Europium retention onto clay minerals from 25 to 150 °C: Experimental measurements, spectroscopic features and sorption modelling

The sorption of Eu(III) onto kaolinite and montmorillonite was investigated up to 150 °C. The clays were purified samples, saturated with Na in the case of montmorillonite. Batch experiments were conducted at 25, 40, 80 and 150 °C in 0.5 M NaClO₄ solutions to measure the distribution coefficients (Kd) of Eu as a trace element (<10⁻⁶ mol/L) between the solution and kaolinite. For the Na-montmorillonite, we used Kd results from a previous study [Tertre, E., Berger, G., Castet, S., Loubet, M., Giffaut, E., 2005. Experimental study of adsorption of Ni²⁺, Cs⁺ and Ln³⁺ onto Na-montmorillonite up to 150 °C. Geochim. Cosmochim. Acta69, 4937-4948] obtained under exactly the same conditions. The number and nature of the Eu species sorbed onto both clay minerals were investigated by time resolved laser fluorescence spectroscopy (TRLFS) in specific experiments in the same temperature range. We identified a unique inner-sphere complex linked to the aluminol sites in both clays, assumed to be AlOEu²⁺ at the edge of the particles, and a second exchangeable outer-sphere complex for montmorillonite, probably in an interlayer position. The Kd values were used to adjust the parameters of a surface complexation model (DLM: diffuse layer model) from 25 to 150 °C. The number of Eu complexes and the stoichiometry of reactions were constrained by TRLFS. The acidity constants of the amphoteric aluminol sites were taken from another study [Tertre, E., Castet, S., Berger, G., Loubet, M., Giffaut, E. Acid/base surface chemistry of kaolinite and Na-montmorillonite at 25 and 60 °C: experimental study and modelling. Geochim. Cosmochim. Acta, in press], which integrates the influence of the negative structural charge of clays on the acid/base properties of edge sites as a function of temperature and ionic strength. The results of the modelling show that the observed shift of the sorption edge towards low pH with increasing temperature results solely from the contribution of the AlOEu²⁺ edge complexes. Finally, we successfully tested the performance of our model by confronting the predictions with experimental Kd data. We used our own data obtained at lower ionic strength (previous study) or higher suspension density and higher starting concentration (TRLFS runs, this study), as well as published data from other experimental studies [Bradbury, M.H., Baeyens, B., 2002. Sorption of Eu on Na and Ca-montmorillonite: experimental investigations and modeling with cation exchange and surface complexation. Geochim. Cosmochim. Acta66, 2325-2334; Kowal-Fouchard, A., 2002. Etude des mécanismes de rétention des ions U(IV) et Eu(III) sur les argiles: influence des silicates. Ph.D. Thesis, Université Paris Sud, France, 330p].     

A metabolism-based trophic index for comparing the ecological values of shallow-water sediment habitats

We determined fluxes of oxygen and nutrients between water and sediments at 21 sites primarily in Virginia and North Carolina estuaries, over the past 15 yr. These sites represented broad ranges in salinity, tidal amplitude, hydrology, nutrient availability, turbidity, light availability, depth, sediment grain size, and anthropogenic disturbance. In general, we found that heterotrophically dominated sediments had the potential to degrade water quality, whereas photoautotrophy in the sediments ameliorated this impact. We propose a benthic trophic state index as a management tool to make general assessments of the degree to which sediments support ecological processes related to photoautotrophy. The index can be based on simple measurements of metabolic parameters. We also evaluated the relative significance of variability in the index across a number of spatial and temporal scales. Reduced photoautotrophy and/or enhanced heterotrophy tended to be associated with finer-grained, organic-rich sediments. This sediment type was common in oligohaline areas at water depths exceeding 2 m. Temporally, autotrophy declined from winter to spring particularly at sandy sites, while interannual variability was more pronounced for mud sites. *** DIRECT SUPPORT *** A01BY074 00011     

Chemical composition of spinel from Uralian-Alaskan-type Mafic–Ultramafic complexes and its petrogenetic significance

