Global occurrence of tellurium-rich ferromanganese crusts and a model for the enrichment of tellurium

Hydrogenetic ferromanganese oxyhydroxide crusts (Fe-Mn crusts) precipitate out of cold ambient ocean water onto hard-rock surfaces (seamounts, plateaus, ridges) at water depths of about 400 to 4000 m throughout the ocean basins. The slow-growing (mm/Ma) Fe-Mn crusts concentrate most elements above their mean concentration in the Earth’s crust. Tellurium is enriched more than any other element (up to about 50,000 times) relative to its Earth’s crustal mean of about 1 ppb, compared with 250 times for the next most enriched element.We analyzed the Te contents for a suite of 105 bulk hydrogenetic crusts and 140 individual crust layers from the global ocean. For comparison, we analyzed 10 hydrothermal stratabound Mn-oxide samples collected from a variety of tectonic environments in the Pacific. In the Fe-Mn crust samples, Te varies from 3 to 205 ppm, with mean contents for Pacific and Atlantic samples of about 50 ppm and a mean of 39 ppm for Indian crust samples. Hydrothermal Mn samples have Te contents that range from 0.06 to 1 ppm. Continental margin Fe-Mn crusts have lower Te contents than open-ocean crusts, which is the result of dilution by detrital phases and differences in growth rates of the hydrogenetic phases.Correlation coefficient matrices show that for hydrothermal deposits, Te has positive correlations with elements characteristic of detrital minerals. In contrast, Te in open-ocean Fe-Mn crusts usually correlates with elements characteristic of the MnO₂, carbonate fluorapatite, and residual biogenic phases. In continental margin crusts, Te also correlates with FeOOH associated elements. In addition, Te is negatively correlated with water depth of occurrence and positively correlated with crust thickness. Q-mode factor analyses support these relationships. However, sequential leaching results show that most of the Te is associated with FeOOH in Fe-Mn crusts and ≤10% is leached with the MnO₂.Thermodynamic calculations indicate that Te occurs predominantly as H₅TeO₆⁻ in ocean water. The speciation of Te in ocean water and charge balance considerations indicate that Te should be scavenged by FeOOH, which is in agreement with our leaching results. The thermodynamically more stable Te(IV) is less abundant by factors of 2 to 3.5 than Te(VI) in ocean water. This can be explained by preferential (not exclusive) scavenging of Te(IV) by FeOOH at the Fe-Mn crust surface and by Fe-Mn colloids in the water column. We propose a model in which the extreme enrichment of Te in Fe-Mn crusts is likely the result of an oxidation reaction on the surface of FeOOH. A similar oxidation process has been confirmed for Co, Ce, and Tl at the surface of MnO₂ in crusts, but has not been suggested previously to occur in association with FeOOH in Fe-Mn crusts. Mass-balance considerations indicate that ocean floor Fe-Mn deposits are the major sink for Te in the oceans. The concentration and redox chemistry of Te in the global ocean are likely controlled by scavenging on Fe-Mn colloids in the water column and Fe-Mn deposits on the ocean floor, as is also the case for Ce.     

International greenhouse gas inventory systems: A comparison between CORINAIR and IPCC methodologies in the EU

There are several different approaches currently taken by the 15 EU countries in compiling their IPCC inventories for the FCCC. Six countries (France, Ireland, Italy, Luxembourg, Portugal, Spain) use the CORINAIR system and then aggregate and reformat the data into the required IPCC format. Of the remaining countries, two strictly follow the IPCC methodology (Finland and Greece), five (Denmark, Germany, Netherlands, Sweden, United Kingdom) estimate emissions using a combination of national and IPCC methodologies, while the final two (Austria and Belgium) use a combination of national and CORINAIR methodologies (transformed to IPCC). Comparison of the national inventories in both the IPCC and CORINAIR formats shos some revealing discrepancies between the two systems at both sector and gas level that by chance cancel out when aggregated at the EU level.     

Doubtful Events Reported in Current Italian Earthquake Catalogues: The Medieval Earthquakes of Subiaco (Central Italy)

Within the framework of a study of the seismicity of the Aniene Valley (Central Italy), we analysed the medieval earthquakes of Subiaco (1216, 1227, 1299), the largest events reported for the area. Our main goal was to investigate some doubtful events reported in earthquake catalogues and, as such, currently utilised for seismic hazard estimates. A careful screening of the oldest available sources and their filiation pattern up to the present pointed out the uncertainty on the date and nature of these phenomena. A multidisciplinary approach based on the joint analysis of archaeological, geomorphologic and historical evidence allowed us to propose new interpretations concerning these events and their significance for the assessment of seismic hazard in the Aniene Valley. The main conclusion is that the dates of the 1216 and 1227 events are fairly unsupported. In particular, the 1216 earthquake could be dated back to between AD 1159 and 1181.     

