Ar / Ar dating of high-pressure rocks from the Ligurian Alps: Evidence for a continuous subduction–exhumation cycle

We present ³⁹Ar–⁴⁰Ar dating of phengite, muscovite and paragonite from a set of mafic and metasedimentary rocks sampled from the high-pressure (HP) metaophiolites of the Voltri Group (Western Alps) and from clasts in the basal layer conglomerates from the Tertiary molasse which overlie the high-pressure basement. The white mica-bearing rocks display peak eclogitic and blueschist-facies parageneses, locally showing complex greenschist-facies replacement textures. The internal discordance of age spectra is proportional to the chemical complexity of the micas. High-Si phengites from eclogite clasts record a ³⁹Ar–⁴⁰Ar age of ca. 49 Ma for the eclogite stage and ca. 43 Ma for the blueschist retrogression; phengites from a blueschist basement sample yield an age of ca. 40 Ma; low-Si muscovite from a metasediment dates the formation of the greenschist paragenesis at ca. 33 Ma. Our data indicate that the analyzed samples reached high-pressure conditions at different times over a time-span of c.a. 10 Ma. Subduction was continuing during exhumation and blueschist retrograde re-equilibration of higher-pressure, eclogite-facies rocks. This process kept the isotherms depressed, allowing the older HP-rocks to escape thermal re-equilibration. Our results, added to literature data, fit a tectonic model of a subduction–exhumation cycle, with different tectonic slices subducted at different times from Early Eocene until the Eocene–Oligocene boundary.     

Production of a molybdophore during metal-targeted dissolution of silicates by soil bacteria

Although many bioessential metals are scarce in natural water and rock systems, microbial secretion of high-affinity ligands for metal extraction from solid phases has only been documented for Fe. However, we have discovered that Mo is extracted from a silicate by a high-affinity ligand (a possible “molybdophore”) secreted by an N₂-fixing soil bacterium. The putative molybdophore, aminochelin, is secreted as a siderophore under Fe-depleted conditions, but is also secreted under Fe-sufficient, Mo-depleted conditions. Presumably, molybdophore production facilitates uptake of Mo for use in Mo enzymes. In contrast, an Fe-requiring soil bacterium without a special Mo requirement only enhances the release of Fe from the silicate. Fractionation of Mo stable isotopes during uptake to cells may provide a “fingerprint” for the importance of chelating ligands in such systems. Many such metal-specific ligands secreted by prokaryotes for extraction of bioessential metals, their effects on Earth materials, and their possible utility in the recovery of economic metals remain to be discovered.     

Exploring the impact of diagenesis on (isotope) geochemical and microstructural alteration features in biogenic aragonite

For the Quaternary and Neogene, aragonitic biogenic and abiogenic carbonates are frequently exploited as archives of their environment. Conversely, pre‐Neogene aragonite is often diagenetically altered and calcite archives are studied instead. Nevertheless, the exact sequence of diagenetic processes and products is difficult to disclose from naturally altered material. Here, experiments were performed to understand biogenic aragonite alteration processes and products. Shell subsamples of the bivalve Arctica islandica were exposed to hydrothermal alteration. Thermal boundary conditions were set at 100°C, 175°C and 200°C. These comparably high temperatures were chosen to shorten experimental durations. Subsamples were exposed to different ¹⁸O‐depleted fluids for durations between two and twenty weeks. Alteration was documented using X‐ray diffraction, cathodoluminescence, fluorescence and scanning electron microscopy, as well as conventional and clumped isotope analyses. Experiments performed at 100°C show redistribution and darkening of organic matter, but lack evidence for diagenetic alteration, except in Δ₄₇ which show the effects of annealing processes. At 175°C, valves undergo significant aragonite to calcite transformation and neomorphism. The δ¹⁸O signature supports transformation via dissolution and reprecipitation, but isotopic exchange is limited by fluid migration through the subsamples. Individual growth increments in these subsamples exhibit bright orange luminescence. At 200°C, valves are fully transformed to calcite and exhibit purple‐blue luminescence with orange bands. The δ¹⁸O and Δ₄₇ signatures reveal exchange with the aqueous fluid, whereas δ¹³C remains unaltered in all experiments, indicating a carbonate‐buffered system. Clumped isotope temperatures in high‐temperature experiments show compositions in broad agreement with the measured temperature. Experimentally induced alteration patterns are comparable with individual features present in Pleistocene shells. This study represents a significant step towards sequential analysis of diagenetic features in biogenic aragonites and sheds light on reaction times and threshold limits. The limitations of a study restricted to a single test organism are acknowledged and call for refined follow‐up experiments.     

