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Opencast mining of sulfide ore deposits may lead to the formation of anthropogenic acidic lakes with highly polluted waters. In these systems, it is crucial to understand the hydrological connections between surface and groundwater and their contribution to the pollutant load delivered to the downgradient streams. This study characterizes the interactions between surface and groundwater in an acidic pit lake using different geochemical tracers (i.e., REE and other trace metals). The San Telmo pit lake, located in one of the most pollutant sources of the Iberian Pyrite Belt (IPB), can be considered as a flow-through pit lake except during dry periods, when it behaves as a terminal lake due to lower inputs by surface waters and higher outputs by evaporation. Results based on geochemical tracers indicate that the main inputs to the pit lake come from surface waters, with minor groundwater inputs rich in As, Cr, Cu, Fe and Pb. The contaminant load released from the mining area is very high (e.g., median values of 520 kg/day of Fe and 38 kg/day of Zn), causing the degradation of the fluvial network downstream. Most of released pollutants come from waste dumps located at the W of the mining zone (~50-70% of Al, Cd, Mg, Mn, Ni, SO 4 and Zn and > 70% for Cu, Cr, Fe and, V), while the contribution of the water coming out the pit lake and other dumps is much lower. Thus, remediation efforts to improve the area and fluvial courses downstream must focus on the W waste dumps., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

This paper addresses the behaviour of several technology critical metals (TCMs), i.e., rare earth elements (REEs), Y, Sc, Ga and Tl, in the Tinto River (SW Spain), quantifying their fluxes to the Atlantic Ocean and unravelling the governing geochemical processes controlling their solubility. To accomplish this goal, a high-resolution (2-24 h) sampling was performed during the hydrological year 2017/18. Mean dissolved concentrations of 380 μg/L of REE, 99 μg/L of Y, 15 μg/L of Sc, 9.2 μg/L of Ga and 4.8 μg/L of Tl were found. Most TCMs followed a behaviour similar to that of sulphate and base metals throughout the year, exhibiting a quasi-conservative behaviour due to acidic conditions. However, dissolved Tl concentrations seem to be strongly controlled by Tl incorporation onto secondary minerals and diatoms deposited on the riverbed, especially during the dry season. The remobilization of riverbed sediments led to the transport of significant amounts of TCMs associated with particulate matter, especially Al oxy-hydroxy-sulphates or Al-silicates rather than Fe precipitates (except for Tl and Ga). Around 5.8 t of REE, 1.3 t of Y, 248 kg of Sc, 139 kg of Ga and 138 kg of Tl were delivered annually in their dissolved forms by the Tinto River to the Atlantic Ocean, which constitutes around 0.09% of the dissolved global flux into the oceans of Y, 0.02% of the REE flux, 0.01% of the Ga flux and 0.001% of the Sc flux., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

This research evaluates the feasibility of an alkaline treatment system for highly acid leachates from a phosphogypsum stack located in an estuarine environment degraded by such pollution. The presented methodology consists of the addition of a Ca(OH) 2 solution to the different types of phosphogypsum-related acidic leachates with the aim to increase their pH and subsequently, to provoke the precipitation and immobilization of the dissolved contaminants. In fact, phosphates and fluorides reached removal of 100% and 90%, respectively. As regards metals, removal values close to 100% were reached for Fe, Al, Cr, Cd, U and Zn, whereas it did not seem to be totally effective for other elements such as As (removal of 57-82%) and Sb (4-36%). The decrease of contaminant concentrations was caused probably by co-precipitation and/or adsorption to phosphate phases, together with by fluoride precipitation. The solid phases formed during the treatment were subjected to two standard leaching tests (EN 12457-2 from the EU and TCLP from the US) in order to conduct a risk and management assessment. In this context, some of the precipitates formed during the treatment would be classified as hazardous wastes, due to the high concentration of As leached. Moreover, the potential economic costs of a convectional active treatment system were also explored. This study sets the basis for a new research line with the aim to minimise the impact of the phosphogypsum stacks worldwide to their adjacent environment., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This study