Chemical and isotopic equilibrium between CO2 and CH4 in fumarolic gas discharges: Generation of CH4 in arc magmatic-hydrothermal systems

The chemical and isotopic composition of fumarolic gases emitted from Nisyros Volcano, Greece, and of a single gas sample from Vesuvio, Italy, was investigated in order to determine the origin of methane (CH₄) within two subduction-related magmatic-hydrothermal environments.Apparent temperatures derived from carbon isotope partitioning between CH₄ and CO₂ of around 340°C for Nisyros and 470°C for Vesuvio correlate well with aquifer temperatures as measured directly and/or inferred from compositional data using the H₂O-H₂-CO₂-CO-CH₄ geothermometer. Thermodynamic modeling reveals chemical equilibrium between CH₄, CO₂ and H₂O implying that carbon isotope partitioning between CO₂ and CH₄ in both systems is controlled by aquifer temperature.N₂/³He and CH₄/³He ratios of Nisyros fumarolic gases are unusually low for subduction zone gases and correspond to those of midoceanic ridge environments. Accordingly, CH₄ may have been primarily generated through the reduction of CO₂ by H₂ in the absence of any organic matter following a Fischer-Tropsch-type reaction. However, primary occurrence of minor amounts of thermogenic CH₄ and subsequent re-equilibration with co-existing CO₂ cannot be ruled out entirely. CO₂/³He ratios and δ¹³C_CO2 values imply that the evolved CO₂ either derives from a metasomatized mantle or is a mixture between two components, one outgassing from an unaltered mantle and the other released by thermal breakdown of marine carbonates. The latter may contain traces of organic matter possibly decomposing to CH₄ during thermometamorphism.     

An approach for quantifying geomorphological impacts for EIA of transportation infrastructures: a case study in northern Spain

A methodological proposal for the assessment of impacts due to linear infrastructures such as motorways, railways, etc. is presented. The approach proposed includes a series of specific issues to be addressed for each geomorphological feature analysed—both ‘static’ and ‘dynamic’—as well as a series of steps to be followed in the process.Geomorphic characteristics potentially affected were initially identified on the basis of a conceptual activities/impacts model that helps to single out geomorphic impacts related to environmental concerns for the area. The following issues were addressed for each individual impact: nature of potential effects; indicators that can be used to measure impacts; criteria of ‘geomorphologic performance’; procedure for measurement/prediction of changes; translation of geomorphologic impacts into significant terms from the viewpoint of human concerns; possible mitigation and/or compensation measures.The procedure has been applied to a case study corresponding to a new motorway in the Basque Country, northern Spain. Geomorphological impacts considered in this analysis included: (1) consumable resources; (2) sites of geomorphological interest; (3) land units with high potential for use, high productivity or value for conservation; (4) visual landscape; (5) slope instability processes. The procedure has been designed for implementation in a Geographic Information System (GIS) environment. Details are given on the application of the method to each individual impact analysed and results are presented in both numerical and map form.Impacts assessed were initially expressed by means of heterogeneous magnitudes, depending on the geomorphological feature considered. Those geomorphological impacts were then translated into significant terms and homogeneous magnitudes. Integration was carried out on the basis of impact values thus obtained. Final integrated results were also expressed in numerical and map form.The method proposed enables comparison of alternatives as well as ‘prediction’ and assessment of impacts in terms directly related to geomorphic characteristics. It also facilitates the expression of those impacts in terms that allow integration with other types of environmental impacts.     

Eocene-Pliocene time scale and stratigraphy of the Upper Rhine Graben (URG) and the Swiss Molasse Basin (SMB)

