Structural changes and valence states in the MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript>–FeCr<Subscript>2</Subscript>O<Subscript>4</Subscript> solid solution series

The influence on the structure of Fe²⁺ Mg substitution was studied in synthetic single crystals belonging to the MgCr₂O₄–FeCr₂O₄ series produced by flux growth at 900–1200 °C in controlled atmosphere. Samples were analyzed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption-, infrared- and Mössbauer spectroscopy. The Mössbauer data show that iron occurs almost exclusively as ^IVFe²⁺. Only minor Fe³⁺ (<0.005 apfu) was observed in samples with very low total Fe. Optical absorption spectra show that chromium with few exceptions is present as a trivalent cation at the octahedral site. Additional absorption bands attributable to Cr²⁺ and Cr³⁺ at the tetrahedral site are evident in spectra of end-member magnesiochromite and solid-solution crystals with low ferrous contents. Structural parameters a₀, u and T–O increase with chromite content, while the M–O bond distance remains nearly constant, with an average value equal to 1.995(1) Å corresponding to the Cr³⁺ octahedral bond distance. The ideal trend between cell parameter, T–O bond length and Fe²⁺ content (apfu) is described by the following linear relations: a₀=8.3325(5) + 0.0443(8)Fe²⁺ (Å) and T–O=1.9645(6) + 0.033(1)Fe²⁺ (Å) Consequently, Fe²⁺ and Mg tetrahedral bond lengths are equal to 1.998(1) Å and 1.965(1) Å, respectively.     

Nature and origin of arsenic carriers in shallow aquifer sediments of Bengal Delta,India

Sediments from shallow aquifers in Bengal Delta, India have been found to contain arsenic. Rivers of Ganga-Brahmaputra system, responsible for depositing these sediments in the delta, have created a store of arsenic. Geomorphological domains with different depositional styles regulate the pattern of distribution of zones with widely different content of groundwater arsenic. The high arsenic zones occur as narrow sinuous strips confined to channel deposits. A few iron-bearing clastic minerals and two post-depositional secondary products are arsenic carriers. Secondary siderite concretions have grown on the surface of the clastic carriers in variable intensity. The quantity of arsenic in all clastic carriers is in excess of what is generally expected. Excess arsenic is contributed by the element adsorbed on the concretion grown on the surface of the carriers, which adds up to the arsenic in the structure of the minerals. Variable abundance of concretions is responsible for the variable quantity of arsenic in the carriers and the sediment samples. Fe²⁺ for the growth of siderite concretions is obtained from the iron-bearing clastic carriers. The reaction involves reduction of trivalent iron to bivalent and the required electron is obtained by transformation of As³⁺ to As⁵⁺. It is suggested that oxidation of As³⁺ to As⁵⁺ is microbially mediated. In the Safe zone arsenic is retained in the carriers and groundwater arsenic is maintained below 0.05 mg/l. In the Unsafe zone sorbed arsenic is released from the carriers in the water through desorption and dissolution of concretion, thereby elevating the groundwater arsenic level to above 0.05 mg/l.     

Vulnerability assessment in karstic areas: validation by field experiments

Several methods have been developed for vulnerability mapping in karstic areas. These methods need additional validation by field experiments. Several tests have been carried out in the Swiss Jura with natural and artificial tracers. The protective role of some intrinsic properties of the system, such as glacial deposits covering karst, epikarst storage and system dilution effect, have been clearly demonstrated. Use of three tracers in parallel showed the reactivity of the epikarst: all tracers arrived at the same time, but their relative concentration stayed clearly different. A classification of contamination scenarios into four classes is proposed. It is shown that the relevance of some intrinsic properties depends on the considered scenario class. The hydrodynamic state of the aquifer influences greatly flow velocities and can strongly modify contaminant concentrations at the output of the system. The spatial repartition (point vs diffuse) and the quantity of contaminant entering the system will also influence the output response. Hence, results from tracing experiments cannot be used straightforward for obtaining a representative value of flow velocity, dispersion or recovery rate.     

Granulometric and chemical composition of the Sava River sediments upstream and downstream of the Krsko nuclear power plant

Total concentrations of 13 elements (K, Ca, Ti, Cr, Mn, Fe, Cu, Zn, Rb, Sr, Y, Zr, Pb) in the size-fractionated Sava River sediments upstream and downstream of the Krsko nuclear power plant together with metal speciation within bulk sediment have been investigated. Trace metals generally increase with decreasing particle size, however, because of entrapment of organic matter in the 0.63–1 mm fraction, concentrations in the coarser sediment fraction are higher than expected. Exchangeable Pb, Zn, Cu, Mn, Cr and Fe are generally found to represent a negligible fraction of the total metal concentration of the bulk sediment. Seasonal variations of the Pb, Zn and Cu concentrations in the <0.5 mm fraction reflect decreased values during the spring period. Heavy metal concentrations in the 2003 waste water discharges from the Krsko nuclear power plant released into the Sava River were much lower than their maximum allowed values. Combined rubidium and organic matter normalization of the Zn, Pb and Cu concentrations, which was applied on the minus 0.063 mm fraction, indicated three potential sources of contaminants.     

