Rb-Sr and in situ 40Ar/39Ar dating of exhumation-related shearing and fluid-induced recrystallization in the Sesia zone (Western Alps, Italy)

The Sesia zone in the Italian Western Alps is a piece of continental crust that has been subducted to eclogite-facies conditions and records a complex metamorphic history. The exact timing of events and the significance of geochronological information are debated due to the interplay of tectonic, metamorphic, and metasomatic processes. Here we present new geochronological data using Rb-Sr internal mineral isochrons and in situ Ar-40/Ar-39 laser ablation data to provide constraints on the relative importance of fluid-mediated mineral replacement reactions and diffusion for the interpretation of radiogenic isotope signatures, and on the use of these isotopic systems for dating metamorphic and variably deformed rocks. Our study focuses on the shear zone at the contact between two major lithological units of the Sesia zone, the eclogitic micaschists and the gneiss minuti. Metasedimentary rocks of the eclogitic micaschists unit contain phengite with step-like zoning in major element chemistry as evidence for petrologic disequilibrium. Distinct Ar-40/Ar-39 spot ages of relict phengite cores and over-printed rims demonstrate the preservation of individual age domains in the crystals. The eclogitic micaschists also show systematic Sr isotope disequilibria among different phengite populations, so that minimum ages of relict assemblage crystallization can be differentiated from the timing of late increments of deformation. The preservation of these disequilibrium features shows the lack of diffusive re-equilibration and underpins that fluid-assisted dissolution and recrystallization reactions are the main factors controlling the isotope record in these subduction-related metamorphic rocks. Blueschist-facies mylonites record deformation along the major shear zone that separates the eclogitic micaschists from the gneiss minuti. Two Rb-Sr isochrones that comprise several white mica fractions and glaucophane constrain the timing of this deformation and accompanying near-complete blueschist-facies re-equilibration of the Rb-Sr system to 60.1 +/- 0.9 Ma and 60.9 +/- 2.1 Ma, respectively. Overlapping ages in eclogitic micaschists of 60.1 +/- 1.1 (Rb-Sr isochron of sheared matrix assemblage), 58.6 +/- 0.8, and 60.9 +/- 0.4 Ma (white mica Ar-40/Ar-39 inverse isochron ages) support the significance of this age and show that fluid-rock interaction and partial re-equilibration occurred as much as several kilometers away from the shear zone. An earlier equilibration during high-pressure conditions in the eclogitic mica schists is recorded in minimum Rb-Sr ages for relict assemblages (77.2 +/- 0.8 and 72.4 +/- 1.1 Ma) and an Ar-40/Ar-39 inverse isochron age of 75.4 +/- 0.8 Ma for white mica cores, again demonstrating that the two isotope systems provide mutually supporting geochronological information. Local reactivation and recrystallization along the shear zone lasted >15 m.y., as late increments of deformation are recorded in a greenschist-facies mylonite by a Rb-Sr isochron age of 46.5 +/- 0.7 Ma

EarthN: A new Earth System Nitrogen Model

The amount of nitrogen in the atmosphere, oceans, crust, and mantle have important ramifications for Earth's biologic and geologic history. Despite this importance, the history and cycling of nitrogen in the Earth system is poorly constrained over time. For example, various models and proxies contrastingly support atmospheric mass stasis, net outgassing, or net ingassing over time. In addition, the amount available to and processing of nitrogen by organisms is intricately linked with and provides feedbacks on oxygen and nutrient cycles. To investigate the Earth system nitrogen cycle over geologic history, we have constructed a new nitrogen cycle model: EarthN. This model is driven by mantle cooling, links biologic nitrogen cycling to phosphate and oxygen, and incorporates geologic and biologic fluxes. Model output is consistent with large (2-4x) changes in atmospheric mass over time, typically indicating atmospheric drawdown and nitrogen sequestration into the mantle and continental crust. Critical controls on nitrogen distribution include mantle cooling history, weathering, and the total Bulk Silicate Earth+atmosphere nitrogen budget. Linking the nitrogen cycle to phosphorous and oxygen levels, instead of carbon as has been previously done, provides new and more dynamic insight into the history of nitrogen on the planet.Comment: 36 pages, 12 figure

Effects of fluid-rock interaction on 40Ar/39Ar geochronology in high-pressure rocks (Sesia-Lanzo Zone, Western Alps)

