Discovery of Ordovician–Silurian metamorphic monazite in garnet metapelites of the Alpine External Aiguilles Rouges Massif

The pre-Mesozoic, mainly Variscan metamorphic basement of the Col de Bérard area (Aiguilles Rouges Massif, External domain) consists of paragneisses and micaschists together with various orthogneisses and metabasites. Monazite in metapelites was analysed by the electron microprobe (EMPA-CHIME) age dating method. The monazites in garnet micaschists are dominantly of Variscan age (330–300 Ma). Garnet in these rocks displays well developed growth zonations in Fe–Mg–Ca–Mn and crystallized at maximal temperatures of 670°C/7 kbar to the west and 600°C/7–8 kbar to the east. In consequence the monazite is interpreted to date a slightly pressure-dominated Variscan amphibolite-facies evolution. In mylonitic garnet gneisses, large metamorphic monazite grains of Ordovician–Silurian (~440 Ma) age but also small monazite grains of Variscan (~300 Ma) age were discovered. Garnets in the mylonitic garnet gneisses display high-temperature homogenized Mg-rich profiles in their cores and crystallized near to ~800°C/6 kbar. The Ordovician–Silurian-age monazites can be assigned to a pre-Variscan high-temperature event recorded by the homogenised garnets. These monazite age data confirm Ordovician–Silurian and Devonian–Carboniferous metamorphic cycles which were already reported from other Alpine domains and further regions in the internal Variscides.     

Geochronological and isotopic records of crustal storage and assimilation in the Wolverine Creek–Conant Creek system,Heise eruptive centre,Snake River Plain

Understanding the processes of differentiation of the Yellowstone–Snake River Plain (YSRP) rhyolites is typically impeded by the apparent lack of erupted intermediate compositions as well as the complex nature of their shallow interaction with the surrounding crust responsible for their typically low O isotopic ratios. A pair of normal-δ¹⁸O rhyolitic eruptions from the Heise eruptive centre in eastern Idaho, the Wolverine Creek Tuff and the Conant Creek Tuff, represent unique magmatic products of the Yellowstone hotspot preserving abundant vestiges of the intermediate differentiation steps leading to rhyolite generation. We address both shallow and deep processes of magma generation and storage in the two units by combining high-precision ID–TIMS U–Pb zircon geochronology, trace element, O and Hf isotopic studies of zircon, and Sr isotopic analyses of individual high-Mg# pyroxenes inherited from lower- to mid-crustal differentiation stages. The zircon geochronology confirms the derivation of both tuffs from the same rhyolitic magma reservoir erupted at 5.5941 ± 0.0097 Ma, preceded by at least 92 ± 14 ky of continuous or intermittent zircon saturation approximating the length of pre-eruptive magma accumulation in the upper crust. Some low-Mg# pyroxenes enclosing zircons predate the eruption by at least 45 ± 27 ky, illustrating the co-crystallisation of major and accessory phases in the near-liquidus rhyolitic melts of the YSRP over a significant period of time. Coeval zircon crystals are isotopically heterogeneous (two populations at εHf ~?5 and ?13), requiring the assembly of isotopically distinct melt pockets directly prior to, or during, the eruption. The primitive Mg# 60–90 pyroxenes are out of isotopic equilibrium with the host rhyolitic melt (⁸⁷Sr/⁸⁶Sr_i = 0.70889), covering a range of ⁸⁷Sr/⁸⁶Sr_i = 0.70705–0.70883 corresponding to ratios typical of the most radiogenic YSRP basalts to the least radiogenic YSRP rhyolites. Together with the low εHf in zircon, the Sr isotopic ratios illustrate limited assimilation dominated by radiogenic Archean crustal source materials incorporated into variably evolved YSRP melts as they progress towards rhyolitic compositions by assimilation–fractional crystallisation.     

