Biogenic nanoparticulate UO2: Synthesis, characterization, and factors affecting surface reactivity

The surface reactivity of biogenic, nanoparticulate UO₂ with respect to sorption of aqueous Zn(II) and particle annealing is different from that of bulk uraninite because of the presence of surface-associated organic matter on the biogenic UO₂. Synthesis of biogenic UO₂ was accomplished by reduction of aqueous uranyl ions, by Shewanella putrefaciens CN32, and the resulting nanoparticles were washed using one of two protocols: (1) to remove surface-associated organic matter and soluble uranyl species (NAUO2), or (2) to remove only soluble uranyl species (BIUO2). A suite of bulk and surface characterization techniques was used to examine bulk and biogenic, nanoparticulate UO₂ as a function of particle size and surface-associated organic matter. The N₂-BET surface areas of the two biogenic UO₂ samples following the washing procedures are 128.63 m² g⁻¹ (NAUO2) and 92.56 m² g⁻¹ (BIUO2), and the average particle sizes range from 5-10 nm based on TEM imaging. Electrophoretic mobility measurements indicate that the surface charge behavior of biogenic, nanoparticulate UO₂ (both NAUO2 and BIUO2) over the pH range 3-9 is the same as that of bulk. The U L_III-edge EXAFS spectra for biogenic UO₂ (both NAUO2 and BIUO2) were best fit with half the number of second-shell uranium neighbors compared to bulk uraninite, and no oxygen neighbors were detected beyond the first shell around U(IV) in the biogenic UO₂. At pH 7, sorption of Zn(II) onto both bulk uraninite and biogenic, nanoparticulate UO₂ is independent of electrolyte concentration, suggesting that Zn(II) sorption complexes are dominantly inner-sphere. The maximum surface area-normalized Zn(II) sorption loadings for the three substrates were 3.00 ± 0.20 μmol m⁻² UO₂ (bulk uraninite), 2.34 ± 0.12 μmol m⁻² UO₂ (NAUO2), and 2.57 ± 0.10 μmol m⁻² UO₂ (BIUO2). Fits of Zn K-edge EXAFS spectra for biogenic, nanoparticulate UO₂ indicate that Zn(II) sorption is dependent on the washing protocol. Zn-U pair correlations were observed at 2.8 ± 0.1 Å for NAUO2 and bulk uraninite; however, they were not observed for sample BIUO2. The derived Zn-U distance, coupled with an average Zn-O distance of 2.09 ± 0.02 Å, indicates that Zn(O,OH)₆ sorbs as bidentate, edge-sharing complexes to UO₈ polyhedra at the surface of NAUO2 nanoparticles and bulk uraninite, which is consistent with a Pauling bond-valence analysis. The absence of Zn-U pair correlations in sample BIUO2 suggests that Zn(II) binds preferentially to the organic matter coating rather than the UO₂ surface. Surface-associated organic matter on the biogenic UO₂ particles also inhibited particle annealing at 90 °C under anaerobic conditions. These results suggest that surface-associated organic matter decreases the reactivity of biogenic, nanoparticulate UO₂ surfaces relative to aqueous Zn(II) and possibly other environmental contaminants.     

Modelling weathering processes at the catchment scale: The WITCH numerical model

A numerical model of chemical weathering in soil horizons and underlying bedrock (WITCH) has been coupled to a numerical model of water and carbon cycles in forest ecosystems (ASPECTS) to simulate the concentration of major species within the soil horizons and the stream of the Strengbach granitic watershed, located in the Vosges Mountains (France). For the first time, simulations of solute concentrations in soil layers and in the catchment river have been performed on a seasonal basis. The model is able to reproduce the concentrations of most major species within the soil horizons, as well as catching the first-order seasonal fluctuations of aqueous calcium, magnesium and silica concentrations. However, the WITCH model underestimates concentrations of Mg²⁺ and silica at the spring of the catchment stream, and significantly underestimates Ca²⁺ concentration. The deficit in calculated calcium can be compensated for by dissolution of trace apatite disseminated in the bedrock. However, the resulting increased Ca²⁺ release yields important smectite precipitation in the deepest model layer (in contact with the bedrock) and subsequent removal of large amount of silica and magnesium from solution. In contrast, the model accurately accounts for the concentrations of major species (Ca, Mg and silica) measured in the catchment stream when precipitation of clay minerals is not allowed. The model underestimation of Mg²⁺ and H₄SiO₄ concentrations when precipitation of well crystallized smectites is allowed strongly suggests that precipitation of well crystallized clay minerals is overestimated and that more soluble poorly crystallized and amorphous materials may be forming. In agreement with observations on other watersheds draining granitic rocks, this study indicates that highly soluble trace calcic phases control the aqueous calcium budget in the Strengbach watershed.     