Author Posting. © The Author(s), 2013. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 126 (2014):475-494, doi:10.1016/j.gca.2013.10.023.in situ UV laser spot 40Ar/39Ar analyses of distinct phengite types in eclogite-facies rocks from the Sesia-Lanzo Zone (Western Alps, Italy) were combined with SIMS boron isotope analyses as well as boron (B) and lithium (Li) concentration data to link geochronological information with constraints on fluid-rock interaction. In weakly deformed samples, apparent 40Ar/39Ar ages of phengite cores span a range of ∼20 Ma, but inverse isochrons define two distinct main high-pressure (HP) phengite core crystallization periods of 88-82 Ma and 77-74 Ma, respectively. The younger cores have on average lower B contents (∼36 mg/g) than the older ones (∼43-48 mg/g), suggesting that loss of B and resetting of the Ar isotopic system were related. Phengite cores have variable d11B values (-18 to -10 ‰), indicating the lack of km scale B homogenization during HP crystallization. Overprinted phengite rims in the weakly deformed samples generally yield younger apparent 40Ar/39Ar ages than the respective cores. They also show variable effects of heterogeneous excess 40Ar incorporation and Ar loss. One acceptable inverse isochron age of 77.1 ±1.1 Ma for rims surrounding older cores (82.6 ±0.6 Ma) overlaps with the second period of core crystallization. Compared to the phengite cores, all rims have lower B and Li abundances but similar d11B values (-15 to -9 ‰), reflecting internal redistribution of B and Li and internal fluid buffering of the B isotopic composition during rim growth. The combined observation of younger 40Ar/39Ar ages and boron loss, yielding comparable values of both parameters only in cores and rims of different samples, is best explained by a selective metasomatic overprint. In low permeability samples, this overprint caused recrystallization of phengite rims, whereas higher permeability in other samples led to complete recrystallization of phengite grains. Strongly deformed samples from a several km long, blueschist-facies shear zone contain mylonitic phengite that forms a tightly clustered group of relatively young apparent 40Ar/39Ar ages (64.7 to 68.8 Ma), yielding an inverse isochron age of 65.0 ±3.0 Ma. Almost complete B and Li removal in mylonitic phengite is due to leaching into a fluid. The B isotopic composition is significantly heavier than in phengites from the weakly deformed samples, indicating an external control by a high-d11B fluid (d11B = +7 ±4 ‰). We interpret this result as reflecting phengite recrystallization related to deformation and associated fluid flow in the shear zone. This event also caused partial resetting of the Ar isotope system and further B loss in more permeable rocks of the adjacent unit. We conclude that geochemical evidence for pervasive or limited fluid flow is crucial for the interpretation of 40Ar/39Ar data in partially metasomatized rocks.Funding of this work by the Deutsche Forschungsgemeinschaft (grant KO-3750/2-1) is gratefully acknowledged

Fluid-induced breakdown of white mica controls nitrogen transfer during fluid–rock interaction in subduction zones

Author Posting. © The Author(s), 2016. This is the author's version of the work. It is posted here by permission of Taylor & Francis for personal use, not for redistribution. The definitive version was published in International Geology Review 59 (2017): 702-720, doi:10.1080/00206814.2016.1233834.In order to determine the effects of fluid–rock interaction on nitrogen elemental and isotopic systematics in high-pressure metamorphic rocks, we investigated three different profiles representing three distinct scenarios of metasomatic overprinting. A profile from the Chinese Tianshan (ultra)high-pressure–low-temperature metamorphic belt represents a prograde, fluid-induced blueschist–eclogite transformation. This profile shows a systematic decrease in N concentrations from the host blueschist (~26 μg/g) via a blueschist–eclogite transition zone (19–23 μg/g) and an eclogitic selvage (12–16 μg/g) towards the former fluid pathway. Eclogites and blueschists show only a small variation in δ15Nair (+2.1 ± 0.3‰), but the systematic trend with distance is consistent with a batch devolatilization process. A second profile from the Tianshan represents a retrograde eclogite–blueschist transition. It shows increasing, but more scattered, N concentrations from the eclogite towards the blueschist and an unsystematic variation in δ15N values (δ15N = + 1.0 to +5.4‰). A third profile from the high-P/T metamorphic basement complex of the Southern Armorican Massif (Vendée, France) comprises a sequence from an eclogite lens via retrogressed eclogite and amphibolite into metasedimentary country rock gneisses. Metasedimentary gneisses have high N contents (14–52 μg/g) and positive δ15N values (+2.9 to +5.8‰), and N concentrations become lower away from the contact with 11–24 μg/g for the amphibolites, 10–14 μg/g for the retrogressed eclogite, and 2.1–3.6 μg/g for the pristine eclogite, which also has the lightest N isotopic compositions (δ15N = + 2.1 to +3.6‰). Overall, geochemical correlations demonstrate that phengitic white mica is the major host of N in metamorphosed mafic rocks. During fluid-induced metamorphic overprint, both abundances and isotopic composition of N are controlled by the stability and presence of white mica. Phengite breakdown in high-P/T metamorphic rocks can liberate significant amounts of N into the fluid. Due to the sensitivity of the N isotope system to a sedimentary signature, it can be used to trace the extent of N transport during metasomatic processes. The Vendée profile demonstrates that this process occurs over several tens of metres and affects both N concentrations and N isotopic compositions.Support of this project was partly provided by National Science Foundation grant EAR-0711355 to GEB.2017-10-1

