ALBERT

Description: We present a detailed field and petrological study of charnockites and ultra-high temperature (UHT) granulites from the Gruf Complex, eastern Central Alps. Charnockites occur as up to 0.5 km wide and 8 km long, internally boudinaged, opx-bearing sheet-like bodies within the regionally dominant migmatitic biotite-orthogneisses. Granulites occur as garnet–orthopyroxene–biotite–alkali feldspar-bearing schlieren (± sapphirine, sillimanite, cordierite, corundum, spinel, plagioclase, and quartz) within charnockites and as residual enclaves both in the charnockites and the migmatitic orthogneisses. Thermobarometric calculations, P–T pseudosections and orthopyroxene Al content, show that both charnockites and granulites equilibrated at metamorphic peak conditions of T = 920–940 °C and P = 8.5–9.5 kbar. Peak assemblages were subsequently overprinted by intergrowth, symplectite and corona textures involving orthopyroxene, sapphirine, cordierite and spinel at T = 720–740 °C and P = 7–7.5 kbar. We suggest that granulites and charnockites are lower crustal relicts preserved in the migmatitic orthogneisses. Garnet diffusion modelling shows that metamorphic garnet–opx ± sapphirine ± sillimanite peak assemblages and post-peak reaction textures always involving cordierite developed during two separate metamorphic cycles. Peak assemblages reflect UHT metamorphism related to post-Varican Permian extension, but post-peak coronae and symplectites formed during the mid-Tertiary, upper amphibolite facies, Alpine regional metamorphism. Fluid-absent partial melting of pelitic and psammitic sediments during the Permian UHT event lead to the formation of charnockitic magmas and granulitic residues. Intense melt loss and thorough dehydration of the granulites (although retaining biotite) favoured the partial preservation of peak mineral assemblages during Alpine metamorphism.

Description: A geochemical survey of 197 fluid discharges (cold and thermal waters and bubbling pools) and 15 gas emissions from the western sector of the Sabatini Volcanic District and the Tolfa Mountains (Latium, Central Italy) was carried out in 2007–2008. The chemical and isotopic compositions of the fluid discharges indicate the occurrence of two main sources: 1) relatively shallow aquifers with Ca(Na,K)–HCO3 and Ca(Mg)–HCO3 compositions when trapped in volcanic and sedimentary formations, respectively; and 2) a deep reservoir, which is hosted in the Mesozoic carbonate sequence, rich in CO2 and having a Ca–SO4(HCO3) composition. Dissolution of a CO2-rich gas phase into the shallow aquifers produces high-TDS and high-pCO2 cold waters, while oxidation of deep-derived H2S to SO4 2− generates low-pH (b4) sulfate waters. The δ13C–CO2 values for gas emissions (from−2.8 to+2.7‰vs. VPDB) suggest that the origin of CO2 associated with the deep fluids ismainly related to thermo-metamorphic reactions within the carbonate reservoir, although significant mantle contribution may also occur. However, R/Ra values (0.37–0.62) indicate that He is mainly produced by a crustal source, with a minor component from a crust-contaminated mantle. On the basis of the δ13C–CH4 and δD–CH4 values (from −25.7 to −19.5‰ vs. VPDB and from −152 to −93.4‰ vs. VSMOW, respectively) CH4 production is associated with thermogenic processes, possibly related to abiogenic CO2 reduction within the carbonate reservoir. The δ34S–H2S values (from+9.3 to +10.4‰ vs. VCDT) are consistent with the hypothesis of a sedimentary source of sulfur from thermogenic reduction of Triassic sulfates. Geothermometric evaluations based on chemical equilibria CO2–CH4 and, separately, H2S suggest that the reservoir equilibriumtemperature is up to ~300 °C. The δDand δ18O data indicate thatwater recharging both the shallow and deep aquifers has a meteoric origin. Fluid geochemistry, coupled with gravimetric data and tectonic lineaments, supports the idea that significant contributions from a deep-seated geothermal brine are present in the Stigliano thermal fluid discharges. Exploration surveys investigated this area during 70's–90's for geothermal purposes. Nevertheless, presently the area is still under-exploited. The presence of thermal waters and anomalous heat flow together with the demographic growth of the last years,makes this site a suitable location for direct applications of the geothermal resource.

