Effect of adsorbed metal ions on the transport of Zn- and Ni-EDTA complexes in a sand and gravel aquifer

Adsorption, complexation, and dissolution reactions strongly influenced the transport of metal ions complexed with ethylenediaminetetraacetic acid (EDTA) in a predominantly quartz-sand aquifer during two tracer tests conducted under mildly reducing conditions at pH 5.8 to 6.1. In tracer test M89, EDTA complexes of zinc (Zn) and nickel (Ni), along with excess free EDTA, were injected such that the lower portion of the tracer cloud traveled through a region with adsorbed manganese (Mn) and the upper portion of the tracer cloud traveled through a region with adsorbed Zn. In tracer test S89, Ni- and Zn-EDTA complexes, along with excess EDTA complexed with calcium (Ca), were injected into a region with adsorbed Mn. The only discernable chemical reaction between Ni-EDTA and the sediments was a small degree of reversible adsorption leading to minor retardation. In the absence of adsorbed Zn, the injected Zn was displaced from EDTA complexes by iron(III) [Fe(III)] dissolved from the sediments. Displacement of Zn by Fe(III) on EDTA became increasingly thermodynamically favorable with decreasing total EDTA concentration. The reaction was slow compared to the time-scale of transport. Free EDTA rapidly dissolved aluminum (Al) from the sediments, which was subsequently displaced slowly by Fe. In the portion of tracer cloud M89 that traveled through the region contaminated with adsorbed Zn, little displacement of Zn complexed with EDTA was observed, and Al was rapidly displaced from EDTA by Zn desorbed from the sediments, in agreement with equilibrium calculations. In tracer test S89, desorption of Mn dominated over the more thermodynamically favorable dissolution of Al oxyhydroxides. Comparison with results from M89 suggests that dissolution of Al oxyhydroxides in coatings on these sediment grains by Ca-EDTA was rate-limited whereas that by free EDTA reached equilibrium on the time-scale of transport. Rates of desorption are much faster than rates of dissolution of Fe oxyhydroxides from sediment-grain surfaces and, therefore, adsorbed metal ions can strongly influence the speciation of ligands like EDTA in soils and sediments, especially over small temporal and spatial scales.     

Afternoon mid-latitude current system and low-latitude geomagnetic field asymmetry during geomagnetic storms

For four geomagnetic storms of middle intensity the relationship between the low-latitude magnetic field asymmetry using ASY indices and the intensity of the auroral eastward and westward electro-jet was considered. It was asked whether there exists a connection between ASY and the eastward electrojet. To answer this question equivalent current systems were estimated in mid-latitudes. It was found that the observations obviously show no correlative relationship between the low-latitude magnetic-field asymmetry and the eastward electrojet, whereas one exists between ASY and the westward electrojet. To explain the generally accepted common three-dimensional current system between the partial ring current and the eastward electrojet, a condensor model of the three-dimensional current system was developed. It could be shown that the short periodic variations of the partial ring current are shielded by the condensor and cannot influence the eastward-electrojet current.     

Comparison Between Large-Eddy Simulation and Reynolds-Averaged Navier–Stokes Computations for the MUST Field Experiment. Part II: Effects of Incident Wind Angle Deviation on the Mean Flow and Plume Dispersion

Large-eddy simulations (LES) and Reynolds-averaged Navier–Stokes (RANS) computations of pollutant dispersion are reported for the Mock Urban Setting Test (MUST) field experiment flow. In particular we address the effects of incident wind angle deviation on the mean velocity and on the mean concentration fields. Both computational fluid dynamical methods are assessed by comparing the simulation results with experimental field data. The comparative analysis proposes to relate the plume deflection with the flow channelling effects. The results show that the plume deflection angle varies with the altitude. As the ground is approached the plume is shown to be almost aligned with the street canyon direction and independent of the incident wind directions considered. At higher altitudes well above the obstacles, the plume direction is aligned with the mean wind direction as in dispersion over flat terrain. The near-ground plume deflection is the consequence of a strong channelling effect in the region near the ground. The mean concentration profiles predicted by LES and RANS are both in good qualitative agreement with experimental data but exhibit discrepancies that can be partly explained by the influence of small incident wind angle deviation effects. Compared to RANS, LES predicts a higher channelling and thus a higher deflection of the plume. Results on the fluctuating intensity of the concentration obtained from LES show a satisfactory agreement with experiments. This information is not available from RANS for which only the mean concentration modelling is considered.     

The geological history and geodynamics of the Earth

The Earth formed through a hot accretion process. Almost simultaneously, the core and the mantle were separated from each other. At the final stages of the accretion process, the outer layer approximately 2000 km thick was molten, thus representing a magma ocean. This magma ocean produced the primary crust of the Earth. Surface waters were precipitated from the atmosphere and released from the crystallizing magma ocean. The plate tectonic processes started at around 4.3 to 4 Ga BP. In the Archean, the overall tectonic mechanism was quite specific, due to substantially higher mantle temperature and thicker oceanic crust. The normal plate tectonics acted during the Proterozoic and Phanerozoic with the periodic assembly of continents, which are known as supercontinent cycles.     

Geochemistry and Petrogenesis of Siwana Peralkaline Granites, West of Barmer, Rajasthan, India

The bimodal Malani suite, West of Barmer, Rajasthan is characterized by discontinuous, ring shaped outcrops of Siwana peralkaline granite with minor outcrops of basalt. The peralkaline, within- plate and A-type nature of granite are evident by its chemical characteristics. The granite is characterized by high Na₂O+K₂O, Fe/Mg, Zr, Nb, Y, Zn; low Al₂O₃, CaO and Sr and is significantly low in absolute abundance of trace and REE elements compared to type area Siwana granite. The granite is correlated to the “Pan-African” event and its petrogenesis and tectonic significance are discussed.     