Eclogite relics in the Variscan orogenic belt of Bulgaria (SE Europe)

Eclogitic rocks were sampled from two zones in the basement of the Sredna Gora terrane (central western Bulgaria): (1) partially retrogressed eclogites and amphibolites embedded in sillimanite-bearing garnet-micaschists with kyanite relics and migmatites and (2) banded amphibolites associated with muscovite-bearing metagranites within two-mica paragneisses. Rutile relics and oligoclase + green hornblende + epidote ± biotite pseudomorphs after garnet suggest an eclogite facies event. A tholeiitic, transitional affinity was determined for the protoliths, suggesting a continental rift environment, consistent with several eclogite-bearing complexes in the eastern segments of the Variscan belt that arose from the Cambro-Ordovician Gondwana break-up. Decreasing pressure after the eclogite overprint was demonstrated by (a) diopside-albite symplectite, and (b) plagioclase + red–brown to green amphibole kelyphite. The early static re-equilibration, dated to 398 ± 5.2 Ma by ⁴⁰Ar–³⁹Ar technique, was followed by an amphibolite facies foliation, which was pervasive in amphibolites, gneisses and micaschists, and poorly developed in eclogites. The lithospheric PT paths corresponding to higher and lower metamorphic gradients reflect the juxtaposition of crustal and lithospheric mantle units, respectively. In the build-up of the basement of the Balkan orogen, the physical properties of the lithological complexes might have influenced the collisional pattern of involved microplates.     

Flow dynamics at the origin of thin clayey sand lacustrine turbidites: Examples from Lake Hazar,Turkey

Turbidity currents and their deposits can be investigated using several methods, i.e. direct monitoring, physical and numerical modelling, sediment cores and outcrops. The present study focused on thin clayey sand turbidites found in Lake Hazar (Turkey) occurring in eleven clusters of closely spaced thin beds. Depositional processes and sources for three of those eleven clusters are studied at three coring sites. Bathymetrical data and seismic reflection profiles are used to understand the specific geomorphology of each site. X‐ray, thin sections and CT scan imagery combined with grain‐size, geochemical and mineralogical measurements on the cores allow characterization of the turbidites. Turbidites included in each cluster were produced by remobilization of surficial slope sediment, a process identified in very few studies worldwide. Three types of turbidites are distinguished and compared with deposits obtained in flume studies published in the literature. Type 1 is made of an ungraded clayey silt layer issued from a cohesive flow. Type 2 is composed of a partially graded clayey sand layer overlain by a mud cap, attributed to a transitional flow. Type 3 corresponds to a graded clayey sand layer overlain by a mud cap issued from a turbulence‐dominated flow. While the published experimental studies show that turbulence is damped by cohesion for low clay content, type 3 deposits of this study show evidence for a turbulence‐dominated mechanism despite their high clay content. This divergence may in part relate to input variables, such as water chemistry and clay mineralogy, that are not routinely considered in experimental studies. Furthermore, the large sedimentological variety observed in the turbidites from one coring site to another is related to the evolution of a sediment flow within a field‐scale basin made of a complex physiography that cannot be tackled by flume experiments.     

Adsorption of Copper, Nickel, and Cadmium on Goethite in the Presence of Organic Ligands

Adsorption of copper, cadmium and nickel at low concentrations on goethite was studied in the presence of the simple organic ligands oxalate, salicylate, and pyromellitate. The experimental metal adsorption behavior was compared to calculations with a surface complexation model to evaluate the most important interactions. Oxalate mostly decreased Cu and Ni adsorption at high pH-values by competition between solution and surface complexation but had no effect on Cd adsorption. Cu adsorption in the presence of oxalate below pH 6 could best be described by defining a ternary complex of type A (surface-metal-ligand). Salicylate had only minor effects on metal adsorption. The adsorption of Cu in the presence of salicylate above pH 5 could be explained by a ternary complex of type A. Pyromellitate increased the adsorption of Cu and Cd in the acidic pH-range, likely by formation of ternary surface complexes of type B (surface-ligand-metal).     