Catalytic peptide hydrolysis by mineral surface: Implications for prebiotic chemistry

The abiotic polymerization of amino acids may have been important for the origin of life, as peptides may have been components of the first self-replicating systems. Though amino acid concentrations in the primitive oceans may have been too dilute for significant oligomerization to occur, mineral surface adsorption may have provided a concentration mechanism. As unactivated amino acid polymerization is thermodynamically unfavorable and kinetically slow in aqueous solution, we studied mainly the reverse reaction of polymer degradation to measure the impact of mineral surface catalysis on peptide bonds.Aqueous glycine (G), diglycine (GG), diketopiperazine (DKP), and triglycine (GGG) were reacted with minerals (calcite, hematite, montmorillonite, pyrite, rutile, or amorphous silica) in the presence of 0.05 M, pH 8.1, KHCO₃ buffer and 0.1 M NaCl as background electrolyte in a thermostatted oven at 25, 50 or 70 °C. Below 70 °C, reaction kinetics were too sluggish to detect catalytic activity over amenable laboratory time-scales. Minerals were not found to have measurable effects on the degradation or elongation of G, GG or DKP at 70 °C in solution. At 70 °C pyrite was the most catalytic mineral with detectible effects on the degradation of GGG, although several others also displayed catalytic behavior. GGG degraded ∼1.5-4 times faster in the presence of pyrite than in control reactions, depending on the ratio of solution concentration to mineral surface area. The rate of pyrite catalysis of GGG hydrolysis was found to be saturable, suggesting the presence of discrete catalytic sites on the mineral surface. The mineral-catalyzed degradation of GGG appears to occur via a GGG → DKP + G mechanism, rather than via GGG → GG + G, as in solution-phase reactions. These results are compatible with many previous findings and suggest that minerals may have assisted in peptide synthesis in certain geological settings, specifically by speeding the approach to equilibrium in environments where amino acids were already highly concentrated, but that minerals may not significantly alter the expected solution-phase equilibria. Thus the abiotic synthesis of long peptides may have required activating agents, dry heating at higher temperatures, or some form of phase separation.     

Phosphorus retention in calcareous soils and the effect of organic matter on its mobility

A survey of the interactions between phosphorus (P) species and the components of calcareous soils shows that both surface reactions and precipitation take place, especially in the presence of calcite and limestone. The principal products of these reactions are dicalcium phosphate and octacalcium phosphate, which may interconvert after formation. The role of calcium carbonate in P retention by calcareous soils is, however, significant only at relatively high P concentrations – non-carbonate clays play a more important part at lower concentrations. In the presence of iron oxide particles, occlusion of P frequently occurs in these bodies, especially with forms of the element that are pedogenic in origin. Progressive mineralization and immobilization, often biological in nature, are generally observed when P is added as a fertilizer.     

Petrology,geochemistry and U–Pb geochronology of magmatic rocks from the high-sulfidation epithermal Au–Cu Chelopech deposit,Srednogorie zone,Bulgaria

The Chelopech deposit is one of the largest European gold deposits and is located 60 km east of Sofia, within the northern part of the Panagyurishte mineral district. It lies within the Banat–Srednegorie metallogenic belt, which extends from Romania through Serbia to Bulgaria. The magmatic rocks define a typical calc-alkaline suite. The magmatic rocks surrounding the Chelopech deposit have been affected by propylitic, quartz–sericite, and advanced argillic alteration, but the igneous textures have been preserved. Alteration processes have resulted in leaching of Na₂O, CaO, P₂O₅, and Sr and enrichment in K₂O and Rb. Trace element variation diagrams are typical of subduction-related volcanism, with negative anomalies in high field strength elements (HFSE) and light element, lithophile elements. HFSE and rare earth elements were relatively immobile during the hydrothermal alteration related to ore formation. Based on immobile element classification diagrams, the magmatic rocks are andesitic to dacitic in compositions. Single zircon grains, from three different magmatic rocks spanning the time of the Chelopech magmatism, were dated by high-precision U–Pb geochronology. Zircons of an altered andesitic body, which has been thrust over the deposit, yield a concordant ²⁰⁶Pb/²³⁸U age of 92.21 ± 0.21 Ma. This age is interpreted as the crystallization age and the maximum age for magmatism at Chelopech. Zircon analyses of a dacitic dome-like body, which crops out to the north of the Chelopech deposit, give a mean ²⁰⁶Pb/²³⁸U age of 91.95 ± 0.28 Ma. Zircons of the andesitic hypabyssal body hosting the high-sulfidation mineralization and overprinted by hydrothermal alteration give a concordant ²⁰⁶Pb/²³⁸U age of 91.45 ± 0.15 Ma. This age is interpreted as the intrusion age of the andesite and as the maximum age of the Chelopech epithermal high-sulfidation deposit. ¹⁷⁶Hf/¹⁷⁷Hf isotope ratios of zircons from the Chelopech magmatic rocks, together with published data on the Chelopech area and the about 92-Ma-old Elatsite porphyry–Cu deposit, suggest two different magma sources in the Chelopech–Elatsite magmatic area. Magmatic rocks associated with the Elatsite porphyry–Cu deposit and the dacitic dome-like body north of Chelopech are characterized by zircons with ɛHf_T90 values of ∼5, which suggest an important input of mantle-derived magma. Some zircons display lower ɛHf_T90 values, as low as −6, and correlate with increasing ²⁰⁶Pb/²³⁸U ages up to about 350 Ma, suggesting assimilation of basement rocks during magmatism. In contrast, zircon grains in andesitic rocks from Chelopech are characterized by homogeneous ¹⁷⁶Hf/¹⁷⁷Hf isotope ratios with ɛHf_T90 values of ∼1 and suggest a homogeneous mixed crust–mantle magma source. We conclude that the Elatsite porphyry–Cu and the Chelopech high-sulfidation epithermal deposits were formed within a very short time span and could be partly contemporaneous. However, they are related to two distinct upper crustal magmatic reservoirs, and they cannot be considered as a genetically paired porphyry–Cu and high-sulfidation epithermal related to a single magmatic–hydrothermal system centered on the same intrusion.     