Characteristics of rapid giant landslides in China

Factual data for 70 rapid, giant landslides since 1900 show that the occurrence of these landslides was largely predisposed by tectonics, geological structures, lithology and topography, and often triggered by rainfall and earthquakes. In terms of mobile behavior, the giant landslides can be classified into three types: slides, slide-flows and flows. It is found that each type of landslide was constrained to certain geologic and topographic regimes. There are good correlations between kinematic parameters of landslides and slope geometries, which confirm the important role played by topographical condition in the mobile behavior of landslides. Moreover, it is also found that each type of landslide presents distinct geotechnical characteristics in terms of nature of the slip zone and properties of sliding mass. Brief analyses of five typical cases illustrate that landslide mechanisms can be conceptually depicted by failure mechanisms of their slip zones prior to onset of movement and following energy conversion during movement. Problems and questions related to experience in China suggest that comprehensive and systematic investigation and study on rapid giant landslides are urgently needed.     

Evolution of geochemistry and depositional settings of Early Palaeozoic siliciclastics of the Barrandian (Teplá-Barrandian Unit,Bohemian Massif,Czech Republic)

Cambrian and Ordovician-Middle Devonian sequences of two successive Early Palaeozoic basins of the Barrandian unconformably overlie Cadomian basement in the Bohemian Massif NW interior (Teplá-Barrandian unit) which is the easternmost peri-Gondwanan remnant within the Variscides. Correlation of stratigraphy and geochemistry of the Early Palaeozoic siliciclastic rocks elucidated sediment provenances. Sandstones of the Middle Cambrian Píbram-Jince Basin were derived from a Cadomian Neoproterozoic island arc. The source area of the Ordovician shallow-marine siliciclastics of the successor Prague Basin is a dissected Cadomian orogen. Late Cambrian acid volcanics of the Barrandian and Cambrian (meta)granitoids emplaced in the W part of the Teplá-Barrandian Cadomian basement are also discernible in these sediments. Old sedimentary component increased during the Ordovician. Early Llandovery siliciclastic rocks show characteristics of an abruptly weakened supply of terrigenous material and an elevated proportion of synsedimentary basic volcanics as a result of Silurian transgression. Emsian siliciclastics (intercalated in the Late Silurian to Early Devonian limestone suite) presumably comprise an addition of coeval basic/ultrabasic volcaniclastics. Middle Devonian flysch-like siliciclastics indicate reappearance of Cadomian source near the Barrandian during early Variscan convergences of Armorican microplates that preceeded accretion of the Teplá-Barrandian unit within the Bohemian Massif terrane mosaic.Dr. Patoka deceased in July 2004.     

Carbon isotope stratigraphy of Lochkovian to Eifelian limestones from the Devonian of central and southern Europe

Lower to Middle Devonian carbonates of the Prague Syncline, the Carnic Alps, the Montagne Noire, and the Cantabrian Mountains were investigated for δ¹³C_carb and δ¹³C_org. These values were measured on bulk rocks, selected components and cements. Many carbonates exhibit primary marine values, but some are altered by diagenesis. A δ¹³C curve can be presented for the latest Pridolian to Emsian time interval. Several sharp or broad positive excursions are obvious in the woschmidti-postwoschmidti, sulcatus, kitabicus, Late serotinus, and kockelianus conodont zones. The excursion at the Silurian–Devonian boundary is known worldwide and therefore considered global in nature. Some of the others are described for the first time from central and southern Europe, and their global nature has to be verified by further investigations in other regions. Most excursions relate to and/or started during major regressions whereas sea-level highstands correspond to minimal δ¹³C values. Similar relationships between sea-level changes and δ¹³C have been observed from other early Palaeozoic intervals. The transgressive Chote? (?) and Ka?ák events are marked by positive isotope excursions, this type of combination is usually observed in late Palaeozoic to Cenozoic black shale events.     

A field evaluation of enhanced reductive dechlorination of chlorinated solvents in groundwater,New York Metropolitan Area

An initial assessment of an old manufacturing site with groundwater impacted by trichloroethene (TCE) contamination in the metropolitan New York area showed that the TCE was being removed naturally by reductive dechlorination. However, complete dechlorination was not expected at the site because the process was progressing too slowly under transitional to aerobic conditions at a degradation constant of –0.0013 and a TCE half life of 533 days. A pilot test was conducted at the site in which a carbohydrate substrate (molasses) was injected into the groundwater to create an In-Situ Reactive Zone (IRZ). Post-pilot test groundwater sampling and analysis indicated that an IRZ was created successfully as the total organic carbon (TOC) content and conductivity increased significantly while oxidation-reduction (REDOX) potential and dissolved oxygen (DO) decreased. The created IRZ caused enhanced reductive dechlorination of TCE at the site, found to proceed with a degradation constant of –0.0158 and a TCE half life of 44 days.