Comparison of garnet-biotite, calcite-graphite, and calcite-dolomite thermometry in the Grenville Orogen; Ontario, Canada

The Elzevir Terrane of the Grenville Orogen in southern Ontario contains metapelites and abundant graphitic marbles that were regionally metamorphosed from the upper greenschist to upper amphibolite facies. Comparative thermometry was undertaken with widely used calibrations for the systems garnet-biotite, calcite-dolomite, and calcite-graphite. Temperatures that are obtained from matrix biotites paired with prograde garnet near-rim analyses are usually consistent with those determined using calcite-graphite thermometry. However, calcite-graphite thermometry occasionally yields low temperatures due to lack of equilibration of anomalously light graphite. Application of calcite-graphite and garnet-biotite systems may yield temperatures up to 70 °C higher than calcite-dolomite in amphibolite facies rocks. Calcite-dolomite temperatures most closely approach those from calcite-graphite and garnet-biotite when the samples contain a single generation of dolomite and calcite grains contain no visible dolomite exsolution lamellae. However, some of these samples yield temperatures considerably lower than temperatures calculated from calcite-graphite and garnet-biotite thermometry, indicating that the calcite-dolomite thermometer may have been partially reset during retrogression. Estimated peak metamorphic temperatures of regional metamorphism between Madoc (upper greenschist facies) and Bancroft (upper amphibolite facies) range from 500 to 650 °C. These results place the chlorite-staurolite isograd at 540 °C, the kyanite-sillimanite isograd at 590 °C, and the sillimanite-K-feldspar isograd at 650 °C. Although each thermometer may have an absolute uncertainty of as much as ±50 °C, the 50 to 60 °C temperature differences between the isograds are probably accurate to 10 to 20 °C. An incomplete picture of the thermal gradients can result from the application of only one thermometer in a given area. Simultaneous application of several systems allows one to recognize and overcome the inherent limitations of each thermometer. Received: 26 March 1997 / Accepted: 15 April 1998     

Ferromanganese nodules from the Kara Sea: Interrelation between organic matter and ore elements

This study presents data on Fe–Mn nodules first recovered from the northeastern part of the Kara Sea. Analysis of the geochemical indicators of organic matter and major and trace element compositions of nodules showed that samples with strong Mn enrichment (Mn/Fe = 2.38, on average) are dominated by terrestrial organic matter (OM), whereas Fe-rich samples (Mn/Fe = 0.20, on average) are dominated by marine biogenic OM. The variation in the n-alkane abundances in the studied nodules is independent of the sampling sites and nodule morphology. This study was conducted for the first time in the Artic region.

     

Constraints of stable isotopes on the origin of alunite from advanced argillic alteration systems in Bulgaria

Voluminous areas of advanced argillic alteration (AAA) constitute major exploration targets for surficial Cu–Au epithermal and potentially underlying porphyry-type deposits. In Bulgaria, more than 30 alunite occurrences are recognised, few of them being associated with a mineralised system. A mineralogical study combined with a stable isotopic (O, H, S) study has been carried out on nine alunite occurrences of advanced argillic zones hosted by volcanic rocks of Late Cretaceous age in the Srednogorie belt and of Oligocene age in the Rhodopes belt. This work was realised in order to constrain the origin of alunite and to define criteria to discriminate alunite from ore deposits and alunite from large barren alteration systems.Mineralogy of the nine occurrences consists of alunite + quartz + minor alumino-phospho-sulphates, associated with more or less kaolinite, dickite, pyrophyllite, diaspore and zunyite, depending on formation temperature. Alunite generally occurs as tabular crystals but is also present as fine-crystalline pseudocubic phases at Boukovo and Sarnitsa, in Eastern Rhodopes. In the advanced argillic alterations associated with economic ore, the presence of zunyite in the deeper parts indicates acid–fluorine–sulphate hydrothermal systems, whereas it is absent in uneconomic and barren advanced argillic alteration. All occurrences are formed at temperatures between 200 and 300 °C.(H, O, S) isotopic signatures of alunite combined with mineralogical features from all the studied occurrences, whatever their type, show characteristics of magmatic-hydrothermal systems. Sulphur data indicate essentially a magmatic origin for sulphur. Oxygen and hydrogen data suggest that hydrothermal fluids result from a mixing between magmatic fluids and an external component, which is identified as seawater-derived fluids or meteoric water in the vicinity of a sea. In most of the alunite occurrences, magmatic fluids are dominant and H₂S/SO₄ ratios are estimated to be higher than 2. Two exceptions exist in the Rhodopes. At Boukovo and Sarnitsa, where the estimated formation temperatures of alunite are the lowest, the external fluids are dominant and H₂S/SO₄ratios are estimated to be lower than or close to 1.At this stage of the work, the mineralogical and isotopic criteria do not enable a clear distinction between economic and uneconomic systems. However, some features are common in the economic ore deposits: the presence of zunyite in the deeper part of the system, the relatively high temperatures suggested by the zunyite + pyrophyllite + alunite + diaspore assemblages, the (O, H, S) signature of alunite, which is characteristic of dominant magmatic–hydrothermal acid–sulphate–fluorine systems.