The influence of Cr on the garnet–spinel transition in the Earth''s mantle: experiments in the system MgO–Cr2O3–SiO2 and thermodynamic modelling

The position of the transition from spinel peridotite to garnet peridotite in a simplified chemical composition has been determined experimentally at high pressures and high temperatures. The univariant reaction MgCr₂O₄+2Mg₂Si₂O₆=Mg₃Cr₂Si₃O₁₂+Mg₂SiO₄, has a negative slope in P–T space between 1200 °C and 1600 °C. The experimental results, combined with assessed thermodynamic data for MgCr₂O₄, MgSiO₃ and Mg₂SiO₄ give the entropy and enthalpy of formation of knorringite garnet (Mg₃Cr₂Si₃O₁₂). Thermodynamic calculations in simplified chemical compositions indicate that Cr shifts the garnet-in reaction to much higher pressures than previously anticipated. Moreover, in Cr-bearing systems a pressure–temperature field exists where garnet and spinel coexist. The width of this divariant field strongly depends on the Cr/(Cr+Al) of the system.     

Coupled redox transformations of catechol and cerium at the surface of a cerium(III) phosphate mineral

Highly insoluble Ce-bearing phosphate minerals form by weathering of apatite [Ca₅(PO₄)₃.(OH,F,Cl)], and are important phosphorous repositories in soils. Although these phases can be dissolved via biologically-mediated pathways, the dissolution mechanisms are poorly understood. In this paper we report spectroscopic evidence to support coupling of redox transformations of organic carbon and cerium during the reaction of rhabdophane (CePO₄·H₂O) and catechol, a ubiquitous biogenic compound, at pH 5. Results show that the oxic–anoxic conditions influence the mineral dissolution behavior. Under anoxic conditions, the release of P and Ce occurs stoichiometrically. In contrast, under oxic conditions, the mineral dissolution behavior is incongruent, with dissolving Ce³⁺ ions oxidizing to CeO₂. Reaction product analysis shows the formation of CO₂, polymeric C, and oxalate and malate. The presence of more complex forms of organic carbon was also confirmed. Near edge X-ray absorption fine structure spectroscopy measurements at Ce-M_4,5 and C-K absorption edges on reacted CePO₄·H₂O samples in the absence or presence of catechol and dissolved oxygen confirm that (1) the mineral surface converts to the oxide during this reaction, while full oxidation is limited to the near-surface region only; (2) the Ce valence remains unchanged when the reaction between CePO₄·H₂O and O₂ but in the absence of catechol. Carbon K-edge spectra acquired from rhabdophane reacted with catechol under oxic conditions show spectral features before and after reaction that are considerably different from catechol, indicating the formation of more complex organic molecules. Decreases in intensity of characteristic catechol peaks are accompanied by the appearance of new π^* resonances due to carbon in carboxyl (ca. 288.5 eV) and carbonyl (ca. 289.3 eV) groups, and the development of broad structure in the σ^* region characteristic of aliphatic carbon. Evolution of the C K-edge spectra is consistent with aromatic-ring cleavage and polymerization. These results further substantiate that the presence of catechol, O₂ (aq) causes both the oxidation of structural Ce³⁺ and the transformation of catechol to more complex organic molecules. Scanning Transmission X-Ray Microscopy measurements at the C K and Ce M_4,5 edges indicate three dominant organic species, varying in complexity and association with the inorganic phase. Untransformed catechol is loosely associated with CeO₂, whereas more complex organic molecules that exhibit lower aromaticity and stronger CO π^* resonances of carboxyl-C and carbonyl-C groups are only found in association with the grains. These results further serve as basis to postulate that, in the presence of O₂, CeO₂ can mediate the oxidative polymerization of catechol to form higher molecular weight polymers. The present work provides evidence for a pathway of biologically-induced, non-enzymatic oxidation of cerium and formation of small CeO₂ particles at room temperature. These findings may have implications for carbon cycling in natural and cerium-contaminated soils and aqueous environments.     

Effects of natural attenuation processes on groundwater contamination caused by abandoned waste sites in Berlin

The aim of this research project is to identify, characterize and quantify natural attenuation (NA) processes in groundwater affected by emissions of abandoned waste disposal sites in Berlin-Kladow/Gatow, Germany. It is part of the funding priority called KORA established by the Federal Ministry for Education and Research (BMBF) to explore the extent to which NA can be used for remedial purposes for varied forms of soil and groundwater contamination. Information on the emission behaviour of individual parameters is generated on the basis of hydrogeochemical comparison of 20 years old and new data. Using groundwater-modelling and CFC-analysis, information on the transport and retention of pollutants in groundwater is compiled. The microbial colonization of contaminated aquifers is characterized by molecular biological methods [polymerase chain reaction (PCR) and denaturing gradient gel electrophoresis (DGGE)] to differentiate between contaminated and not contaminated zones.     

