Radium uptake during barite recrystallization at 23 ± 2 °C as a function of solution composition: An experimental Ba and Ra tracer study

High-purity synthetic barite powder was added to pure water or aqueous solutions of soluble salts (BaCl₂, Na₂SO₄, NaCl and NaHCO₃) at 23 ± 2 °C and atmospheric pressure. After a short pre-equilibration time (4 h) the suspensions were spiked either with ¹³³Ba or ²²⁶Ra and reacted under constant agitation during 120-406 days. The pH values ranged from 4 to 8 and solid to liquid (S/L) ratios varied from 0.01 to 5 g/l. The uptake of the radiotracers by barite was monitored through repeated sampling of the aqueous solutions and radiometric analysis. For both ¹³³Ba and ²²⁶Ra, our data consistently showed a continuous, slow decrease of radioactivity in the aqueous phase.Mass balance calculations indicated that the removal of ¹³³Ba activity from aqueous solution cannot be explained by surface adsorption only, as it largely exceeded the 100% monolayer coverage limit. This result was a strong argument in favor of recrystallization (driven by a dissolution-precipitation mechanism) as the main uptake mechanism. Because complete isotopic equilibration between aqueous solution and barite was approached or even reached in some experiments, we concluded that during the reaction all or substantial fractions of the initial solid had been replaced by newly formed barite.The ¹³³Ba data could be successfully fitted assuming constant recrystallization rates and homogeneous distribution of the tracer into the newly formed barite. An alternative model based on partial equilibrium of ¹³³Ba with the mineral surface (without internal isotopic equilibration of the solid) could not reproduce the measured activity data, unless multistage recrystallization kinetics was assumed. Calculated recrystallization rates in the salt solutions ranged from 2.8 × 10⁻¹¹ to 1.9 × 10⁻¹⁰ mol m⁻² s⁻¹ (2.4-16 μmol m⁻² d⁻¹), with no specific trend related to solution composition. For the suspensions prepared in pure water, significantly higher rates (∼5.7 × 10⁻¹⁰ mol m⁻² s⁻¹ or ∼49 μmol m⁻² d⁻¹) were determined.Radium uptake by barite was determined by monitoring the decrease of ²²⁶Ra activity in the aqueous solution with alpha spectrometry, after filtration of the suspensions and sintering. The evaluation of the Ra uptake experiments, in conjunction with the recrystallization data, consistently indicated formation of non-ideal solid solutions, with moderately high Margules parameters (W_AB = 3720-6200 J/mol, a₀ = 1.5-2.5). These parameters are significantly larger than an estimated value from the literature (W_AB = 1240 J/mol, a₀ = 0.5).In conclusion, our results confirm that radium forms solid solutions with barite at fast kinetic rates and in complete thermodynamic equilibrium with the aqueous solutions. Moreover, this study provides quantitative thermodynamic data that can be used for the calculation of radium concentration limits in environmentally relevant systems, such as radioactive waste repositories and uranium mill tailings.     

Geotechnical,Geological, and Hydrologic Characterization of a 52 km Electrical Power Transmission Line Alignment Route in Southeastern Nigeria

A 132 kVA electrical transmission line has been proposed to connect the towns of Eket and Ikot Abasi in the eastern Niger delta in Nigeria. A geotechnical and hydrological study was performed to geotechnically characterize the route alignment and to provide data for design of the foundations for the transmission towers. In this paper, we introduce the study location and its geological, topographical and physiological characteristics, present the hydrological and geotechnical investigations and their results, and make recomendations for the design of the transmission tower foundations. Hydrological inspection of the power line alignment revealed that the route is traversed by numerous tributaries of the Qua-Iboe and Imo Rivers, the two major rivers that control the drainage of the study area. In-situ geotechnical tests consisted of cone penetration tests (CPTs), vane shear tests, test pit sampling (0–2.0 m depth) and lithologic boreholes (20 and 50 m deep). Laboratory tests included grain size analysis, pH determination and Atterberg Limits. Based on the CPT log pattern, no of stratum, and refusal depths, the soils along the transmission alignment were classified into twelve structural domains having common geotechnical properties. Because of the elevated water levels, and the nature of the soils, deep pile foundations were recommended for the towers. Software from the Louisiana Transportation Research Center, was employed to estimate skin friction, end bearing, and ultimate bearing capacities for assumed 225 mm square shaped reinforced concrete pile in each of the different zones of the alignment.     