Effects of fluid-rock interaction on Ar-40/Ar-39 geochronology in high-pressure rocks (Sesia-Lanzo Zone, Western Alps)

In situ UV laser spot 40Ar/39Ar analyses of distinct phengite types in eclogite-facies rocks from the Sesia-Lanzo Zone (Western Alps, Italy) were combined with SIMS boron isotope analyses as well as boron (B) and lithium (Li) concentration data to link geochronological information with constraints on fluid–rock interaction. In weakly deformed samples, apparent 40Ar/39Ar ages of phengite cores span a range of ∼20 Ma, but inverse isochrons define two distinct main high-pressure (HP) phengite core crystallization periods of 88–82 and 77–74 Ma, respectively. The younger cores have on average lower B contents (∼36 μg/g) than the older ones (∼43–48 μg/g), suggesting that loss of B and resetting of the Ar isotopic system were related. Phengite cores have variable δ11B values (−18‰ to −10‰), indicating the lack of km scale B homogenization during HP crystallization. Overprinted phengite rims in the weakly deformed samples generally yield younger apparent 40Ar/39Ar ages than the respective cores. They also show variable effects of heterogeneous excess 40Ar incorporation and Ar loss. One acceptable inverse isochron age of 77.1 ± 1.1 Ma for rims surrounding older cores (82.6 ± 0.6 Ma) overlaps with the second period of core crystallization. Compared to the phengite cores, all rims have lower B and Li abundances but similar δ11B values (−15‰ to −9‰), reflecting internal redistribution of B and Li and internal fluid buffering of the B isotopic composition during rim growth. The combined observation of younger 40Ar/39Ar ages and boron loss, yielding comparable values of both parameters only in cores and rims of different samples, is best explained by a selective metasomatic overprint. In low permeability samples, this overprint caused recrystallization of phengite rims, whereas higher permeability in other samples led to complete recrystallization of phengite grains. Strongly deformed samples from a several km long, blueschist-facies shear zone contain mylonitic phengite that forms a tightly clustered group of relatively young apparent 40Ar/39Ar ages (64.7–68.8 Ma), yielding an inverse isochron age of 65.0 ± 3.0 Ma. Almost complete B and Li removal in mylonitic phengite is due to leaching into a fluid. The B isotopic composition is significantly heavier than in phengites from the weakly deformed samples, indicating an external control by a high-δ11B fluid (δ11B = +7 ± 4‰). We interpret this result as reflecting phengite recrystallization related to deformation and associated fluid flow in the shear zone. This event also caused partial resetting of the Ar isotope system and further B loss in more permeable rocks of the adjacent unit. We conclude that geochemical evidence for pervasive or limited fluid flow is crucial for the interpretation of 40Ar/39Ar data in partially metasomatized rocks

Large-scale database mining reveals hidden trends and future directions for cancer immunotherapy

