Dispersion of natural arsenic in the Malcantone watershed, Southern Switzerland: field evidence for repeated sorption-desorption and oxidation-reduction processes

In recent years, elevated arsenic concentrations have been found in waters and soils of many, countries, often resulting in a health threat for the local population. Switzerland is not an exception and this paper deals with the release and subsequent fate of arsenic in a 200-km(2) mountainous watershed, characterized by crystalline silicate rocks (gneisses, schists, amphibolites) that contain abundant As-bearing sulfide ore deposits, some of which have been mined for iron and gold in the past. Using analytical methods common for mineralogical, ground water and soil studies (XRD, XRF, XAS-XANES and -EXAFS, electron microprobe, extraction, ICP, AAS with hydride generator, ion chromatography), seven different field situations and related dispersion processes of natural arsenic have been studied: (1) release by rock weathering, (2) transport and deposition by water and ice; (3) release of As to the ground and surface water due to increasing pH; (4) accumulation in humic soil horizons; (5) remobilization by reduction in water-saturated soils and stagnant ground waters; (6) remobilization by using P-rich fertilizers or dung and (7) oxidation, precipitation and dilution in surface waters. Comparison of the results with experimental adsorption studies and speciation diagrams from the literature allows us to reconstruct and identify the typical behavior of arsenic in a natural environment under temperate climatic conditions. The main parameters identified are: (a) once liberated from the primary minerals, sorption processes on Fe-oxy-hydroxides dominate over Al-phases, such as Al-hydroxides or clay minerals and limit the As concentrations in the spring and well waters between 20 and 300 mug/l. (b) Precipitation as secondary minerals is limited to the weathering domain, where the As concentrations are still high and not yet too diluted by rain and soils waters. (c) Although neutral and alkaline pH conditions clearly increase the mobility of As, the main factor to mobilize As is a low redox potential (Eh close or below 0 mV), which favors the dissolution of the Fe-oxy-hydroxides on which the As is sorbed. (d) X-ray absorption spectroscopy (XAS) of As in water-logged humic forest soils indicates that the reduction to As III only occurs at the solid-water interface and that the solid contains As as As V (e) A and Bh horizons of humic cambisols can effectively capture As when As-rich waters flow through them. Complex spatial and temporal variation of the various parameters in a watershed results in repeated mobilization and immobilization of As, which continuously transports As from the upper to the lower part of a watershed and ultimately to the ocean. (C) 2004 Elsevier B.V. All rights reserved.

Comprendre la dispersion des espèces dans l'espace et dans le temps : un défi pour les biogéographes

De tout temps, l'homme s'est interrogé sur les facteurs qui régissent la distribution des espèces. Comment se dispersent-elles? Comment occupent-elles un milieu? Pourquoi certaines caractéristiques biologiques d'une même entité spécifique varient-elles en différents points de l'espace? Pour répondre à ces questions, il faut faire appel à de nombreuses disciplines scientifiques, telles que l'écologie, la géologie, la climatologie ou la paléontologie. Comprendre la distribution spatiale de la vie, quel que soit le niveau taxonomique, tel est l'objectif de la biogéographie