A 44-year high-resolution ocean and atmospheric hindcast for the Mediterranean Basin developed within the HIPOCAS Project

A set of 44-year (1958–2001) homogeneous and high-resolution hindcasts of atmospheric, sea level residuals, and wave states was performed for the Mediterranean Basin within the framework of the HIPOCAS European Project. To this aim, different numerical models were used. As a first step, a Mediterranean high-resolution atmospheric database, suitable to provide realistic and homogeneous forcing for ocean hindcast runs was generated. The HIPOCAS atmospheric database was created by means of dynamical downscaling from the global reanalysis NCEP, using for that the limited area model SN-REMO along with a spectral nudging technique. In a second stage, different Mediterranean oceanic hindcasts were performed. On one hand a long-term database of sea state over the western Mediterranean was generated by means of the wave model WAM and on the other hand a sea level residual database containing storm surge events was obtained from a long-term integration of the HAMSOM model over the entire basin. The three different hindcast runs have been exhaustively validated. On that score, various simulated parameters have been compared to both satellite and in situ measurements. Such comparisons provide a measure of the skills of the different simulated fields to realistically reproduce the observed features. Once these skills are evaluated, a study of the ocean and atmospheric climate trends as well as the interannual variability for the whole 44-year period was carried out with the hindcasted data. The reliability of the data as shown by its comparison to measurements and a proven temporal homogeneity over the 44 years of simulation make the Mediterranean HIPOCAS ocean–atmosphere hindcasted database a useful tool for studies focused on regional climatic variability, as well as for further applications in coastal and environmental decision processes in the Mediterranean area.     

Cadmium and phosphorus cycling in the water column of the South China Sea: The roles of biotic and abiotic particles

The concentrations of cadmium, phosphorus, and aluminum in size-fractionated phytoplankton, zooplankton, and sinking particles are determined using ICPMS to evaluate the roles of biotic and abiotic particles on the cycling and ratios of Cd and P in the water column. Plankton were collected with a filtration apparatus equipped with 10-, 60-, and 150-μm aperture plankton nets on two occasions (2002 and 2006), and sinking particles were sampled by moored sediment traps deployed at depths of 120, 600, and 3500 m from 2004 to 2005. In contrast to what our previous study revealed, i.e., that most of the other bioactive trace metals in plankton were strongly correlated with abiotic Al and adsorbed on phytoplankton [Ho, T.Y., Wen, L.S., You, C.F., Lee, D.C., 2007. The trace metal composition of size-fractionated plankton in the South China Sea: biotic versus abiotic sources. Limnol Oceanogr 52, 1776–88.], Cd/P ratios, ranging from 0.12 to 0.34 mmol/mol P, did not vary with Al and exhibited fairly consistent values among different sizes of plankton, showing that Cd was mostly incorporated on an intracellular basis. In terms of the sinking particles, fluxes in Cd and P as well as in Cd/P ratios were strongly influenced by both biotic and abiotic particles. Overall, the Cd/P ratios in the sinking particles ranged from 0.03 to 1.2 mmol/mol, with the highest value observed in traps at 120 m during the productive season. The lowest value was observed in deep water during high flux periods for lithogenic particles. At surface depth, flux and Cd/P ratios were elevated during the most productive season in the region. The elevated ratios in the traps at 120 m were most likely related to preferential uptake of Cd for the dominant species (coccolithophores) during the productive period. Relatively, Cd/P ratios sharply decreased with increasing Al flux in deep water and ratios were much lower than the expected Cd/P ratios obtained from the relative portion of lithogenic and biogenic particles, indicating that the adsorption of soluble P into lithogenic particles was significant in the deep water during high lithogenic particle flux periods. Using averaged annual fluxes and standing stock in the water column, the residence time of biogenic Cd and P are 0.10 and 0.20, 250 and 100, and 9100 and 5000 years respectively in the top 120 m, 600 m, and water column as a whole, also showing preferential removal for Cd in the euphotic zone but relatively higher removal rates for P in the deep water. Our study suggests that the shift in microalgal community structure along with input of lithogenic minerals are both potentially important factors in influencing Cd/P ratios in oceanic water on a geological time scale.     

Geological structure of the Curonian Spit (of the Baltic Sea) and its evolution history (revised)

The origin and evolution history of the Curonian Spit in the Baltic Sea are discussed based on geological and geomorphologic data. Evidence of the correlation between the spit formation stages and the Holocene sea level oscillations is presented. The ledges of moraine basement and marine accumulative features formed a single barrier. Its subsequent transformation occurred under the influence of the wave-related lithodynamic and eolian processes.     

