Search

Each scientist is specialized in his or her field of research and in the tools that he or she uses during the research in a specified site. Thus, he or she is the most suitable person for improving the tools by overcoming their limitations to realize faster and higher quality analysis. However, most scientists are not software developers. Hence, it is necessary to provide them with an easy approach that enables non-software developers to improve and customize their tools. This paper presents an approach for easily improving and customizing any hydrogeological software. It is the result of experiences with updating several interdisciplinary case studies. The main insights of this approach have been demonstrated using four examples: MIX (FORTRAN-based), BrineMIX (C++-based), EasyQuim and EasyBal (both spreadsheet-based). The improved software has been proven to be a better tool for enhanced analysis by substantially reducing the computation time and the tedious processing of the input and output data files.

Artificial recharge of aquifers is a technique for improving water quality and increasing groundwater resources. Understanding the fate of a potential contaminant requires knowledge of the residence time distribution (RTD) of the recharged water in the aquifer beneath. A simple way to obtain the RTDs is to perform a tracer test. We performed a pulse injection tracer test in an artificial recharge system through an infiltration basin to obtain the breakthrough curves, which directly yield the RTDs. The RTDs turned out to be very broad and we used a numerical model to interpret them, to characterize heterogeneity, and to extend the model to other flow conditions. The model comprised nine layers at the site scaled to emulate the layering of aquifer deposits. Two types of hypotheses were considered: homogeneous (all flow and transport parameters identical for every layer) and heterogeneous (diverse parameters for each layer). The parameters were calibrated against the head and concentration data in both model types, which were validated quite satisfactorily against 1,1,2-Trichloroethane and electrical conductivity data collected over a long period of time with highly varying flow conditions. We found that the broad RTDs can be attributed to the complex flow structure generated under the basin due to three-dimensionality and time fluctuations (the homogeneous model produced broad RTDs) and the heterogeneity of the media (the heterogeneous model yielded much better fits). We conclude that heterogeneity must be acknowledged to properly assess mixing and broad RTDs, which are required to explain the water quality improvement of artificial recharge basins.

Se han utilizado dos modelos numéricos de transporte reactivo para analizar el proceso de dedolomitización: reemplazamiento de dolomita por calcita debido a la infiltración de agua en un estrato dolomítico. Los resultados de sucesivos cálculos en diferentes escenarios se han comparado con observaciones preliminares en las «carniolas» desarrolladas en las dolomías del Triásico de Prades (Tarragona). El modelo basado en la hipótesis de equilibrio local entre el agua y la roca no predice el desarrollo de porosidad asociadad reemplazamiento. En cambio, el modelo basado en leyes cinéticas de disolución y precipitación mineral es capaz de predecir las proporciones de dolomita, calcita y porosidad observadas. El resultado de la modelización mediante leyes cinéticas es sensible a determinados parámetros como la velocidad del flujo, la composición química del agua de recarga y la superficie reactiva de los minerales El desarrollo del reemplazamiento y porosidad asociada requiere caudales de infiltración superiores a 100 mm/año. El agua debe tener pH neutro a ligeramente alcalino, lejos del equilibrio con la atmósfera y con carbonatos, y concentraciones de calcio un orden de magnitud superior a la media de aguas superficiales, probablemente debido a la disolución de evaporitas. La superficie reactiva de la calcita que precipita se ha estimado a partir de la teoría de la nucleación y crecimiento cristalino. Esta superficie es al menos dos órdenes de magnitud inferior a la de la dolomita, estimada a partir de un modelo geométrico de fracturas. La diferencia entre la superficie reactiva de ambos minerales es un factor clave en el desarrollo de porosidad asociada a la disolución/precipitación. La dedolomitización y generación de porosidad tiene lugar sobre todo en el primer metro de una columna vertical de acuífero, mientras que aguas abajo el reemplazamiento se atenúa y no genera porosidad.

