Origin of chondritic forsterite grains

Iron-poor and refractory lithophile element (RLE) rich forsterite grains occur in all major types of unequilibrated chondrites. In our laser ablation inductively coupled mass spectrometry (LA-ICPMS) minor and trace element study we show that refractory forsterites (RF) from carbonaceous (CC), unequilibrated ordinary (UOC) and a Rumuruti chondrite (RC) have similar chemical compositions with high RLE concentrations and low concentrations of Mn, Fe, Co and Ni. Fractionation of RLEs and rare earth elements (REEs) is in agreement with formation by crystallization from a RLE rich silicate melt. Low concentrations and the fractionation of moderately siderophile elements (Fe, Co, Ni) in RFs suggests formation at low oxygen fugacity, possibly in equilibrium with primitive Fe,Ni metal condensates in a gas of solar composition. Anomalously high Ti in the parental melt can be explained by Ti³⁺/Ti⁴⁺ ∼1.5, supporting formation of RF in highly reducing conditions. Low Mn concentrations indicate formation at high temperatures (>∼1160 K). The model of formation of RFs and the accompanying physico-chemical conditions during their formation as well as their relation to non refractory olivine are discussed.     

Spatial and temporal structure of the Denmark Strait Overflow revealed by acoustic observations

In spite of the fundamental role the Atlantic Meridional Overturning Circulation (AMOC) plays for global climate stability, no direct current measurement of the Denmark Strait Overflow, which is the densest part of the AMOC, has been available until recently that resolve the cross-stream structure at the sill for long periods. Since 1999, an array of bottom-mounted acoustic instruments measuring current velocity and bottom-to-surface acoustic travel times was deployed at the sill. Here, the optimization of the array configuration based on a numerical overflow model is discussed. The simulation proves that more than 80% of the dense water transport variability is captured by two to three acoustic current profilers (ADCPs). The results are compared with time series from ADCPs and Inverted Echo Sounders deployed from 1999 to 2003, confirming that the dense overflow plume can be reliably measured by bottom-mounted instruments and that the overflow is largely geostrophically balanced at the sill.     

Multi-metal contaminant dynamics in temporarily flooded soil under sulfate limitation

In many river basins, floodplain soils have accumulated a variety of metal contaminants, which might be released during periods of flooding. We investigated the dynamics of copper, cadmium, lead, zinc, and nickel in a contaminated freshwater floodplain soil under a realistic sulfate-limited flooding regime in microcosm experiments. We found that most contaminants were initially mobilized by processes driven by the reductive dissolution of Fe(III) and Mn(IV, III) (hydr)oxides. Subsequently, bacterial sulfate respiration resulted in the transformation of the entire available sulfate (2.3 mmol/kg) into chromous reducible sulfur (CRS). Cu K-edge X-ray absorption fine structure (XAFS) spectroscopy revealed that the soil Cu speciation changed from predominantly Cu(II) bound to soil organic matter (SOM) intermittently to 14% metallic Cu(0) and subsequently to 66% copper sulfide (Cu_xS). These Cu_xS precipitates accounted for most of the formed CRS, suggesting that Cu_xS was the dominant sulfide phase formed in the flooded soil. Sequential metal extractions, in agreement with CRS results, suggested that easily mobilizable Cd was completely and Pb partially sequestered in sulfide precipitates, controlling their dissolved concentrations to below detection limits. In contrast, Zn and Ni (as well as Fe) were hardly sequestered into sulfide phases, so that micromolar levels of dissolved Zn and Ni (and millimolar dissolved Fe(II)) persisted in the reduced soil. The finding that Cu, Cd, and Pb were sequestered (but hardly any Zn, Ni, and Fe) is consistent with the thermodynamically predicted sulfide ladder following the increasing solubility products of the respective metal sulfides. The observation that Cd and Pb were sequestered in sulfides despite the presence of remaining SOM-bound Cu(II) suggested that the kinetics of Cu(II) desorption, diffusion, and/or Cu_xS precipitation interfered with the sulfide ladder. We conclude that the dynamics of multiple metal contaminants are intimately coupled under sulfate limitation by the relative thermodynamic stabilities and formation kinetics of the respective metal sulfides.     

Modelling the Spoon IRS diagnostic diagram

We explore whether our models for starbursts, quiescent star-forming galaxies and for active galactic nuclei (AGN) dust tori are able to model the full range of Spitzer Infrared Spectrograph (IRS) spectra measured with Spitzer . The diagnostic plot of 9.7 μm silicate optical depth versus 6.2 μm polycyclic aromatic hydrocarbon (PAH) equivalent width, introduced by Spoon and coworkers in 2007, gives a good indication of the age and optical depth of a starburst, and of the contribution of an AGN dust torus. However, there is aliasing between age and optical depth at later times in the evolution of a starburst, and between age and the presence of an AGN dust torus. Modelling the full IRS spectra and using broad-band 25–850 μm fluxes can help to resolve these aliases. The observed spectral energy distributions require starbursts of a range of ages with initial dust optical depth ranging from 50–200, optically thin dust emission ('cirrus') illuminated by a range of surface brightnesses of the interstellar radiation field, and AGN dust tori with a range of viewing angles.     

