Isotopic and chemical investigations on Angra dos Reis

We report on extensive isotopic studies of Pb, Sr and Xe and on chemical abundance measurements of K, Rb, Sr, Ba, Nd, Sm, U and Th for total meteorite and mineral separates of the Angra dos Reis achondrite. U-Pb, Th-Pb and Pb-Pb ages are concordant at 4.54 AE for the total meteorite and for high-purity whitlockite in Angra dos Reis. This establishes Angra dos Reis as an early planetary differentiate which has not been disturbed for these systems since 4.54 AE ago. Measured⁸⁷Sr/⁸⁶Sr in pyroxene and whitlockite for Angra dos Reis (ADOR) are distinctly below BABI by two parts in 10⁴ and only one part in 10⁴ above the lowest⁸⁷Sr/⁸⁶Sr (ALL) measured in an Allende inclusion. The difference in ADOR-ALL corresponds to an interval of condensation in the solar nebula of ～3 m.y. If²⁶Al was the heat source for the magmatism on the parent planets of Angra dos Reis and the basaltic achondrites (BABI) then the relatively large difference in⁸⁷Sr/⁸⁶Sr, BABI - ALL, must be the result of planetary evolution rather than condensation over ～10 m.y. Xe isotopic measurements confirm the presence of large amounts of²⁴⁴Pu-produced fission Xe and show that²⁴⁴Pu was enriched in the whitlockite relative to the pyroxene by a factor of ～18. We present chemical element enrichment factors between the whitlockite and the fassaitic pyroxene in Angra dos Reis. The enrichment factors demonstrate close analogy between the rare earth elements and their actinide analogs. The enrichment factor for Pu is intermediate to the enrichment factors of Nd and Sm.     

The incorporation of Mg2+ and Sr2+ into calcite overgrowths: influences of growth rate and solution composition

The concentrations of Mg²⁺ and Sr²⁺ incorporated within calcite overgrowths precipitated from seawater and related solutions, determined at 25°C, were independent of the precipitation rate over approximately an order of magnitude. The saturation states used to produce this range of precipitation rates varied from 3 to 17 depending on the composition of the solution.The amount of Mg²⁺ incorporated in the overgrowths was not directly proportional to $\text{Mg}{}^{\mathrm{2+}}\text{Ca}{}^{\mathrm{2+}}$ in solution over the entire range (1–20) of ratios studied. Below a ratio of 7.5, the overgrowth was enriched in MgCO₃ relative to what is predicted by the constant distribution coefficient measured above a ratio of 7.5. This increased MgCO₃ correlates with the relative enrichment of adsorbed Mg²⁺. Above a ratio of 7.5 the concentration of MgCO₃ in the calcite overgrowths followed a classical thermodynamic behavior characterized by a constant distribution coefficient of 0.0123 (±0.008 std dev).The concentration of SrCO₃ incorporated in the overgrowths was linearly related to the MgCO₃ content of the overgrowths, and is attributed to increased solubility of SrCO₃ in calcite due to the incorporation of the smaller Mg²⁺ ions.The kinetic data indicate that the growth mechanism involves the adsorption of the cations on the surface of the calcite prior to dehydration and final incorporation. It is suggested that dehydration of cations at the surface is the rate controlling step.     

DFT study of the cation arrangements in the octahedral and tetrahedral sheets of dioctahedral 2:1 phyllosilicates

Quantum mechanical calculations based on the density functional theory (DFT) are used to study the crystal structures of dioctahedral 2:1 phyllosilicates. The isomorphous cation substitution is investigated by exploring different substitutions of octahedral Al³⁺ by Mg²⁺ or Fe³⁺, tetrahedral substitution of Si⁴⁺ by Al³⁺, and different interlayer cations (IC) (Na⁺, K⁺, Ca²⁺, and Mg²⁺). Samples with different kinds of layer charges are studied: only tetrahedrally charged, only octahedrally charged, or mixed octahedral/tetrahedral charged. The effect of the relative arrangements of these substitutions on the lattice parameters and total energy is studied. The experimental observation of segregation tendency of Fe³⁺ and dispersion tendency of Mg²⁺ in the octahedral sheet is reproduced and explained with reference to the relative energies of the octahedral cation arrangements. These energies are higher than those due to the IC/tetrahedral and IC/octahedral relative arrangements. The tetrahedral and octahedral substitutions that generate charged layers also tend to be dispersed. The octahedral cation exchange potentials change with the IC-charge/ionic radius value.     