Dissolution of carbonates has been commonly predicted by geochemical models to occur at the seawater-freshwater mixing zone of coastal aquifers along a geological time scale. However, field evidences are inconclusive: dissolution vs. lack of dissolution. In this study we investigate the process of calcite dissolution by mixing waters of different salinities and pCO2, by means of geochemical modeling and laboratory experiments. Our calculations show that saturation is not always a good indicator of the real dissolution potential of the mixture. In a closed system, the maximum subsaturation occurs for mixing ratios of about 15%-salty, while the dissolved calcite is maximum for 50%. Dissolution is affected by carbonate speciation, and by the dependence of activity coefficients on salinity. Laboratory experiments confirmed a strong dependence of the dissolution on the mixing ratio and pointed out the critical role of CO2 variations at the local atmosphere. The maximum dissolution was observed for mixtures less than 17%-salty, which is attributed to the CO2 exchange between the reaction cell and the laboratory atmosphere. The reaction cell gains CO2 for mixtures less than 17%-salty and calcite dissolution is enhanced with respect to a closed system. The opposite also occurs for mixtures higher than 17% salty. Including CO2 exchange, the model consistently predicts the experimental results. Both calculations and dissolution experiments at different flow rates demonstrated a high sensitivity of the amount of calcite dissolved to minor variations of CO2 partial pressure of the local atmosphere. This could be relevant in field scale interpretations. CO2 pressure measurements in the field are not easy to obtain and could account for the different and “contradictory” field observations.

Chalcopyrite dissolution kinetics in the pH range of 1 to 3 were studied by means of long-term flow-through experiments to obtain a dissolution rate law which can be coupled with reactive transport models to forecast Acid Rock Drainage. In the range of conditions under study, the rate of chalcopyrite dissolution is only slightly dependent on hydrogen ion activity, increasing with decreasing pH. The steady-state dissolution rates obtained in the present study were combined with earlier results presented by Acero et al. (2007a) to obtain the following expression for chalcopyrite dissolution rate law: where Rchalcopyrite is the chalcopyrite dissolution rate (mol m-2 s-1), aH+ is the activity of hydrogen ion in solution, R is the gas constant (kJ mol-1 K-1) and T is the temperature (K). This expression can applied through a wide range of environmental conditions similar to the ones found in systems affected by acid drainage. In agreement with earlier chalcopyrite kinetic studies, iron was released to solution preferentially over copper and sulfur, compared with the stoichiometry of the pristine mineral. Consistently, XPS examination of the samples showed that reacted surfaces were enriched in sulfur and copper (relative to iron) compared with the initial, pristine chalcopyrite surface. However, this surface layer does not exert any passivating effect on chalcolpyrite dissolution and the kinetics of the overall process in the long term seems to be surface-controlled.

This study focuses on the synthesis at a pilot plant scale of zeolitic material obtained from the coal fly ashes of the Teruel and Narcea power plants in Spain. After the optimisation of the synthesis parameters at laboratory scale, the Teruel and Narcea fly ashes were selected as low and high glass fly ashes. The pilot plant scale experiments were carried out in a 10 m3 reactor of Clariant SA (Barcelona, Spain). The results allowed obtaining 1.1 and 2.2 tonnes of zeolitic material with 40 and 55% of NaP1 content, in two single batch experiments of 24 and 8 hours, for Teruel and Narcea fly ashes, respectively. The cation exchange capacities (CEC) of the final product reached 2.0 and 2.7 meq g-1 for Teruel and Narcea zeolitic material, respectively, which are very close to the usual values reached by the high quality natural zeolitic products. Finally, with the aim of testing possible applications of the commercial NaP1-IQE and pilot plant NaP1-Narcea zeolitic products in water decontamination, efficiency for metal uptake from waste waters from electroplating baths was investigated

The code RETRASO (REactive TRAnsport of SOlutes) simulates reactive transport of dissolved and gaseous species in non-isothermal saturated or unsaturated problems. Possible chemical reactions include aqueous complexation (including redox reactions), sorption, precipitation-dissolution of minerals and gas dissolution. Various models for sorption of solutes on solids are available, from experimental relationships (linear KD, Freundlich and Langmuir isotherms) to cation exchange and surface complexation models (constant capacitance, diffuse layer and triple layer models). Precipitation-dissolution and aqueous complexation can be modelled in equilibrium or according to kinetic laws. For the numerical solution of the reactive transport equations it uses the Direct Substitution Approach. The use of the code is demonstrated by three examples. The first example models various sorption processes in a smectite barrier. The second example models a complex chemical system in a two dimensional cross-section. The last example models pyrite weathering in an unsaturated medium.

