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.     

A methodology for locating the original quarries used for constructing historical buildings: application to Málaga Cathedral, Spain

It is often necessary to locate the original quarry which supplied the stone for a particular historical building. This stones could be used for future restoration work and for testing in the laboratory (artificial aging tests, physical properties determination, control of the efficacy of conservation treatments, etc.). Generally, reviewing historical documentation gives information about the geographical setting of quarries and location of the stones in the monument, but this information needs to be proved by field and laboratory studies. The comparative study of stone from quarries and monuments should basically include the following: (1) mineralogical and petrographical studies; (2) the chemical analysis of major, minor and trace elements; (3)stable isotopes determinations; (4) physical properties of quarry materials and unweathered building stone (water absorption, ultrasound transmission velocity, porosity and porous system, density, bulk density, compressive strength, etc.). This methodology was applied to Málaga Cathedral stones represented in the main façade, towers, and the western zone of the terrace, which, according to historical literature, came from Almayate (Miocene–Pliocene limestones) and Cerro Coronado (Permotriassic sandstone) in Málaga. The conclusion of the comparative study carried out on quarries and building stones was consistent with the information available from the historical documentation.     

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.     

North Atlantic atmospheric circulation and surface wind in the Northeast of the Iberian Peninsula: uncertainty and long term downscaled variability

The variability and predictability of the surface wind field at the regional scale is explored over a complex terrain region in the northeastern Iberian Peninsula by means of a downscaling technique based on Canonical Correlation Analysis. More than a decade of observations (1992–2005) allows for calibrating and validating a statistical method that elicits the main associations between the large scale atmospheric circulation over the North Atlantic and Mediterranean areas and the regional wind field. In an initial step the downscaling model is designed by selecting parameter values from practise. To a large extent, the variability of the wind at monthly timescales is found to be governed by the large scale circulation modulated by the particular orographic features of the area. The sensitivity of the downscaling methodology to the selection of the model parameter values is explored, in a second step, by performing a systematic sampling of the parameters space, avoiding a heuristic selection. This provides a metric for the uncertainty associated with the various possible model configurations. The uncertainties associated with the model configuration are considerably dependent on the spatial variability of the wind. While the sampling of the parameters space in the model set up moderately impact estimations during the calibration period, the regional wind variability is very sensitive to the parameters selection at longer timescales. This fact illustrates that downscaling exercises based on a single configuration of parameters should be interpreted with extreme caution. The downscaling model is used to extend the estimations several centuries to the past using long datasets of sea level pressure, thereby illustrating the large temporal variability of the regional wind field from interannual to multicentennial timescales. The analysis does not evidence long term trends throughout the twentieth century, however anomalous episodes of high/low wind speeds are identified.     

Estimation of Surface-Layer Scaling Parameters in the Unstable Boundary Layer: Implications for Orographic Flow Speed-Up

A method is proposed for estimating the surface-layer depth \((z_s)\) and the friction velocity \((u_*)\) as a function of stability (here quantified by the Obukhov length, L) over the complete range of unstable flow regimes. This method extends that developed previously for stable conditions by Argaín et al. (Boundary-Layer Meteorol 130:15–28, 2009), but uses a qualitatively different approach. The method is specifically used to calculate the fractional speed-up \((\varDelta S)\) in flow over a ridge, although it is suitable for more general boundary-layer applications. The behaviour of \(z_s \left( L\right) \) and \(u_*\left( L\right) \) as a function of L is indirectly assessed via calculation of \(\varDelta S\left( L\right) \) using the linear model of Hunt et al. (Q J R Meteorol Soc 29:16–26, 1988) and its comparison with the field measurements reported in Coppin et al. (Boundary-Layer Meteorol 69:173–199, 1994) and with numerical simulations carried out using a non-linear numerical model, FLEX. The behaviour of \(\varDelta S\) estimated from the linear model is clearly improved when \(u_*\) is calculated using the method proposed here, confirming the importance of accounting for the dependences of \(z_s\left( L \right) \) and \(u_*\left( L \right) \) on L to better represent processes in the unstable boundary layer.     

