A Multi‐Element Ion‐Pair Extraction for Trace Metals Determination in Environmental Samples

A multi‐element ion‐pair extraction method was described for the preconcentration of Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Ni(II), Pb(II), and Zn(II) ions in environmental samples prior to their determinations by flame atomic absorption spectrometry (FAAS). As an ion‐pair ligand 2‐(4‐methoxybenzoyl)‐N′‐benzylidene‐3‐(4‐methoxyphenyl)‐3‐oxo‐N‐phenyl‐propono hydrazide (MBMP) was used. Some analytical parameters such as pH of sample solution, amount of MBMP, shaking time, sample volume, and type of counter ion were investigated to establish optimum experimental conditions. No interferences due to major components and some metal ions of the samples were observed. The detection limits of the proposed method were found in the range of 0.33–0.9 µg L^?1 for the analyte ions. Recoveries were found to be higher than 95% and the relative standard deviation (RSD) was less than 4%. The accuracy of the procedure was estimated by analyzing the two certified reference materials, LGC6019 river water and RTC‐CRM044 soil. The developed method was applied to several matrices such as water, hair, and food samples.     

Depositional mechanics of turbulent nuées ardentes (surges) from their grain sizes

The ability of turbulent nuées ardentes (surges) to transport coarse pyroclasts has been questioned on the basis that settling velocities of coarse fragments in the deposits are much too high for them to have been supported by turbulence in a dilute gas suspension. A computer model is used to evaluate the settling velocity of pyroclasts in suspensions of varying concentration and temperature. Since suspension of grains in low-concentration surges occurs if the shear velocity exceeds the settling velocity, the shear velocities related to the 16th and 84th percentiles, and the mean of the grain-size distribution are compared in surge deposits of the Vulsini, with the shear velocity necessary to move the coarsest grain on the bed surface (the Shields criterion). The results show that the settling velocities do not vary significantly in gaseous suspensions having volume concentrations lower than 15%, and that an increase in concentration to 25% is not sufficient to decrease the settling velocity of the coarser fraction, if it represents flow shear velocity. It is shown that the settling velocity of the mean grain size (M _z ) best depicts the shear velocity of a dilute turbulent suspension. Applying the results to the May 1902 paroxysmal nuées ardentes of Mount Pelée shows that the estimated mean velocities are well within the observed velocities, and sufficient to support all the clasts in dilute, turbulent suspensions.     

Description de deux nouvelles Cyclotelles (Bacillariophyceae) de milieux alcalins et eutrophes:Cyclotella costei nov. sp. etCyclotella wuethrichiana nov. sp.

Two new species of the genus Cyclotella are presented which have been discovered during ecological and paleoecological research studies in the littoral zone of two small alkaline eutrophic lakes in France (Lake Paladru) and in Switzerland (Lake Le Loclat). These new species are namedCyclotella costei nov. sp. andCyclotella wuethrichiana nov. sp.     

Nature and role of CO2 in some hot and cold HCO3/Na/CO2-rich Portuguese mineral waters: a review and reinterpretation

 At the northern part of the Portuguese mainland, the upflow zone of several hot and cold HCO₃/Na/CO₂-rich mineral waters is mainly associated with important NNE–SSW faults. Several geochemical studies have been carried out on thermal and non-thermal hydromineral manifestations that occur along or near these long tectonic alignments. The slight chemical differences that exist between these meteoric hot and cold HCO₃/Na/CO₂-rich mineral waters seem to be mainly caused by CO₂. δ¹³C_(TIDC) values observed in these groundwaters range between –6.00 and –1.00‰ versus V-PDB (V denotes Vienna, the site of the International Atomic Energy Agency; PDB originates from the CaCO₃ of the rostrum of a Cretaceous belemnite, Belemnitella americana, collected in the Peedee formation of South Carolina, USA) indicating a deep-seated (mantle) origin for most of the CO₂. Nevertheless, in the case of the heavier δ¹³C_(TIDC) values, the contribution of metamorphic CO₂ or the dissolution of carbonate rock levels at depth cannot be excluded. Concerning the hot waters, the lack of a positive ¹⁸O-shift should be attributed to water-rock interaction in a low temperature environment, rather than to the isotopic influence of CO₂ on the δ¹⁸O-value of the waters. Received: 9 August 1999 · Accepted: 8 March 2000     

