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.     

Emplacement age and thermal footprint of the diamondiferous Ellendale E9 lamproite pipe, Western Australia

The diamondiferous Ellendale 9 (E9) pipe is a funnel-shaped maar-diatreme volcano consisting of inward-dipping tuff sequences intruded by lamproite plugs and dykes. The host rocks for the E9 pipe are Permian sandstones. The multiple lithological contacts exposed within the mined maar volcano provide a natural laboratory in which to study the effect of volcanic processes on U–Th–Pb–He systematics. Zircon from the regional sandstone and E9 lamproite display a bimodal distribution of ages on (U–Th)/He–U/Pb plots. The zircon U/Pb ages for the E9 pipe (n?=?52) range from 440 to 2,725 Ma, while the cluster of (U–Th)/He ages for the lamproite dyke zircon indicate that dyke emplacement occurred at 20.6?±?2.8 Ma, concordant with a maximum emplacement age of about ≤22 Ma from phlogopite ⁴⁰Ar/³⁹Ar. These ages indicate a xenocrystic origin for the zircon entrained in the E9 dyke. The U/Pb ages of detrital zircon from the regional sandstone host (373–3,248 Ma; n?=?41) are indistinguishable from those of the lamproite zircon xenocrysts, whereas the detrital zircon in the host sandstone yield (U–Th)/He ages from 260 to 1,500 Ma. A thermochronology traverse across the E9 lamproite dyke reveals that the zircon (U–Th)/He ages in the host sandstone have not been significantly thermally reset during dyke emplacement, even at the contact. The capability of the zircon (U–Th)/He method to distinguish deep, mantle source lithologies from upper crustal source lithologies could be used in geochemical exploration for diamonds. Pre-screening of detrital samples using etching and helium assay methods will improve the efficiency and decrease the cost of greenfields exploration.     

Petrology and geochemistry of komatiites and tholeiites from Gorgona Island,Colombia

Komatiitic rocks from Gorgona Island, Colombia, in contrast to their Archaean counterparts, occur as rather structureless flows. In addition, textural and mineralogical features indicate that the Gorgona komatiites may have crystallized from superheated liquids. Komatiitic rocks have MgO contents which range from 24 to 11 wt.% and plot on well-defined olivine (Fo₉₀) control lines. Calculations show that potential evolved liquids (MgO<11 wt%) will be SiO₂-poor. Komatiites, in this case, cannot be regarded as parental to the associated tholeiitic basalt sequence.On the basis of REE concentrations and Sr, Nd isotopic compositions, the associated basalts are found to be of two types. One type (K-tholeiite) is characterized by noticeably fractionated REE patterns and relatively primitive isotopic compositions similar to those of the komatiites. K-tholeiites, together with komatiites, are regarded as comprising a distinctive komatiitic suite. REE patterns within this suite show progressive depletion in the LREE from K-tholeiites to komatiites, and represent increasingly higher degrees of melting of the same mantle source region. The other type (T-tholeiite), representative of the bulk of the exposed basalt sequence, has flat REE patterns and relatively evolved isotopic compositions. This tholeiitic suite is clearly genetically unrelated to the komatiitic suite.     

Fabric transpositions in granite plutons — An insight from non-scaled analogue modelling

Investigations on a set of experimental models of highly viscous intrusions were carried out in order to study the internal strain pattern during vertical ascent and emplacement of granite intrusions. The strain pattern was determined by means of anisotropy of magnetic susceptibility (AMS) resulting from the orientation of magnetite particles in a liquid plaster medium. The modelled intrusions show distinct fabrics reflecting the flow of a rheologically complex, non-Newtonian material. During the vertical growth of the intrusion, constrictional vertical fabrics are transposed into flattening fabrics, and along with the development of low-intensity fabric domains are passively transported upwards. Vertical growth takes place along subvertical thrust shear zones that satisfactorily explain the discordant magmatic fabrics in granites along intrusion sides. The resulting complex fabric patterns suggest that the vertical movement of material in ascending intrusions is accommodated by various flow mechanisms operating simultaneously.     