Uralian-Alaskan-type mafic–ultramafic complexes are recognized as a distinct class of intrusions regarding lithologic assemblage, mineral chemistry and petrogenetic setting. In the present study, we discuss new data on the distribution of major elements in minerals of the spinel group in rocks from Uralian-Alaskan-type complexes in the Ural Mountains, Russia. Cr-rich spinel (Cr₂O₃ = 20–53 wt%) in dunite with interstitial clinopyroxene and in wehrlite cumulates indicate that it reacted with interstitial liquid resulting in the progressive substitution of Al₂O₂ and Cr₂O₃ by Fe₂O₃ and TiO₂. A distinct change in the spinel chemistry in dunite (Cr₂O₃ = 47–53 wt%), towards Al₂O₃- and Cr₂O₃-poor but Fe₂O₃-rich compositions monitors the onset of clinopyroxene fractionation in wehrlite (Cr₂O₃ = 15–35 wt%, Al₂O₃ = 1–8 wt%, Fe₂O₃ = 25–55 wt%). In more fractionated mafic rocks, the calculated initial composition of exsolved spinel traces the sustained crystallization of clinopyroxene by decreasing Cr₂O₃ and increasing FeO, Fe₂O₃ and fO₂. Finally, the initiation of feldspar crystallization buffers the Al₂O₃ content in most of the spinels in mafic rocks at very low Cr₂O₃ contents (<5 wt%). The fractionation path all along and the reaction with interstitial liquid are accompanied by increasing Fe₂O₃ contents in the spinel. This likely is caused by a significant increase in the oxygen fugacity, which suggests closed system fractionation processes. Spinel with Cr₂O₃ < 27 wt% is exsolved into a Fe₂O₃-rich and an Al₂O₃-rich phase forming a variety of textures. Remarkably, exsolved spinel in different lithologies from complexes 200 km apart follows one distinct solvus line defining a temperature of ca. 600°C. This indicates that the parental magmas were emplaced and eventually cooled at similar levels in the lithosphere, likely near the crust–mantle boundary. Eventually, these 600°C hot bodies were rapidly transported into colder regions of the upper crust during a regional tectonic event, probably during the major active phase of the Main Uralian Fault.     

The reduction of aliasing in gravity anomalies and geoid heights using digital terrain data

Observations of gravity can be aliased by virtue of the logistics involved in collecting these data in the field. For instance, gravity measurements are often made in more accessible lowland areas where there are roads and tracks, thus omitting areas of higher relief in between. The gravimetric determination of the geoid requires mean terrain-corrected free-air anomalies; however, anomalies based only on the observations in lowland regions are not necessarily representative of the true mean value over the topography. A five-stage approach is taken that uses a digital elevation model, which provides a more accurate representation of the topography than the gravity observation elevations, to reduce the unrepresentative sampling in the gravity observations. When using this approach with the Australian digital elevation model, the terrain-corrected free-air anomalies generated from the Australian gravity data base change by between 77.075 and −84.335 mgal (−0.193 mgal mean and 2.687 mgal standard deviation). Subsequent gravimetric geoid computations are used to illustrate the effect of aliasing in the Australian gravity data upon the geoid. The difference between 'aliased' and 'non-aliased' gravimetric geoid solutions varies by between 0.732 and −1.816 m (−0.058 m mean and 0.122 m standard deviation). Based on these conceptual arguments and numerical results, it is recommended that supplementary digital elevation information be included during the estimation of mean gravity anomalies prior to the computation of a gravimetric geoid model.     

Formation of a local atmospheric electric field

We have estimated the variations in the atmospheric electrostatic field (AEF, E _Z(0)) strength in the surface layer caused by variations in conductivity due to radon influences, cosmic ray intensity, changes in the balance of light and heavy ions during sunset and sunrise, and under the effect of the ionospheric electric current potential on the AEF potential. It is shown that the air conductivity varies due to ionization under the effect of radon emanations and is determined by the radon exhalation and turbulent diffusion of the surface air layer, while the cosmic ray intensity affects the surface air conductivity through changes in the ion recombination conditions. A decrease in the air conductivity due to a decrease in the cosmic ray intensity (Forbush decrease) also decreases E _Z(0), while a decrease in radon fluxes results in an increase in E _Z(0). We have estimated the effect of illumination conditions on the AEF due to variations in the relative concentration of heavy and light ions under the influence of photodetachment and photoattachment processes. The work has been done on the basis of data received from the Paratunka observatory (Kamchatka).     

