Fractionation of rare earth elements in greisen and hydrothermal veins related to A-type magmatism

This study focuses on concentrations and fractionation of rare earth elements (REE) in a variety of minerals and bulk materials of hydrothermal greisen and vein mineralization in Paleoproterozoic monzodiorite to granodiorite related to the intrusion of Mesoproterozoic alkali- and fluorine-rich granite. The greisen consists of coarse-grained quartz, muscovite, and fluorite, whereas the veins mainly contain quartz, calcite, epidote, chlorite, and fluorite in order of abundance. A temporal and thus genetic link between the granite and the greisen/veins is established via high spatial resolution in situ Rb-Sr dating, supported by several other isotopic signatures (δ34S, 87Sr/86Sr, δ18O, and δ13C). Fluid-inclusion microthermometry reveals that multiple pulses of moderately to highly saline aqueous to carbonic solutions caused greisenization and vein formation at temperatures above 200–250°C and up to 430°C at the early hydrothermal stage in the veins. Low calculated ∑REE concentration for bulk vein (15 ppm) compared to greisen (75 ppm), country rocks (173–224 ppm), and the intruding granite (320 ppm) points to overall low REE levels in the hydrothermal fluids emanating from the granite. This is explained by efficient REE retention in the granite via incorporation in accessory phosphates, zircon, and fluorite and unfavorable conditions for REE partitioning in fluids at the magmatic and early hydrothermal stages. A noteworthy feature is substantial heavy REE (HREE) enrichment of calcite in the vein system, in contrast to the relatively flat patterns of greisen calcite. The REE fractionation of the vein calcite is explained mainly by fractional crystallization, where the initially precipitated epidote in the veins preferentially incorporates most of the light REE (LREE) pool, leaving a residual fluid enriched in the HREE from which calcite precipitated. Fluorite occurs throughout the system and displays decreasing REE concentrations from granite towards greisen and veins and different fractionation patterns among all these three materials. Taken together, these features confirm efficient REE retention in the early stages of the system and minor control of the REE uptake by mineral-specific partitioning. REE-fractionation patterns and fluid-inclusion data suggest that chloride complexation dominated REE transport during greisenization, whereas carbonate complexation contributed to the HREE enrichment in vein calcite

Isotopic evidence for microbial production and consumption of methane in the upper continental crust throughout the Phanerozoic eon

Microorganisms produce and consume methane in terrestrial surface environments, sea sediments and, as indicated by recent discoveries, in fractured crystalline bedrock. These processes in the crystalline bedrock remain, however, unexplored both in terms of mechanisms and spatiotemporal distribution. Here we have studied these processes via a multi-method approach including microscale analysis of the stable isotope compositions of calcite and pyrite precipitated in bedrock fractures in the upper crust (down to 1.7 km) at three sites on the Baltic Shield. Microbial processes have caused an intriguing variability of the carbon isotopes in the calcites at all sites, with δ13C spanning as much as −93.1‰ (related to anaerobic oxidation of methane) to +36.5‰ (related to methanogenesis). Spatiotemporal coupling between the stable isotope measurements and radiometric age determinations (micro-scale dating using new high-spatial methods: LA-ICP-MS U–Pb for calcite and Rb–Sr for calcite and co-genetic adularia) enabled unprecedented direct timing constraints of the microbial processes to several periods throughout the Phanerozoic eon, dating back to Devonian times. These events have featured variable fluid salinities and temperatures as shown by fluid inclusions in the calcite; dominantly 70–85 °C brines in the Paleozoic and lower temperatures (<50–62 °C) and salinities in the Mesozoic. Preserved organic compounds, including plant signatures, within the calcite crystals mark the influence of organic matter in descending surficial fluids on the microbial processes in the fracture system, thus linking processes in the deep and surficial biosphere. These findings substantially extend the recognized temporal and spatial range for production and consumption of methane within the upper continental crust

Constraining the timing of veins, faults and fractures in crystalline rocks by in situ Rb-Sr geochronology