characterizes the hydrogeochemical behavior of one of the most pollutant sources in the Iberian Pyrite Belt, namely, the Poderosa adit outflow. This artificial spring arises from an anthropogenic mine aquifer with a similar hydrogeological behavior to karstic systems, where the infiltration area is an endorheic zone and the aquifer shows allogenic recharge. Recent mining has markedly increased the contaminant levels. The pollutant load released from the adit to the receiving water body is very high, with average loads of 280 kg/day of Fe, 47 kg/day of Al, 17 kg/day of Cu and so on. However, a high variability is observed related to hydrological and geochemical factors, especially during intense rainy episodes. Thus, the pollutant load during these events suffers a dramatic increase, i.e., from ~100-200 kg/day of Fe during base flow to almost 2200 kg/day during the flow peak. These data highlight the importance of short but intense rainy events on metal fluxes from mining areas, which has been previously reported in surface waters but scarcely reported in mine adits, with expected lower response times to rainfall. The pollutant load released by non-point sources, i.e., spoil heaps, is lower than that released from the adit most of the year, although it increased noticeably during intense rainy events. Some remediation measures were adopted during the 1990s without a suitable hydrogeological characterization and were shown to be ineffective. On the basis of the obtained results, potential restoration measures are discussed., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This paper investigates the mobility and fluxes of REE, Y and Sc under weathering conditions from an anomalously metal-rich phosphogypsum stack in SW Spain. The interactions of the phosphogypsum stack with rainfall and organic matter-rich solutions, simulating the weathering processes observed due to its location on salt-marshes, were simulated by leaching tests (e.g. EN 12457-2 and TCLP). Despite the high concentration of REE, Y and Sc contained in the phosphogypsum stack, their mobility during the leaching tests was very low; <0.66% and 1.8% of the total content of these elements were released during both tests. Chemical and mineralogical evidences suggest that phosphate minerals may act as sources of REE and Y in the phosphogypsum stack while fluoride minerals may act as sinks, controlling their mobility. REE fractionation processes were identified in the phosphogypsum stack; a depletion of LREE in the saturated zone was identified due probably to the dissolution of secondary LREE phosphates previously formed during apatite dissolution in the industrial process. Thus, the vadose zone of the stack would preserve the original REE signature of phosphate rocks. On the other hand, an enrichment of MREE in relation to HREE of edge outflows is observed due to the higher influence of estuarine waters on the leaching process of the phosphogypsum stack. Despite the low mobility of REE, Y and Sc in the phosphogypsum, around 104kg/yr of REE and 40kg/yr of Y and Sc are released from the stack to the estuary, which may imply an environmental concern. The information obtained in this study could be used to optimize extraction methods aimed to recover REE, Y and Sc from phosphogypsum, mitigating the pollution to the environment., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Phosphogypsum wastes from phosphate fertilizer industries are stockpiled in stacks with high contamination potential. An assessment of the environmental impact, including the use of geochemical tracers such as rare earth elements (REE) and Cl/Br ratios, was carried out in the phosphogypsum stack located at the Estuary of Huelva (SW Spain). Inside the pile, highly polluted acid pore-waters flows up to the edge of the stack, emerging as small fluvial courses, known as edge outflows, which discharge directly into the estuary. The disposal area is divided into four zones; two unrestored zones with surface ponds of industrial process water and two a priori already-restored zones. However, an extensive sampling of edge outflows conducted in the perimeter of the four zones demonstrates the high potential of contamination of the whole stack, including those zones that were supposedly restored. These solutions are characterized by a pH of 1.9 and concentrations of 6100 mg/L for P, 1970 mg/L for S, 600 mg/L for F, 200mg/L for NH4(+), 100mg/L for Fe, 10-30 mg/L for Zn, As and U, and 1-10mg/L for Cr, Cu and Cd. Preliminary restoration actions and those planned for the future prioritize removal of ponded process water and cover of the phosphogypsum with