Geo-Characterization at selected accelerometric stations in Crete (Greece) and comparison of earthquake data recordings with EC8 elastic spectra

To estimate the seismic response according to Eurocode (EC8) and almost all other national codes, site conditions have to be properly characterized so that soil amplification and the corresponding peak ground motion can be calculated. In this work, different geophysical and geotechnical methods are combined in order to define the detailed ground conditions in selected sites of the Hellenic Accelerometric Network (HAN) in Crete. For this purpose, the geological information of the sites and shear wave velocity, calculated from surface wave measurements, is used. Additionally, ground acceleration data recorded through HAN have been utilized from intermediate depth earthquakes in the broader area of South Aegean Sea. Using the recorded ground motion data and the procedure defined in EC8, the corresponding elastic response spectrum is calculated for the selected sites. The resulting information is compared to the values defined in the corresponding EC8 spectrum for the seismic zone that includes the island of Crete. The comparison shows that accurate definition of ground type through geological, geotechnical and geophysical investigations is important. However, our current comparison focuses on the distribution of values rather than the absolute values of EC8-prescribed spectra, and the results should be considered in this context.     

Monitoring Large-Scale Tests for Nuclear Waste Disposal

Two large-scale “in situ” demonstration experiments and their instrumentation are described. The first test (FEBEX Experiment) involves the hydration of a compacted bentonite barrier under the combined effect of an inner source of heat and an outer water flow from the confining saturated granite rock. In the second case, the progressive de-saturation of Opalinus clay induced by maintained ventilation of an unlined tunnel is analyzed. The paper shows the performance of different sensors (capacitive cells, psychrometers, TDR’s) and a comparison of fill behaviour with modelling results. The long term performance of some instruments could also be evaluated specially in the case of FEBEX test. Capacitive sensors provide relative humidity data during long transient periods characterised by very large variations of suction within the bentonite.     

Interpretation of transient electromagnetic soundings over three-dimensional structures for the central-loop configuration

Summary. An assessment is made of the bias of fitting constrained layered-earth models to transient electromagnetic data obtained over 3-D structures. In this assessment we use the central-loop configuration and show that accurate estimates of the depth of burial of 3-D structures can be obtained with layered-earth model fitting. However, layered-earth interpretations are not reliable for estimating depth extents and resistivities of 3-D structures. When layered earths are used for interpretation, it is advantageous in some cases to use data based on the magnetic field instead of the voltage. A magnetic-field definition of apparent resistivity, in contrast to a definition based on the voltage, eliminates apparent-resistivity overshoots and undershoots in the data. A resistivity undershoot in the data can produce an extraneous and misleading layer in an interpretation of a 3-D resistive structure. Due to 3-D effects, apparent-resistivity soundings (magnetic field and voltage) may rise so steeply at late times that it may not be possible to fit a sounding to a reasonable layered-earth model. Truncating such a sounding, over a buried conductor, allows for a reasonable layered-earth fit and an accurate estimate of the depth to the conductor. However, the resistivity of the conductor is overestimated.
Measurements of the horizontal field in the central-loop configuration can map 3-D structures, provided the sensor is located accurately at the centre of the transmitting loop. Horizontal-field calculations show that the transients peak on the flanks of a 3-D structure, but are depressed over the structure's centre. Weak transient responses flanked by two large transient responses, which are opposite in sign, locate the structure. The sign reversal is caused by a corresponding reversal in the currents that are channelled through or deflected away from conductive or resistive structures, respectively.     

The geochronology and origin of mantle sources for late cenozoic intraplate volcanism in the frontal part of the Arabian plate in the Karacadağ neovolcanic area of Turkey. Part 1. The results of isotope-geochronological studies

This paper considers results from isotope-geochronological (K-Ar) studies of the products of Neogene-Quaternary volcanism in the Karacada? area, which is situated within the northern frontal part of the Arabian plate. It was found that magmatic activity has been evolving at this location for at least the last 11–10 Myr and was distinctly discrete in character. Three stages of volcanism have been identified: (I) Early or Miocene, ～11–6.7 Ma; (II) Middle or Pliocene-Early Quaternary, 4–1 Ma; and (III) Late or Late Quaternary, 0.4–0.1 Ma. The most recent manifestations of magmatic activity in the region date back to about 100000 years ago. An analysis of the spatial distribution of volcanic centers of different ages in the Karacada? neovolcanic area shows that the magmatism of that region involved a lateral migration of activity from northwest to southeast along a major regional tectonic fault. The migration was caused by the movement of local tension zones where the lithosphere was thinner and deep-seated mantle magmas were ascending.