Precambrian cratons are continent cores archiving the oldest crustal histories on Earth. The crystalline basement of cratons is typically characterized by complex arrays of multiple fracture and fault generations hosting minerals formed by fluids flowing through fracture networks. Disentangling absolute chronologies of the various fracturing, faulting and fluid flow events have to date been difficult given the micro-scale mineral intergrowths and zonations, inhibiting conventional dating techniques. In the general lack of age constraints, deformation and mineralization mechanisms cannot be attributed to specific tectonic regimes, hampering reconstruction of local and regional events of fluid flow and mineral precipitation, and ultimately of the geological evolution of cratons. This thesis presents diverse studies utilizing the radiogenic decay of fracture, fault and shear zone mineral assemblages sampled from the crystalline basement of the Fennoscandian Shield, aiming at detecting episodic fracturing reactivation, mineralization and microbial processes throughout the craton history. The analytical procedures involve, foremost, Rb-Sr geochronology, along with U-Pb and (U-Th)/He geochronology, stable isotope and trace element geochemistry, fluid inclusion thermometry and biomarkers. The in situ age determinations enabled 1) linking of greisen and distal veins to magmatic and post-magmatic fluid circulation, 2) slickenfibre growth to distinct faulting episodes, and 3) mineral precipitation in fractures, veins and shear zones to regionally extending deformation events across the Fennoscandian Shield. In addition, dating of mineralization related to deep fracture-hosted microbial life constrained the timing of such activity at several sites. The precipitation episodes stretch from Paleoproterozoic to Jurassic times with overgrowth generations separated in time by up to one billion years in single veins and even within individual crystals. The findings of the thesis demonstrate that the methodological protocol has potential to directly date a wide range of mineral assemblages in fractures, faults, veins and shear zones given that the isochron requirements are fulfilled. Fulfillment is ensured through detailed petrological and structural characterization followed by geochronological analysis and thorough data reduction allowing validation of isotopic data down to submicrometer level. The outcomes have implications for tectonic reconstructions at various scales, for the tracing of the deep ancient biosphere and for comprehending hydrothermal ore deposition, with direct societal relevance in the detection of ancient microbial activity and fracture reactivation at the candidate site for a spent nuclear fuel repository in Sweden

Constraining the timing of veins, faults and fractures in crystalline rocks by in situ Rb-Sr geochronology

Precambrian cratons are continent cores archiving the oldest crustal histories on Earth. The crystalline basement of cratons is typically characterized by complex arrays of multiple fracture and fault generations hosting minerals formed by fluids flowing through fracture networks. Disentangling absolute chronologies of the various fracturing, faulting and fluid flow events have to date been difficult given the micro-scale mineral intergrowths and zonations, inhibiting conventional dating techniques. In the general lack of age constraints, deformation and mineralization mechanisms cannot be attributed to specific tectonic regimes, hampering reconstruction of local and regional events of fluid flow and mineral precipitation, and ultimately of the geological evolution of cratons. This thesis presents diverse studies utilizing the radiogenic decay of fracture, fault and shear zone mineral assemblages sampled from the crystalline basement of the Fennoscandian Shield, aiming at detecting episodic fracturing reactivation, mineralization and microbial processes throughout the craton history. The analytical procedures involve, foremost, Rb-Sr geochronology, along with U-Pb and (U-Th)/He geochronology, stable isotope and trace element geochemistry, fluid inclusion thermometry and biomarkers. The in situ age determinations enabled 1) linking of greisen and distal veins to magmatic and post-magmatic fluid circulation, 2) slickenfibre growth to distinct faulting episodes, and 3) mineral precipitation in fractures, veins and shear zones to regionally extending deformation events across the Fennoscandian Shield. In addition, dating of mineralization related to deep fracture-hosted microbial life constrained the timing of such activity at several sites. The precipitation episodes stretch from Paleoproterozoic to Jurassic times with overgrowth generations separated in time by up to one billion years in single veins and even within individual crystals. The findings of the thesis demonstrate that the methodological protocol has potential to directly date a wide range of mineral assemblages in fractures, faults, veins and shear zones given that the isochron requirements are fulfilled. Fulfillment is ensured through detailed petrological and structural characterization followed by geochronological analysis and thorough data reduction allowing validation of isotopic data down to submicrometer level. The outcomes have implications for tectonic reconstructions at various scales, for the tracing of the deep ancient biosphere and for comprehending hydrothermal ore deposition, with direct societal relevance in the detection of ancient microbial activity and fracture reactivation at the candidate site for a spent nuclear fuel repository in Sweden