Recognizing soft-sediment structures in deformed rocks of orogens

Soft-sediment deformation structures are common on passive continental margins, in trenches at subduction zones, and in strike-slip environments. Rocks from all these tectonic environments are incorporated into orogens, where soft-sediment deformation structures should be common. However, recognizing soft-sediment structures is difficult where superimposed tectonic structures are present. In seeking characteristic features of soft-sediment deformation, it is important to separate questions that relate to physical state (lithified or unlithified) from those that address the overall kinematic style (rooted or gravity driven). One recognizable physical state is liquefaction, which produces sand that has much lower strength than interbedded mud. Hence structures which indicate that mud was stronger than adjacent sand at the time of deformation can be used as indicators of soft-sediment deformation. These include angular fragments of mud surrounded by sand, dykes of sand cutting mud, and most usefully, folded sandstone layers displaying class 3 geometry interbedded with mud layers that show class 1 geometry. All these geometries have the potential to survive overprinting by later superimposed tectonic deformation; when preserved in deformed sedimentary rocks at low metamorphic grade they are indicators of liquefaction of unlithified sediment during deformation.     

A spectrophotometric measurement of soil cation exchange capacity based on cobaltihexamine chloride absorbance

Among numerous methods for cation exchange capacity (CEC) determination for soils and sediments, the cobaltihexamine chloride method is frequently used due to its ability to measure CEC at soil pH. After exchange with Co(NH₃)₆³⁺ ions, CEC is estimated via the measurement of the Co remaining in solution. The modified method proposed allows a more rapid determination of CEC based on the measurement of the absorbance at 472 nm of the cobaltihexamine chloride solution before and after exchange. This method has been applied to various soil's horizons from four sites, selected to cover a wide range of CEC and pH values. The model obtained allows one to calculate CEC from absorbance at 472 nm with 95% confidence intervals. As CEC is of relevant meaning in agronomical and environmental purposes, and more recently in ecotoxicological studies, this modified method can be proposed as a rapid test for CEC evaluation.     

The landslides threatening Tasova town (Central Anatolia, Turkey) and their environmental impacts

There exist a number of landslides along the north Anatolian fault zone (NAFZ) between Tasova and Alparslan in Amasya province in Turkey. These landslides extending over an area of 2.5 × 6.0 km are triggered by steepening of slopes due to undercutting by the Yesilirmak River and groundwater fluctuations. The landslides have affected 30 buildings in the western part of Tasova. In this study, in order to investigate the engineering geological characteristics of the landslides and their environmental impacts, representative samples from geological units were collected and a total of six boreholes were drilled. Plastic pipes were installed into the boreholes to measure the groundwater fluctuations and to determine the position of the sliding surface. For a two-year monitoring period, using a GPS linked to a fixed station system, the magnitude of the movements ranged between 11.7 and 17.6 cm at the toe of landslide. The landslides that occurred in the study area were in the form of retrogressive circular and multiple circular failures. The factor of safety along a number of cross-sections calculated by the limit-equilibrium method of analysis is 0.96 in static condition. After further analyses, construction of a toe buttress with surface drainage may be suggested as a remedial measure to minimize the effects of these landslides.     

Petrogenesis of plio-quaternary intra-plate continental alkaline lavas from the İskenderun Gulf (Southern Turkey): Evidence for metasomatized lithospheric mantle

The Quaternary alkaline volcanic field of Southern Turkey is characterized by intra-continental plate-type magmatic products, exposed to the north of the ?skenderun Gulf along a NE-SW trending East Anatolian Fault, to the west of its intersection with the N–S trending Dead Sea Fault zone. The ?skenderun Gulf alkaline rocks are mostly silica-undersaturated with normative nepheline and olivine and are mostly classified as basanites and alkaline basalts with their low-silica contents ranging between 43 and 48?wt.% SiO₂. They display Ocean Island Basalt (OIB)–type trace element patterns characterized by enrichments in large-ion-lithophile elements (LILE) and light rare earth element (LREE), and have (La/Yb)_N?=?8.8–17.7 and (Hf/Sm)_N?=?0.9–1.6 similar to those of basaltic rocks found in intraplate suites. The basanitic rocks have limited variations Sr-Nd isotopic ratios (⁸⁷Sr/⁸⁶Sr?=?0.70307–0.70324, ¹⁴³Nd/¹⁴⁴Nd?=?0.512918–0.521947), whereas the alkali basalts display more evolved Sr-Nd isotopic ratios (⁸⁷Sr/⁸⁶Sr?=?0.70346-0.70365, ¹⁴³Nd/¹⁴⁴Nd?=?0.512887–0.521896). The ?skenderun Gulf alkaline rocks also display limited Pb isotopic variations with ²⁰⁶Pb/²⁰⁴Pb?=?18.75–19.09 ²⁰⁷Pb/²⁰⁴Pb?=?15.61–15.66 and²⁰⁸Pb/²⁰⁴Pb?=?38.65–39.02, indicating that they originated from an enriched lithospheric mantle source. Calculated fractionation vectors indicate that clinopyroxene and olivine are the main fractionating mineral phases. Similarly, based on Sr-Nd isotopic ratios, the assimilation and fractional crystallization (AFC) modeling shows that the alkali basalts were affected by AFC processes (r?=?0.2) and were slightly contaminated by the upper crustal material.The high TiO₂ contents, enrichments in Ba and Nb, and depletions in Rb can likely be explained by the existence of amphibole in the mantle source, which might, in turn, indicate that the source mantle has been affected by metasomatic processes. The modeling based on relative abundances of trace elements suggests involvement of amphibole-bearing peridotite as the source material. ?skenderun Gulf alkaline rocks can thus be interpreted as the products of variable extent of mixing between melts from both amphibole-bearing peridotite and dry peridotite.     