Description: Published

Description: 160-181

Description: 2.4. TTC - Laboratori di geochimica dei fluidi

Description: JCR Journal

Description: reserved

Description: For the past 50 years it has been assumed that the principal pathway for the deep limb of the Atlantic Meridional Overturning Circulation (AMOC) is the Deep Western Boundary Current (DWBC). However, recent observations of Lagrangian floats have shown that the DWBC is not necessarily a unique, dominant, or continuous pathway for these deep waters. A significant portion of the deep water export from the subpolar to the subtropical gyres follows a pathway through the interior of the Newfoundland and subtropical basins, which is constrained by the western boundary and the western flank of the Mid-Atlantic Ridge. The hypothesis that deep eddy-driven recirculation gyres are a mechanism for partitioning the deep limb of the AMOC into the DWBC and this interior pathway is investigated here. Eulerian and Lagrangian analyses of the output of ocean general circulation models at eddy-resolving, eddy-permitting, and non-eddy permitting resolutions are used to test this hypothesis. Eddy-driven recirculation gyres, simulated in the eddy-resolving and eddy-permitting models and similar to recirculations inferred from hydrographic data, are shown to shape the export pathways of deep water from the subpolar to the subtropical gyres.

Description: The understanding of the paleoenvironment during initiation and early development of deep cold-water coral carbonate mounds in the NE Atlantic is currently a focus of international research. The Integrated Ocean Drilling Program (IODP) Expedition 307 drilled the 155 m high Challenger Mound in the Porcupine Seabight (SW off Ireland) in order to investigate for the first time sediments from the base of a giant carbonate mound. In this study we focus in high resolution on 12 m of sediments from Site 1317 encompassing the mound base. The mound initiation and start-up phase coincide with the intensification of the Northern Hemisphere Glaciation (INHG) at around 2.7 Ma. Further carbonate mound development seems to be strongly dependent on rapid changes in paleoceanographic and climatic conditions at the Pliocene–Pleistocene boundary, especially characterized and caused by the interaction of intermediate water masses, the Mediterranean Outflow Water (MOW), the Eastern North Atlantic Water (ENAW) and the influence of Southern Component Water (SCW). This study is based on well-established proxies such as δ18O and δ13C of planktonic (Globigerina bulloides) and benthic foraminifera (Fontbotia wuellerstorfi, Discanomalina coronata, Lobatula lobatula, Lobatula antarctica, and Planulina ariminensis) as well as grain size parameters to identify the paleoenvironmental and paleoecological setting favourable for the initial coral colonization on the mound. Stable oxygen and carbon isotope records of benthic foraminiferal species indicate that L. lobatula provides a reliable isotopic signature for paleoenvironmental reconstructions. In particular, δ18O values of L. lobatula indicate that initial mound growth started in a glacial mode with moderate excursions in δ18O values. Carbon isotope values of D. coronata are significantly offset compared to other epibenthic species. This offset may be related to vital effects. Bottom water temperatures, calculated using standard equations based on δ18O of foraminiferal tests, range between 7 and 11 °C, consistent with the known temperature range conducive for cold-water coral growth and development. Bottom currents transporting intermediate water masses of southern origin (Mediterranean and Bay of Biscay) enhanced at 2.6 Ma supporting first coral settlements with the INHG. The benthic δ13C and the sortable silt records indicate that the early Pleistocene hydrodynamic regime was characterized by weaker current intensities associated with vertical movements of MOW or its replacement by SCW at intermediate depth. After these sluggish phases enhanced MOW flow dominated again and led to stronger current intensities and most probably sediment erosion on Challenger Mound. Erosion in combination with early diagenetic (oxidation) processes overprinted the sediment layers as indicated by dissolved coral skeletons, the increase in Ca-content and sediment density, minimum δ13Cplanktonic values, as well as the occurrence of gypsum and pyrite, implying a careful evaluation of original and overprinted geochemical signals. We conclude that the Challenger Mound development was already influenced by short-term variability of water masses from southern origin and possible erosional events comparable to the late Pleistocene setting.