Multiscale approach to geo‐composite cellular structures subjected to rock impacts

Geo‐composite cellular structures are an efficient technological solution for various applications in civil engineering. This type of structure is particularly well adapted to resisting rockfalls and can act as a defensive structure. However, the design of such structures is for the most part empirically based; this lack of research‐based design stagnates optimization and advanced development. In this paper, the mechanical behaviour of a geo‐composite cellular structure is investigated using a multi‐scale approach, from the individual cell made up of an assembly of rocky particles contained in a wire netting cage to the entire structure composed of a regular array of cells. Based on discrete modelling of both the cell and structure scales, a computational tool has been developed for design purposes. Copyright © 2007 John Wiley & Sons, Ltd.     

Bifurcation and second‐order work in geomaterials

In this paper, the ability of a material rate‐independent system to evolve toward another mechanical state from an equilibrium configuration, with no change in the control parameters, is investigated. From a mechanical point of view, this means that the system can spontaneously develop kinetic energy with no external disturbance from an equilibrium state, which corresponds to a particular case of bifurcation. The existence of both conjugate incremental strain and stress such that the second‐order work vanishes is established as a necessary and sufficient condition for the appearance of this bifurcation phenomenon. It is proved that this fundamental result is independent of the constitutive relation of the rate‐independent material considered. Then the case of homogeneous loading paths is investigated, and, as an illustration, the subsequent results are applied to interpret the well‐known liquefaction observed under isochoric triaxial loading conditions with loose granular materials. Copyright © 2006 John Wiley & Sons, Ltd.     

The effect of the geomagnetic activity to the hourly variations of ionospheric foF2 values at low latitudes

In this study, the relationship between the hourly changes of the ionospheric critic frequency values of F2 layers in low latitudes and geomagnetic activity is examined by using statistical methods. The ionospheric critical frequency data has been taken from the Manila (121.1° E, 14.7° N) ionosonde station. In order to investigate the effect of sun activity on ionospheric critical frequency, the data of 1981 when the sun was active and of 1985 when the sun was less active has been used. According to the Granger causality test results, on 5 % significance level, a causality relationship from disturbance storm time (Dst) index values to ionospheric critical frequency values direction has been observed. However, a causality relationship from ionospheric critical frequency values to Dst values has not been observed. From the results of cause-and-effect analysis, it is evaluated that the effect of a shockwave occurring in geomagnetic activity on ionospheric critical frequency continues along 72 h, that is, geomagnetic activity has a long-term effect on ionospheric critical frequency. The response of ionospheric critical frequency to geomagnetic activity substantially depends on seasons. This response is more observed especially in equinox period when the sun is active and in winter months. The increase in geomagnetic activity causes ionospheric critical frequency to decrease in night hours and increase in day hours. The same relationship has not been observed exactly, though observed very little in winter months, for 1985 when the sun was less active.     

Fracturation tertiaire et évolution des contraintes en Bavière orientale: le Jura franconien et la forêt bavaroise (R.F.A.)

Résumé L'analyse géométrique et cinématique de la fracturation dans le Jura franconien et la bordure occidentale du Massif bohémien met en évidence les mécanismes de la tectonique cassante d'âge teriaire, essentiellement ceux des grands accidents SE-NW (lignes de Pfahl et de Franconie) qui ont présenté successivement des jeux en coulissement dextre, en faille normale et en faille inverse. Cinq états de contrainte ont été caractérisés et comparés à ceux définis antérieurement dans le Jura souabe, en liaison avec la cinématique des plaques Europe et Afrique: compression N-S, distension E-W, compression NE-SW puis E-W, distension N-S.