Lower crustal melting and the role of open-system processes in the genesis of syn-orogenic quartz diorite–granite–leucogranite associations: constraints from Sr–Nd–O isotopes from the Bandombaai Complex, Namibia

The Bandombaai Complex (southern Kaoko Belt, Namibia) consists of three main intrusive rock types including metaluminous hornblende- and sphene-bearing quartz diorites, allanite-bearing granodiorites and granites, and peraluminous garnet- and muscovite-bearing leucogranites. Intrusion of the quartz diorites is constrained by a U–Pb zircon age of 540±3 Ma.

Quartz diorites, granodiorites and granites display heterogeneous initial Nd- and O isotope compositions (_{Nd (540 Ma)}=−6.3 to −19.8; δ¹⁸O=9.0–11.6‰) but rather low and uniform initial Sr isotope compositions (⁸⁷Sr/⁸⁶Sr_initial=0.70794–0.70982). Two leucogranites and one aplite have higher initial ⁸⁷Sr/⁸⁶Sr ratios (0.70828–0.71559), but similar initial _Nd (−11.9 to −15.8) and oxygen isotope values (10.5–12.9‰). The geochemical and isotopic characteristics of the Bandombaai Complex are distinct from other granitoids of the Kaoko Belt and the Central Zone of the Damara orogen. Our study suggests that the quartz diorites of the Bandombaai Complex are generated by melting of heterogeneous mafic lower crust. Based on a comparison with results from amphibolite-dehydration melting experiments, a lower crustal garnet- and amphibole-bearing metabasalt, probably enriched in K₂O, is a likely source rock for the quartz diorites. The granodiorites/granites show low Rb/Sr (<0.6) ratios and are probably generated by partial melting of meta-igneous (intermediate) lower crustal sources by amphibole-dehydration melting. Most of the leucogranites display higher Rb/Sr ratios (>1) and are most likely generated by biotite-dehydration melting of heterogeneous felsic lower crust. All segments of the lower crust underwent partial melting during the Pan-African orogeny at a time (540 Ma) when the middle crust of the central Damara orogen also underwent high T, medium P regional metamorphism and melting. Geochemical and isotope data from the Bandombaai Complex suggest that the Pan-African orogeny in this part of the orogen was not a major crust-forming episode. Instead, even the most primitive rock types of the region, the quartz diorites, represent recycled lower crustal material.     

Countergradient Fluxes of Conserved Variables in the Clear convective and Stratocumulus-topped Boundary Layer: The role of the Entrainment Flux

Large-eddy simulations of a clear convective boundary layer (CBL)and a stratocumulus-topped boundary layer are studied. Bottom-upand a top-down scalars were included in the simulations, and theprinciple of linear superposition of variables was applied toreconstruct the fields of any arbitrary conserved variable.This approach allows a systematic analysis of countergradient fluxesas a function of the flux ratio, which is defined as the ratio betweenthe entrainment flux and the surface flux of the conserved quantity.In general, the turbulent flux of an arbitrary conserved quantityis counter to the mean vertical gradient if the heights where thevertical flux and the mean vertical gradient change sign do notcoincide. The regime where the flux is countergradient is thereforebounded by the so-called zero-flux and zero-gradient heights. Becausethe vertical flux changes sign only if the entrainment flux has anopposite sign to the surface flux, countergradient fluxes arepredominantly found for negative flux ratios. In the CBL the fluxratio for the virtual potential temperature is, to a good approximation,constant, and equal to -0.2. Only if the moisture contribution to thevirtual potential temperature is negligibly small will the flux ratio forthe potential temperature be equal to this value. Otherwise, theflux ratio for the potential temperature can have any arbitrary(negative) value, and, as a consequence, the fluxes for thepotential temperature and the virtual potential temperature willbe countergradient at different heights. As a practical application ofthe results, vertical profiles of the countergradient correction termfor different entrainment-to-surface-flux ratios are discussed.     