LLC Cancer immunotherapy has fundamentally changed the landscape of oncology in recent years and significant resources are invested into immunotherapy research. It is in the interests of researchers and clinicians to identify promising and less promising trends in this field in order to rationally allocate resources. This requires a quantitative large-scale analysis of cancer immunotherapy related databases. We developed a novel tool for text mining, statistical analysis and data visualization of scientific literature data. We used this tool to analyze 72002 cancer immunotherapy publications and 1469 clinical trials from public databases. All source codes are available under an open access license. The contribution of specific topics within the cancer immunotherapy field has markedly shifted over the years. We show that the focus is moving from cell-based therapy and vaccination towards checkpoint inhibitors, with these trends reaching statistical significance. Rapidly growing subfields include the combination of chemotherapy with checkpoint blockade. Translational studies have shifted from hematological and skin neoplasms to gastrointestinal and lung cancer and from tumor antigens and angiogenesis to tumor stroma and apoptosis. This work highlights the importance of unbiased large-scale database mining to assess trends in cancer research and cancer immunotherapy in particular. Researchers, clinicians and funding agencies should be aware of quantitative trends in the immunotherapy field, allocate resources to the most promising areas and find new approaches for currently immature topics

Deciphering the Jurassic–Cretaceous evolution of the Hamadan metamorphic complex during Neotethys subduction, western Iran

The Hamadan high-grade metapelites in the northwestern part of the Sanandaj–Sirjan zone, Iran, show a polymetamorphic evolution with relics of a garnet-bearing metamorphic mineral assemblage (M1), a contact metamorphic overprint (M2) related to the emplacement of the Middle to Late Jurassic Alvand composite pluton and a Buchan-type regional metamorphic event (M3) marked by 40Ar/39Ar ages in the 80–70 Ma range that is associated with penetrative ductile deformation producing a foliation and a thermal overprint onto the M2 assemblages. The M1 event is exclusively preserved as small garnet grains and mineral inclusions contained therein, incorporated into M2-stage cordierite porphyroblasts. Distinct metamorphic zones are developed over a region of ~ 600 km2, which are partly correlated with distance to the composite pluton: zones (1) cordierite + K-feldspar hornfels, and (2) andalusite ± cordierite hornfels that surround the Alvand composite pluton at a distance of up to 5 km. These two zones are clearly related to M2 metamorphism associated with pluton emplacement. Zones (3) staurolite schist, (4) andalusite schist, and (5) sillimanite schist are found outside of the contact aureole and are considered to be the result of regional M3 metamorphism in the eastern part distant to the Alvand composite pluton. Conventional thermobarometry shows that temperatures in the area vary between ~ 560 and 660 °C for zones 1 and 2 and ~ 490 and 690 °C for zones 3–5. Phase equilibria modelling in the MnNCKFMASHT system indicates two distinct isobaric prograde paths at low pressures, at ~ 2.7 kbar for zones 1 and 2 and slightly higher pressures of around 3.5–5.5 kbar for zones 3–5. U–Th–Pb monazite geochronology revealed overlapping ages of 168 ± 11 Ma and 149 ± 19 Ma in the hornfels (1 and 2) and schistose (3–5) zones, respectively. These ages are similar to the intrusion age of the Alvand composite pluton (153.3 ± 2.7 to 166.5 ± 1.8 Ma) and are interpreted to reflect heating due to the emplacement of the composite pluton (M2 contact metamorphic event). However, 40Ar/39Ar dating of white mica and amphibole yielded plateau ages ranging from 80 to 69 Ma over the entire transect. The formation of schistosity in zones 3–5 postdates the intrusion and is thus related to M3 metamorphism. The white mica fabric indicates formation of the foliation during M3 garnet growth, which is followed by local retrogression of garnet to chlorite during exhumation. Consequently, the 40Ar/39Ar white mica and amphibole ages likely indicate reheating during M3 to more than ca. 500 ± 25 °C (argon retention temperature in amphibole). These data establish the occurrence of a Cretaceous, Buchan-style regional metamorphic event that had not been firmly identified before. Subsequent Late Cretaceous exhumation of the Hamadan complex with its high-grade metapelites is due to extension along the Tafrijan–Mangavi–Kandelan fault, which represents a major ductile low-angle normal fault. Metamorphic temperatures coupled with mineral ages from this and published work suggest a fast stage of cooling with a rate of ~ 6 °C/Ma during exhumation after M3 metamorphism

Magmatic and metasomatic effects of magma-carbonate interaction recorded in calc-silicate xenoliths from Merapi volcano (Indonesia)