The presence of cavities filled with new minerals in carbonate rocks is a common feature in oil reservoirs and lead-zinc deposits. Since groundwater equilibrates rapidly with carbonates, the presence of dissolution cavities in deep carbonate host rocks is a paradox. Two alternative geochemical processes have been proposed to dissolve carbonates at depth: hydrogen sulfide oxidation to sulfuric acid, and metal sulfide precipitation. With the aid of geochemical modeling we show that mixing two warm solutions saturated with carbonate results in a new solution that dissolves limestone. Variations in the proportion of the end-member fluids can also form a supersaturated mixture and fill the cavity with a new generation of carbonate. Mixing is in general more effective in dissolving carbonates than the aforementioned processes. Moreover, mixing is consistent with the wide set of textures and mineral proportions observed in cavity infillings.

La distribución espacial de un soluto reactivo y su movimiento a través del medio subterráneo están controlados por procesos hidrodinámicos de transporte de masa (advección, difusión y dispersión) y procesos químicos asociados a reacciones de diversa naturaleza. La mayoría de los modelos de transporte de solutos tienen en cuenta de forma rigurosa los procesos hidrodinámicos, pero sólo consideran las interacciones de tipo químico de forma muy simplificada. Por otro lado, los modelos de especiación química contemplan una gran variedad de procesos químicos en condiciones de equilibrio químico, aunque sólo son aplicables a sistemas acuáticos estáticos sin flujo. En la última década se han desarrollado un número considerable de modelos acoplados que contemplan, con grados muy variables de sofisticación, tanto los procesos hidrodinámicos como los químicos. Estos modelos contienen por un lado las ecuaciones diferenciales en derivadas parciales (EDP) correspondientes al transporte de solutos y las correspondientes a los. procesos químicos, que en la hipótesis de equilibrio químico, son ecuaciones algebraicas no lineales. Un aspecto importante en la solución del problema es la adecuada selección de las variables primarias dependientes, las cuales satisfacen las ecuaciones de transporte. La inadecuada elección de las variables primarias limita la aplicabilidad del método de solución a sistemas químicos mixtos que contienen reacciones lentas (cinética) y rápidas (equilibrio). Una característica común de la mayoría de los modelos existentes es la extraordinaria exigencia de tiempos de cálculo que motiva que con determinados enfoques sólo sea viable la solución de problemas unidimensionales.

Acidic mine Drainage (AMD) is still considered one of the greatest mining sustainability challenges due to the large volumes of wastes generated and the high associated treatment cost. New regulation initiatives on sustainable development, circular economy and the need for strategic elements as Rare Earth Elements (REE) may overcome the traditional research initiatives directed to developing low cost treatment options and to develop research initiatives to identify the potential benefit of considering such AMD as a potential secondary resource. As an example, this study develops the integration of a three-stage process where REE are selectively separated from base metals (e.g. Fe, Al, Mn, Ca, Mg, Cd, Pb) and then concentrate to produce a rich REE by-product recovered as REE-phosphates. Selective separation of Fe (>99%) was achieved by total oxidation to Fe(III) and subsequent precipitation as schwertmannite at pH 3,6 ± 0.2. REE were then extracted from AMD using a sulfonic ion-exchange resin to produce concentrated REE sulfuric solutions up to 0.25 gREE/L. In a final stage selective separation of REE from Al(III), Ca(II) and Mg(II) and transitions elements (Cu, Zn, Ni) was achieved by precipitation with phosphate solutions under optimized pH control and total phosphate concentration. XRD analysis identified low-crystalline minerals. By using a thermal treatment the presence of PrPO 4 (s) and Cheralite (CePO 4 (s)) where Ce is substituted by La and Ca and Xenotime (YPO 4 (s)) were found as main minerals AlPO 4 (s) Ca,MgYPO 4 (s) were also identified., 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 © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

The most common reactive material used for the construction of a permeable reactive barrier (PRB) is zero valent iron (ZVI), however, its processing can generate corrosive effects that reduce the efficiency of the barrier. The present study makes a major contribution to understanding new reactive materials as natural and synthetic, easy to obtain, economical and environmentally friendly as possible substitutes for the traditional ZHV to be used as filters in the removal of three transition metals (Zn, Cu, Cd). To assess the ability to remove these pollutants, a series of batch and column tests were carried out at laboratory scale with these materials. Through BACH tests, four of seven substances with a removal percentage higher than 99% were prioritized (cabuya, natural clinoptilolite zeolites, sodium mordenite and mordenite). From this group of substances, column tests were performed where it is evidenced that cabuya fiber presents the lowest absorption time (≈189 h) while natural zeolite mordenite shows the highest time (≈833 h). The latter being the best option for the PRB design. The experimental values were also reproduced by the RETRASO code; through this program, the trend between the observed and simulated values with respect to the best reactive substance was corroborated.