Ancient Microbial Activity in Deep Hydraulically Conductive Fracture Zones within the Forsmark Target Area for Geological Nuclear Waste Disposal, Sweden

Recent studies reveal that organisms from all three domains of life—Archaea, Bacteria, and even Eukarya—can thrive under energy-poor, dark, and anoxic conditions at large depths in the fractured crystalline continental crust. There is a need for an increased understanding of the processes and lifeforms in this vast realm, for example, regarding the spatiotemporal extent and variability of the different processes in the crust. Here, we present a study that set out to detect signs of ancient microbial life in the Forsmark area—the target area for deep geological nuclear waste disposal in Sweden. Stable isotope compositions were determined with high spatial resolution analyses within mineral coatings, and mineralized remains of putative microorganisms were studied in several deep water-conducting fracture zones (down to 663 m depth), from which hydrochemical and gas data exist. Large isotopic variabilities of δ13Ccalcite (−36.2 to +20.2‰ V-PDB) and δ34Spyrite (−11.7 to +37.8‰ V-CDT) disclose discrete periods of methanogenesis, and potentially, anaerobic oxidation of methane and related microbial sulfate reduction at several depth intervals. Dominant calcite–water disequilibrium of δ18O and 87Sr/86Sr precludes abundant recent precipitation. Instead, the mineral coatings largely reflect an ancient archive of episodic microbial processes in the fracture system, which, according to our microscale Rb–Sr dating of co-genetic adularia and calcite, date back to the mid-Paleozoic. Potential Quaternary precipitation exists mainly at ~400 m depth in one of the boreholes, where mineral–water compositions corresponded

Zircon, titanite, and apatite (U-Th)/He ages and age-eU correlations from the Fennoscandian Shield, southern Sweden

Craton cores far from plate boundaries have traditionally been viewed as stable features that experience minimal vertical motion over 100-1000Ma time scales. Here we show that the Fennoscandian Shield in southeastern Sweden experienced several episodes of burial and exhumation from similar to 1800Ma to the present. Apatite, titanite, and zircon (U-Th)/He ages from surface samples and drill cores constrain the long-term, low-temperature history of the Laxemar region. Single grain titanite and zircon (U-Th)/He ages are negatively correlated (104-838Ma for zircon and 160-945Ma for titanite) with effective uranium (eU=U+0.235xTh), a measurement proportional to radiation damage. Apatite ages are 102-258Ma and are positively correlated with eU. These correlations are interpreted with damage-diffusivity models, and the modeled zircon He age-eU correlations constrain multiple episodes of heating and cooling from 1800Ma to the present, which we interpret in the context of foreland basin systems related to the Neoproterozoic Sveconorwegian and Paleozoic Caledonian orogens. Inverse time-temperature models constrain an average burial temperature of similar to 217 degrees C during the Sveconorwegian, achieved between 944Ma and 851Ma, and similar to 154 degrees C during the Caledonian, achieved between 366Ma and 224Ma. Subsequent cooling to near-surface temperatures in both cases could be related to long-term exhumation caused by either postorogenic collapse or mantle dynamics related to the final assembly of Rodinia and Pangaea. Our titanite He age-eU correlations cannot currently be interpreted in the same fashion; however, this study represents one of the first examples of a damage-diffusivity relationship in this system, which deserves further research attention.6 month embargo; published online: 15 July 2017This item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at [email protected]

In Situ Rb/Sr Geochronology and Stable Isotope Geochemistry Evidence for Neoproterozoic and Paleozoic Fracture‐Hosted Fluid Flow and Microbial Activity in Paleoproterozoic Basement, SW Sweden