Rutile occurrence and trace element behavior in medium-grade metasedimentary rocks: example from the Erzgebirge, Germany

Metamorphic textures in medium-grade (~500–550°C) metasedimentary rocks from the Erzgebirge give evidence of prograde rutile crystallization from ilmenite. Newly-crystallized grains occur as rutile-rich polycrystalline aggregates that pseudomorph the shape of the ilmenites. In-situ trace element data (EMP and SIMS) show that rutiles from the higher-grade samples record large scatter in Nb content and have Nb/Ti ratios higher than coexisting ilmenite. This behavior can be predicted using prograde rutile crystallization from ilmenite and indicates that rutiles are reequilibrating their chemistry with remaining ilmenites. On the contrary, rutiles from the lowest grade samples (~480°C) have Nb/Ti ratios that are similar to the ones in ilmenite. Hence, rutiles from these samples did not equilibrate their chemistry with remaining ilmenites. Our data suggest that temperature may be one of the main factors determining whether or not the elements are able to diffuse between the phases and, therefore, reequilibrate. Newly-crystallized rutiles yield temperatures (from ~500 to 630°C, Zr-in-rutile thermometry) that are in agreement with the metamorphic conditions previously determined for the studied rocks. In quartzites from the medium-grade domain (~530°C), inherited detrital rutile grains are detected. They are identified by their distinct chemical composition (high Zr and Nb contents) and textures (single grains surrounded by fine grained ilmenites). Preliminary calculation, based on grain size distribution of rutile in medium-grade metapelites and quartzites that occur in the studied area, show that rutiles derived from quartzites can be anticipated to dominate the detrital rutile population, even if quartzites are a minor component of the exposure.     

Polar Low genesis over the North Pacific under different global warming scenarios

Following an earlier climatological study of North Pacific Polar Lows by employing dynamical downscaling of NCEP1 reanalysis in the regional climate model COSMO-CLM, the characteristics of Polar Low genesis over the North Pacific under different global warming scenarios are investigated. Simulations based on three scenarios from the Special Report on Emissions Scenarios were conducted using a global climate model (ECHAM5) and used to examine systematic changes in the occurrence of Polar Lows over the twenty first century. The results show that with more greenhouse gas emissions, global air temperature would rise, and the frequency of Polar Lows would decrease. With sea ice melting, the distribution of Polar Low genesis shows a northward shift. In the scenarios with stronger warming there is a larger reduction in the number of Polar Lows.     

