On the breakdown of zircon upon “dry” thermal annealing

Zircon samples without and with secondary chemical alteration from diverse sources were subjected to heat treatment at 1400 °C for 96 h. Resulting new phases and textures suggest that decomposition of zircon into component oxides occurred in all experiments to various degrees. The crucible material was found to have a strong influence on the extent of breakdown, especially in the case of altered starting materials. In this study the progressive stages of the breakdown of zircon grains are described. The factors that may govern the decomposition are discussed, including radiation damage, secondary alteration and external reaction conditions (sample container, atmosphere). Alumina crucibles should generally be avoided in dry annealing of zircon, to minimise uncontrolled breakdown into oxides.     

Natural Arsenic Attenuation via Metal Arsenate Precipitation in Soils Contaminated with Metallurgical Wastes: I. Wet Chemical and Thermodynamic Evidences

Arsenic from natural and anthropogenic sources is a worldwide contaminant of aqueous environments, such as groundwater and soils. The present investigation was performed on Mexican soils contaminated with residues from metallurgical processes that have shown a natural As attenuation. Experimental aqueous arsenic extractions in these were successfully simulated for almost half of the soil samples using a database updated for all known metal arsenate formation constants, revealing the predominance of solubility-controlled As mobility via Pb, mixed Pb–Cu, and Ca arsenate solid formation. The relatively low total Fe/As ratios (2–13 w/w) present in the soils studied, together with the high and equivalent contents of As, Pb, and Cu in these, favor the precipitation process over As(V) adsorption to Fe oxides, despite a 2% average Fe content in the soils studied. Under these conditions bicarbonate was found to be a highly unsuitable extractant due to its indirect As release from the solid arsenates, via heavy metal carbonate precipitation processes.     

Pyrite formation driven by MSW landfill leachate in the Madrid Basin, Spain

The role of municipal solid waste (MSW) landfill leachate on the genesis of minor amounts of pyrite associated with gypsum in an otherwise predominantly evaporitic sequence was studied in geological and geochemical terms. The potential association between landfill leachate and the conditions required for bacterial reduction of sulfate and fixation of H₂S as pyrite were examined. The lithological column was generally found to contain little or no Fe. The δ³⁴S values for sulfates were consistent with previously reported data; however, the measured δ¹⁸O values were slightly higher. Sulfides disseminated in the marl/lutite exhibited higher δ³⁴S values (≈−8‰) than gypsum-coating pyrite crystals (δ³⁴S < −30‰). Dissolution of gypsum to sulfate and the supply of metabolizable organic matter and Fe required for H₂S fixation as sulfides may have originated from landfill leachate. Intermittent availability of leachate, a result of the precipitation regime, can facilitate sulfur disproportionation and lead to fractionations as high as      

The Removal of Dissolved Metals by Hydroxysulphate Precipitates during Oxidation and Neutralization of Acid Mine Waters, Iberian Pyrite Belt

This study examines the removal of dissolved metals during the oxidation and neutralization of five acid mine drainage (AMD) waters from La Zarza, Lomero, Esperanza, Corta Atalaya and Poderosa mines (Iberian Pyrite Belt, Huelva, Spain). These waters were selected to cover the spectrum of pH (2.2–3.5) and chemical composition (e.g., 319–2,103 mg/L Fe; 2.85–33.3 g/L SO₄⁼) of the IPB mine waters. The experiments were conducted in the laboratory to simulate the geochemical evolution previously recognized in the field. This evolution includes two stages: (1) oxidation of dissolved Fe(II) followed by hydrolysis and precipitation of Fe(III), and (2) progressive pH increase during mixing with fresh waters. Fe(III) precipitates at pH < 3.5 (stages 1 and 2) in the form of schwertmannite, whereas Al precipitates during stage 2 at pH 5.0 in the form of several hydroxysulphates of variable composition (hydrobasaluminite, basaluminite, aluminite). During these stages, trace elements are totally or partially sorbed and/or coprecipitated at different rates depending basically on pH, as well as on the activity of the SO₄⁼ anion (which determines the speciation of metals). The general trend for the metals which are chiefly present as aqueous free cations (Pb²⁺, Zn²⁺, Cu²⁺, Cd²⁺, Mn²⁺, Co²⁺, Ni²⁺) is a progressive sorption at increasing pH. On the other hand, As and V (mainly present as anionic species) are completely scavenged during the oxidation stage at pH < 3.5. In waters with high activities (> 10⁻¹) of the SO ₄⁼ ion, some elements like Al, Zn, Cd, Pb and U can also form anionic bisulphate complexes and be significantly sorbed at pH < 5. The removal rates at pH 7.0 range from around 100% for As, V, Cu and U, and 60–80% for Pb, to less than 20% for Zn, Co, Ni and Mn. These processes of metal removal represent a significant mechanism of natural attenuation in the IPB.     