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 paper tries to analyse the technical and economic performance of a full-scale passive Disperse Alkaline Substrate (DAS) treatment plant steadily operating for 28 months (840 days) to treat extremely acidic and metal rich mine waters in the Iberian Pyrite Belt (SW Spain). For the first time, an economic evaluation of this technology and its comparison with other passive treatments is reported. During this period, around 56,000 m 3 of mine waters have been treated, without significant clogging or exhaustion of the alkaline substrate. The efficiency of the system is demonstrated by a significant decrease in the average net acidity (from 2005 to -43 mg/L as CaCO 3 equivalent) and the total elimination of Al, Cu, REY, Zn, As, Cr, Mo, V, Cd, Pb, Co and other trace metals. Water quality of the treated output discharge meets the threshold values for irrigation and drinking standards, except for Fe, Mn and sulphate. The accumulation of elements of economic interest in the waste (e.g., 32 t of Fe, 6.1 t of Al, 0.8 t of Cu, 0.8 t of Zn, 39.4 kg of REE, 20 kg of Co or 1 kg of Sc), easily extractable with diluted acids, may turn a hazardous waste into a valuable resource. The benefits associated with the revalorization of this metal-rich waste could reach a total of 27478 USD, but is more reliably estimated to be around 8243 USD due to technologic limitations. This benefit would help to defray the maintenance costs (8428 €) and make DAS an economically self-sustainable treatment. The annual treatment cost for DAS was 0.27 €/m 3 , being the lowest value found among other reported conventional passive schemes, and from 8 to 12 times lower compared to active technologies. The results obtained prove that the DAS technology is the most technically and economically sustainable way to decontaminate acid and metal-rich mine waters in abandoned mines., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Reducing the potential leaching of Mo and Ni from the fly ash (FA) of petroleum coke is an increasingly important issue as Asia and Europe's demand is expected to drastically intensify as continuing urbanisation and technological innovation demands ever more electricity. In the present study, we investigated coal combustion products (CCP) from a large coal-fired power station fed with a 56:44 coal/petroleum coke blend. Results revealed that leachable concentrations of Mo and Ni from FA were in the upper non-hazardous limit and in the inert limit, respectively (2003/33/EC). Whilst common prevention measures for Mo and Ni based on the adsorption capacity of boiler slag (BS), a mixture of BS: goethite, and jarosite, were considered insufficient to reduce the potential leaching of Mo into FA leachates, a novel chemical stabilisation method based on an aggregate product of portlandite and FA immobilised both Mo and Ni such that the resulting concentrations were below the limits established in the abovementioned 2003 EC Decision. Precipitation may be responsible for the fixation of Mo and Ni in the FA: portlandite aggregates as Ca(MoO 4 ) and NiMoO 4 , respectively. The findings of this novel study support the use of this aggregate to reduce FA pollutants, which will be of particular interest to nations that remain largely coal/petroleum coke-dependant., (Copyright © 2020 The Authors. Published by Elsevier Inc. All rights reserved.)

The Salar de Atacama (SdA) is the largest Li reserve globally. The origin of Li, together with the rest of solutes, has been object of debate. Thus, rock weathering at low temperature, hydrothermal leaching or magmatic origin together with subsequent evaporation has been hypothesized. However, the extreme Li enrichment (>4000 mg/L) and the location of the Li-Mg-rich brines around the Salar Fault System (SFS) that crosses the nucleus of the SdA in half remain unexplained. The objective of this work is to define the thermohaline groundwater flow in the SdA basin to account for the genesis of its extreme Li enrichment. Thermohaline flow modelling has demonstrated the critical effect of the minimum hydraulic head (MHH) of the regional water table on the groundwater flow of salt flats. The MHH divides the basin into two isolated hydrodynamic systems and constitutes the endpoint towards which the most evaporated brines converge. The spatial mismatch between the locations of the Li-Mg-rich brines in the central-western zone of the nucleus (in the SFS) and the MHH in the easternmost zone of the nucleus discards recent evaporative concentration of the recharge water as the main mechanism of Li enrichment. Moreover, the persistence of a saline interface surrounding the nucleus at depth, regardless of the temperature gradient, also precludes lateral recharge (predominantly from the east) to ascend along the SFS. On the other hand, the computed thermohaline flow is compatible with the remobilization of buried layers of Li-Mg-enriched salts and/or clays by dilute recharge waters coming from the west or southwest of the basin. Here, the role of faults and density-driven flow is key to allow efficient downward and upward flow rates that favour the remobilization of Li and Mg., 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.)