Late Neoproterozoic crustal growth in the European Variscides: Nd isotope and geochemical evidence from the Sierra de Córdoba Andesites (Ossa-Morena Zone, Southern Spain)

Because the Hercynian overprint was extremely weak, the Sierra de Córdoba (southeastern Ossa-Morena Zone, OMZ) provides an excellent opportunity to study the tectonic evolution of sequences deposited close to the Late Neoproterozoic–Early Palaeozoic boundary. In order to put constraints on the sources and geodynamic significance of the Late Proterozoic magmatism, a representative set of 18 igneous rocks, and 3 interbedded sedimentary rocks from the San Jerónimo Formation have been studied for major and trace element geochemistry and for the Sm–Nd isotopic systematics. The igneous rocks are generally porphyritic to microporphyritic andesites, with abundant plagioclase (±amphibole) phenocrysts. With the exception of two intrusive rocks, possibly not related to the Late Proterozoic episode, all the samples display positive _{Nd550 Ma} values, ranging from +2.9 to +7.6. Most of them, with +4<_{Nd550 Ma}<+6, exhibit LREE enrichment, high La/Nb ratios, and elevated Zr/Nb ratios ranging from 21 to 32. There is no obvious correlation between the shape of REE patterns, La/Nb ratios and _{Nd550 Ma} values, precluding simple models of late-stage interaction with typical crustal components having low _Nd and high LREE/HREE and La/Nb ratios. Based on their major element composition and enriched, continental crust-like trace element characteristics, combined with distinctly positive _Nd initial values, the Córdoba andesites document an episode of crustal growth through the addition of calc-alkaline magmas, extracted from a mantle reservoir which was strongly depleted in LREE on a time-integrated basis. The occurrence of interlayered sediments of continental provenance (negative _Nd values) does not favour a purely ensimatic arc setting, remote from continental land masses, for this subduction-related magmatism, but the geochemical data suggest an active margin environment located on relatively juvenile crust. In any case, the Córdoba andesites document the addition of materials chemically similar to the bulk continental crust which were extracted from mantle sources with strong time-integrated LREE depletion. Therefore, they provide evidence for crustal growth related to Cadomian orogenic events during Late Proterozoic times.     

The Differential Geochemical Behavior of Arsenic and Phosphorus in the Water Column and Sediments of the Saguenay Fjord Estuary, Canada

The distribution and partitioning of dissolved andparticulate arsenic and phosphorus in the water columnand sediments of the Saguenay Fjord in Quebec, Canada,are compared. In addition, selective and/or sequentialextractions were carried out on the suspendedparticulate matter (SPM) and solid sediments tocontrast their geochemical behaviors in this naturalaquatic system.Results of our analyses show that both arsenic andsoluble reactive phosphate are actively scavenged fromthe water column by settling particles. Upon theiraccumulation at the sediment-water interface some Asand P may be released to porewaters following thedegradation of organic matter to which they areassociated. The porewater concentrations are, however,limited by their strong affinity for authigenic,amorphous iron oxyhydroxides which accumulate in theoxic sediments near the sediment-water interface.The geochemical behavior of arsenic and phosphorusdiverge most strikingly upon the development of anoxicconditions in the sediments. Following their burial inthe anoxic zone, amorphous iron oxyhydroxides arereduced and dissolved, releasing phosphate and arsenicto the porewaters. We observed, however, thatporewater arsenic concentrations increase at shallowerdepths than phosphate in the sediments. The reductionof arsenate, As(V), to arsenite, As(III), and itsdesorption prior to the reductive dissolution of thecarrier phase(s) may explain this observation.Driven by the strong concentration gradientestablished in the suboxic zone, phosphate diffuses uptowards the oxic layer where it is readsorbed byauthigenic iron oxyhydroxides. In the organic-rich andrapidly accumulating sediments at the head of theFjord, porewater sulfate depletion and the resultingabsence of a sulfide sink for Fe(II), may lead to theformation of vivianite in the fermentation zone, apotential sink for phosphate. Arsenite released to theporewaters in the suboxic and anoxic zones of thesediments diffuses either down, where it is adsorbedto or incorporated with authigenic iron sulfides, orup towards the oxic boundary. Arsenite appears tomigrate well into the oxic zone where it may beoxidized by authigenic manganese oxides before beingadsorbed by iron oxyhydroxides present at the samedepth. Whereas, in the absence of authigenic carbonatefluorapatite precipitation, the ability of oxicsediments to retain mineralized phosphate is afunction of their amorphous iron oxyhydroxide content,arsenic retention may depend on the availability ofmanganese oxides, the thickness of the oxic layer and,its co-precipitation with iron sulfides at depth.     

