Indentor-escape, delamination and orogenic collapse of the ca. 600-500 Ma East African/Antarctic Orogen in Mozambique and Dronning Maud Land (East Antarctica)

The East African/Antarctic Orogen (EAAO) is one of the largest orogenic belts on the planet, resulting from the collision of various parts of East and West- Protogondwana between ca. 600 and 550 Ma. The central and southern parts of the orogen are typified by high-grade rocks, representing the overprinted margins of the various colliding continental blocks. New fieldwork and geochronology in northern Mozambique reveals a protracted polyphase Ediacaran/Cambrian deformation history. New age constraints reveal high-grade metamorphism at 600-550 Ma, overprinting and older basement

Importance of water for Archaean granitoid petrology: a comparative study of TTG and potassic granitoids from Barberton Mountain Land, South Africa

A new model for Archaean granitoid magmatism is presented which reconciles the most important geochemical similarities and differences between tonalite-trondhjemite-granodiorite (TTG) and potassic granitoids. Trace element abundances reveal a strong arc magmatism signature in all studied granitoids from Barberton Mountain Land. Characteristic features include HFSE depletion as well as distinct enrichment peaks of fluid-sensitive trace elements such as Pb in N-MORB normalisation, clearly indicating that all studied granitoids are derived from refertilised mantle above subduction zones. We envisage hydrous basaltic (s.l.) melts as parental liquids, which underwent extensive fractional crystallisation. Distinctive residual cumulates evolved depending on initial water content. High-H2O melts crystallised garnet/amphibole together with pyroxenes and minor plagioclase, but no olivine. This fractionation path ultimately led to TTG-like melts. Less hydrous basaltic melts also crystallised garnet/amphibole, but the lower compatible element content indicates that olivine was also a liquidus phase. Pronounced negative Eu-anomalies of the granitic melts, correlating with Na, Ca and Al, indicate plagioclase to be of major importance. In the context of our model, the post-Archaean disappearance of TTG and concomitant preponderance of granites (s.l.), therefore, is explained with secular decrease of aqueous fluid transport into subduction zones and/or efficiency of deep fluid release from slab

Der Vierkanthof und seine Bedeutung

Die Diplomarbeit "Der Vierkanthof und seine Bedeutung. Nutzungswandel und Entwicklungstendenzen eines landschaftsprägenden und identitätsstiftenden Kulturgutes" beschäftigt sich mit der gegenwärtigen Situation und der heutigen Bedeutung der Vierkanthöfe. Mit Hilfe theoretischer Grundlagen (Haus- und Gehöftforschung, Begriffsdefinitionen, Konzept der raumbezogenen Identität, etc.), aber vor allem auch mit qualitativen Interviews (ExpertInnen und HofbesitzerInnen), sowie einer abschließenden Analyse konnten Erkenntnisse zur Veränderung und zur gegenwärtigen Nutzung der Vierkanthöfe, zu diesbezügliche Herausforderungen für HofbesitzerInnen, zu möglichen Entwicklungstendenzen, sowie Erkenntnisse zur Bedeutung der Vierkanthöfe für die Region und die Menschen gewonnen werden. Entstanden aus der landwirtschaftlichen Nutzung verändert sich der Vierkanthof aufgrund vieler Faktoren (z.B. Strukturwandel, EU-Politik und veränderte Bedürfnisse der HofbewohnerInnen). Immer mehr nicht-landwirtschaftliche Nutzungen finden sich in dem Gebäude (z.B. Büros, Gewerbe, Tourismus, etc.) und verändern auch sein Aussehen. Im Leader-Projekt "Vierkanter" thematisieren drei Leader-Regionen das regionaltypische Gebäude. Anhand der Leader-Region "Tourismusverband Moststraße" und dem Projekt wird im Rahmen dieser Arbeit auch gezeigt, wie der Vierkanter aufgrund seiner guten Gestaltqualität und seiner Besonderheiten auch einen Beitrag zur Regionalentwicklung, zur Identität und zur stärkeren Bindung an die Region beitragen kann. Der Vierkanthof befindet sich seit jeher im Wandel. Verändern sich die Vierkanthöfe schneller und radikaler, hat das auch Auswirkungen auf das Aussehen der Kulturlandschaft. Jede Generation muss für sich entscheiden, wie sie mit Kulturlandschaft und den darin enthaltenen Elementen umgeht und was erhalten werden soll. Aus diesem Grund bilden die Handlugen der HofbesitzerInnen und der BewohnerInnen der Region bezüglich der Vierkanthöfe auch die Grundlage für zukünftige Generationen und die zukünftige Kulturlandschaft

