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.     

Hydrogeology and sustainable future groundwater abstraction from the Agua Verde aquifer in the Atacama Desert,northern Chile

The hyper-arid conditions prevailing in Agua Verde aquifer in northern Chile make this system the most important water source for nearby towns and mining industries. Due to the growing demand for water in this region, recharge is investigated along with the impact of intense pumping activity in this aquifer. A conceptual model of the hydrogeological system is developed and implemented into a two-dimensional groundwater-flow numerical model. To assess the impact of climate change and groundwater extraction, several scenarios are simulated considering variations in both aquifer recharge and withdrawals. The estimated average groundwater lateral recharge from Precordillera (pre-mountain range) is about 4,482 m³/day. The scenarios that consider an increase of water withdrawal show a non-sustainable groundwater consumption leading to an over-exploitation of the resource, because the outflows surpasses inflows, causing storage depletion. The greater the depletion, the larger the impact of recharge reduction caused by the considered future climate change. This result indicates that the combined effects of such factors may have a severe impact on groundwater availability as found in other groundwater-dependent regions located in arid environments. Furthermore, the scenarios that consider a reduction of the extraction flow rate show that it may be possible to partially alleviate the damage already caused to the aquifer by the continuous extractions since 1974, and it can partially counteract climate change impacts on future groundwater availability caused by a decrease in precipitation (and so in recharge), if the desalination plant in Taltal increases its capacity.     

Pennsylvanian carbonate platforms adjacent to deltaic systems in an active marine foreland basin (Escalada Fm., Cantabrian Zone,NW Spain)

The Pennsylvanian marine foreland basin of the Cantabrian Zone (NW Spain) is characterized by the unique development of kilometre‐size and hundred‐metre‐thick carbonate platforms adjacent to deltaic systems. During Moscovian time, progradational clastic wedges fed by the orogen comprised proximal alluvial conglomerates and coal‐bearing deltaic sequences to distal shelfal marine deposits associated with carbonate platforms (Escalada Fm.) and distal clay‐rich submarine slopes. A first phase of carbonate platform development (Escalada I, upper Kashirian‐lower Podolskian) reached a thickness of 400 m, nearly 50 km in width and developed a distal high‐relief margin facing a starved basin, nearly 1000‐m deep. Carbonate slope clinoforms dipped up to 30° and consisted of in situ microbial boundstone, pinching out downslope into calciturbidites, argillaceous spiculites and breccias. The second carbonate platform (Escalada II, upper Podolskian‐lower Myachkovian) developed beyond the previous platform margin, following the basinward progradation of siliciclastic deposits. Both carbonate platforms include: (1) a lower part composed of siliciclastic‐carbonate cyclothems characterized by coated‐grain and ooid grainstones; and (2) a carbonate‐dominated upper part, composed of tabular and mound‐shaped wackestone and algal‐microbial boundstone strata alternating at the decametre scale with skeletal and coated‐grain grainstone beds. Carbonate platforms initiated in distal sectors of the foreland marine shelf during transgressions, when terrigenous sediments were stored in the proximal part, and developed further during highstands of 3rd‐order sequences in a high‐subsidence context. During the falling stage and lowstand systems tracts, deltaic systems prograded across the shelf burying the carbonate platforms. Key factors involved in the development of these unique carbonate platforms in an active foreland basin are: (1) the large size of the marine shelf (approaching 200 km in width); (2) the subsidence distribution pattern across the marine shelf, decreasing from proximal shoreline to distal sectors; (3) Pennsylvanian glacio‐eustacy affecting carbonate lithofacies architecture; and (4) the environmental conditions optimal for fostering microbial and algal carbonate factories.     

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.     

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.     

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.     

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.     

Long-term deforestation in NW Spain: linking the Holocene fire history to vegetation change and human activities

The Holocene fire regime is thought to have had a key role in deforestation and shrubland expansion in Galicia (NW Spain) but the contribution of past societies to vegetation burning remains poorly understood. This may be, in part, due to the fact that detailed fire records from areas in close proximity to archaeological sites are scarce. To fill this gap, we performed charcoal analysis in five colluvial soils from an archaeological area (Campo Lameiro) and compared the results to earlier studies from this area and palaeo-ecological literature from NW Spain. This analysis allowed for the reconstruction of the vegetation and fire dynamics in the area during the last ca 11 000 yrs. In the Early Holocene, Fabaceae and Betula sp. were dominant in the charcoal record. Quercus sp. started to replace these species around 10 000 cal BP, forming a deciduous forest that prevailed during the Holocene Thermal Maximum until ～5500 cal BP. Following that, several cycles of potentially fire-induced forest regression with subsequent incomplete recovery eventually led to the formation of an open landscape dominated by shrubs (Erica sp. and Fabaceae). Major episodes of forest regression were (1) ～5500–5000 cal BP, which marks the mid-Holocene cooling after the Holocene Thermal Maximum, but also the period during which agropastoral activities in NW Spain became widespread, and (2) ～2000–1500 cal BP, which corresponds roughly to the end of the Roman Warm Period and the transition from the Roman to the Germanic period. The low degree of chronological precision, which is inherent in fire history reconstructions from colluvial soils, made it impossible to distinguish climatic from human-induced fires. Nonetheless, the abundance of synanthropic pollen indicators (e.g. Plantago lanceolata and Urtica dioica) since at least ～6000 cal BP strongly suggests that humans used fire to generate and maintain pasture.     