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The analysis of both the geometric and the kinematic cenozoic faulting in the Franconian Jura and in western Bohemia enables to characterize the mechanisms of cenozoic tectonics. More especially dextral strike-slip, normal fault and reverse fault have successively occurred along large SE-NW fault line, as the Pfahl and the Franconian fault systems. Five main stress patterns have thus been identified and then compared with those previously described in Swabian Jura. They are related to the kinematic of Europe and Africa plates, i. e.: (1) N-S compression, (2) E-W distension, (3) SW-NE compression, (4) E-W compression, (5) N-S distension.

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Zusammenfassung Durch die geometrische und kinematische Analyse der Brüche wird die tertiäre Bruchtektonik (tectonique cassante) im Fränkischen Jura und am westlichen Rand des Böhmischen Massifs belegt. Es handelt sich im wesentlichen um die großen SE-NW orientierten Störungen der Linie von Pfahl und der Fränkischen Linie, die nacheinander als dextrale Blattverschiebungen, als Normalverwerfungen und als inverse Verwerfungen wirkten. Fünf Spannungszustände können charakterisiert und mit jenen, die bereits im Schwäbischen Jura definiert wurden, verglichen werden. Sie spiegeln die verschiedenen Stadien der kinematischen Entwicklung der europäischen und afrikanischen Platte wider: Kompression N-S, Zerrung E-W, Kompression NE-SW, sodann E-W, Zerrung N-S.

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Mg isotope constraints on soil pore-fluid chemistry: Evidence from Santa Cruz, California

Mg isotope ratios (²⁶Mg/²⁴Mg) are reported in soil pore-fluids, rain and seawater, grass and smectite from a 90 kyr old soil, developed on an uplifted marine terrace from Santa Cruz, California. Rain water has an invariant ²⁶Mg/²⁴Mg ratio (expressed as δ²⁶Mg) at −0.79 ± 0.05‰, identical to seawater δ²⁶Mg. Detrital smectite (from the base of the soil profile, and therefore unweathered) has a δ²⁶Mg value of 0.11‰, potentially enriched in ²⁶Mg by up to 0.3‰ compared to the bulk silicate Earth Mg isotope composition (although within the range of all terrestrial silicates). The soil pore-waters show a continuous profile with depth for δ²⁶Mg, ranging from −0.99‰ near the surface to −0.43‰ at the base of the profile. Shallow pore-waters (<1 m) have δ²⁶Mg values that are similar to, or slightly lower than the rain waters. This implies that the degree of biological cycling of Mg in the pore-waters is relatively small and is quantified as <32%, calculated using the average Mg isotope enrichment factor between grass and rain (δ²⁶Mg_grass-δ²⁶Mg_rain) of 0.21‰. The deep pore-waters (1-15 m deep) have δ²⁶Mg values that are intermediate between the smectite and rain, ranging from −0.76‰ to −0.43‰, and show a similar trend with depth compared to Sr isotope ratios. The similarity between Sr and Mg isotope ratios confirms that the Mg in the pore-waters can be explained by a mixture between rain and smectite derived Mg, despite the fact that Mg and Sr concentrations may be buffered by the exchangeable reservoir. However, whilst Sr isotope ratios in the pore-waters span almost the complete range between mineral and rain inputs, Mg isotopes compositions are much closer to the rain inputs. If Mg and Sr isotope ratios are controlled uniquely by a mixture, the data can be used to estimate the mineral weathering inputs to the pore-waters, by correcting for the rain inputs. This isotopic correction is compared to the commonly used chloride correction for precipitation inputs. A consistent interpretation is only possible if Mg isotope ratios are fractionated either by the precipitation of a secondary Mg bearing phase, not detected by conventional methods, or selective leaching of ²⁴Mg from smectite. There is therefore dual control on the Mg isotopic composition of the pore-waters, mixing of two inputs with distinct isotopic compositions, modified by fractionation. The data provide (1) further evidence for Mg isotope fractionation at the surface of the Earth and (2) the first field evidence of Mg isotope fractionation during uptake by natural plants. The coherent behaviour of Mg isotope ratios in soil environments is encouraging for the development of Mg isotope ratios as a quantitative tracer of both weathering inputs of Mg to waters, and the physicochemical processes that cycle Mg, a major cation linked to the carbon cycle, during continental weathering.