Geochemistry and mineralogy of shallow alluvial aquifers in Daudkandi upazila in the Meghna flood plain, Bangladesh

The shallow alluvial aquifers of the delta plains and flood plains of Bangladesh, comprises about 70% of total land area are mostly affected by elevated concentrations of arsenic (As) in groundwater exposing a population of more than 35 million to As toxicity. Geochemical studies of shallow alluvial aquifer in the Meghna flood plain show that the uppermost yellowish grey sediment is low in As (1.03 mg/kg) compared to the lower dark grey to black sediment (5.24 mg/kg) rich in mica and organic matter. Sequential extraction data show that solid phase As bound to poorly crystalline and amorphous metal (Fe, Mn, Al)-oxyhydroxides is dominant in the grey to dark grey sediment and reaches its maximum level (3.05 mg/kg) in the mica rich layers. Amount of As bound to sulphides and organic matter also peaks in the dark grey to black sediment. Vertical distributions of major elements determined by X-ray fluorescence (XRF) show that iron (Fe₂O₃), aluminum (Al₂O₃) and manganese (MnO) follow the general trend of distribution of As in the sediments. Concentrations of As, Mn, Fe, HCO₃ ⁻, SO₄ ²⁻ and NO₃ ⁻ in groundwater reflect the redox status of the aquifer and are consistent with solid phase geochemistry. Mineralogical analysis by X-ray diffraction (XRD) and scanning electron microscopy (SEM) fitted with energy dispersive X-ray spectrometer (EDS) revealed dominance of crystalline iron oxides and hydroxides like magnetite, hematite and goethite in the oxidised yellowish grey sediment. Amorphous Fe-oxyhydroxides identified as grain coating in the mica and organic matter rich sediment suggests weathering of biotite is playing a critical role as the source of Fe(III)-oxyhydroxides which in turn act as sink for As. Presence of authigenic pyrite in the dark grey sediment indicates active reduction in the aquifer.     

High-frequency climatic oscillations during the last deglaciation as revealed by oxygen-isotope records of benthic organisms (Ammersee,southern Germany)

High-resolution oxygen-isotope records of benthic ostracods and molluscs from Ammersee, southern Germany, show high-frequency climatic changes during the last deglaciation and parallel in great detail published faunal and floral variations reconstructed from Norwegian Sea sediments and isotope variations in Greenland ice cores. The marine and the terrestrial records give evidence of a synchronous late glacial climatic development in Greenland, NW- and Mid-Europe. However,¹⁴C-ages of the supraregional climatic events and of two tephra layers in the marine sediments of the northeastern Atlantic Ocean are significantly older than the¹⁴C-ages of the corresponding horizons on land. These differences strongly suggest that major short-term events have affected the exchangeable carbon on earth during the dramatic environmental changes related to the deglaciation and in particular have affected the CO₂-distribution within the ocean and between ocean and atmosphere. Dating methods independent of climatic variations and of the global carbon budget should be given priority to refine the timescales of the marine and atmospheric processes during the last deglaciation.This is the fourth paper in a series of papers published in this issue on high-resolution paleolimnology. These papers were presented at the Sixth International Palaeolimnology Symposium held 19–21 April, 1993 at the Australian National University, Canberra, Australia. Dr. A. F. Lotter and Dr. M. Sturm served as guest editors for these papers.     

Durbachites–Vaugnerites – a geodynamic marker in the central European Variscan orogen

Durbachites–Vaugnerites are K–Mg‐rich magmatic rocks derived from an enriched mantle source. Observed throughout the European Variscan basement, their present‐day geographical distribution does not reveal any obvious plate‐tectonic context. Published geochronological data show that most durbachites–vaugnerites formed around 335–340 Ma. Plotted in a Visean plate‐tectonic reconstruction, the occurrences of durbachites–vaugnerites are concentrated in a hotspot like cluster in the Galatian superterrane, featuring a distinctive regional magmatic province. Reviewing the existing local studies on Variscan durbachite–vaugnerite rocks, we interpret their extensive appearance in the Visean in terms of two factors: (i) long‐term mantle enrichment above early Variscan subduction systems; and (ii) melting of this enriched subcontinental mantle source during the Variscan collision stage due to thermal anomalies below the Galatian superterrane, possibly created by slab windows and and/or the sinking of the subducted Rheic slab into the mantle. The tectonic reorganization of Europe in the Late Palaeozoic and during the Alpine orogeny has torn apart and blurred this marked domain of durbachites–vaugnerites.