Dating Polygenetic Metamorphic Assemblages along a Transect across the Western Alps

Multichronometric analyses were performed on samples from a transect in the French-Italian Western Alps crossing nappes derived from the Briançonnais terrane and the Piemonte-Liguria Ocean, in an endeavour to date both high-pressure (HP) metamorphism and retrogression history. Twelve samples of white mica were analysed by 39Ar-40Ar stepwise heating, complemented by two samples from the Monte Rosa nappe 100 km to the NE and also attributed to the Briançonnais terrane. One Sm-Nd and three Lu-Hf garnet ages from eclogites were also obtained. White mica ages decrease from c. 300 Ma in the westernmost samples (Zone Houillère), reaching c. 300°C during Alpine metamorphism, to 6·45 atoms per formula unit increases eastward. Across the whole traverse, phengitic mica grown during HP metamorphism defines the D1 foliation. Syn-D2 mica is more Si-poor and associated with nappe stacking, exhumation, and hydrous retrogression under greenschist-facies conditions. Syn-D1 phengite is very often corroded, overgrown by, or intergrown with, syn-D2 muscovite. Most importantly, syn-D2 recrystallization is not limited to S2 schistosity domains; micrometre-scale chemical fingerprinting reveals muscovite pseudomorphs after phengite crystals, which could be mistaken for syn-D1 mica based on microstructural arguments alone. The Cl/K ratio in white mica is a useful discriminator, as D2 retrogression was associated with a less saline fluid than eclogitization. As petrology exerts the main control on the isotope record, constraining the petrological and microstructural framework is necessary to correctly interpret the geochronological data, described in both the present study and the literature. Our approach, which ties geochronology to detailed geochemical, petrological and microstructural investigations, identifies 47-48 Ma as the age of HP formation of syn-D1 mica along the studied transect and in the Monte Rosa area. Cretaceous apparent mica ages, which were proposed to date eclogitization by earlier studies based on conventional ‘thermochronology', are due to Ar inheritance in incompletely recrystallized detrital mica grains. The inferred age of the probably locally diachronous, greenschist-facies, low-Si, syn-D2 mica ranges from 39 to 43 Ma. Coexistence of D1 and D2 ages, and the constancy of non-reset D1 ages along the entire transect, provides strong evidence that the D1 white mica ages closely approximate formation ages. Volume diffusion of Ar in white mica (activation energy E = 250 kJ mol−1; pressure-adjusted diffusion coefficient D'0 < 0·03 cm2 s−1) has a subordinate effect on mineral ages compared with both prograde and retrograde recrystallization in most sample

Exploiting the Lability of Metal Halide Perovskites for Doping Semiconductor Nanocomposites

Cesium lead halides have intrinsically unstable crystal lattices and easily transform within perovskite and nonperovskite structures. In this work, we explore the conversion of the perovskite CsPbBr3 into Cs4PbBr6 in the presence of PbS at 450 °C to produce doped nanocrystal-based composites with embedded Cs4PbBr6 nanoprecipitates. We show that PbBr2 is extracted from CsPbBr3 and diffuses into the PbS lattice with a consequent increase in the concentration of free charge carriers. This new doping strategy enables the adjustment of the density of charge carriers between 1019 and 1020 cm-3, and it may serve as a general strategy for doping other nanocrystal-based semiconductors.M.C. has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie Grant Agreement No. 665385. ICN2 acknowledges funding from Generalitat de Catalunya 2017 SGR 327. ICN2 is supported by the Severo Ochoa program from Spanish MINECO (Grant No. SEV-2017-0706) and is funded by the CERCA Programme/Generalitat de Catalunya. This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 823717 – ESTEEM3. M.V.K. acknowledges the support by the European Research Council under the Horizon 2020 Framework Program (ERC Consolidator Grant SCALE-HALO Grant Agreement No. 819740) and by FET-OPEN project no. 862656 (DROP-IT)

Geochemische Klassifikation und Sm-Nd Isotopensystematik proterozoischer Metasedimente des Baltischen Schildes (Västervik Region, SESchweden)

