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

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

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

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

Silicon and chromium stable isotopic systematics during basalt weathering and lateritisation: A comparison of variably weathered basalt profiles in the Deccan Traps, India

Global biomass production is fundamentally affected by the hydrological cycling of elements at the Earth's surface. Continental weathering processes are the major source for most bio-essential elements in marine environments and therefore affect primary productivity. In addition, critical zone biomass depends on energy and chemical exchange reactions in weathering profiles. The latter reservoirs are in turn influenced by different climatic conditions that control weathering and pore water parameters like pH and Eh, which regulate mineral break down rates and dictate the mobility and mass flux of elements. Two Deccan Traps basalt weathering profiles of contrasting age and alteration intensity provide a natural laboratory for investigating the effects of rock alteration on Si and Cr and their isotopic. systematics. The Quaternary Chhindwara profile has progressed to a moderate degree of alteration (saprolite), while the Paleogene Bidar example displays an extremely altered laterite. The Chhindwara saprolite profile shows a near uniform Cr and Si concentration and isotopic composition, whereas the Bidar laterite profile is characterised by an intense loss of Si, a large enrichment of Cr within the most altered uppermost levels, and a wide range of Cr stable isotope ratios (-0.85 to 0.36 parts per thousand delta Cr-53/52). A co-variation between Si and Cr isotopes, as well as their co-variation with iron content, provides empirical evidence that iron redistribution within the profile has a large effect on Cr mobility and Si isotopic fractionation. Therefore, it is concluded that iron oxides exert a primary control over the isotopic composition of both Cr and Si in pore waters of laterites. Since laterite formation is promoted by tropical climates, the results of this study provide new evidence to suggest that the hydrological Cr and Si fluxes originating from continental weathering have changed in accordance with large-scale, deep time climate variation and continental plate configuration. An increased flux of Si and greater magnitude of Cr mobility and isotopic fractionation are possibly amplified under CO2-rich, greenhouse episodes and/or when large landmasses were tectonically arranged at near equatorial latitudes