Description: Understanding metal and proton toxicity under field conditions requires consideration of the complex nature of chemicals in mixtures. Here, we demonstrate a novel method that relates streamwater concentrations of cationic metallic species and protons to a field ecological index of biodiversity. The model WHAM-FTOX postulates that cation binding sites of aquatic macroinvertebrates can be represented by the functional groups of natural organic matter (humic acid), as described by the Windermere Humic Aqueous Model (WHAM6), and supporting field evidence is presented. We define a toxicity function (FTOX) by summing the products: (amount of invertebrate-bound cation) × (cation-specific toxicity coefficient, αi). Species richness data for Ephemeroptera, Plecoptera and Trichoptera (EPT), are then described with a lower threshold of FTOX, below which all organisms are present and toxic effects are absent, and an upper threshold above which organisms are absent. Between the thresholds the number of species declines linearly with FTOX. We parameterised the model with chemistry and EPT data for low-order streamwaters affected by acid deposition and/or abandoned mines, representing a total of 412 sites across three continents. The fitting made use of quantile regression, to take into account reduced species richness caused by (unknown) factors other than cation toxicity. Parameters were derived for the four most common or abundant cations, with values of αi following the sequence (increasing toxicity) H+ 〈 Al 〈 Zn 〈 Cu. For waters affected mainly by H+ and Al, FTOX shows a steady decline with increasing pH, crossing the lower threshold near to pH 7. Competition effects among cations mean that toxicity due to Cu and Zn is rare at lower pH values, and occurs mostly between pH 6 and 8.

Description: The global surface air temperature record of the last 150 years is characterized by a long-term warming trend, with strong multidecadal variability superimposed. Similar multidecadal variability is also seen in other (societal important) parameters such as Sahel rainfall or Atlantic hurricane activity. The existence of the multidecadal variability makes climate change detection a challenge, since Global Warming evolves on a similar timescale. The ongoing discussion about a potential anthropogenic signal in the Atlantic hurricane activity is an example. A lot of work was devoted during the last years to understand the dynamics of the multidecadal variability, and external as well as internal mechanisms were proposed. This review paper focuses on two aspects. First, it describes the mechanisms for internal variability using a stochastic framework. Specific attention is given to variability of the Atlantic Meridional Overturning Circulation (AMOC), which is likely the origin of a considerable part of decadal variability and predictability in the Atlantic Sector. Second, the paper discusses the decadal predictability and the factors limiting its realisation. These include a poor understanding of the mechanisms involved and large biases in state-of-the-art climate models. Enhanced model resolution, improved subgrid scale parameterisations, and the inclusion of additional climate subsystems, such as a resolved stratosphere, may help overcome these limitations.

Description: In marine recirculating aquaculture systems ozone, as a strong oxidant, is often used to improve water quality by reducing the pathogen load and removing inorganic and organic wastes. However, mainly when disinfection of recirculating water is desired, high ozone dosage is required, which may lead to toxicity problems for the cultured species. Acute toxicity of ozone-produced oxidants (OPO) to juvenile Pacific white shrimp, Litopenaeus vannamei, was assessed by determining the medium lethal concentration (LC50). Shrimp were exposed to a series of OPO concentrations for 96 h. Toxicity was analysed using standard probit regression. The 24, 48, 72 and 96 h LC50 values were 0.84, 0.61, 0.54 and 0.50 mg/l chlorine equivalent, respectively. A safe level for residual oxidant concentration was calculated and further verified by chronic exposure experiments. While long-term exposure of juvenile white shrimp to an OPO concentration of 0.06 mg/l revealed no observable effect, long-term exposures to 0.10 and 0.15 mg/l induced incidence of soft shell syndrome which led to mortalities due to cannibalism. Thus, an OPO concentration of 0.06 mg/l is suggested to be the maximum safe exposure level for rearing juvenile L. vannamei. Furthermore, we proved this safe level to be sufficient to control and reduce bacterial biomass in the recirculating process water.

Description: Volcano edifice volume calculations are presented for 65 volcanoes of the 1400 km long Chilean Southern Volcanic Zone (SVZ) as a basic step in subduction zone mass budgets. Volume calculations are performed in a Geographical Information System that integrates Digital Elevation Models based on of Shuttle Radar Topography Mission as well as ASTER-GDEM topographic data, LANDSAT satellite images and geological maps. The method of volume calculation is straightforward for isolated, morphologically well-defined stratovolcanoes. Uncertainties increase for volcanic edifices that formed on pre-existing rugged terrain, for multi-phase eruptive centers, as well as for eroded edifices. A revised segmentation of the arc is used to describe the spatial volume distribution of extruded magma along the SVZ and to discuss controlling tectonic factors. Peak volumes between arc and back arc are offset by 400 km. The total volcanic extrusion is in the range of 10–13 km3/km/Ma. Major differences between the SVZ and the Central American subduction system are notable with regard to volcano density and maximum volumes.

