Enhanced Oxygen Isotope Determination in Uranium Oxides Using BrF5 Fluorination

A new method for accurate determination of oxygen isotopes in uranium oxides encountered in the nuclear fuel cycle was developed using the conventional BrF₅ fluorination technique. Laser‐assisted fluorination was tested for comparison. We focused on fine powders of triuranium octoxide (U₃O₈), uranium dioxide (UO_2±x with 0 ≤ x ≤ 0.25), uranium trioxide (UO₃.nH₂O, with 0.8 ≤ n ≤ 2) and diuranates (M₂U₂O₇.nH₂O, with M = NH₄, Na or Mg_0.5 and 0 ≤ n ≤ 6). Fluorination at room temperature and heating under vacuum at 150 °C are shown to eliminate both adsorbed and structural water from the powder samples. Precision fit for purpose of δ¹⁸O values (± 0.3‰, 1s) and oxygen yields (close to 100%) were obtained for U₃O₈ and UO₂ where oxygen is only bound to uranium. A lower precision was observed for UO₃.nH₂O and M₂U₂O₇.nH₂O where oxygen is both present in the structural H₂O and bonded to uranium and where the extracted O_2(g) can be contaminated by NF₃ and NO_x compounds. Laser‐assisted fluorination gave shifted δ¹⁸O values between +0.8 and +1.4‰ for U₃O₈, around ?0.8‰ for UO₃.nH₂O and between ?3.9 and ?4.5‰ for M₂U₂O₇.nH₂O (± 0.3‰, 1s) compared with the conventional method.     

Fitting the Linear Model of Coregionalization by Generalized Least Squares

In geostatistical studies, the fitting of the linear model of coregionalization (LMC) to direct and cross experimental semivariograms is usually performed with a weighted least-squares (WLS) procedure based on the number of pairs of observations at each lag. So far, no study has investigated the efficiency of other least-squares procedures, such as ordinary least squares (OLS), generalized least squares (GLS), and WLS with other weighing functions, in the context of the LMC. In this article, we compare the statistical properties of the sill estimators obtained with eight least-squares procedures for fitting the LMC: OLS, four WLS, and three GLS. The WLS procedures are based on approximations of the variance of semivariogram estimates at each distance lag. The GLS procedures use a variance–covariance matrix of semivariogram estimates that is (i) estimated using the fourth-order moments with sill estimates (GLS₁), (ii) calculated using the fourth-order moments with the theoretical sills (GLS₂), and (iii) based on an approximation using the correlation between semivariogram estimates in the case of spatial independence of the observations (GLS₃). The current algorithm for fitting the LMC by WLS while ensuring the positive semidefiniteness of sill matrix estimates is modified to include any least-squares procedure. A Monte Carlo study is performed for 16 scenarios corresponding to different combinations of the number of variables, number of spatial structures, values of ranges, and scale dependence of the correlations among variables. Simulation results show that the mean square error is accounted for mostly by the variance of the sill estimators instead of their squared bias. Overall, the estimated GLS₁ and theoretical GLS₂ are the most efficient, followed by the WLS procedure that is based on the number of pairs of observations and the average distance at each lag. On that basis, GLS₁ can be recommended for future studies using the LMC.     

Microstructure and hydraulic conductivity of a compacted lime-treated soil

Under a given compaction energy and procedure, it is known that maximum dry density of a soil is lowered due to lime addition. This modification of maximum dry density could alter the hydraulic conductivity of the soil. The main object of this study was to assess the impact of lime-stabilization on a silt soil microstructure and then on saturated hydraulic conductivity. An investigation at the microscopic level with mercury intrusion porosimetry showed that lime treatment induced the formation of a new small class, with a diameter lower than 3 × 10³ Å in the compacted soil. This class is responsible for the difference in dry density between the treated and the untreated sample after compaction. It is shown that this small pores class was not altered by the compaction water content, the compaction procedure or the dry density. As in untreated soils, only the larger pores were modified by the compaction water content and the compaction procedure in the lime treated samples. The hydraulic conductivity appeared to be only related to the largest pores volume of the tested silt, regardless of lime treatment. Therefore, this study demonstrated that even if addition of lime resulted in a dramatic change of the maximum dry density of the tested silty soil, its effect on hydraulic conductivity is limited.     

Numerical simulation of the 30–45 ka debris avalanche flow of Montagne Pelée volcano,Martinique: from volcano flank collapse to submarine emplacement

Natural Hazards - In November 2015, China government announced that the national carbon emissions trading market is expected to start in 2017. Carbon emission trading system is a raising concern...     

From subduction to transform motion: a seabeam survey of the Hellenic trench system

Preliminary results of a multi-narrow beam survey of the Hellenic trench system, in the Eastern Mediterranean, are presented. The southwestern Ionian branch is divided in small basins, partly filled with Pleistocene sediments. The morphology suggests that the basins are deformed by a compressional stress acting roughly perpendicularly to the trench along N50°E. This direction is the direction of the regional slip vector of the shallow thrust-type earthquakes. The structure of the southeastern Pliny-Strabo branch is quite different. Narrow en-e´chelon slots, oriented N40°E, have been mapped within the main troughs oriented N60°E. The regional earthquake slip vector is also oriented along N40°E. We conclude that the Hellenic trench system is an active subduction system, dominated by thrust along the Ionian branch and by transform motion along the Pliny-Strabo branch.     

Micro-environmental controls on biomineralization: superficial processes of apatite and calcite precipitation in Quaternary soils, Roussillon, France

Calcium hydroxyapatite and calcite precipitates around bacteria were observed in 2-week-old alluvial topsoil (Roussillon area, SE France). This observation prompted a laboratory study of Ca²⁺ and PO₄³⁻ incorporation into hydroxyapatite and Ca²⁺ into calcite mediated by bacteria using similar topsoil material, but free from apatite and calcite. Subsamples were prepared using three different grain sizes, and experiments were undertaken using sucrose and different contents of Ca²⁺ and PO₄³⁻. Mineralization experiments proceeded over 5 days. Calcium and PO₄³⁻ sorption onto clay influenced the Ca/P ratio in the solutions. Hydroxyapatite and calcite precipitation only occurred in unsterilized samples. The presence of clay minerals promoted biomineralization.     

Groundwater chemistry and mass transfers in the Independence aquifer,central Mexico,by using multivariate statistics and mass-balance models

In the light of progressive depletion of groundwater reservoir and water quality deterioration of the Independence aquifer, an investigation on chemical data of dissolved major and minor constituents in 246 recent groundwater samples was performed. The main objective was the detection of processes responsible for the geochemical evolution and mineralization throughout the area. Multivariate techniques revealed different sources of solutes (a) dissolution of calcium and magnesium carbonate minerals, (b) weathering of acid volcanic minerals, (c) alteration of manganese containing alkaline silicates, (d) leaching of halite deposits of meteoric origin, (e) contamination from agricultural and urban wastewaters, and (f) evaporative effects due to intensive irrigation. Although nitrate contamination is associated with pollution from intensive cultivated areas, natural contamination plays an important role in the study area. The investigation reveals that weathering of acid volcanic rocks (rhyolite) and oxidation of arsenic bearing sulfide minerals are the responsible processes for high fluorine (up to 16 mg/l) and arsenic (up to 0.12 mg/l) contents, respectively, exceeding the Mexican maximum admissible concentration for drinking water. Except for kaolinite, all recharge processes are dissolution oriented (CO₂, calcite, dolomite, K-feldspar, plagioclase). Silicate precipitation (amorphous silica and chalcedony) is of growing importance in discharge zones. Cation exchange is not an important issue in the whole study area.