Changes in extremes and hydroclimatic regimes in the CREMA ensemble projections

We analyze changes of four extreme hydroclimatic indices in the RCP8.5 projections of the Phase I CREMA experiment, which includes 21st century projections over 5 CORDEX domains (Africa, Central America, South America, South Asia, Mediterranean) with the ICTP regional model RegCM4 driven by three CMIP5 global models. The indices are: Heat Wave Day Index (HWD), Maximum Consecutive Dry Day index (CDD), fraction of precipitation above the 95th intensity percentile (R95) and Hydroclimatic Intensity index (HY-INT). Comparison with coarse (GPCP) and high (TRMM) resolution daily precipitation data for the present day conditions shows that the precipitation intensity distributions from the GCMs are close to the GPCP data, while the RegCM4 ones are closer to TRMM, illustrating the added value of the increased resolution of the regional model. All global and regional model simulations project predominant increases in HWD, CDD, R95 and HY-INT, implying a regime shift towards more intense, less frequent rain events and increasing risk of heat wave, drought and flood with global warming. However, the magnitudes of the changes are generally larger in the global than the regional models, likely because of the relatively low “climate sensitivity” of the RegCM4, especially when using the CLM land surface scheme. In addition, pronounced regional differences in the change signals are found. The data from these simulations are available for use in impact assessment studies.     

Rare earth and trace elements in igneous and high-temperature metamorphic minerals of oceanic gabbros (MARK area, Mid-Atlantic Ridge)

SIMS analyses have been carried out on clinopyroxenes, plagioclases and amphiboles of six gabbroic samples from Holes 921–924 of the Ocean Drilling Program Leg 153 sited in the MARK area of the Mid-Atlantic Ridge at the ridge–transform intersection, to investigate the rare earth, trace and volatile element distribution in the lower ocean crust during igneous crystallization and higher grade metamorphic conditions. The metagabbros underwent granulite to subgreenschist facies conditions through three main tectono-metamorphic phases: (1) ductile regime (750 < T < 1000 °C and P ≈ 0.3 GPa); (2) transitional regime (600 < T < 700 °C and P ≈ 0.2 GPa); (3) brittle regime (350 ≤ T < 600 °C and P < 0.2 GPa). Igneous clinopyroxenes show C1-chondrite normalized patterns depleted in LREE, and nearly flat for HREE. The rare earth and trace element distributions in igneous clinopyroxenes and plagioclases indicate that these minerals act as REE reservoirs, and comprise the main contribution to the overall rock content. The abundances in igneous minerals reflect the degree of fractionation of the parent liquids. In metamorphic clinopyroxenes recrystallized in anhydrous assemblages, the REE and trace elements patterns mimic those of the primary ones. Conversely, clinopyroxene re-equilibrated in amphibole-bearing assemblages shows a significant increase in REE, Ti, Zr, Y and V, a negative Eu anomaly, and slight decreases in Sr and Ba. An overall increase of REE and some trace elements is evident in hydrous assemblages, with preferential partitioning in the amphibole. It shows high Ti (18196–22844 ppm), LREE depleted patterns and La_N/Sm_N=0.10–0.33, La_N/Yb_N=0.10–0.30. Amphiboles from granoblastic assemblages show homogeneous patterns with no or a positive anomaly for Ti_N and negative anomalies for Sr_N and Zr_N. Volatiles in amphibole are low, with Cl/F < 1; H₂O% is significantly lower than the stoichiometric ratio (1.33–1.53%). The composition of the clinopyroxene and amphibole recrystallized in low-strain domains records evidence of incomplete re-equilibration, and element diffusion and partitioning is in part controlled by the textural site. The possible origins of the fluids involved in the metamorphic recrystallization are discussed: (1) remobilization from igneous amphibole; (2) exsolution from evolved melts; (3) introduction of seawater-derived fluids modified in rock-dominated systems; (4) injection of highly evolved hydrous melts during the metamorphic process. Received: 6 September 1999 / Accepted: 6 March 2000     

Study of an unexpected convective storm

The occurrence of a severe storm in the Argentine littoral has been analyzed. Although general atmospheric conditions were not favorable to the development of deep convection, this storm produced strong winds and hail of considerable intensity. Its occurrence was associated with the entrance of a pulse of humid air at low levels and could be related to the development of two vorticity centers in the region. Atmospheric conditions existing above a low-level inversion are used to simulate two possible clouds, with base altitudes at 2200 and 3000 m and updraft speeds reaching maximum values of 27 and 29 m s⁻¹ respectively. It is noted that the base temperature of about 13°C, found for the first cloud, can be correlated with the prevalence of frozen drop embryos, observed in an analyzed hailstone sample. Hailstone vertical trajectories are simulated in both modeled clouds, assuming spheroidal and spherical particles and assigning different values to the drag coefficient C_d.