The multi-component Hekla Ö Tephra,Iceland: a complex widespread mid-Holocene tephra layer

Large Plinian eruptions from Hekla volcano, Iceland, produce compositionally zoned tephra used as key markers in tephrochronology. However, spatial variations in chemical composition of a tephra layer may complicate its identification. An example is the 5950–6180 cal a bp Hekla Ö tephra layer, which shows compositional spread from rhyolite, dacite and andesite to basalt. In soil sections north of Hekla, the SiO₂ content of the tephra glass reaches 76 wt% in the lowest unit of the Hekla Ö deposit and decreases to 62–63 wt% in the uppermost unit. Intermingled within the whole deposit are basalt tephra grains having 46–47 wt% SiO₂. The composition of the basalt glass includes primitive basalt and a more evolved basalt (MgO >6 and <6 wt%, respectively). Together with literature data, the Hekla Ö tephra and the so-called T-Tephra/Hekla-T are most likely from contemporaneous eruptions of different vents on the Hekla volcanic system, forming a single important marker tephra (Hekla ÖT) deposited over 80% of Iceland. Identification is complicated by its spatial compositional heterogeneity, such as systematic decrease in SiO₂ content from the east to the west of Hekla volcano. Consequently, an individual tephra layer from a large explosive eruption can have different composition at different locations. © 2020 John Wiley & Sons, Ltd.     

Crustal segments in the North Patagonian Massif,Patagonia: An integrated perspective based on Sm–Nd isotope systematics

New insights on the Paleozoic evolution of the continental crust in the North Patagonian Massif are presented based on the analysis of Sm–Nd systematics. New evidence is presented to constrain tectonic models for the origin of Patagonia and its relations with the South American crustal blocks. Geologic, isotopic and tectonic characterization of the North Patagonian Massif and comparison of the Nd parameters lead us to conclude that: (1) The North Patagonian Massif is a crustal block with bulk crustal average ages between 2.1 and 1.6 Ga T_DM (Nd) and (2) At least three metamorphic episodes could be identified in the Paleozoic rocks of the North Patagonian Massif. In the northeastern corner, Famatinian metamorphism is widely identified. However field and petrographic evidence indicate a Middle to Late Cambrian metamorphism pre-dating the emplacement of the ca. 475 Ma granitoids. In the southwestern area, are apparent 425–420 Ma (?) and 380–360 Ma metamorphic peaks. The latter episode might have resulted from the collision of the Antonia terrane; and (3) Early Paleozoic magmatism in the northeastern area is coeval with the Famatinian arc. Nd isotopic compositions reveal that Ordovician magmatism was associated with attenuated crust. On the southwestern border, the first magmatic recycling record is Devonian. Nd data shows a step by step melting of different levels of the continental crust in the Late Palaeozoic. Between 330 and 295 Ma magmatism was likely the product of a crustal source with an average 1.5 Ga T_DM (Nd). Widespread magmatism represented by the 295–260 Ma granitoids involved a lower crustal mafic source, and continued with massive shallower-acid plutono volcanic complexes which might have recycled an upper crustal segment of the Proterozoic continental basement, resulting in a more felsic crust until the Triassic. (4) Sm–Nd parameters and detrital zircon age patterns of Early Paleozoic (meta)-sedimentary rocks from the North Patagonian Massif and those from the neighboring blocks, suggest crustal continuity between Eastern Sierras Pampeanas, southern Arequipa-Antofalla and the northeastern sector of the North Patagonian Massif by the Early Paleozoic. This evidence suggests that, at least, this corner of the North Patagonian Massif is not allochthonous to Gondwana. A Late Paleozoic frontal collision with the southwestern margin of Gondwana can be reconcilied in a para-autochthonous model including a rifting event from a similar or neighbouring position to its post-collision location. Possible Proterozoic or Early Paleozoic connections of the NPM with the Kalahari craton or the western Antartic blocks should be investigated.