U–Pb evidence for a polyorogenic evolution of the HP–HT units of the NW Iberian Massif

. A isotope dilution thermal ionisation mass spectrometry U-Pb geochronological study was carried out on the high-pressure and high-temperature units (HP-HT units) overlying the oceanic suture in the Allochthonous Complexes of the NW Iberian Variscan Belt. The rocks investigated are seven granulite- to eclogite-facies paragneisses and one leucosome within mafic high-pressure granulites in the Ordenes and Cabo Ortegal Complexes of NW Spain. U-Pb dating of zircon, monazite, titanite and rutile reveal the presence of a pervasive Early Ordovician metamorphic event at ca. 500-480 Ma and a later Early Devonian event at ca. 400-380 Ma. The U-Pb ages, in conjunction with petrological and structural data, indicate that the high-pressure event recorded by these rocks is Early Ordovician in age. Monazite ages in the paragneisses suggest that peak metamorphic conditions were reached at ca. 500-485 Ma. Subsequently, the rock ensemble underwent exhumation accompanied by partial melting and zircon growth at ca. 485-470 Ma. Melting of mafic granulites was coeval with this latter episode as indicated by zircon crystallisation age in the leucosomes dated at ca. 486 Ma. Based on these data and on the general features of magmatism and metamorphic evolution, it is proposed that this process took place at a convergent plate boundary within a peri-Gondwanan oceanic domain. Monazite, titanite and rutile data in some of the samples studied show evidence of a second metamorphic episode that took place between ca. 400 and 380 Ma (with a peak at ca. 390-385 Ma). This Early Devonian event, at variance with the previous one, was not pervasive, but, rather, was localised in areas of intense Variscan tectonothermal reworking. It is claimed that this later metamorphic event was recorded by the U-Pb system in areas where monazite and titanite growth was enhanced by fluid circulation in highly strained rocks (Variscan shear zones). According to previous structural studies and Ar-Ar dating of fabrics, this Early Devonian episode took place as the HP-HT units were deformed and thrusted upon the ophiolitic units in the early stages of the Variscan collision.     

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.     

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.     

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.     

From brightening to dimming in sunshine duration over the eastern and central Tibetan Plateau (1961–2005)

The Tibetan Plateau (TP) with an average elevation of over 4,000 m asl is the highest and most extensive highland in the world. We used monthly mean sunshine duration from the Chinese Meteorological Administration to examine the spatial and temporal variability of sunshine duration at 71 stations with elevations above 2,000 m asl in the eastern and central TP during the 1961–2005 period. The temporal evolution of the mean annual sunshine duration series shows a significant increase from 1961 to 1982 at a rate of 49.8 h/decade, followed by a decrease from 1983 to 2005 at a rate of ?65.1 h/decade, with an overall significant decrease at a rate of ?20.6 h/decade during the whole 1961–2005 period, which is mainly due to the summer and spring seasons. This confirms the evidence that sunshine duration in the TP ranges from brightening to dimming in accordance with sunshine duration trends in the rest of China. The surface solar radiation downwards from ERA-40 reanalysis data in the same region confirms the brightening/dimming phenomenon shown by the sunshine duration before/after the 1980s. Otherwise, additional climatic variables such as low cloud amount, total cloud amount, precipitation, relative humidity and water vapor pressure, in most cases, exhibit significant negative correlation with sunshine duration in the TP on an annual and seasonal basis before and after 1982, respectively. The trends of these variables suggest that changes in some of them might be related to the brightening and dimming detected with the use of sunshine duration measurements over the TP. We also hypothesize that the impact of anthropogenic aerosols upon the climatic variables analyzed cannot be rejected, especially in the significant increase in low cloud cover since approximately 1980.     

Genetic and chemical relationships between berthierine,chlorite and cordierite in nodules associated to granitic pegmatites of Sierra Albarrana (Iberian Massif,Spain)

Chlorite and berthierine occur through alteration of cordierite within enclaves of metamorphic rocks transformed by the Sierra Albarrana pegmatites. The coexistence of both phyllosilicates allows us to study their stability relationships and to compare their chemical compositions. Samples showing incipient replacement of cordierite by small cryptocrystalline aggregates can be identified by X-ray diffraction (XRD) as berthierine with small quantities of chlorite. Electron Microprobe (EMP) analyses give mixed compositions of berthierine and cordierite. Samples with extensive replacement of cordierite by aggregates show similar characteristics to those with incipient replacement, but some small crystals are present. The last type of sample shows complete replacement of cordierite by crystals showing optical properties of chlorite and EMPA compositions coherent with chlorite or berthierine. Their XRD pattern corresponds to chlorite and their high resolution transmission electron microscopy (HRTEM) images only show perfect sequences of 14 Å lattice fringes. The cryptocrystalline aggregates of the samples with incipient and extensive replacement present coexistent areas of 14 Å and 7 Å lattice fringes that are intergrown at different levels: (1) large areas (> 1 m) of 7 Å layers; (2) packets of 7 Å layers between 14 Å layer areas, with visible 7 Å to 14 Å lateral changes; (3) random mixed-layers 7 Å/14 Å. Chlorite is the final stable product of alteration of cordierite, with berthierine as an intermediate metastable phase. Energy dispersive X-ray spectrometry microanalyses of 14 Å, 7 Å and (14+7) Å areas show lack of systematic differences in chemical compositions between both phyllosilicates which may be considered as true polymorphs.