Scientific uncertainty and climate change: Part II. Uncertainty and mitigation

In public debate surrounding climate change, scientific uncertainty is often cited in connection with arguments against mitigative action. This article examines the role of uncertainty about future climate change in determining the likely success or failure of mitigative action. We show by Monte Carlo simulation that greater uncertainty translates into a greater likelihood that mitigation efforts will fail to limit global warming to a target (e.g., 2 °C). The effect of uncertainty can be reduced by limiting greenhouse gas emissions. Taken together with the fact that greater uncertainty also increases the potential damages arising from unabated emissions (Lewandowsky et al. 2014), any appeal to uncertainty implies a stronger, rather than weaker, need to cut greenhouse gas emissions than in the absence of uncertainty.     

Late Quaternary solifluction sheets in the British uplands

Solifluction sheets are large-scale and extensive valley-floor and valley-side landforms developed widely in the British Isles from mass-wasting of glacial and periglacial sediments during late-glacial times. We describe their geographical distribution and review the processes that have led to their development. We use data from the Cheviot Hills, the one site in the British Isles where sedimentology and optically stimulated luminescence dating have been combined, to assess their age and nature of deposition. We also present data from central Wales where a new mapping and resistivity survey has reconstructed the nature of valley-side solifluction sheets. We explore the relative lack of recent research on these landforms and argue that solifluction sheets represent a clear example of how upland geomorphological systems have responded to late-glacial climate change. We end by identifying a number of areas where research on these enigmatic features could be focussed, including better understanding of their distribution, sedimentology and age.     

The pre-weichselian glaciations of North-West Europe

In North-West Europe no evidence has been found for glaciations older than the Elsterian. The Elsterian seems to consist of at least two separate ice advances with a minor interval in between. During the Elsterian in the area south of the Baltic Sea over 400 m deep channels were cut into the underlying substratum by a combination of glacial erosion and meltwater activity. The channels were active until the Late Elsterian and were subsequently filled with meltwater deposits and glaciolacustrine silt and clay. During the Saalian no comparative channels were being formed. Three different ice advances can be distinguished within the Saalian, the stratigraphical correlation of which is to be discussed. No convincing evidence was found for any interglacial within the Saalian sequence. There are good reasons to assume that the ice advances were only separated from each other by minor ice-free intervals.     

40Ar-39Ar Ages of Types 3 and 4, L and H Chondrites from Antarctica

Abstract— This is a report on ⁴⁰Ar-³⁹Ar studies of 7 low petrographic type L and H chondrites from Antarctica. From petrographic similarities it has been argued that the L3 chondrites ALHA77015, ?77167, ?77249, and ?77260 are pieces from a common fall (McKinley et al., 1981). Our results now confirm this supposition: The four meteorites have identical characteristic Ar-degassing patterns, very similar K, Ca, Cl, and ³⁶Ar_trapped contents, and similar ⁴⁰Ar-³⁹Ar ages of <4 Ga which are rather unusual for ordinary chondrites and might be due to shock. The undulating age patterns could be due to weathering or to ³⁹Ar recoil. The L4 chondrite ALHA77230 shows no age plateau and only a lower limit for the time of a severe degassing, 4.0 Ga, can be given. ALHA77226 and RKPA78002, two H4 chondrites, exhibit reasonably well defined age plateaus at about 4.3 and 4.4 Ga. Two individual chondrules from RKPA78002 have the same age as the whole rock sample.     

The provenance of Australian uranium ore concentrates by elemental and isotopic analysis

Elemental and isotopic ratio analyses of U ore concentrate samples, from the 3 operating U mining facilities in Australia, were carried out to determine if significant variations exist between their products, thereby allowing the U ore concentrate’s origin to be identified. Elemental analyses were conducted using inductively coupled plasma mass spectrometry (ICP-MS) and X-ray fluorescence spectrometry (XRF). Lead isotope ratios were measured using ICP-MS and U isotope analyses were conducted using thermal ionisation mass spectrometry (TIMS). Minute quantities of sample, such as that obtained from a swipe, were also examined for elemental concentrations using secondary ion mass spectrometry (SIMS). The results of multivariate statistical analysis show clear patterns in the trace elemental composition of the processed U ores, indicating that it is possible to use this feature as a unique identifier of an Australian U ore concentrate’s source. Secondary ion mass spectrometry analyses also allow individual particles to be differentiated using this ‘fingerprinting’ technique. Isotope ratios determined using TIMS reveal that there is a significant difference in the n(²³⁴U)/n(²³⁸U) isotope ratio between the U ore concentrate from each mine.