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.

Salt flats are hydrogeological systems with highly valuable wetland and lake ecosystems. The brine pumping carried out to extract lithium is modifying the natural evaporation discharge of salt flats. A methodology to evaluate the impacts caused on water table and evaporation discharge by brine exploitation in salt flats is proposed and applied to the Salar de Atacama. The methodology included field measurements of water table and evaporation rate, followed by its spatio-temporal analysis and the application of the results to a numerical model to improve the brine exploitation design. The spatio-temporal analysis of the water table depth and evaporation rates measured in the field concluded that the evaporation discharge decreased from 12.85 to 10.95 m 3 ·s - 1 between 1986 and 2018, that is around 15%. This reduction compensated part of the extractions and could contribute to the preservation of the mixing zone ecosystems. At present, this damping capacity is already amortized in the nucleus and the marginal zone is beginning to be affected by the brine pumping. The sensitivity of the phreatic evaporation on the water table depth justified the great uncertainty of the previous evaporation discharge estimations. Thus, an average error lower than 0.5 m was enough to modify the evaporation by >60%. Therefore, considerable effort should invested to faithfully quantify the discharge by evaporation which is critical in water balance of salt flat basins. The numerical model pointed out that the total pumping outflow should be distributed in the largest possible area. This minimizes the water table drawdown and maximizes the capacity of the evaporation decline to compensate the extractions. The results of this work serve as guidelines to improve the efficiency of future salt flat exploitations., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The groundwater contamination by hexavalent chromium (Cr(VI)) in a site of the Matanza-Riachuelo River basin (MRB), Argentina, has been evaluated by determining the processes that control the natural mobility and attenuation of Cr(VI) in the presence of high nitrate (NO 3 - ) contents. The groundwater Cr(VI) concentrations ranged between 1.9E-5 mM and 0.04 mM, while the NO 3 - concentrations ranged between 0.5 mM and 3.9 mM. In order to evaluate the natural attenuation of Cr(VI) and NO 3 - in the MRB groundwater, Cr and N isotopes were measured in these contaminants. In addition, laboratory batch experiments were performed to determine the isotope fractionation (ε) during the reduction of Cr(VI) under denitrifying conditions. While the Cr(VI) reduction rate is not affected by the presence of NO 3 - , the NO 3 - attenuation is slower in the presence of Cr(VI). Nevertheless, no significant differences on ε values were observed when testing the absence or presence of each contaminant. The ε 53 Cr determined in the batch experiments describe a two- stage trend, in which Stage I is characterized by ε 53 Cr ~-1.8‰ and Stage II by ε 53 Cr ~-0.9‰. The respective ε 15 N NO3 obtained is -23.9‰ whereas ε 18 O NO3 amount to -25.7‰. Using these ε values and a Rayleigh fractionation model we estimate that an average of 60% of the original Cr(VI) is removed from the groundwater of the contaminated site. Moreover, the average degree of NO 3 - attenuation by denitrification is found to be about 20%. This study provides valuable information about the dynamics of a complex system that can serve as a basis for efficient management of contaminated groundwater in the most populated and industrialized basin of Argentina., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The presence of high levels of arsenic in waters poses a threat to the human health in many countries all over the world. Effective surveillance programs of water quality require the implementation of in-field tests to assess early the presence of this metal ion and other contaminants. To date, there exist few market-available analytical approaches that suffer from important limitations related to cost, in addition to complex reactions, very long analysis times, and/or high limits of detection. This work describes a robust electrochemical sensor integrated into a modular microfluidic system that shows a clear potential to be deployed for the on-site monitoring of inorganic As(III) species. Flexible and transparent microfluidic modules are fabricated by rapid prototyping techniques and include different microfluidic components among them, flow cells where electrochemical sensors can be easily and reversibly inserted. The electrochemical sensor comprises a gold nanoparticle (AuNP)-modified gold thin-film electrode that is readily applied to the sensitive detection of As(III) by anodic stripping linear sweep voltammetry. The microfluidic system enables the automatic sensor calibration, sample uptake, and preconditioning as well as As(III) detection. The system response to As(III) is linear in a concentration range of 1-150 μg L -1 , with a detection limit of 0.42 μg L -1 , which is well below the threshold value of 10 μg L -1 set by the World Health Organization. Analysis of tap water and two water samples from two Argentinean aquifers, spiked with different As(III) concentrations, demonstrates the excellent performance of the system.