Die Västervik Region liegt an einer Haupt-Terran-Grenze im Baltischen Schild. Im NE schließen sich die Einheiten des Südsvecofennischen Vulkanitgürtels mit Altern >1,85Ga an, im SW folgen die Granitoide des Transskandinavischen Magmatitgürtles (TMZ) mit Altern <1,85Ga. Die Metasedimente der Västervik Formation bilden die stratigraphisch älteste Einheit der Västervik Region. Ihre Stellung in Bezug auf die svecofennischen Metasedimente des Bothnischen Beckens ist noch unklar. Sie können nach ihren mineralogischen Paragenesen in vier Gruppen klassifiziert werden: reine Quarzite, glimmerführende Quarzite, Glimmerquarzite und quarzitische Gneise. Vermutlich zeitgleich mit der Intrusion der großvolumigen Granitoidmagmen ab 1.85 Ga wurde die Västervik Formation amphibolitfaziell überprägt. Dies führte innerhalb der Metasedimente zur Bildung von Cordierit, Sillimanit und Andalusit sowie akzessorischem Granat. Der Beginn der Sedimentation ist begrenzt durch das Vorkommen detritischer Zirkone mit Altern ab 1.87Ga. Etwa 75% der gemessenen detritische Zirkone zeigt eine Altersgruppierung von 1,8 bis 2,1 Ga, die restlichen 25% zeigen archaische U/Pb-Alter von 2,8 bis 3,0 Ga (Claesson et al. 1993, Sultan et al. 2005). Die Nd-Isotopensignaturen der Proben zeigen eine sehr homogene Mischung und Schüttung der Sedimente mit subparallelem Verlauf der Nd- Entwicklungslinien und einem sehr engen TDM (Nd) Altersspektrum von 2,2 bis 2,4Ga. Diese Ergebnisse deuten auf ein konstantes Mischungsverhältnis von proterozoischen und archaischen Anteilen hin...conferenc

Pervasively anoxic surface conditions at the onset of the Great Oxidation Event: new multi-proxy constraints from the Cooper Lake paleosol

Oceanic element inventories derived from marine sedimentary rocks place important constraints on oxidative continental weathering in deep time, but there remains a scarcity in complementary observations directly from continental sedimentary reservoirs. This study focuses on better defining continental weathering conditions near the Archean-Proterozoic boundary through the multi-proxy (major and ultra-trace element, Fe and Cr stable isotopes, μ-XRF elemental mapping, and detrital zircon U-Pb geochronology) investigation of the ca. 2.45 billion year old (giga annum, Ga) Cooper Lake paleosol (saprolith), developed on a sediment-hosted mafic dike within the Huronian Supergroup (Ontario, Canada). Throughout the variably altered Cooper Lake saprolith, ratios of immobile elements (Nb, Ta, Zr, Hf, Th, Al, Ti) are constant, indicating a uniform pre-alteration dike composition, lack of extreme pH weathering conditions, and no major influence from ligand-rich fluids during weathering or burial metasomatism/metamorphism. The loss of Mg, Fe, Na, Sr, and Li, a signature of albite and ferromagnesian silicate weathering, increases towards the top of the preserved profile (unconformity) and dike margins. Coupled bulk rock behaviour of Fe-Mg-Mn and co-localization of Fe- Mn in clay minerals (predominantly chlorite) indicates these elements were solubilized primarily in their divalent state without Fe/Mn-oxide formation. A lack of a Ce anomaly and immobility of Mo, V, and Cr further support pervasively anoxic weathering conditions. Subtle U enrichment is the only geochemical evidence, if primary, that could be consistent with oxidative element mobilization. The leaching of ferromagnesian silicates was accompanied by variable mobility and depletion of transition metals with a relative depletion order of Fe≈Mg≈Zn\u3eNi\u3eCo\u3eCu (Cu being significantly influenced by secondary sulfide formation). Mild enrichment of heavy Fe isotopes (δ56/54Fe from 0.169 to 0.492 ‰) correlating with Fe depletion in the saprolith indicates loss of isotopically light aqueous Fe(II). Minor REE+Y fractionation with increasing alteration intensity, including a decreasing Eu anomaly and Y/Ho ratio, is attributed to albite breakdown and preferential scavenging of HREE\u3eY by clay minerals, respectively. Younger metasomatism resulted in the addition of several elements (K, Rb, Cs, Be, Tl, Ba, Sn, In, W), partly or wholly obscuring their earlier paleo-weathering trends. The behavior of Cr at Cooper Lake can help test previous hypotheses of an enhanced, low pH-driven continental weathering flux of Cr(III) to marine reservoirs between ca. 2.48-2.32 Ga and the utility of the stable Cr isotope proxy of Mn-oxide induced Cr(III) oxidation. Synchrotron μ- XRF maps and invariant Cr/Nb ratios reveal complete immobility of Cr despite its distribution amongst both clay-rich groundmass and Fe-Ti oxides. Assuming a pH-dependent, continental source of Cr(III) to marine basins, the Cr immobility at Cooper Lake indicates either that signatures of acidic surface waters were localized to uppermost and typically unpreserved regolith horizons or were geographically restricted to acid-generating point sources. However, in given detrital pyrite preservation in fluvial sequences overlying the paleosol, we propose that the oxidative sulphide corrosion required to drive surface pH(δ53/52Cr: -0.321 ± 0.038 ‰, 2sd, n=34) that cannot be linked to Cr(III) oxidation and is instead interpreted to have a magmatic origin. The combined chemical signatures and continued preservation of detrital pyrite/uraninite indicate low atmospheric O2 during weathering at ca. 2.45 Ga preserved in the rift-related sedimentary rocks of the Lower Huronian. The aqueous flux from the reduced weathering of mafic rocks was characterized by a greater abundance of transition metals (Fe, Mn, Zn, Co, Ni) with isotopically light Fe(II), as well as higher Eu/Eu* and Y/Ho. In most models of Precambrian ocean element inventories, hydrothermal fluids are viewed as the main supplier of several metals (e.g., Fe, Zn), although the results herein suggest that a riverine metal supply may have been substantial and that using Eu-excess as a strict proxy for hydrothermal flux may be misleading in near-shore marine sedimentary environments