Feeding Monsters – A Study of Active Galaxies

We present new interferometric observations of the molecular gas distribution and kinematics in the nuclei of different active galaxies at high angular resolution and high sensitivity carried out with the IRAM Plateau de Bure interferometer (PdBI). The observations cover galaxies in a redshift range of 0.03–1.4. We have so far observed five different active galaxies: NGC3718, NGC1068, HE1029–1831, 3C48 and Q0957+561. The first two objects belong to the NUGA (NUclei of GAlaxies) project – an international collaboration mainly between Spain, France and Germany – containing about 30 Seyfert and LINER galaxies. Both are at the same distance of 14Mpc and show a warped gas and dust disk. The new mosaic map of NGC3718 corrected for short-spacing effects with IRAM 30 m observations well demonstrates the existence of the warped gas disk with several secondary maxima in the projected gas distribution caused by orbit crowding effects. Based on these new data we have improved recent simulations of the warped disk in NGC3718. HE1029–1831 and 3C48 are nearby QSOs. HE1029–1831 is taken out of the Cologne nearby QSO sample. The maps of the integrated CO(1–0) and CO(2–1) emission clearly show that the molecular gas is mostly related to the central bulge with a non-negligible fraction distributed along the bar known from optical observations. Our new CO data of 3C48 unveil new information about the kinematics of its molecular gas complementing and improving further studies based on previous infrared observations and detailed multi-particle simulations. Finally, new measurements of the CO(1–0) line in Q0957+561 – a highly-red-shifted, gravitationally lensed quasar – will be presented as a link to earlier evolutionary stages of active galaxies and their hosts.     

Evaluation of Combined Direct-Push Methods Used for Aquifer Model Generation

Most established methods to characterize aquifer structure and hydraulic conductivities of hydrostratigraphical units are not capable of delivering sufficient information in the spatial resolution that is desired for sophisticated numerical contaminant transport modeling and adapted remediation design. With hydraulic investigation methods based on the direct-push (DP) technology such as DP slug tests, DP injection logging, and the hydraulic profiling tool, it is possible to rapidly delineate hydrogeological structures and estimate their hydraulic conductivity in shallow unconsolidated aquifers without the need for wells. A combined application of these tools was used for the investigation of a contaminated German refinery site and for the setup of hydraulic aquifer models. The quality of DP investigation and the models was evaluated by comparisons of tracer transport simulations using these models and measured breakthroughs of two natural gradient tracer tests. Model scenarios considering the information of all tools together showed good reproduction of the measured breakthroughs, indicating the suitability of the approach and a minor impact of potential technical limitations. Using the DP slug tests alone yielded significantly higher deviations for the determined hydraulic conductivities compared to considering two or three of the tools. Realistic aquifer models developed on basis of such combined DP investigation approaches can help optimize remediation concepts or identify flow regimes for aquifers with a complex structure.     

A kinetic model of metamorphism: an application to siliceous dolomites

We use a kinetic model of a metamorphic system to study the effect of competing rates of reaction, fluid injection, and heating on the evolution of the reaction pathway in temperature/composition space at constant pressure. We show that for rocks in contact with mixed volatile (e.g., CO₂-H₂O) fluids the reaction path may be quite different from what is expected from equilibrium-based petrologic models. Equilibrium-based models, used to understand the development of rock systems undergoing mineral reactions during a metamorphic event, rely on the Gibbs phase rule and only consider stable phases. For constant pressure, the temperature-composition paths follow univariant curves and significant reactions may occur at invariant points. By contrast, the more general kinetic treatment is not constrained by equilibrium, although with the proper competing rates equilibrium is a possible endmember of the kinetic approach. The deviation from equilibrium depends on the competing rates of reaction, heating, and fluid injection. A key element required by the kinetic approach is the inclusion of metastable reactions in the formulation, whereas such reactions are irrelevant for equilibrium-based models. Metastable reactions are often involved in a complex interplay with common prograde stable metamorphic reactions. We present model results for the well-studied CaO-MgO-SiO₂-CO₂-H₂O (CMS) system to show how the system evolves under kinetic control. Our simulations and discussion focus on the behavior of the CMS system under a number of closed and open system conditions. Special attention is paid to closed system behavior in the vicinity of the (first) isobaric invariant point (with Dol, Qtz, Tlc, Cal, and Tr). Also, for open systems with massive fluid infiltration we consider heating rates varying from contact to regional metamorphic conditions. For some geologically reasonable rates of reactions, heating, and fluid injection, our results demonstrate that equilibrium conditions may be significantly overstepped in metamorphic systems. We used overall mineral reactions in this model with rates based on experimental results. Future models could rely on more fundamental dissolution and precipitation reactions. Such an extension would require additional kinetic rate data, as well as mineral solubilities in mixed volatile fluids.Editorial responsibility: J. Hoefs     

Human-biometeorological assessment of heat waves in Athens

The goal of this study is the analysis of heat waves and their impact on humans, using human biometeorological indices, which are based on the energy balance of the human body. The implications for humans are not only described through the intensity of the heat waves, but also through their duration over consecutive days. Both intensity and duration were analyzed for the Greater Athens Area during the period 1955 to 2001. The analysis was carried out using the daily physiologically equivalent temperature and the daily minimum air temperature. Based on these two parameters, the results showed an increase in the average duration of heat waves. Furthermore, the use of the Gaussian filter revealed the intra-annual variation of heat stress conditions and their relevance to humans. The results could be used for the management of the negative consequences of heat waves in cities suffering from environmental pollution and also for climate impact studies.     