Stability of massive ground ice bodies in University Valley,McMurdo Dry Valleys of Antarctica: Using stable O–H isotope as tracers of sublimation in hyper-arid regions

To date, studies of the stability of subsurface ice in the McMurdo Dry Valleys of Antarctica have been mainly based on climate-based vapor diffusion models. In University Valley (1800 m), a small glacier is found at the base of the head of the valley, and adjacent to the glacier, a buried body of massive ice was uncovered beneath 20–40 cm of loose cryotic sediments and sandstone boulders. This study assesses the origin and stability of the buried body of massive ice by measuring the geochemistry and stable O–H isotope composition of the ice and applies a sublimation and molecular diffusion model that accounts for the observed trends. The results indicate that the buried massive ice body represents an extension of the adjacent glacier that was buried by a rock avalanche during a cold climate period. The contrasting δ¹⁸O profiles and regression slope values between the uppermost 6 cm of the buried massive ice (upward convex δ¹⁸O profile and S_D-18O = 5.1) and that below it (progressive increase in δ¹⁸O and S_D-18O = 6.4) suggest independent post-depositional processes affected the isotope composition of the ice. The upward convex δ¹⁸O profile in the uppermost 6 cm is consistent with the ice undergoing sublimation. Using a sublimation and molecular diffusion model, and assuming that diffusion occurred through solid ice, the sublimation rate needed to fit the measured δ¹⁸O profile is 0.2 ? 10^? 3 mm yr^? 1, a value that is more similar to net ice removal rates derived from ³He data from cobbles in Beacon Valley till (7.0 ? 10^? 3 mm yr^? 1) than sublimation rates computed based on current climate (0.1–0.2 mm yr^?1). We suggest that the climate-based sublimation rates are offset due to potential ice recharge mechanisms or to missing parameters, particularly the nature and thermo-physical properties of the overlying sediments (i.e., temperature, humidity, pore structure and ice content, grain size).     

Modeling aquifer�Criver interactions under the influence of groundwater abstraction in the Mancha Oriental System (SE Spain)

The Mancha Oriental System (MOS, 7,260?km²) is one of the largest aquifers within Spain, and is encompassed by the Jucar River Basin. Over the past 30?years, socioeconomic development within the region has been largely due to intensive use of groundwater resources for irrigating crops (1,000?km²). Groundwater pumping (406 million m³/year) has provoked a steady drop in the groundwater level and a reduction of MOS discharge to the Jucar River. The study aims to characterize the river?Caquifer relationship, to determine the influence that groundwater abstraction has on the river discharge. This research has advanced a three-dimensional large-scale numerical groundwater-flow model (MODFLOW 2000) in order to spatially and temporally evaluate, quantify and predict the river?Caquifer interactions that are influenced by groundwater abstraction in MOS. It is demonstrated that although groundwater abstraction increased considerably from the early 1980s to 2000, the depletion of water stored in the aquifer was lower than might be expected. This is mainly due to aquifer recharge from the Jucar River, induced by groundwater abstraction. The area of disconnection between the river and the water table (i.e. where groundwater head is lower than the riverbed) is found to have spread 20?km downstream from its position before pumping started.     

Waiting Time Distribution of Emissions in Complex Coronal Mass Ejections

The waiting time distribution of emissions in Coronal Mass Ejections (CMEs) with several emissions is examined. We define the waiting time as the time interval between the commencement of an emission and the commencement of the next emission considered as parts of a unique CME. The distribution seems to follow a power-law. Two classes of CMEs several emissions are considered: “close” and “separate” depending on angular distance between emissions.