The importance of surface adsorbates in solution-processed thermoelectric materials: the case of SnSe

Solution synthesis of particles emerges as an alternative to prepare thermoelectric materials with less demanding processing conditions than conventional solid-state synthetic methods. However, solution synthesis generally involves the presence of additional molecules or ions belonging to the precursors or added to enable solubility and/or regulate nucleation and growth. These molecules or ions can end up in the particles as surface adsorbates and interfere in the material properties. This work demonstrates that ionic adsorbates, in particular Na+ ions, are electrostatically adsorbed in SnSe particles synthesized in water and play a crucial role not only in directing the material nano/microstructure but also in determining the transport properties of the consolidated material. In dense pellets prepared by sintering SnSe particles, Na remains within the crystal lattice as dopant, in dislocations, precipitates, and forming grain boundary complexions. These results highlight the importance of considering all the possible unintentional impurities to establish proper structure–property relationships and control material properties in solution-processed thermoelectric materials.Peer ReviewedPostprint (author's final draft

Iron Isotope Fractionation during Fe(II) Oxidation Mediated by the Oxygen-Producing Marine Cyanobacterium Synechococcus PCC 7002

In this study, we couple iron isotope analysis to microscopic and mineralogical investigation of iron speciation during circumneutral Fe(II) oxidation and Fe(III) precipitation with photosynthetically produced oxygen. In the presence of the cyanobacterium Synechococcus PCC 7002, aqueous Fe(II) (Fe(II)aq) is oxidized and precipitated as amorphous Fe(III) oxyhydroxide minerals (iron precipitates, Feppt), with distinct isotopic fractionation (ε56Fe) values determined from fitting the δ56Fe(II)aq (1.79‰ and 2.15‰) and the δ56Feppt (2.44‰ and 2.98‰) data trends from two replicate experiments. Additional Fe(II) and Fe(III) phases were detected using microscopy and chemical extractions and likely represent Fe(II) and Fe(III) sorbed to minerals and cells. The iron desorbed with sodium acetate (FeNaAc) yielded heavier δ56Fe compositions than Fe(II)aq. Modeling of the fractionation during Fe(III) sorption to cells and Fe(II) sorption to Feppt, combined with equilibration of sorbed iron and with Fe(II)aq using published fractionation factors, is consistent with our resulting δ56FeNaAc. The δ56Feppt data trend is inconsistent with complete equilibrium exchange with Fe(II)aq. Because of this and our detection of microbially excreted organics (e.g., exopolysaccharides) coating Feppt in our microscopic analysis, we suggest that electron and atom exchange is partially suppressed in this system by biologically produced organics. These results indicate that cyanobacteria influence the fate and composition of iron in sunlit environments via their role in Fe(II) oxidation through O2 production, the capacity of their cell surfaces to sorb iron, and the interaction of secreted organics with Fe(III) minerals