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 Monte Carlo Model Of The Nocturnal Surface Temperatures In Urban Canyons

A model for the urban canyon is formulated for meteorologicalconditions of weak winds at night time. Thermal radiation, conductivity and convection are simulated by means of the Monte Carlo method. These are the main physical processesof energy transfer that give rise to the characteristic temperaturedistribution in these systems. The model has been satisfactory tested under ideal conditions for which analytical solutions exist.The predictions of the model under morerealistic conditions accurately reproduce the observationalresults. A strong temperature gradient across streets, with the canyon corners up to 4 °C warmer than the canyon centre, is found for the deepest canyons. This theoretical predictionhas been successfully verified with measurementstaken in a number of streets of the city of Granada in Spain.     

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.     

Regional retrograde alteration of sub-greenschist facies chlorite to smectite

Dioctahedral smectite is present as a retrograde alteration product of chlorite in Permian-Triassic red slates of the Malaguide Complex in Sierra de Espuña (Betic Cordillera). Mineral assemblages and textures, illite crystallinity indices, and fluid inclusion data indicate sub-greenschist facies conditions that reached at least 180°C in the higher-grade tectonic unit of the Malaguide Complex, preceding formation of smectite. Smectite, having K as the dominant interlayer cation, occurs ubiquitously intercalated with trioctahedral chlorite as thin packets of layers and as individual layers that commonly change to chlorite along layers. Although some chlorite is typically homogeneous and trioctahedral, much chlorite shows signs of alteration and has compositions corresponding to different degrees of smectite contaimination. The incompatibility of metamorphic grade with the occurrence of smectite, the general association of chlorite and smectite, and the textural relations collectively show that dioctahedral smectite is derived through replacement of trioctahedral chlorite. Such replacement occurs on a regional basis and demonstrates that caution must be used in interpreting the occurrence of smectite in pelites as being due to prograde processes. Alteration of trioctahedral chlorite under oxidizing conditions due to introduction of phreatic water after uplift of the Betic Cordillera is proposed as the cause of formation of smectite.     

Spherical integral transforms of second-order gravitational tensor components onto third-order gravitational tensor components

New spherical integral formulas between components of the second- and third-order gravitational tensors are formulated in this article. First, we review the nomenclature and basic properties of the second- and third-order gravitational tensors. Initial points of mathematical derivations, i.e., the second- and third-order differential operators defined in the spherical local North-oriented reference frame and the analytical solutions of the gradiometric boundary-value problem, are also summarized. Secondly, we apply the third-order differential operators to the analytical solutions of the gradiometric boundary-value problem which gives 30 new integral formulas transforming (1) vertical-vertical, (2) vertical-horizontal and (3) horizontal-horizontal second-order gravitational tensor components onto their third-order counterparts. Using spherical polar coordinates related sub-integral kernels can efficiently be decomposed into azimuthal and isotropic parts. Both spectral and closed forms of the isotropic kernels are provided and their limits are investigated. Thirdly, numerical experiments are performed to test the consistency of the new integral transforms and to investigate properties of the sub-integral kernels. The new mathematical apparatus is valid for any harmonic potential field and may be exploited, e.g., when gravitational/magnetic second- and third-order tensor components become available in the future. The new integral formulas also extend the well-known Meissl diagram and enrich the theoretical apparatus of geodesy.     

Biases in the diurnal temperature range in Central Europe in an ensemble of regional climate models and their possible causes

The study examines how regional climate models (RCMs) reproduce the diurnal temperature range (DTR) in their control simulations over Central Europe. We evaluate 30-year runs driven by perfect boundary conditions (the ERA40 reanalysis, 1961–1990) and a global climate model (ECHAM5) of an ensemble of RCMs with 25-km resolution from the ENSEMBLES project. The RCMs’ performance is compared against the dataset gridded from a high-density stations network. We find that all RCMs underestimate DTR in all seasons, notwithstanding whether driven by ERA40 or ECHAM5. Underestimation is largest in summer and smallest in winter in most RCMs. The relationship of the models’ errors to indices of atmospheric circulation and cloud cover is discussed to reveal possible causes of the biases. In all seasons and all simulations driven by ERA40 and ECHAM5, underestimation of DTR is larger under anticyclonic circulation and becomes smaller or negligible for cyclonic circulation. In summer and transition seasons, underestimation tends to be largest for the southeast to south flow associated with warm advection, while in winter it does not depend on flow direction. We show that the biases in DTR, which seem common to all examined RCMs, are also related to cloud cover simulation. However, there is no general tendency to overestimate total cloud amount under anticyclonic conditions in the RCMs, which suggests the large negative bias in DTR for anticyclonic circulation cannot be explained by a bias in cloudiness. Errors in simulating heat and moisture fluxes between land surface and atmosphere probably contribute to the biases in DTR as well.     

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.