Uranium (U) concentration and its genetic significance in the phosphorites of the Paleoproterozoic Bijawar Group of the Lalitpur district,Uttar Pradesh,India

The paper presents the uranium (U) concentration and distribution pattern in the Paleoproterozoic phosphorites of Lalitpur district of Uttar Pradesh. The study of thin sections, SEM and XRD reveal that apatite is the essential phosphate mineral while quartz and feldspars are the dominant gangue in the phosphorites of the investigated area. The collophane is observed to be mostly oolitic in form and microspherulitic in texture. The major element geochemistry indicated that the phosphorite samples are rich in P₂O₅, CaO, SiO₂ and Fe₂O₃ whereas depletion of MgO, MnO, K₂O and Al₂O₃ was observed. The CaO/P₂O₅ ratio ranges from 1.13 to 1.46 which is slightly lower than that of cations and anions substituted francolite (1.621) and close to that of carbonate-fluorapatite (1.318). The trace element geochemistry indicates that the phosphorites of Lalitpur have the significant range of U concentration (1.67 to 129.67 μg/g) which is more than that of Th (0.69 to 0.09 μg/g) among the analysed trace elements in the phosphorite samples of the area. The positive correlation of U with P₂O₅, CaO and U/P₂O₅ indicates a close association of U with phosphate minerals like collophane (apatite), whereas negative correlation of U with SiO₂ and Fe₂O₃ may be due to mutual replacement. The antipathetic relationship of U with Ni may be an indication of high oxidizing conditions, whereas sympathetic relationship of U with K₂O points towards higher alkaline conditions of the basin of deposition during phosphatization. The variable concentration of U and its relationship with significant major and trace elements in most of the phosphorite samples lead one to believe that the deposition of these phosphorites might have taken place in highly alkaline medium during fairly oxidizing to weakly reducing environmental conditions of geosynclinal basin.     

Changes in the onset and length of seasons from an ensemble of regional climate models over Spain for future climate conditions

This study analyses the length and onset of the four seasons based on the annual climatic cycle of maximum and minimum temperatures. Previous studies focused over climatically homogeneous mid-high latitude areas, employing fixed temperature thresholds (related to climatic features such as freezing point) that can be inadequate when different climate conditions are present. We propose a method related to the daily minimum and maximum temperature 25th and 75th point-dependent climatic percentiles. It is applied to an ensemble of regional climate models (RCMs) of 25-km horizontal resolution over the peninsular Spain and Balearic Islands, where a large variety of climatic regimes, from alpine to semi-desertic conditions, are present. First, baseline climate (1961–2000) ERA40-forced RCM simulations are successfully compared with the Spain02 daily observational database, following astronomical season length (around 90 days). This result confirms the validity of the proposed method and capability of the RCMs to describe the seasonal features. Future climate global climate model-forced RCMs (2071–2100) compared with present climate (1961–1990) simulations indicate the disappearance of winter season, a summer enlargement (onset and end) and a slight spring and autumn increase.     

Investigation about the dependence of spectral diffuse-to-direct-beam irradiance ratio on atmospheric turbidity and solar zenith angle