Iron(III) accumulations in inland saline waterways,Hunter Valley,Australia: Mineralogy,micromorphology and pore-water geochemistry

Discharge of Fe(II)-rich groundwaters into surface-waters results in the accumulation of Fe(III)-minerals in salinized sand-bed waterways of the Hunter Valley, Australia. The objective of this study was to characterise the mineralogy, micromorphology and pore-water geochemistry of these Fe(III) accumulations. Pore-waters had a circumneutral pH (6.2–7.2), were sub-oxic to oxic (Eh 59–453 mV), and had dissolved Fe(II) concentrations up to 81.6 mg L⁻¹. X-ray diffraction (XRD) on natural and acid-ammonium-oxalate (AAO) extracted samples indicated a dominance of 2-line ferrihydrite in most samples, with lesser amounts of goethite, lepidocrocite, quartz, and alumino-silicate clays. The majority of Fe in the samples was bound in the AAO extractable fraction (Fe^Ox) relative to the Na-dithionite extractable fraction (Fe^Di), with generally high Fe^Ox:Fe^Di ratios (0.52–0.92). The presence of nano-crystalline 2-line ferrihydrite (Fe₅HO₃·4H₂O) with lesser amounts of goethite (α-FeOOH) was confirmed by scanning electron microscopy (SEM) coupled with energy dispersive X-ray analysis (EDX), and transmission electron microscopy (TEM) coupled with selected area electron diffraction (SAED). In addition, it was found that lepidocrocite (γ-FeOOH), which occurred as nanoparticles as little as ∼5 lattice spacings thick perpendicular to the (0 2 0) lattice plane, was also present in the studied Fe(III) deposits. Overall, the results highlight the complex variability in the crystallinity and particle-size of Fe(III)-minerals which form via oxidation of Fe(II)-rich groundwaters in sand-bed streams. This variability may be attributed to: (1) divergent precipitation conditions influencing the Fe(II) oxidation rate and the associated supply and hydrolysis of the Fe(III) ion, (2) the effect of interfering compounds, and (3) the influence of bacteria, especially Leptothrix ochracea.     

中国东部新生代玄武岩及其地幔包体的氧逸度

地幔环境的氧逸度与温度和压力一样,是控制许多地幔过程的一个重要参数。本文计算了中国东部几个具有代表性地区的玄武岩和尖晶石二辉橄榄岩的氧逸度,尖晶石二辉橄榄岩的氧逸度变化不大,均位于１ｏｇ（ｆｏ２）＝ｌｏｇ（ｆｏ２ＦＭＱ）＋０．０左右,而各地区玄武岩的氧逸度却变化很大,其平均值从尚志地区的ｌｏｇ（ｆｏ２ＦＭＱ＋０．６到长白山地区的ｌｏｇ（ｆｏ２ＦＭＱ）＋３．３左右（其中东北地区钾质玄武岩的氧逸度比除尚志以外其它地区的低）,并且总体具有比地幔橄榄岩高得多的氧逸度。推测钾质玄武岩和尚志地区破性玄武岩的氧逸度比中国东部其它地区玄武岩的氧逸度低的可能原因是,前二个地区的玄武岩来源于更深部的（金云母）石榴石二辉橄榄岩,而其它地区的玄武岩来源于略浅部的尖晶石二辉橄榄岩。     

Late Mesozoic magmatism and Cenozoic tectonic deformations of the Barents Sea continental margin: Effect on hydrocarbon potential distribution

The paper is focused on the two tectonic-geodynamic factors that made the most appreciable contribution to the transformation of the lithospheric and hydrocarbon potential distribution at the Barents Sea continental margin: Jurassic-Cretaceous basaltic magmatism and the Cenozoic tectonic deformations. The manifestations of Jurassic-Cretaceous basaltic magmatism in the sedimentary cover of the Barents Sea continental margin have been recorded using geological and geophysical techniques. Anomalous seismic units related to basaltic sills hosted in terrigenous sequences are traced in plan view as a tongue from Franz Josef Land Archipelago far to the south along the East Barents Trough System close to its depocentral zone with the transformed thinned Earth’s crust. The Barents Sea igneous province has been contoured. The results of seismic stratigraphy analysis and timing of basaltic rock occurrences indicate with a high probability that the local structures of the hydrocarbon (HC) fields and the Stockman-Lunin Saddle proper were formed and grew almost synchronously with intrusive magmatic activity. The second, no less significant multitectonic stress factor is largely related to the Cenozoic stage of evolution, when the development of oceanic basins was inseparably linked with the Barents Sea margin. The petrophysical properties of rocks from the insular and continental peripheries of the Barents Sea shelf are substantially distinct as evidence for intensification of tectonic processes in the northwestern margin segment. These distinctions are directly reflected in HC potential distribution.