We present a general stratigraphic synthesis for the Upper Rhine Graben (URG) and the Swiss Molasse Basin (SMB) from Eocene to Pliocene times. The stratigraphic data were compiled both from literature and from research carried out by the authors during the past 6 years ; an index of the stratigraphically most important localitites is provided. We distinguish 14 geographical areas from the Helvetic domain in the South to the Hanau Basin in the North. For each geographical area, we give a synthesis of the biostratigraphy, lithofacies, and chronostratigraphic ranges. The relationships between this stratigraphic record and the global sea-level changes are generally disturbed by the geodynamic (e.g., subsidence) evolution of the basins. However, global sea-level changes probably affected the dynamic of transgression–regression in the URG (e.g., Middle Pechelbronn Beds and Serie Grise corresponding with sea-level rise between Ru1/Ru2 and Ru2/Ru3 sequences, respectively) as well as in the Molasse basin (regression of the UMM corresponding with the sea-level drop at the Ch1 sequence). The URGENT-project (Upper Rhine Graben evolution and neotectonics) provided an unique opportunity to carry out and present this synthesis. Discussions with scientists addressing sedimentology, tectonics, geophysics and geochemistry permitted the comparison of the sedimentary history and stratigraphy of the basin with processes controlling its geodynamic evolution. Data presented here back up the palaeogeographic reconstructions presented in a companion paper by the same authors (see Berger et al. in Int J Earth Sci 2005).     

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.     

Preparation and Measurement of Cassiterite for Sn Isotope Analysis

Increased interest in the fractionation of Sn isotopes has led to the development of several techniques for preparing cassiterite (SnO₂, the primary ore of Sn) for isotopic analysis. Two distinct methods have been applied in recent isotopic studies of cassiterite: (a) reduction to tin metal with potassium cyanide (KCN) at high temperature (800 °C), with subsequent dissolution in HCl, and (b) reduction to a Sn solution with hydriodic acid (HI) at low temperature (100 °C). This study compares the effectiveness and accuracy of these two methods and contributes additional methodological details. The KCN method consistently yielded more Sn (> 70% in comparison with < 5%), does not appear to fractionate Sn isotopes at high temperatures over a 2‐hour period and produced consistent Sn isotope values at flux mass ratios of ≥ 4:1 (flux to mineral) with a minimum reduction time of 40 min. By means of a distillation experiment, it was demonstrated that HI could volatilise Sn, explaining the consistently low yields by this method. Furthermore, the distillation generated Sn vapour, which is up to 0.38‰ per mass unit different from the starting material, the largest induced Sn fractionation reported to date. Accordingly, the HI method is not recommended for cassiterite preparation for Sn isotopic analysis.     

Development of satellite green vegetation fraction time series for use in mesoscale modeling: application to the European heat wave 2006

A method is presented for development of satellite green vegetation fraction (GVF) time series for use in the Weather Research and Forecasting (WRF) model. The GVF data is in the WRF model used to describe the temporal evolution of many land surface parameters, in addition to the evolution of vegetation. Several high-resolution GVF products, derived from high-quality satellite retrievals from Moderate Resolution Imaging Spectroradiometer images, were produced and their performance was evaluated in long-term WRF simulations. The atmospheric conditions during the 2006 heat wave year over Europe were simulated since significant interannual variability in vegetation seasonality was found. Such interannual variability is expected to increase in the coming decades due to climatic changes. The simulation using a quadratic normalized difference vegetation index to GVF relationship resulted in consistent improvements of modeled temperatures. The model mean temperature cold bias was reduced by 10 % for the whole domain and by 20–45 % in areas affected by the heat wave. The study shows that WRF simulations during heat waves and droughts, when vegetation conditions deviate from the climatology, require concurrent land surface properties in order to produce accurate results.     

A Holocene high-resolution record of aquatic productivity,seasonal anoxia and meromixis from varved sediments of Lake Łazduny,North-Eastern Poland: insight from a novel multi-proxy approach

Anthropogenic eutrophication and spreading anoxia in freshwater systems is a global concern. Little is known about anoxia in earlier historic times under weaker human impact, or under prehistoric natural conditions with different trophic, land cover and climatic regimes. We use a novel approach that combines high-resolution hyperspectral imaging with µ-XRF and HPLC-pigment data, which allows us to assess chloropigments (productivity) and bacteriopigments (anoxia) at seasonal subvarve-scale resolution. Our ~9700 cal a bp varved sediment record from NE Poland suggests that productivity increased stepwise from oligotrophic Early Holocene conditions (until ~9200 cal a bp ) to mesotrophic conditions in the Mid- and Late Holocene. Natural eutrophication was mainly a function of progressing landscape evolution with intense weathering under dense forest and warm-moist climatic conditions. Generally, anoxia increased with increasing productivity. Seasonal anoxia and some multi-decadal periods of meromixis were the common mixing patterns throughout the Holocene except for a period of persisting meromixis between ~5200 and 2000 cal a bp. Anthropogenic deforestation around 400 cal a bp resulted in substantially better lake oxygenation despite high productivity. In this small lake, aquatic productivity and lakeshore forest cover (wind shield) were more important factors controlling oxic/anoxic conditions than Holocene temperature variability.