Yttrium belongs to the rare earth elements (REEs) together with lanthanides and scandium. REEs are commonly used in modern technologies, and their limited supply has made it necessary to look for new alternative resources. Acid mine drainage (AMD) is a potential resource since it is moderately enriched in REEs. In fact, in passive remediation systems, which are implemented to minimize the environmental impacts of AMD, REEs are mainly retained in basaluminite, an aluminum hydroxysulfate precipitate. In this study, the solid and liquid speciation and the local structure of yttrium are studied in high-sulfate aqueous solutions, basaluminite standards, and samples from remediation columns using synchrotron-based techniques and molecular modeling. Pair distribution function (PDF) analyses and ab initio molecular dynamics density functional theory models of the yttrium sulfate solution show that the YSO 4 + ion pair forms a monodentate inner-sphere complex. Extended X-ray absorption fine structure (EXAFS) and PDF analyses show that Y is retained by basaluminite, forming a monodentate inner-sphere surface complex on the aluminum hydroxide surface. EXAFS of the column samples shows that more than 72% of their signal is represented by the signal of basaluminite with which YSO 4 + forms an inner-sphere complex. The atomic view of the REE configuration in AMD environments could facilitate a deeper research of REE recovery from waste generated in AMD remediation systems.

The Salar de Atacama is used as a case study to analyse and quantify coupled natural (evaporation and recharge) and anthropogenic processes (pumping of lithium-rich brine) to abstract their patterns to other salt flats using a three-dimensional groundwater flow model. Important changes in the dynamics of the water table between the pre-operational period (1986-1994) and operational period (1994-2015) are observed. The water table exhibited a gradual drawdown during the pre-operational period because the evaporation was greater than the recharge for most of these periods. This negative balance was counteracted by some sharp rises that were produced by direct rainfall events on the salt flat. The deep lateral recharge that arrived from the mountains did not produce abrupt changes in the water table because the rainfall events in the mountains were damped by the distance of the recharge zone and great thickness of the unsaturated zone. The natural evolution of the water table was modified by the intensive brine pumping that was performed in the south-western Salar de Atacama during the operational period. As evaporation depends on the water table depth, the pumping caused a drawdown of the water table, resulting in an evaporation rate reduction that partially compensated for the pumped brine in the water balance of the basin. This effect is defined as the damping capacity of salt flats. Thus, salt flats have a high capacity for dampening oscillations in their water table in response to both natural and anthropogenic disturbances which is of great importance for the management of lake and wetland ecosystems and brine exploitation. The limit of the dampening capacity of salt flats is defined by the evaporation extinction depth, which is in the range of 0.5-2 m., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The Salar de Atacama is one of the most well-known saline endorheic basins in the world. It accumulates the world main lithium reserves and contains very sensitive ecosystems. The objective of this work is to characterize the hydrodynamics of the Salar de Atacama, and to quantify its complex water balance prior to the intense brine extraction. The methodology and results can be extrapolated to the groundwater flow and recharge of other salt flats. A three-dimensional groundwater flow model using low computational effort was calibrated against hundreds of hydraulic head measurements. The water infiltrated from the mountains ascends as a vertical flux through the saline interface (mixing zone) produced by the density contrast between the recharged freshwater and the evaporated brine of the salt flat nucleus. This water discharges and is largely evaporated from lakes or directly from the shallow water table. On the other hand, the very low hydraulic gradients, coupled with the presence of the mixing zone that operates as barrier, leads the salt flat nucleus to act as a hydrodynamically quasi-isolated area. The computed water table shows the lowest hydraulic head in the salt flat nucleus near the discharge at the mixing zone. The groundwater balance of the Salar de Atacama in its natural regime was quantified resulting in an inflow/outflow of 14.9 m 3 ·s -1 . This balance considers the basin as an endorheic system. The very low infiltration values that are generally assumed for hyperarid basins are not consistent with the hydrogeology of the Salar de Atacama. Indeed, very high infiltration rates (up to 85% of rainfall) occur because of the high degree of fracturing of rocks and the scarce vegetation. This high infiltration is consistent with the light isotopic composition of the water from the recharge area (Altiplano). Therefore, the existence of additional inflows outside the basin is unlikely., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The water drained in mining operations (galleries, shafts, open pits) usually comes from different sources. Evaluating the contribution of these sources is very often necessary for water management. To determine mixing ratios, a conventional mass balance is often used. However, the presence of more than two sources creates uncertainties in mass balance applications. Moreover, the composition of the end-members is not commonly known with certainty and/or can vary in space and time. In this paper, we propose a powerful tool for solving such problems and managing groundwater in mining sites based on multivariate statistical analysis. This approach was applied to the Cobre Las Cruces mining complex, the largest copper mine in Europe. There, the open pit water is a mixture of three end-members: runoff (RO), basal Miocene (Mb) and Paleozoic (PZ) groundwater. The volume of water drained from the Miocene base aquifer must be determined and compensated via artificial recharging to comply with current regulations. Through multivariate statistical analysis of samples from a regional field campaign, the compositions of PZ and Mb end-members were firstly estimated, and then used for mixing calculations at the open pit scale. The runoff end-member was directly determined from samples collected in interception trenches inside the open pit. The application of multivariate statistical methods allowed the estimation of mixing ratios for the hydrological years 2014-2015 and 2015-2016. Open pit water proportions have changed from 15% to 7%, 41% to 36%, and 44% to 57% for runoff, Mb and PZ end-members, respectively. An independent estimation of runoff based on the curve method yielded comparable results., (Copyright © 2017 Elsevier B.V. All rights reserved.)

