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].     

Amino acids in the Murchison meteorite

Continued investigation of the Murchison meteorite by gas chromatography combined with mass spectrometry has led to the characterization of at least 17 amino acids in addition to the 18 identified in earlier work. The total population consists of a wide variety of linear and cyclic difunctional and polyfunctional amino acids, of which the linear difunctional amino acids show a general decrease in concentration as the number of carbon atoms in the amino acid molecule increases. These results are consistent with the hypothesis that the amino acids are present as the result of an extraterrestrial, abiotic synthesis.     

Hydrochemical and Multivariate Statistical Evaluation of Heavy Metals in Shallow Alluvial Aquifers of North Brahmaputra Plain,India

The aim of this study was to display distribution and relationships of heavy elements in the unconfined, shallow alluvial aquifers of the lower Jia Bharali catchment and adjoining areas in central part of North Brahmaputra Plain (NBP), India using hydrochemical as well as multivariate statistical techniques such as principal component analysis (PCA) and cluster analysis. The original matrix was made up of 10 trace elements (As, Cd, Cu, Co, Cr, Fe, Mn, Pb, Ni and Zn) estimated from 50 shallow alluvial dug wells in both the wet and the dry season for a duration of 3 hydrological years (2008–2011). Except As, Cu and Zn all the other toxic metals in the shallow aquifers were found exceeding the WHO maximum permissible limits for drinking water. PCA extracted five varimax factors as geogenic, agricultural and anthropogenic explaining about 71.2% of the total variance in the wet season and 69.3% total variance in the dry season. Hierarchical cluster analysis classified the dug wells into two groups in the wet season and three groups in the dry season with respect to the heavy elements. The results emphasized the need for routine monitoring and management in order to avoid contamination of groundwater sources in the NBP with respect to the dissolved trace elements.     

The source of sulfur in sulfide deposits in the Siberian Platform traps (from isotope data)

The source of sulfur in giant Norilsk-type sulfide deposits is discussed. A review of the state of the problem and a critical analysis of existing hypotheses are made. The distribution of δ³⁴S in sulfides of ore occurrences and small and large deposits and in normal sedimentary, metamorphogenic, and hypogene sulfates is considered. A large number of new δ³⁴S data for sulfides and sulfates in various deposits, volcanic and terrigenous rocks, coals, graphites, and metasomatites are presented. The main attention is focused on the objects of the Norilsk and Kureika ore districts. The δ³⁴S value varies from -14 to + 22.5‰ in sulfides of rocks and ores and from 15.3 to 33‰ in anhydrites. In sulfide-sulfate intergrowths and assemblages, δ³⁴S is within 4.2-14.6‰ in sulfides and within 15.3-21.3‰ in anhydrites. The most isotopically heavy sulfur was found in pyrrhotite veins in basalts (δ³⁴S = 21.6‰), in sulfate veins cutting dolomites (δ³⁴S = 33‰), and in subsidence caldera sulfates in basalts (δ³⁴S = 23.2-25.2‰). Sulfide ores of the Tsentral’naya Shilki intrusion have a heavy sulfur isotope composition (δ³⁴S = + 17.7‰ (n = 15)). Thermobarogeochemical studies of anhydrites have revealed inclusions of different types with homogenization temperatures ranging from 685 °C to 80 °C. Metamorphogenic and hypogene anhydrites are associated with a carbonaceous substance, and hypogene anhydrites have inclusions of chloride-containing salt melts. We assume that sulfur in the trap sulfide deposits was introduced with sulfates of sedimentary rocks (δ³⁴S = 22-24‰). No assimilation of sulfates by basaltic melt took place. The sedimentary anhydrites were “steamed” by hydrocarbons, which led to sulfate reduction and δ³⁴S fractionation. As a result, isotopically light sulfur accumulated in sulfides and hydrogen sulfide, isotopically heavy sulfur was removed by aqueous calcium sulfate solution, and “residual” metamorphogenic anhydrite acquired a lighter sulfur isotope composition as compared with the sedimentary one. The wide variations in δ³⁴S in sulfides and sulfates are due to changes in the physicochemical parameters of the ore-forming system (first of all, temperature and P_ch4) during the sulfate reduction. The regional hydrocarbon resources were sufficient for large-scale ore formation.     