artificial topsoil. These actions presuppose that the ponded process water percolates through the porous medium towards the edge up to reach the estuary. However, geochemical tracers rule out this connection and point to an estuarine origin for these leachates, suggesting a possible tidal-induced leaching of the waste pile in depth. These findings would explain the ineffectiveness of preliminary restoration measures and should be considered for the development of new action plans., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Water resources management and restoration strategies, and subsequently ecological and human life quality, are highly influenced by the presence of short and long term cycles affecting the intensity of a targeted pollution. On this respect, a typical acid mine drainage (AMD) groundwater from a sulfide mining district with dry Mediterranean climate (Iberian Pyrite Belt, SW Spain) was studied to unravel the effect of long term weather changes in water flow rate and metal pollutants concentration. Three well differentiated polluting stages were observed and the specific geochemical, mineralogical and hydrological processes involved (pyrite and enclosing rocks dissolution, evaporitic salts precipitation-redisolution and pluviometric long term fluctuations) were discussed. Evidencing the importance of including longer background monitoring stage in AMD management and restoration strategies, the present study strongly advise a minimum 5-years period of AMD continuous monitoring previous to the design of any AMD remediation system in regions with dry Mediterranean climate., (Copyright © 2015 Elsevier B.V. All rights reserved.)

The aim of this study was to evaluate the chemical characteristics and ecotoxicity of a mine soil developed on gossan materials and amended with hydrophilic polyacrylate polymers after a growth cycle of Spergularia purpurea. Different acute bioassays (Daphnia magna immobilization; microalgae growth inhibition; germination and growth of lettuce and oat) were carried out with simulated leachates, pore water and soil samples. The germination and growth of native shrubs (Cistus ladanifer and Lavandula sampaioana) were also evaluated in the lysimeters where S. purpurea had grown. The soil had high total concentrations (g/kg) of Al (3.50-8.60), As (2.55-2.73), Cu (0.13-0.91) and Pb (4.48-6.16). However, the percentages of elements in aqueous extracts (simulating leachates, pore water, and the conditions of the rhizosphere soil) were small when compared to their total soil concentrations (less than 9% except for Na in leachates). Growth of S. purpurea and other natural colonization of plant species (Poaceae, Fabaceae and Asteraceae families) improved chemical characteristics but the application of the polyacrylate polymers contributed to a further improvement of soil quality. However, this was not sufficient to ensure the growth of a large number of shrubs despite a great germination rate. Among the several species used on the ecotoxicological assessment, the D. magna test was the only bioassay that showed a clear toxicity of soil leachates, suggesting the importance of using several ecotoxicological tests to assess the environmental risk of soil contamination and its rehabilitation. Although the studied soil can be considered contaminated taking into account the total soil concentrations of Al, As, Cu and Pb, the low concentrations of the same chemical elements in extractable solutions, that simulated the fractions really available for organisms, did not demonstrate a substantial toxic effects in the organisms and, consequently, negative impact on the environment., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Complete metal removal from highly-polluted acid mine drainage was attained by the use of a pilot multi-step passive remediation system. The remediation strategy employed can conceptually be subdivided into a first section where the complete trivalent metal removal was achieved by the employment of a previously tested limestone-based passive remediation technology followed by the use of a novel reactive substrate (caustic magnesia powder dispersed in a wood shavings matrix) obtaining a total divalent metal precipitation. This MgO-step was capable to abate high concentrations of Zn together with Mn, Cd, Co and Ni below the recommended limits for drinking waters. A reactive transport model anticipates that 1 m(3) of MgO-DAS (1 m thick × 1 m(2) section) would be able to treat a flow of 0.5 L/min of a highly acidic water (total acidity of 788 mg/L CaCO(3)) for more than 3 years., (Copyright © 2012 Elsevier B.V. All rights reserved.)