± 5 Ma (95% CL) low Y + HREE cores and mottled grains, (2) 370 ± 7 Ma high Y + REE mantles and cores, (3) 342 ± 6 Ma cores with high Y + REE and no Eu anomaly, and (4) 295 ± 6 Ma LREE-depleted rims. We interpret the increase in titanite Y + HREE between ca. 397 and ca. 370 Ma to constrain the timing of diopside fracturing and recrystallization and amphibole breakdown. Apparent Zr-in-titanite temperatures (803 ± 36°C at 0.5 ± 0.2 GPa) and increased XDi suggest a thermal maximum at ca. 370 Ma. Population 3 domains dated to ca. 342 Ma exhibit no Eu anomaly and are observed only in compositional bands dominated by diopside (>80 vol%), suggesting limited equilibrium between titanite and plagioclase. Finally, low LREE and high U/Th in Population 4 titanite dates the formation of hydrous phases, such as allanite, during high XH2O fluid infiltration at ca. 295 Ma. In contrast to the well-defined date–composition–texture relationships observed for titanite from SSP18-1B, titanite grains from sample SSP18-1A exhibit complex zoning patterns and little correlation between texture, composition, and date. We hypothesize that the incorporation of variable amounts of radiogenic Pb from dissolved titanite into recrystallized domains resulted in mixed dates spanning 380–330 Ma. Although titanite may reliably record multiple phases of metamorphism, these data highlight the importance of considering U–Pb data along with chemical and textural data to screen for inherited radiogenic Pb.
Reliable identification of chondrules, calcium-aluminum-rich inclusions (CAIs), carbonate grains, and Ca-phosphate grains at depth within untouched, unprepared chondritic samples by a nondestructive analytical method, such as synchrotron X-ray fluorescence (SXRF) computed tomography (CT), is an essential first step before intrusive analytical and sample preparation methods are performed. The detection of a local Ca-enrichment could indicate the presence of such a component, all of which contain Ca as major element and/or Ca-bearing minerals, allowing it to be precisely located at depth within a sample. However, the depth limitation from which Ca-K fluorescence can travel through a chondrite sample (e.g., ∼115 µm through material of 1.5 g cm−3) to XRF detectors leaves many Ca-bearing components undetected at deeper depths. In comparison, Sr-K lines travel much greater distances (∼1700 µm) through the same sample density and are, thus, detected from much greater depths. Here, we demonstrate a clear, positive, and preferential correlation between Ca and Sr and conclude that Sr-detection can be used as proxy for the presence of Ca (and, thus, Ca-bearing components) throughout mm-sized samples of carbonaceous chondritic material. This has valuable implications, especially for sample return missions from carbonaceous C-type asteroids, such as Ryugu or Bennu. Reliable localization, identification, and targeted analysis by SXRF of Ca-bearing chondrules, CAIs, and carbonates at depth within untouched, unprepared samples in the initial stages of a multianalysis investigation insures the valuable information they hold of pre- and post-accretion processes in the early solar system is neither corrupted nor destroyed in subsequent processing and analyses.