Recent studies have shown that biosignatures of ancient microbial life exist in mineral coatings in deep bedrock fractures of Precambrian cratons, but such surveys have been few and far between. Here, we report results from southwestern Sweden in an area of 1.6–1.5 Ga Paleoproterozoic rocks heavily reworked by the 1.14–0.96 Ga Sveconorwegian orogeny, a terrane previously scarcely explored for ancient microbial biosignatures. Calcite-pyrite-adularia-illite-coated fractures were analyzed for stable isotopes via Secondary Ion Mass Spectrometry (δ13C, δ18O, δ34S) and in situ Rb/Sr geochronology via Laser-ablation inductively coupled plasma mass spectrometry. The Rb/Sr ages for calcite-adularia and calcite-illite show that several fluid flow events can be discerned (797 ± 18–769 ± 7, 391 ± 5–387 ± 6, 356 ± 5–347 ± 4, and 301 ± 7 Ma). The δ13C, δ18O and 87Sr/86Sr values of different calcite growth zones further confirmed episodic fluid flow. Pyrite δ34S values down to −49.9‰V-CDT, together with systematically increased δ34S from crystal core to rim, suggest formation following microbial sulfate reduction under semi-closed conditions. Assemblages involving MSR-related pyrite generally have Devonian to Permian Rb/Sr ages, indicating an association to extension-related fracturing and fluid mixing during foreland-basin formation linked to Caledonian orogeny in the northwest. An assemblage with an age of 301 ± 7 Ma is potentially related to Oslo Rift extension, whereas the Neo-Proterozoic ages relate to post-Sveconorwegian extensional tectonics. Remnants of short-chained fatty acids in the youngest calcite coatings further indicate a biogenic origin, while the absence of organic molecules in older calcite is in line with thermal degradation, potentially related to heating during Caledonian foreland basin burial

Re-Evaluating the Age of Deep Biosphere Fossils in the Lockne Impact Structure

Impact-generated hydrothermal systems have been suggested as favourable environments for deep microbial ecosystems on Earth, and possibly beyond. Fossil evidence from a handful of impact craters worldwide have been used to support this notion. However, as always with mineralized remains of microorganisms in crystalline rock, certain time constraints with respect to the ecosystems and their subsequent fossilization are difficult to obtain. Here we re-evaluate previously described fungal fossils from the Lockne crater (458 Ma), Sweden. Based on in-situ Rb/Sr dating of secondary calcite-albite-feldspar (356.6 &#177; 6.7 Ma) we conclude that the fungal colonization took place at least 100 Myr after the impact event, thus long after the impact-induced hydrothermal activity ceased. We also present microscale stable isotope data of 13C-enriched calcite suggesting the presence of methanogens contemporary with the fungi. Thus, the Lockne fungi fossils are not, as previously thought, related to the impact event, but nevertheless have colonized fractures that may have been formed or were reactivated by the impact. Instead, the Lockne fossils show similar features as recent findings of ancient microbial remains elsewhere in the fractured Swedish Precambrian basement and may thus represent a more general feature in this scarcely explored habitat than previously known

In situ Rb-Sr dating of slickenfibres in deep crystalline basement faults

Establishing temporal constraints of faulting is of importance for tectonic and seismicity reconstructions and predictions. Conventional fault dating techniques commonly use bulk samples of syn-kinematic illite and other K-bearing minerals in fault gouges, which results in mixed ages of repeatedly reactivated faults as well as grain-size dependent age variations. Here we present a new approach to resolve fault reactivation histories by applying high-spatial resolution Rb-Sr dating to fine-grained mineral slickenfibres in faults occurring in Paleoproterozoic crystalline rocks. Slickenfibre illite and/or K-feldspar together with co-genetic calcite and/or albite were targeted with 50 µm laser ablation triple quadrupole inductively coupled plasma mass spectrometry analyses (LA-ICP-MS/MS). The ages obtained disclose slickenfibre growth at several occasions spanning over 1 billion years, from at least 1527 Ma to 349 ± 9 Ma. The timing of these growth phases and the associated structural orientation information of the kinematic indicators on the fracture surfaces are linked to far-field tectonic events, including the Caledonian orogeny. Our approach links faulting to individual regional deformation events by minimizing age mixing through micro-scale analysis of individual grains and narrow crystal zones in common fault mineral assemblages