Description: Methods and results for parameter optimization and uncertainty analysis for a one-dimensional marine biogeochemical model of NPZD type are presented. The model, developed by Schartau and Oschlies, simulates the distribution of nitrogen, phytoplankton, zooplankton and detritus in a water column and is driven by ocean circulation data. Our aim is to identify parameters and fit the model output to given observational data. For this model, it has been shown that a satisfactory fit could not be obtained, and that parameters with comparable fits can vary significantly. Since these results were obtained by evolutionary algorithms (EA), we used a wider range of optimization methods: A special type of EA (called quantum-EA) with coordinate line search and a quasi-Newton SQP method, where exact gradients were generated by Automatic/Algorithmic Differentiation. Both methods are parallelized and can be viewed as instances of a hybrid, mixed evolutionary and deterministic optimization algorithm that we present in detail. This algorithm provides a flexible and robust tool for parameter identification and model validation. We show how the obtained parameters depend on data sparsity and given data error. We present an uncertainty analysis of the optimized parameters w.r.t. Gaussian perturbed data. We show that the model is well suited for parameter identification if the data are attainable. On the other hand, the result that it cannot be fitted to the real observational data without extension or modification, is confirmed. (C) 2010 Elsevier Ltd. All rights reserved.

Description: Two distinct types of eclogites from the Raspas Complex (Ecuador), which can be distinguished based on petrography and trace element geochemistry, were analyzed for their stable (Li, O) and radiogenic (Sr, Nd) isotope signature to constrain metasomatic changes due to fluid-overprinting in metabasaltic rocks at high-pressure conditions and to identify fluid sources. MORB-type eclogites are characterized by a relative LREE depletion similar to MORB. High-pressure (HP) minerals from this type of eclogite have highly variable oxygen isotope compositions (garnet: + 4.1 to + 9.8 ‰; omphacite: + 6.1 to + 11.0 ‰; phengite: 8.7 to 10.4 ‰; amphibole: 6.2 to 10.1 ‰) and generally show equilibrium oxygen isotope fractionation. Initial 87Sr/86Sr isotope ratios are also variable (0.7037-0.7063), whereas εNd130Ma values (+ 8.3 to + 11.0) are relatively similar. Sr and O isotopic compositional differences among rocks on outcrop scale, the preservation of O isotopic compositions of low-temperature altered oceanic crust, and Sr-Nd isotopic trends typical for seafloor alteration suggest inheritance from variably altered oceanic crust. However, decreasing δ7Li values (-0.5 to -12.9 ‰) with increasing Li concentrations (11-94 ppm) indicate Li isotope fractionation by diffusion related to fluid-rock interaction. Li isotopes prove to be a very sensitive tracer of metasomatism, although the small effects on the Sr-Nd-O isotope systems suggest that the fluid-induced metasomatic event in the MORB-type eclogites was small-scale at low-water/rock ratios. This metasomatic fluid is thought to predominantly derive from in situ dehydration of MORB-type rocks. Zoisite eclogites, the second eclogite type from the Raspas Complex, are characterized by the presence of zoisite and enrichment in many incompatible trace elements compared to the MORB-type eclogites. The zoisite eclogites have a homogenous Sr-Nd isotopic signature (Initial 87Sr/86Sr = 0.7075-0.7081, εNd130Ma = -6.7 to -8.7), interpreted to reflect a metasomatic overprint. The isotopic signature can be attributed to the metasomatic formation of zoisite because associated zoisite veins are isotopically similar. Relatively homogenous O isotope values for garnet (10.9-12.3 ‰) omphacite (9.4 to 10.8 ‰), amphibole (10.0-10.1 ‰) and zoisite (10.5-11.9 ‰) and inter-mineral O isotopic disequilibria are consistent with a metasomatic overprint via open-system fluid input. Li concentrations (46-76 ppm) and δ7Li values of the zoisite eclogites overlap the range of the MORB-type eclogites. The large amount of fluid required for isotopic homogenization, combined with the results from fluid inclusion studies, suggests that deserpentinization played a major role in generating the metasomatic fluid that altered the zoisite eclogites. However, influence of a (meta)sedimentary source is required based on Sr-Nd isotope data and trace element enrichments. The significant geochemical variation in the various eclogites generated by interaction with metasomatic fluids has to be considered in attempts to constrain recycling at convergent margins.