Empirical studies of cloud effects on UV radiation: A review

The interest in solar ultraviolet (UV) radiation from the scientific community and the general population has risen significantly in recent years because of the link between increased UV levels at the Earth's surface and depletion of ozone in the stratosphere. As a consequence of recent research, UV radiation climatologies have been developed, and effects of some atmospheric constituents (such as ozone or aerosols) have been studied broadly. Correspondingly, there are well-established relationships between, for example, total ozone column and UV radiation levels at the Earth's surface. Effects of clouds, however, are not so well described, given the intrinsic difficulties in properly describing cloud characteristics. Nevertheless, the effect of clouds cannot be neglected, and the variability that clouds induce on UV radiation is particularly significant when short timescales are involved. In this review we show, summarize, and compare several works that deal with the effect of clouds on UV radiation. Specifically, works reviewed here approach the issue from the empirical point of view: Some relationship between measured UV radiation in cloudy conditions and cloud-related information is given in each work. Basically, there are two groups of methods: techniques that are based on observations of cloudiness (either from human observers or by using devices such as sky cameras) and techniques that use measurements of broadband solar radiation as a surrogate for cloud observations. Some techniques combine both types of information. Comparison of results from different works is addressed through using the cloud modification factor (CMF) defined as the ratio between measured UV radiation in a cloudy sky and calculated radiation for a cloudless sky. Typical CMF values for overcast skies range from 0.3 to 0.7, depending both on cloud type and characteristics. Despite this large dispersion of values corresponding to the same cloud cover, it is clear that the cloud effect on UV radiation is 15–45% lower than the cloud effect on total solar radiation. The cloud effect is usually a reducing effect, but a significant number of works report an enhancement effect (that is increased UV radiation levels at the surface) due to the presence of clouds. The review concludes with some recommendations for future studies aimed to further analyze the cloud effects on UV radiation

Anomalous rainfall and associated atmospheric circulation in the northeast Spanish Mediterranean area and its relationship to sediment fluidization events in a lake

Changes in the dynamics of sediment transport in a Mediterranean lake (sediment fluidization events) are linked to atmospheric circulations patterns (trough monthly precipitation). In the basins of Lake Banyoles, located in the northeast of Spain, water enters mainly through subterranean springs, and associated fluctuations in the vertical migration of sediment distribution (fluidization events) present episodic behavior as a result of episodic rainfall in the area. The initiation of the fluidization events takes place when the monthly rainfall is ∼2.7 times greater than the mean monthly rainfall of the rainiest months in the area, especially in spring (April and May), October, and December. The duration of these events is found to be well correlated with the accumulated rainfall of the preceding 10 months before the process initiation. The rainfall, in turn, is mainly associated with six atmospheric circulation patterns among the 19 fundamental circulations that emerged in an earlier study focused on significant rainfall days in Mediterranean Spain. Among them, accentuated surface lows over the northeast of Spain, general northeasterly winds by low pressure centered to the east of Balearic Islands and short baroclinic waves over the Iberian Peninsula, with easterly flows over the northeastern coast of Spain, are found the most relevant atmospheric circulations that drive heavy rainfall events

Accurate calculations of intermolecular interaction energies using explicitly correlated coupled cluster wave functions and a dispersion-weighted MP2 method.

Explicitly correlated coupled-cluster calculations of intermolecular interaction energies for the S22 benchmark set of Jurecka, Sponer, Cerny, and Hobza (Chem. Phys. Phys. Chem. 2006, 8, 1985) are presented. Results obtained with the recently proposed CCSD(T)-F12a method and augmented double-zeta basis sets are found to be in very close agreement with basis set extrapolated conventional CCSD(T) results. Furthermore, we propose a dispersion-weighted MP2 (DW-MP2) approximation that combines the good accuracy of MP2 for complexes with predominately electrostatic bonding and SCS-MP2 for dispersion-dominated ones. The MP2-F12 and SCS-MP2-F12 correlation energies are weighted by a switching function that depends on the relative HF and correlation contributions to the interaction energy. For the S22 set, this yields a mean absolute deviation of 0.2 kcal/mol from the CCSD(T)-F12a results. The method, which allows obtaining accurate results at low cost, is also tested for a number of dimers that are not in the training set.

Bulk-plasmon dispersion relations in metals

Using an extended-random-phase-approximation sum-rule technique, we have investigated the bulk-plasmon dispersion relation, incorporating in a simple way exchange and correlation effects within the jellium model. The results obtained are compared with recent experimental findings. The key role played by exchange and correlation effects in improving the agreement between theory and experiment is stressed. The static polarizability has also been calculated as a function of q. The formulas can be easily modified to incorporate band-structure effects (through an intraband electron effective mass) and core-polarization effects (through a static dielectric constant).