Geochemistry of Çoruh River Bed Sediments in NE Turkey: Implications in Weathering-Sedimentary Cycle,Provenance, and Metal Pollution

This study defines the source area, sub-aerial weathering, and sedimentary cycle level, as well as heavy metal content and origin, of the Çoruh River bed sediments. The studied sediments are geochemically classified as litharenite based on the ratio of the major element contents. Relative to the Upper Continental Crust (UCC), trace elements Rb, Sr, Ba, Th, U, Zr, Hf, Y, Nb, and Pb are generally depleted; Co, Ni, Cu, Sc, and V are generally enriched; and Au is depleted in some places and enriched in other places. The rare earth element (REE) distributions of the samples exhibit a trend similar to that of the upper continental crust (UCC); however, low to moderate depletion occurs in the bed sediments in UCC. The analyzed samples exhibit low Chemical Index of Alteration (CIA) values, Plagioclase Index of Alteration (PIA) values (<50), CIA/WIP (Weathering Index ratios <1), and substantially high Index of Compositional Variability values (ICV) (>1). Thus, the samples are not chemically mature and are mainly derived from non-altered sources and were exposed the simple cycling history. REEs are depleted in the river bed sediments, unlike the world river average silt, world river average clay, and suspended sediment in world rivers. Minor enrichment of Zn, Sn, and Sc contents, low-to-moderate enrichment of Cu content, very severe enrichment of as content, and extremely severe enrichment of Ni content of the analyzed samples are observed. Consequently, stream bed sediments are derived from intermediate sources close to mid-continental crust rather than felsic sources Low-to-moderate degrees of chemical weathering of these sediments indicate increased tectonic activity, increased erosion, and rapid sedimentation in semiarid to arid conditions in the source regions over time. Thus, the sediments are chemically immature. These sediments are exposed to lithogenic and anthropogenic contamination.     

Analysis of the FEBEX multi‐barrier system including thermoplasticity of unsaturated bentonite

Deep geological repository involving a multibarrier system constitutes one of the most promising options for isolating high‐level radioactive waste from the human environment. To certify the efficiency of waste isolation, it is essential to understand the behaviour of confining geomaterial under a variety of environmental conditions. To this end, results from a near‐to‐real experiment, the full‐scale engineered barriers in situ experiment, are studied by means of a thermo–hydro–mechanical finite element approach, including a consistent thermoplastic constitutive model for unsaturated soils. Laboratory tests are simulated to calibrate model parameters. The results of the numerical simulations are compared with sensor measurements and show the ability of the model to reproduce the main behavioural features of the system. The influence of the hysteretic and temperature‐dependent retention of water on the mechanical response is exhibited. Finally, those results are interpreted in the light of thermoplasticity of unsaturated soils, which reveals the highly coupled and non‐linear characters of the processes encountered. Copyright © 2011 John Wiley & Sons, Ltd.     

It starts at home? Climate policies targeting household consumption and behavioral decisions are key to low-carbon futures

Through their consumption behavior, households are responsible for 72% of global greenhouse gas emissions. Thus, they are key actors in reaching the 1.5 °C goal under the Paris Agreement. However, the possible contribution and position of households in climate policies is neither well understood, nor do households receive sufficiently high priority in current climate policy strategies. This paper investigates how behavioral change can achieve a substantial reduction in greenhouse gas emissions in European high-income countries. It uses theoretical thinking and some core results from the HOPE research project, which investigated household preferences for reducing emissions in four European cities in France, Germany, Norway and Sweden. The paper makes five major points: First, car and plane mobility, meat and dairy consumption, as well as heating are the most dominant components of household footprints. Second, household living situations (demographics, size of home) greatly influence the household potential to reduce their footprint, even more than country or city location. Third, household decisions can be sequential and temporally dynamic, shifting through different phases such as childhood, adulthood, and illness. Fourth, short term voluntary efforts will not be sufficient by themselves to reach the drastic reductions needed to achieve the 1.5 °C goal; instead, households need a regulatory framework supporting their behavioral changes. Fifth, there is a mismatch between the roles and responsibilities conveyed by current climate policies and household perceptions of responsibility. We then conclude with further recommendations for research and policy.