Varved sediments of Lake Yoa (Ounianga Kebir,Chad) reveal progressive drying of the Sahara during the last 6100 years

The sedimentological and geochemical properties of a 7·47 m long laminated sequence from hypersaline Lake Yoa in northern Chad have been investigated, representing a unique, continuous 6100 year long continental record of climate and environmental change in the eastern Central Sahara. These data were used to reconstruct the Mid to Late Holocene history of this currently hyper‐arid region, in order to address the question of whether the Mid Holocene environmental transition from a humid to a dry Sahara was progressive or abrupt. This study involved a suite of analyses, including petrographic and scanning electron microscope examination of thin sections, X‐ray diffraction, X‐radiography, granulometry, loss on ignition and magnetic susceptibility. The potential of micro‐X‐ray fluorescence core scanning was tested at very high resolution. Detailed microscopic investigation revealed the sedimentary processes responsible for the formation of the fine laminations, identified the season during which they were formed, and confirmed their annually rhythmic nature. High‐resolution X‐ray fluorescence core scanning allowed the distinction of each individual lamination over the entire record, opening new perspectives for the study of finely laminated sediment sequences. Geochemical and mineralogical data reveal that, due to decreasing monsoon rainfall combined with continuous and strong evaporation, the hydrologically open and fresh Mid Holocene Lake Yoa slowly evolved into the present‐day hypersaline brine depleted in calcium, which has existed for about the past 1050 years. During the oldest part of the investigated period, Lake Yoa probably contained a permanently stratified lower water column that was nevertheless disrupted relatively frequently by mixing events. Deep‐water anoxia became more stable because of increased salinity‐driven density stratification. In parallel, the sediment grain‐size proxies record a progressive increase of aeolian input in the course of the last 6100 years. Altogether, all geochemical and sedimentological indicators point to a progressive drying of the eastern Central Sahara, strengthening previous conclusions based on palaeoecological indicators.     

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.     

Links between NAO fluctuations and inter-annual variability of winter-months precipitation in the Seine River watershed (north-western France)

The inter-annual to multi-decadal winter variability (DJFM) of precipitation on the Seine River watershed (France) was analysed using continuous wavelet transform analysis and compared to the winter North Atlantic Oscillation Index (NAOI). Nine weather stations were used over the 1951 to 2004 period and confirmed the homogeneity of inter-annual fluctuations for all stations but one. Wavelet coherence between SLP over the Icelandic and Azores regions and precipitation highlighted coherence for different scales of variability according to the centre of action considered. Segmentation and wavelet analysis and coherence between precipitation and NAOI over a long period of time (1873–2004) showed: i) increasing variability across the last century at most time scales, especially for NAOI; ii) the existence of change points for the mean and variance of both signals; iii) overall discontinuity of the coherence whatever the scale considered, especially between ∼1910 and ∼1955 for inter-decennial to pluri-decennial scales.     

Early Miocene adakite-like volcanism in the Balkuyumcu region, central Anatolia, Turkey: Petrology and geochemistry

The Balkuyumcu region, located in the southwestern part of Ankara in the Izmir-Ankara suture zone (central Anatolia, Turkey), consists of basic andesitic, andesitic, dacitic and rhyolitic rocks extruded during the Early Miocene (20–22 Ma) as a result of post-collisional volcanism. Balkuyumcu volcanic rocks can be divided into two groups on the basis of their mineralogy and composition: The basic andesitic (BA) and andesitic, dacitic and rhyolitic (ADR) groups. The ADR and BA group of rocks have adakite-like and calc-alkaline characteristics, respectively. The ADR group has higher SiO₂ content, Sr/Y and La/Yb ratios and low MgO, Mg#, Y and Yb contents than the BA group. Both groups have nearly the same Sr, Nd isotopic compositions and display similar normalized multi-element patterns with enrichments in LILE and LREE, depletions in Nb, Ti, Zr, P and a lack of Eu anomalies. Major, trace element and Sr, Nd isotopic data indicate that both groups of rocks were derived from the same source but affected by different magmatic processes during ascent. The adakite-like rocks may have been produced by partial melting of thickened lower continental crust. Fractional crystallization also played a major role in their formation. However, the BA group rocks were derived from partial melting of lower continental crust that was probably delaminated. These rocks appear to have had limited interaction with mantle peridodite during ascent to the surface.     

Tracing of variabilities within a geological barrier by molecular organic geochemistry.: Case of the Callovo-Oxfordian sedimentary series in the East of the Paris Basin (France)

The Callovo-Oxfordian claystones located at 500 m depth at Bure (Meuse, France) are currently being investigated by Andra (the French National Radioactive Waste Management Agency) for testing the feasibility of long-term and deep geological nuclear waste disposal. In order to evaluate its potential as a geological barrier, it is very important to study, assess and describe its physico-chemical variability. The molecular biomarker composition of 150 samples of these claystones and their surrounding limestones carry diverse information on the sources of the sedimentary organic matter, the chemistry of the depositional environment, the preservation and diagenesis conditions. It also allows assessing the degree of lateral and vertical variability of the organic matter within these sedimentary series. The abundance of unsaturated biomarkers, the distribution of steroids and hopanoids and CPI values >2 prove the thermal immaturity of the organic matter. The co-occurrence of plankton, bacteria and land plant biomarkers indicate that the organic matter is a mixture of marine and continental contributions. The data also reveal that the organic matter was deposited under oxic and open-sea conditions except for a brief event of photic zone anoxia at the beginning of the Middle Callovian. In the claystones, the geosynthesis of diasterenes is favored to the detriment of the formation of steranes, especially in smectite-rich levels, and the organic matter is rapidly isolated from oxidizing then reducing conditions after the deposition due to the protective effect of clays. On the scale investigated, the claystones are characterized by a unique molecular facies and are thus homogenous from their organic content point of view. Yet, detailed investigation of specific molecular families indicates changes related to major claystone–limestone transitions. The homogeneity of these claystones can be explained by the paleogeographic position of their depositional setting and the plane and sub-horizontal paleotopography on which they were deposited. This study demonstrates the efficiency of organic geochemistry in the assessment of the variability of geological barriers.     

Fine sediment transport and accumulations at the mouth of the Seine estuary (France)

A comprehensive study of fine sediment transport in the macrotidal Seine estuary has been conducted, including observations of suspended particulate matter (SPM), surficial sediment, and bathymetric data, as well as use of a three dimensional mathematical model. Tide, river regime, wind, and wave forcings are accounted. The simulated turbidity maximum (TM) is described in terms of concentration and location according to tidal amplitude and the discharge of the Seine River. The TM is mainly generated by tidal pumping, but can be concentrated or stretched by the salinity front. The computed deposition patterns depend on the TM location and are seasonally dependent. The agreement with observations is reasonable, although resuspension by waves may be overestimated. Although wave resuspension is likely to increase the TM mass, it generally occurs simultaneously with westerly winds that induce a transverse circulation at the mouth of the estuary and then disperse the suspended material. The resulting effect is an output of material related to wind and wave events, more than to high river discharge. The mass of the computed TM remains stable over 6 months and independent of the river regime, depending mainly on the spring tide amplitude. Computed fluxes at different cross-sections of the lower estuary show the shift to the TM according to the river flow and point out the rapidity of the TM adjustment to any change of river discharge. The time for renewing the TM by riverine particles has been estimated to be one year.