Adaptation of Pressure Based CFD Solvers for Mesoscale Atmospheric Problems

General purpose Computational Fluid Dynamics (CFD) solvers are frequently used in small-scale urban pollution dispersion simulations without a large extent of ver- tical flow. Vertical flow, however, plays an important role in the formation of local breezes, such as urban heat island induced breezes that have great significance in the ventilation of large cities. The effects of atmospheric stratification, anelasticity and Coriolis force must be taken into account in such simulations. We introduce a general method for adapting pressure based CFD solvers to atmospheric flow simulations in order to take advantage of their high flexibility in geometrical modelling and meshing. Compressibility and thermal stratification effects are taken into account by utilizing a novel system of transformations of the field variables and by adding consequential source terms to the model equations of incompressible flow. Phenomena involving mesoscale to microscale coupled effects can be analyzed without model nesting, applying only local grid refinement of an arbitrary level. Elements of the method are validated against an analytical solution, results of a reference calculation, and a laboratory scale urban heat island circulation experiment. The new approach can be applied with benefits to several areas of application. Inclusion of the moisture transport phenomena and the surface energy balance are important further steps towards the practical application of the method.     

Estimating Buoyancy Heat Flux Using the Surface Renewal Technique over Four Amazonian Forest Sites in Brazil

The surface renewal (SR) method was applied for the first time to measurements of air temperature over four Amazonian forest sites and different seasons in order to obtain estimates of buoyancy heat flux. The required calibration of this method against eddy covariance resulted in a value for a specific parameter that is close to the range reported in other studies, contributing to the generalization of the SR method to different kinds of canopies. The comparison with fluxes obtained using the eddy covariance technique revealed a good match between the two methods for different sites, heights and seasons. Sites with high levels of non-stationarity in the signals of temperature and wind speed presented higher scatter in the regression with fluxes from eddy covariance. For a particular site with previously reported influence of low-frequency motions, the regression was only satisfactory, i.e., slope parameter close to unity and small offset, when oscillations with periods longer than $\approx $ ≈ 13 min were filtered out. The SR method has a great potential due to the simplicity of the instrumentation required. However, care should be taken when measuring under the influence of mesoscale motions, which can lead to high levels of non-stationarity, compromising the fundamental concepts of the SR theory.     

Vertical behaviour and meteorological properties of air masses in the southwest of the Iberian Peninsula (1997–2007)

Air masses are characterized by physical (temperature, humidity) and chemical (transported gases and aerosols) properties, being associated their arrival to different meteorological scenarios. The knowledge of the air masses over a region is fundamental as complementary information in several atmospheric studies, being the calculation of back-trajectory the most widely used tool whenever air masses are analyzed. A study of air masses has been carried out in southwestern Iberian Peninsula using 5-day kinematic back trajectories computed by the HYSPLIT model at three heights (500, 1,500 and 3,000 m) from 1997 to 2007. The main aims have been to characterize their vertical behaviour and their thermal and humidity properties. Thirteen trajectory clusters have been defined, showing the northerly and westerly clusters a high coupling degree. Seasonal daily variation of potential temperature and specific humidity has been analyzed, obtaining higher differences among clusters in the cold season.     

Adsorption of cobalt by using inorganic components of sediment samples from water bodies

The adsorption of cobalt ions was evaluated using sediment samples from water bodies to investigate the adsorption properties of sediment and the behavior of these natural materials in the presence of nuclear and industrial waste.The two sediments(S1 and S2)were treated to eliminate humic and fulvic acids and then they were characterized by several techniques.The minerals found in both the sediments(X-ray diffraction)were quartz and albite;plus,goethite and muscovite in S1,and kaolinite and montmorillonite in S2.Point of zero charge(PZC)of S1 and S2 was 6.00 and 5.22,respectively.The specific area of S1(63.3 m²/g)is higher than S2(1.5 m²/g).Adsorption kinetics data for S1 and S2 were best fitted to the pseudo second-order model.The removal efficiency of S1 for cobalt was 96%with an adsorption capacity(qe)of 0.93 mg/g,and for S2 was 45%with a qeof 0.40 mg/g.The experimental data of the adsorption isotherms were adjusted to Langmuir and Freundlich models for S1 and S2,respectively.The thermodynamic parameters(enthalpy,entropy,and Gibb’s free energy)indicated that the adsorption processes were endothermic,spontaneous,and chemisorption mechanism.The results show that the adsorption capacities of the sediments depend on their composition.These water sediments have important adsorption properties for cobalt,and they can be used in the treatment of nuclear and industrial aqueous wastes.