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.     

Fingerprinting of the Atlantic meridional overturning circulation in climate models to aid in the design of proxy investigations

It is desirable to design proxy investigations that target regions where properties reconstructed from calibrated parameters potentially carry high-fidelity information concerning changes in large-scale climate systems. Numerical climate models can play an important role in this task, producing simulations that can be analyzed to produce spatial “fingerprints” of the expected response of various properties under a variety of different scenarios. We will introduce a new method of fingerprinting the Atlantic meridional overturning circulation (AMOC) that not only provides information concerning the sensitivity of the response at a given location to changes in the large-scale system, but also quantifies the linearity, monotonicity and symmetry of the response. In this way, locations that show high sensitivities to changes in the AMOC, but that exhibit, for example, strongly nonlinear behavior can be avoided during proxy investigations. To demonstrate the proposed approach we will use the example of the response of seawater temperatures to changes in the strength of the AMOC. We present results from an earth-system climate model which has been perturbed with an idealized freshwater forcing scenario in order to reduce the strength of the AMOC in a systematic manner. The seawater temperature anomalies that result from the freshwater forcing are quantified in terms of their sensitivity to the AMOC strength in addition to the linearity and monotonicity of their response. A first-order reversal curve (FORC) approach is employed to investigate and quantify the irreversibility of the temperature response to a slowing and recovering AMOC. Thus, FORCs allow the identification of areas that are unsuitable for proxy reconstructions because their temperature versus AMOC relationship lacks symmetry.     

Validation and Application of Plants as Biomonitors of Trace Element Atmospheric Pollution – A Co-Ordinated Effort in 14 Countries

The International Atomic Energy Agency (IAEA) organized a co-ordinated research project (CRP) on Validation and application of plants as biomonitors of trace element atmospheric pollution analysed by nuclear and related techniques involving 14 participating countries. The CRPs objective was to identify appropriate bioindicators for local and/or regional application and validate them for general air pollution monitoring. Activities included quantification studies, research into spatial and time resolution for particular organisms, and physiological studies. A number of suitable bioindicators were identified in different parts of the globe and tested during the CRP. Sampling strategies were reviewed and the recommended approach adopted by the group. Appropriate sample preparation procedures were assessed and harmonised to the degree allowed by different geographic and climatic conditions in the participating countries. Two interlaboratory comparison exercises were carried out on lichen and moss materials. Results confirmed definite improvement in analytical performance of the participating laboratories, but also revealed possible inconsistencies due to different sample processing procedures. Several monitoring surveys were carried out and consequently pollution maps drawn for extended areas or countries. Overall results confirmed applicability of lower plants for assessing the degree of atmospheric pollution and provided several countries with effective monitoring tools not used before.     

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.     

High- and low-Cr chromitite and dunite in a Tibetan ophiolite: evolution from mature subduction system to incipient forearc in the Neo-Tethyan Ocean

The microstructures, major- and trace-element compositions of minerals and electron backscattered diffraction (EBSD) maps of high- and low-Cr# [spinel Cr# = Cr³⁺/(Cr³⁺ + Al³⁺)] chromitites and dunites from the Zedang ophiolite in the Yarlung Zangbo Suture (South Tibet) have been used to reveal their genesis and the related geodynamic processes in the Neo-Tethyan Ocean. The high-Cr# (0.77–0.80) chromitites (with or without diopside exsolution) have chromite compositions consistent with initial crystallization by interaction between boninitic magmas, harzburgite and reaction-produced magmas in a shallow, mature mantle wedge. Some high-Cr# chromitites show crystal-plastic deformation and grain growth on previous chromite relics that have exsolved needles of diopside. These features are similar to those of the Luobusa high-Cr# chromitites, possibly recycled from the deep upper mantle in a mature subduction system. In contrast, mineralogical, chemical and EBSD features of the Zedang low-Cr# (0.49–0.67) chromitites and dunites and the silicate inclusions in chromite indicate that they formed by rapid interaction between forearc basaltic magmas (MORB-like but with rare subduction input) and the Zedang harzburgites in a dynamically extended, incipient forearc lithosphere. The evidence implies that the high-Cr# chromitites were produced or emplaced in an earlier mature arc (possibly Jurassic), while the low-Cr# associations formed in an incipient forearc during the initiation of a new episode of Neo-Tethyan subduction at ~130–120 Ma. This two-episode subduction model can provide a new explanation for the coexistence of high- and low-Cr# chromitites in the same volume of ophiolitic mantle.