Archean high-Mg monzodiorite–syenite,epidote skarn,and biotite–sericite gold lodes in the Granny Smith–Wallaby district,Australia: U–Pb and Re–Os chronometry of two intrusion-related hydrothermal systems

The Granny Smith (37 t Au production) and Wallaby deposits (38 t out of a 180 t Au resource) are located northeast of Kalgoorlie, in 2.7 Ga greenstones of the Eastern Goldfields Province, the youngest orogenic belt of the Yilgarn craton, Western Australia. At Granny Smith, a zoned monzodiorite–granodiorite stock, dated by a concordant titanite–zircon U–Pb age of 2,665 ± 3 Ma, cuts across east-dipping thrust faults. The stock is fractured but not displaced and sets a minimum age for large-scale (1 km) thrust faulting (D2), regional folding (D1), and dynamothermal metamorphism in the mining district. The local gold–pyrite mineralization, controlled by fractured fault zones, is younger than 2,665 ± 3 Ma. In augite–hornblende monzodiorite, alteration progressed from a hematite-stained alkali feldspar–quartz–calcite assemblage and quartz–molybdenite–pyrite veins to a late reduced sericite–dolomite–albite assemblage. Gold-related monazite and xenotime define a U–Pb age of 2,660 ± 5 Ma, and molybdenite from veins a Re–Os isochron age of 2,661 ± 6 Ma, indicating that mineralization took place shortly after the emplacement of the main stock, perhaps coincident with the intrusion of late alkali granite dikes. At Wallaby, a NE-trending swarm of porphyry dikes comprising augite monzonite, monzodiorite, and minor kersantite intrudes folded and thrust-faulted molasse. The conglomerate and the dikes are overprinted by barren (<0.01 g/t Au) anhydrite-bearing epidote–actinolite–calcite skarn, forming a 600-m-wide and >1,600-m-long replacement pipe, which is intruded by a younger ring dike of syenite porphyry pervasively altered to muscovite + calcite + pyrite. Skarn and syenite are cut by pink biotite–calcite veins, containing magnetite + pyrite and subeconomic gold–silver mineralization (Au/Ag = 0.2). The veins are associated with red biotite–sericite–calcite–albite alteration in adjacent monzonite dikes. Structural relations and the concordant titanite U–Pb age of the skarn constrain intrusion-related mineralization to 2,662 ± 3 Ma. The main-stage gold–pyrite ore (Au/Ag >10) forms hematite-stained sericite–dolomite–albite lodes in stacked D2 reverse faults, which offset skarn, syenite, and the biotite–calcite veins by up to 25 m. The molybdenite Re–Os age (2,661 ± 10 Ma) of the ore suggests a genetic link to intrusive activity but is in apparent conflict with a monazite–xenotime U–Pb age (2,651 ± 6 Ma), which differs from that of the skarn at the 95% confidence level. The time relationships at both gold deposits are inconsistent with orogenic models invoking a principal role for metamorphic fluids released during the main phase of compression in the fold belt. Instead, mineralization is related in space and time to late-orogenic, magnetite-series, high-Mg monzodiorite–syenite intrusions of mantle origin, characterized by Mg/(Mg + Fe_TOTAL) = 0.31–0.57, high Cr (34–96 ppm), Ni (22–63 ppm), Ba (1,056–2,321 ppm), Sr (1,268–2,457 ppm), Th (15–36 ppm), and rare earth elements (total REE: 343–523 ppm). At Wallaby, shared Ca–K–CO₂ metasomatism and Th-REE enrichment (in allanite) link Au–Ag mineralization in biotite–calcite veins to the formation of the giant epidote skarn, implicating a Th + REE-rich syenite pluton at depth as the source of the oxidized hydrothermal fluid. At Granny Smith, lead isotope data and the Rb–Th–U signature of early hematite-bearing wall-rock alteration point to fluid released by the source pluton of the differentiated alkali granite dikes.     

DDTs and other chlorinated organic pesticides and polychlorinated biphenyls pollution in the surface sediments of Keratsini harbour, Saronikos gulf, Greece

Sediment samples were collected from Keratsini harbour, Saronikos gulf, Greece and were analysed for chlorinated organic pesticides (DDTs, HCB, Lindane) and polychlorinated biphenyls (PCBs). High total DDTs values were detected in all the sediments samples ranging from 9.1 to 75.6 mug/g, dry weight. PCBs concentrations range from 47.8 to 351.8 ng/g. The results and especially the high concentrations of DDTs reflect the influence of the industrial and urban wastes in the pollution for the Keratsini harbour environment.