A direct comparison of C and Th ages at Searles Lake, California

Thorium-230 dating on saline of the Lower Salt unit in pluvial Searles Lake, California, shows that this unit was formed between 24,500 and 32,000 years ago. The initial apparent ¹⁴C age of the lake is estimated to be about 900 years. After correcting for nonradiogenic ²³⁰Th and for the initial ¹⁴C age, excellent agreement between ²³⁰Th and ¹⁴C ages is obtained. The reliability of ²³⁰Th dating on salt deposit opens a new way for continuation of absolute chronology below the Lower Salt in Searles Lake.     

Sensitivity of GPS and GLONASS orbits with respect to resonant geopotential parameters

The Center for Orbit Determination in Europe (CODE) has been involved in the processing of combined GPS/GLONASS data during the International GLONASS Experiment (IGEX). The resulting precise orbits were analyzed using the program SORBDT. Introducing one satellites positions as pseudo-observations, the program is capable of fitting orbital arcs through these positions using an orbit improvement procedure based on the numerical integration of the satellites orbit and its partial derivative with respect to the orbit parameters. For this study, the program was enhanced to estimate selected parameters of the Earths gravity field. The orbital periods of the GPS satellites are —in contrast to those of the GLONASS satellites – 2:1 commensurable (P _Sid:P _GPS) with the rotation period of the Earth. Therefore, resonance effects of the satellite motion with terms of the geopotential occur and they influence the estimation of these parameters. A sensitivity study of the GPS and GLONASS orbits with respect to the geopotential coefficients reveals that the correlations between different geopotential coefficients and the correlations of geopotential coefficients with other orbit parameters, in particular with solar radiation pressure parameters, are the crucial issues in this context. The estimation of the resonant geopotential terms is, in the case of GPS, hindered by correlations with the simultaneously estimated radiation pressure parameters. In the GLONASS case, arc lengths of several days allow the decorrelation of the two parameter types. The formal errors of the estimates based on the GLONASS orbits are a factor of 5 to 10 smaller for all resonant terms. AcknowledgmentsThe authors would like to thank all the organizations involved in the IGS and the IGEX campaign, in particular those operating an IGS or IGEX observation site and providing the indispensable data for precise orbit determination.     

Late Cainozoic stratigraphy,palaeomagnetic chronology and vegetational history from Lake George,N.S.W.

The sedimentary record from Lake George provides the longest relatively continuous Quaternary continental sequence yet available from Australia, and may record one of the longest Upper Cainozoic lacustrine records in the world.

Palaeomagnetic analysis of a 36 m core from the lake floor identifies a sequence of deposition extending through the Brunhes and Matuyama, to the Gauss magnetic Chron. A longer core from the same site, but with incomplete recovery, extends to 72 m in lacustrine sediment; the age of the base of this core estimated by extrapolation is between 4.2 and 7 Ma. As there are still older and deeper sediments in the basin, extending to an estimated depth of 134 m, the age of the tectonic formation of the Lake George basin must be reckoned as Middle Miocene or older.

The pattern of facies organisation through time demonstrates a phase of deep water deposition extending from the base of the cored sequence (72 m) up to 51.5 m, at which time a major change took place. A disconformity developed at this level, associated with a period of deep weathering and a prolonged phase of slope mantle deposition (from 51.5 to 30.8 m). A gradual return to lacustrine environments, with diminishing proportion of slope wash detritus, resulted in increased rates of deposition coincident with the Jaramillo Subchron at 21.5 m. Thereafter, throughout the Brunhes magnetic Chron, lacustrine conditions dominated, varying from deep to lake dry conditions in a rhythmic fashion, and reflecting the major climatic oscillations of the past 700 000 years, becoming more regular in the past 400 000 years.

The pollen analytical record of the upper 8.6 m, covering the last 350 000 years, provides the main framework for the reconstruction of climatic history. The pollen and algal records indicate a sequence of vegetation and lake level changes, in which four major glacial/interglacial cycles are correlated with stages 1 to 10 of the ¹⁸0 marine record. This provides by far the longest continuous biostratigraphic framework for the Quaternary period in Australia.

Comparison between the palaeoclimatic record and the lake level evidence shows that there is no simple correlation between the lake level fluctuations and the glacial/ interglacial oscillations. In fact, major falls in the lake level occured both at the peak of cold glacials and during the warm interglacials. Though the falls in the lake levels during a warm period (interglacial) can be explained by high rates of evaporation, drying during maximum cold can be explained best in terms of a fall in precipitation. Permanent to deep‐lake conditions generally occurred during intermediate cool periods following warm intervals, when perhaps the seas were still warm and low rates of evaporation on land prevailed. On the other hand, short periods of shallow to deep lake levels also occurred during warm (interglacial) periods, showing that these were associated with reasonably high rates of precipitation.     