A reactive barrier that consisted of vegetable compost, iron oxide and clay was installed in an infiltration basin to enhance the removal of emerging organic compounds (EOCs) in the recharge water. First-order degradation rates and retardation factors were jointly estimated for 10 compounds using a multilayer reactive transport model, whose flow and conservative transport parameters were previously estimated using hydraulic head values and conservative tracer tests. Reactive transport parameters were automatically calibrated against the concentration of EOCs measured at nine monitoring points. The degradation rate of each compound was estimated for three zones defined according to the redox state, and retardation coefficients were estimated in two zones defined according to the organic matter content. The fastest degradation rates were obtained for the reactive barrier, and the estimated values were similar to or higher than those estimated in column and/or field experiments for most of the compounds (8/10). Estimated retardation coefficients in the reactive barrier were higher than in the rest of the aquifer in most cases (8/10) and higher than those values estimated in previous studies. Based on the results obtained in this study the reactive barrier seems to be able to enhance the removal of EOCs., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The Odiel River Basin (SW Spain) drains the central part of the Iberian Pyrite Belt (IPB), a world-class example of sulfide mining district and concomitantly of acid mine drainage (AMD) pollution. The severe AMD pollution and the incipient state of remediation strategies implemented in this region, coupled with the proximity of the deadline for compliance with the European Water Framework Directive (WFD), urge to develop a restoration and water resources management strategy. Furthermore, despite the presence of some reservoirs with acid waters in the Odiel basin, the construction of the Alcolea water reservoir has already started. On the basis of the positive results obtained after more than 10 years of developing a specific passive remediation technology (dispersed alkaline substrate (DAS)) for the highly polluted AMD of this region, a restoration strategy is proposed. The implementation of 13 DAS treatment plants in selected acid discharges along the Odiel and Oraque sub-basins and other restoration measurements of two acidic creeks is proposed as essential to obtain a good water quality in the future Alcolea reservoir. This restoration strategy is also suggested as an economically and environmentally sustainable approach to the extreme metal pollution affecting the waters of the region and could be considered the starting point for the future compliance with the WFD in the Odiel River Basin.

