Behaviour of REE and mass balance calculations in a lateritic profile over chlorite schists in South Cameroon

An in situ weathering profile overlying chlorite schists in the Mbalmayo-Bengbis formations (South Cameroon) was chosen for the study of the behaviour of REE and the evaluation of geochemical mass balance. After physical and mineralogical studies, the chlorite schists and the undisturbed weathered materials were chemically analyzed for major elements (X-ray fluorescence and titrimetry) and REE (ICP-MS). The behaviour of the REE in the Mbalmayo weathering system was established in comparison with the REE of the reference parent rock. Mass balance calculations were applied to both major elements and REE. The mineralogy of the materials was determined with the aid of a Philips 1720, diffractometer. The chlorite schists of the Mbalmayo sector show low REE contents (Σ=153.44 ppm). These rocks are relatively rich in LREE (about 125 times the chondritic value) and relatively poor in HREE (about 20 times the chondritic value). The REE diagram normalized to chondrites shows a slightly split graph ((La/Yb)_N=6.18) with marked enrichment in LREE (LREE/HREE=9.50) in relation to HREE. Moreover, these spectra do not present any Ce anomaly, but a slightly positive Eu anomaly. The imperfectly evolved profile, whose materials are genetically linked, shows an atypical behaviour of REE. In effect, the LREE are more mobile than the HREE during weathering ((La/Yb)NASC<1) with weak Ce anomalies. This has been rarely reported in lateritic profiles characterized by higher HREE mobility than LREE during weathering processes with high Ce anomalies. This is either due to the difference in the stability of REE-bearing minerals, or to the weak acidic to basic pH conditions (6.70<pH<7.80), or even due to the average evolution of the weathering materials. The pathway of the REE along the profile is as follows: (1) leaching in the saprolites and summit of the profile, except for Ce, which precipitates very weakly in the nodular materials and the coarse saprolite materials, (2) at the base of the profile, solutions come in contact with chlorite schist formations, at this level, the pH increases (pH=7.79), HREE and a part of LREE partially void of Ce precipitate and (3) the other part of LREE precipitates further up in the profile. The geochemical mass balance calculations reveal that these elements are leached in the same phases as the relatively high Si, Al, K and Fe²⁺ contents.     

Arsenite sorption at the magnetite-water interface during aqueous precipitation of magnetite: EXAFS evidence for a new arsenite surface complex

The interaction of aqueous As(III) with magnetite during its precipitation from aqueous solution at neutral pH has been studied as a function of initial As/Fe ratio. Arsenite is sequestered via surface adsorption and surface precipitation reactions, which in turn influence the crystal growth of magnetite. Sorption samples were characterized using EXAFS spectroscopy at the As K-edge in combination with HRTEM observations, energy dispersive X-ray analysis at the nanoscale, electron energy loss spectroscopy at the Fe L₃-edge, and XRD-Rietveld analyses of reaction products. Our results show that As(III) forms predominantly tridentate hexanuclear As(III)O₃ complexes (³C), where the As(III)O₃ pyramids occupy vacant tetrahedral sites on {1 1 1} surfaces of magnetite particles. This is the first time such a tridentate surface complex has been observed for arsenic. This complex, with a dominant As-Fe distance of 3.53 ± 0.02 Å, occurs in all samples examined except the one with the highest As/Fe ratio (0.33). In addition, at the two highest As/Fe ratios (0.133 and 0.333) arsenite tends to form mononuclear edge-sharing As(III)O₃ species (²E) within a highly soluble amorphous As(III)-Fe(III,II)-containing precipitate. At the two lowest As/Fe ratios (0.007 and 0.033), our results indicate the presence of additional As(III) species with a dominant As-Fe distance of 3.30 ± 0.02 Å, for which a possible structural model is proposed. The tridentate ³C As(III)O₃ complexes on the {1 1 1} magnetite surface, together with this additional As(III) species, dramatically lower the solubility of arsenite in the anoxic model systems studied. They may thus play an important role in lowering arsenite solubility in putative magnetite-based water treatment processes, as well as in natural iron-rich anoxic media, especially during the reductive dissolution-precipitation of iron minerals in anoxic environments.     

Seismic analysis of non-linearly base-isolated soil-structure interacting reactor building by way of the hybrid frequency-time-domain procedure

The seismic analysis of a reactor building on a sliding-type base isolation is performed by way of the hybrid frequency-time-domain procedure. The frequency dependence of the foundation stiffness coefficients is duly accounted for in the analysis, although the problem is non-linear. The response results are shown to be reliable by way of comparison with the results of a time-stepping algorithm in the specialized case of constant foundation stiffness coefficients. The fact that such an analysis can be performed is an outstanding result, particularly when considering that no difficulties are encountered in the implementation and in the calculation. The flow chart used to implement the procedure is presented in the paper. The reactor building is analysed for three different sites with each site having three sets of material properties. It appears that the structural response is not strongly affected by the frequency dependence of the foundation stiffness coefficients. This also holds true as far as the response of equipment attached to the superstructure is concerned. For all practical purposes this frequency dependence may be disregarded in favour of constant spring and damping coefficients.     

Study of two alteration systems as natural analogues for radionuclide release and migration

U-deposit hosted in hydrothermally altered tuffs in Mexico, together with weathering profiles from Cameroon were studied as natural analogues of radionuclide release and migration. Using petrological and spectroscopic methods (infrared and electron paramagnetic resonance), we have distinguished successive secondary mineral parageneses and the behaviour of radionuclides.