Summary The modifications of the solar spectral diffuse and direct-beam irradiances as well as the diffuse-to-direct-beam ratio, E_dλ/E_bλ, as a function of the aerosol optical depth, AOD, and solar zenith angle, SZA, is investigated. The E_dλ/E_bλ ratios decrease rapidly with wavelength and exponential curves in the form E_dλ/E_bλ = aλ^−b can be fitted with a great accuracy. These curves are strongly modified by the solar spectrum distribution, which is affected by the aerosol loading, aerosol optical properties and SZA. The spectral dependence of the above E_dλ/E_bλ ratios in logarithmic coordinates does not yield a straight line, while a significant departure from the linearity is revealed. The reasons for this departure are investigated in detail and it is established that the aerosol physical properties such as single scattering albedo and size distribution along with the effect of SZA are responsible. These parameters strongly affect the scattering processes in the atmosphere and as a consequence the diffuse spectral distribution. The E_dλ/E_bλ ratio, which is an indicator of the atmospheric transmittance (King, 1979), exhibits a strong wavelength and aerosol-loading dependence. The observed differences between turbid and clear atmospheres constitute a manifestation of contrasting air properties and influence solar irradiance spectra. The present work aims at investigating the effect of atmospheric turbidity and SZA on the E_dλ/E_bλ ratio. For this reason, two distinct cases are examined: one having different atmospheric turbidity conditions but same SZA and a second having different SZAs and same atmospheric turbidity levels.     

Climate change and summer mass tourism: the case of Spanish domestic tourism

This paper investigates the impact of climate change on destination choice decisions in a context of domestic coastal tourism in Spain. Destinations are characterized in terms of travel cost and coastal ‘attractors’, such as temperature and beach-related attributes. By means of a discrete choice model based on the random utility theory, these variables are used to explain the observed pattern of interprovincial domestic trips, showing trade-offs between temperature and attractiveness in the probability of a particular destination being chosen. The model is used to investigate the impact of two climate change scenarios on the allocation of domestic tourism within Spain. The findings show that while Spain’s northern colder provinces would benefit from rising temperatures, provinces in the south would experience a decrease in the frequency of trips.     

Oceanographic Change and Terrestrial Human Impacts in a Post A.D. 1400 Sediment Record from the Southwest Iceland Shelf

Environmental proxies of soil erosion on Iceland, and oceanographic conditions on the adjacent shelf, were measured on a 50 cm box core taken from the southwest Iceland shelf in 1993 during cruise 93030 of the Canadian ship, CSS Hudson. These data, covering the last several centuries, are compared with the documentary record of sea-ice changes around Iceland since A.D. 1600. The site is under the influence of the Irminger Current, which carries warm, saline, Atlantic water northward along the shelf. Because of the relative warmth of this current, sea ice rarely occurs off southwest Iceland, even during the most severe sea-ice intervals of the historical record. In severe sea-ice years, however, the ice drifts clockwise around Iceland from the northeast and east and, in rare cases, reaches the southern coasts (Ogilvie, 1992). The chronology of the core was established by converting the basal radiocarbon date to calendar years and assuming a linear sedimentation rate from the base of the core to the year of collection, 1993. Organic carbon, stable C and O isotope ratios, planktonic foraminiferal assemblages, and sediment magnetic parameters were measured on samples from the core, plotted against calendar years and compared to the Icelandic sea-ice index. The environmental proxies suggest that increased soil erosion, reduced salinity, and, possibly, decreased marine productivity prevailed during the severe sea-ice interval lasting from the last quarter of the eighteenth century to around 1920. Such a situation could develop with climatic cooling, increased storminess, and loss of vegetation cover to stabilise the soil. Although the core site generally lies outside the sea-ice limits, the evidence clearly shows the influence of sea ice and fresh water, and is sensitive to the overall climatic deterioration manifested by the sea-ice record.     

Some Insights into Topographic,Elastic and Self-gravitation Interaction in Modelling Ground Deformation and Gravity Changes in Active Volcanic Areas

Surface displacements and gravity changes due to volcanic sources are influenced by medium properties. We investigate topographic, elastic and self-gravitation interaction in order to outline the major factors that are significant in data modelling. While elastic-gravitational models can provide a suitable approximation to problems of volcanic loading in areas where topographic relief is negligible, for prominent volcanoes the rough topography could affect deformation and gravity changes to a greater extent than self-gravitation. This fact requires the selection, depending on local relief, of a suitable model for use in the interpretation of surface precursors of volcanic activity. We use the three-dimensional Indirect Boundary Element Method to examine the effects of topography on deformation and gravity changes in models of magma chamber inflation/deflation. Topography has a significant effect on predicted surface deformation and gravity changes. Both the magnitude and pattern of the geodetic signals are significantly different compared to half-space solutions. Thus, failure to account for topographic effects in areas of prominent relief can bias the estimate of volcanic source parameters, since the magnitude and pattern of deformation and gravity changes depend on such effects.