Magma-carbonate interaction is an increasingly recognised process occurring at active volcanoes worldwide, with implications for the magmatic evolution of the host volcanic systems, their eruptive behaviour, volcanic CO2 budgets, and economic mineralisation. Abundant calc-silicate skarn xenoliths are found at Merapi volcano, Indonesia. We identify two distinct xenolith types: magmatic skarn xenoliths, which contain evidence of formation within the magma, and exoskarn xenoliths, which more likely represent fragments of crystalline metamorphosed wall-rocks. The magmatic skarn xenoliths comprise distinct compositional and mineralogical zones with abundant Ca-enriched glass (up to 10 wt% relative to lava groundmass), mineralogically dominated by clinopyroxene (En15-43Fs14-36Wo41-51) + plagioclase (An37-100) ± magnetite in the outer zones towards the lava contact and by wollastonite ± clinopyroxene (En17-38Fs8-34Wo49-59) ± plagioclase (An46-100) ± garnet (Grs0-65Adr24-75Sch0-76) ± quartz in the xenolith cores. These zones are controlled by Ca transfer from the limestone protolith to the magma and by transfer of magma-derived elements in the opposite direction. In contrast, the exoskarn xenoliths are unzoned and essentially glass-free, representing equilibration at sub-solidus conditions. The major mineral assemblage in the exoskarn xenoliths is wollastonite + garnet (Grs73-97Adr3-24) + Ca-Al-rich clinopyroxene (CaTs0-38) + anorthite ± quartz, with variable amounts of either quartz or melilite (Geh42-91) + spinel. Thermobarometric calculations, fluid inclusion microthermometry and newly calibrated oxybarometry based on Fe3+/ΣFe in clinopyroxene indicate magmatic skarn xenolith formation conditions of ∼850 ± 45 °C, < 100 MPa and at an oxygen fugacity between the NNO and HM buffer. The exoskarn xenoliths, in turn, formed at 510-910 °C under oxygen fugacity conditions between NNO and air. These high oxygen fugacities are likely imposed by the large volumes of CO2 liberated from the carbonate. Halogen and sulphur-rich mineral phases in the xenoliths testify to the infiltration by a magmatic brine. In some xenoliths this is associated with the precipitation of copper-bearing mineral phases by sulphur dissociation into sulphide and sulphate, indicating potential mineralisation in the skarn system below Merapi. Compositions of many xenolith clinopyroxene and plagioclase crystals overlap with that of magmatic minerals, suggesting that the crystal cargo in Merapi magmas may contain a larger proportion of skarn-derived xenocrysts than previously recognised. Assessment of xenolith formation timescales demonstrates that magma-carbonate interaction and associated CO2 release could affect eruption intensity, as recently suggested for Merapi and similar carbonate-hosted volcanoes elsewhere

Earth’s Nitrogen and Carbon Cycles

Understanding the Earth’s geological nitrogen (N) and carbon (C) cycles is fundamental for assessing the distribution of these volatiles between solid Earth (core, mantle and crust), oceans and atmosphere. This Special Communication about the Earth’s N and C cycles contains material that is relevant for researchers who are interested in the Topical Collection on planetary evolution “Reading Terrestrial Planet Evolution in Isotopes and Element Measurements”. Variations in the fluxes of N and C between these major reservoirs through geological time influenced the evolution and determined the unique composition of the Earth’s atmosphere. Here we review several key geological aspects of the N and C cycles of which our understanding has significantly advanced during the last decade through field-based, experimental and theoretical studies. Subduction zones are the most important pathway of both N and C from the Earth’s surface into the deep Earth. A key question in the flux quantification is how much of the volatile elements is stored in the downgoing slab and introduced into the mantle and how much is returned back to the surface and the atmosphere through arc magmatism. For N, the retention of N as-bearing minerals determines whether N is predominantly retained in the slab to mantle depths (in subduction zones with a low geothermal gradient) or devolatilized (in subduction zones with a high geothermal gradient). Several lines of evidence suggest that the mantle is regassing with respect to N due to a net influx of subducted N over time, but this issue is highly debated and evidence to the contrary also exists. Nevertheless, there is consensus that the majority of the planetary N budget is stored in the Earth’s mantle, with the continental crust also constituting a significant N reservoir. For C, release from the subducting slab occurs through decarbonation reactions, dissolution and formation of carbonatitic liquids, but reprecipitation of C in the slab or the forearc mantle wedge may limit the effectiveness of direct return of C into the atmosphere. Carbon release through regional metamorphism in collision zone orogens also has potentially profound effects on C release into the atmosphere and consensus has emerged that such orogens are sources rather than sinks of atmospheric CO. On shorter timescales, contact metamorphism through interaction of mantle-derived magmas with C-bearing country rocks, and the resulting release of large quantities of CH and/or CO, has been linked to global warming events