Clitellate worms (Annelida) in lateglacial and Holocene sedimentary DNA records from the Polar Urals and northern Norway

While there are extensive macro‐ and microfossil records of a range of plants and animals from the Quaternary, earthworms and their close relatives amongst annelids are not preserved as fossils and therefore the knowledge of their past distributions is limited. This lack of fossils means that clitellate worms (Annelida) are currently underused in palaeoecological research, even though they can provide valuable information about terrestrial and aquatic environmental conditions. Their DNA might be preserved in sediments, which offers an alternative method for detection. Here we analyse lacustrine sediments from lakes in the Polar Urals, Arctic Russia, covering the period 24 000–1300 cal. a BP, and NE Norway, covering 10 700–3300 cal. a BP, using a universal mammal 16S rDNA marker. While mammals were recorded using the marker (reindeer was detected twice in the Polar Urals core at 23 000 and 14 000 cal. a BP, and four times in the Norwegian core at 11 000 cal. a BP and between 3600–3300 cal. a BP), worm extracellular DNA ‘bycatch’ was rather high. In this paper we present the first reported worm detection from ancient DNA. Our results demonstrate that both aquatic and terrestrial clitellates can be identified in late‐Quaternary lacustrine sediments, and the ecological information retrievable from this group warrants further research with a more targeted approach.     

Centennial to millennial geomagnetic secular variation

A time-varying spherical harmonic model of the palaeomagnetic field for 0–7 ka is used to investigate large-scale global geomagnetic secular variation on centennial to millennial scales. We study dipole moment evolution over the past 7 kyr, and estimate its rate of change using the Gauss coefficients of degree 1 (dipole coefficients) from the CALS7K.2 field model and by two alternative methods that confirm the robustness of the predicted variations. All methods show substantial dipole moment variation on timescales ranging from centennial to millennial. The dipole moment from CALS7K.2 has the best resolution and is able to resolve the general decrease in dipole moment seen in historical observations since about 1830. The currently observed rate of dipole decay is underestimated by CALS7K.2, but is still not extraordinarily strong in comparison to the rates of change shown by the model over the whole 7 kyr interval. Truly continuous phases of dipole decrease or increase are decadal to centennial in length rather than longer-term features. The general large-scale secular variation shows substantial changes in power in higher spherical harmonic degrees on similar timescales to the dipole. Comparisons are made between statistical variations calculated directly from CALS7K.2 and longer-term palaeosecular variation models: CALS7K.2 has lower overall variance in the dipole and quadrupole terms, but exhibits an imbalance between dispersion in   g ¹₂  and   h ¹₂  , suggestive of long-term non-zonal structure in the secular variations.     

Heterogenity of planetesimal collisional plume probed by glass inclusions in metal globules of Sierra Gorda 013, an unusual CBa-like chondrite

Metal-rich carbonaceous CB chondrites are generally assumed to be materials accreted from the gas–dust plume formed in catastrophic collisions of planetesimals, at least one of which was differentiated into a metal core and silicate shell. Micron-sized inclusions of siliceous alkali-rich glasses associated with sulfides were found in the metal globules of the Sierra Gorda 013 (SG 013), a CBa-like chondrite. These inclusions are unusual carriers of volatile alkalis which are commonly depleted in CB chondrites. The inclusions are presented by two types: (1) Al-bearing Nb-poor glass associated with daubréelite and (2) Nb-bearing Ca,Al,Mg-poor glass associated with an unknown Na-bearing Cr-sulfide. The glass compositions do not correspond to equilibrium condensation, evaporation, or melting. The Nb-bearing glass has a superchondritic Nb/Ta ratio (31) most likely indicating the fractionation of Nb and Ta in the high-temperature gas–dust impact plume due to condensation from vapor or evaporation of precursor Nb-rich particles. The glasses are interpreted as reaction products between refractory plume condensate particles (or possibly planetary or chondritic solids) with relatively low-temperature K-Na-Si-rich gas in oxidized conditions, possibly in a common plume vapor reservoir. Compositional differences indicate that the glasses and sulfides originated from several different sources under different fO₂, fS₂, and T conditions and were likely combined together and transported to the metal globule formation region by material flows in the heterogeneous impact plume. The glass–sulfide particles were enclosed in the globules aggregated from smaller solid or molten metal grains. The metal globules were further melted during transport to the high-temperature plume region or by plume shockwave heating. Thus, the composition of the glasses, the host metal, and the main mass of SG 013 shows dynamic heterogeneity of physical conditions and impact plume composition after a large-scale planetesimal collision.