In the U-deposit, the mineral parageneses show that uranium migration is mainly controlled by the redox potential and silica activity of the altering solutions. The high silica content of the solutions is caused by the intense alteration of volcanic rocks. Two types of secondary clay mineral parageneses are evidenced: a kaolinization, intense where uranium is accumulated in the welded tuffs, and a smectitization mainly developed in the underlying weakly welded tuffs.

Several types of kaolinite have been defined according to their genesis (fillings in fissures and feldspar pseudomorphs), their location relative to a breccia pipe where uranium has accumulated (core and rim of the pipe; surrounding rhyolitic tuffs), and particle morphology, structural order and substitutional Fecontent. It is shown that the variations of the concentration of paramagnetic defect centres, always more than ten times as important than those measured in weathering kaolinites, are only correlated to the location of the kaolinites. The highest values correspond to the breccia pipe kaolinites, e.g. kaolinites located in the uranium accumulation zones. Moreover, one or two main defects centres are detected depending on the intimate association of kaolinites with uranium-bearing minerals. Besides, in weathering kaolinites from U-depleted laterites, defect centre concentrations are correlated to the total Fe203 content in bulk samples. This means that the defect centre acts as a memory of the travel of uranium when this element was sorbed onto iron gels in the first stage of weathering.

It is concluded that paramagnetic defect centres in kaolinites might allow an efficient fingerprint of successive irradiations in the natural analogues under study and could be an useful tool to control radionuclides migration through kaolinite-containing clayey materials such as those used for waste repository.

A better understanding of radiation efficiency as well as accurate dose-ratekaolinite-containing clayey materials such as those used for waste reposit estimation are needed for a quantitative tracing of the migration ofA better understanding of radiation efficiency as well as accurate dose-ratekaolin radionuclide elements. With this aim, a simulation has been undertaken withestimation are needed for a quantitative tracing of the migration of various radiations sources. We have determined for each irradiation the parameters of the paramagnetic centres created in order to understand the way they are forming. The knowledge of the parameters governing the formation and the stability of the radiation centres in kaolinites allow to use this mineral as a natural dosimeter.     

Electron density profiles above the F-layer

A method for the determination of electron densities up to 1000 km by using data from vertical sounding and Faraday rotation techniques is suggested. Electron density profiles and contours plotted following this method are compared with results obtained by Evans using the incoherent scatter technique.     

A sampler-based technique for the study of near-bed sediment dynamics: application in the eastern English Channel

A simple technique for studying near-bed hydrodynamics and sediment dynamics is presented. The method combines the use of (1) a benthic tripod hosting a series of electromagnetic current meters, and (2) a newly developed near-bed multi-level water-sediment mixture sampler. The instrument package was deployed successfully at a shallow water station in the eastern English Channel. The currents at elevation 0.9 m above the bottom were asymmetrical, the flood current peak being slightly stronger than the ebb current peak. At elevation 0.3 m above the bottom, the ebb/flood current peak asymmetry vanished. The observed SSCs (suspended sediment concentrations) were tidally modulated, with a contrasting vertical distribution over the ebb and flood phases of the tidal current: the profile was uniform in the ebb phase whereas a stratification appeared in the flood phase. The depth dependence and time evolution of the SSCs are attributable to a combination of local resuspension and advection-dispersion of remotely suspended fine sediment by ebb currents. Suspended sediment fluxes were uniform during the ebb phase and increased with elevation above the bottom during the flood phase.     

Technopoles, high-tech industries and regional development: A critical review

Technologies have played an important role in the restructuring of the productive system in the last quarter of the 20th century. The article looks at the macroeconomic context and at the transformation of the industrial organization. It then defines the concept of technopole. The author traces the principal elements of the different attempts of theorization with a critical angle, shows the logic of contemporary industry localisation, as well as the role of technopoles in regional development. Regional and industrial policy are then seen as the basis of the process of industrialization and of the technological transfer.     

AMS radiocarbon dating and varve chronology of Lake Soppensee: 6000 to 12000 14C years BP

For the extension of the radiocarbon calibration curve beyond 10000 ¹⁴C y BP, laminated sediment from Lake Soppensee (central Switzerland) was dated. The radiocarbon time scale was obtained using accelerator mass spectrometry (AMS) dating of terrestrial macrofossils selected from the Soppensee sediment. Because of an unlaminated sediment section during the Younger Dryas (10000–11000 ¹⁴C y BP), the absolute time scale, based on counting annual layers (varves), had to be corrected for missing varves. The Soppensee radiocarbon-verve chronology covers the time period from 6000 to 12000 ¹⁴C y BP on the radiocarbon time scale and 7000 to 13000 calendar y BP on the absolute time scale. The good agreement with the tree ring curve in the interval from 7000 to 11450 cal y BP (cal y indicates calendar year) proves the annual character of the laminations. The ash layer of the Vasset/Killian Tephra (Massif Central, France) is dated at 8230±140 ¹⁴C y BP and 9407±44 cal y BP. The boundaries of the Younger Dryas biozone are placed at 10986±69 cal y BP (Younger Dryas/Preboreal) and 1212±86 cal y BP (Alleröd/Younger Dryas) on the absolute time scale. The absolute age of the Laacher See Tephra layer, dated with the radiocarbon method at 10 800 to 11200 ¹⁴C y BP, is estimated at 12350 ± 135 cal y BP. The oldest radiocarbon age of 14190±120 ¹⁴C y BP was obtained on macrofossils of pioneer vegetation which were found in the lowermost part of the sediment profile. For the late Glacial, the offset between the radiocarbon (10000–12000 ^14C y BP) and the absolute time scale (11400–13000 cal y BP) in the Soppensee chronology is not greater than 1000 years, which differs from the trend of the U/Th-radiocarbon curve derived from corals.