The Sancho reservoir is an acid mine drainage (AMD)-contaminated reservoir located in the Huelva province (SW Spain) with a pH close to 3.5. The water is only used for a refrigeration system of a paper mill. The Sancho reservoir is holomictic with one mixing period per year in the winter. During this mixing period, oxygenated water reaches the sediment, while under stratified conditions (the rest of the year) hypoxic conditions develop at the hypolimnion. A CE-QUAL-W2 model was calibrated for the Sancho Reservoir to predict the thermocline and oxycline formation, as well as the salinity, ammonium, nitrate, phosphorous, algal, chlorophyll-a, and iron concentrations. The version 3.7 of the model does not allow simulating the oxidation of Fe(II) in the water column, which limits the oxygen consumption of the organic matter oxidation. However, to evaluate the impact of Fe(II) oxidation on the oxycline formation, Fe(II) has been introduced into the model based on its relationship with labile dissolved organic matter (LDOM). The results show that Fe oxidation is the main factor responsible for the oxygen depletion in the hypolimnion of the Sancho Reservoir. The limiting factors for green algal growth have also been studied. The model predicted that ammonium, nitrate, and phosphate were not limiting factors for green algal growth. Light appeared to be one of the limiting factors for algal growth, while chlorophyll-a and dissolved oxygen concentrations could not be fully described. We hypothesize that dissolved CO2 is one of the limiting nutrients due to losses by the high acidity of the water column. The sensitivity tests carried out support this hypothesis. Two different remediation scenarios have been tested with the calibrated model: 1) an AMD passive treatment plant installed at the river, which removes completely Fe, and 2) different depth water extractions. If no Fe was introduced into the reservoir, water quality would significantly improve in only two years. Deeper extractions (3m above the bottom) would also improve the water quality by decreasing the hypoxic zone. However, extractions at the epilimnion would increase the amount of hypoxic water in the reservoir., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Rare earth elements and yttrium (REY) are raw materials of increasing importance for modern technologies, and finding new sources has become a pressing need. Acid mine drainage (AMD) is commonly considered an environmental pollution issue. However, REY concentrations in AMD can be several orders of magnitude higher than in naturally occurring water bodies. With respect to shale standards, the REY distribution pattern in AMD is enriched in intermediate and valuable REY, such as Tb and Dy. The objective of the present work is to study the behavior of REY in AMD passive-remediation systems. Traditional AMD passive remediation systems are based on the reaction of AMD with calcite-based permeable substrates followed by decantation ponds. Experiments with two columns simulating AMD treatment demonstrate that schwertmannite does not accumulate REY, which, instead, are retained in the basaluminite residue. The same observation is made in two field-scale treatments from the Iberian Pyrite Belt (IPB, southwest Spain). On the basis of the amplitude of this process and on the extent of the IPB, our findings suggest that the proposed AMD remediation process can represent a modest but suitable REY source. In this sense, the IPB could function as a giant heap-leaching process of regional scale in which rain and oxygen act as natural driving forces with no energy investment. In addition to having environmental benefits of its treatment, AMD is expected to last for hundreds of years, and therefore, the total reserves are practically unlimited.

Scarcity of waters is the main limiting factor of economic development in most arid and semi-arid regions worldwide. The construction of reservoirs may be an optimal solution to assure water availability if the drainage area shows low disturbances. This is the quandary of mining areas where economic development relies on water accessibility. Water acidification trends were investigated in the Sancho Reservoir (SW Spain) in the last 20 years. The acidity (pH3-5) and high dissolved metal concentrations (e.g., 4.4 mg/L of Al, 2.1mg/L of Mn, 1.9 mg/L of Zn) observed in the Sancho, together with the large volume stored (between 37 and 55 Mm(3)), makes this reservoir an extreme case of surface water pollution worldwide. A progressive acidification has been observed since 2003, as evidenced by decreasing pH values and increasing dissolved metal concentrations, especially noticeable after 2007. The increase in the net acidity in the reservoir originates from the higher input of metals and acidity due to the rebound effect after the mining closure in 2001. This trend was not detected in the river feeding the reservoir due to its great hydrological and hydrochemical variability, typical of the Mediterranean climate. Chemical analysis and absolute dating of sediments identified a progressive enrichment in S and metals (i.e., Fe, Zn Cu, Ni, Co and Cd) in the upper 20 cm, which reinforce the year 2002/03 as the onset of the acidification of the reservoir. The decrease of pH values from 4-5 to 3-4 occurred later than the increase in sulfate and metals due to pH-buffering by Al. The acid mine drainage (AMD) pressure has caused an increment of dissolved Fe and other metals, as well as a change in the pH buffering role, exerted now by Fe. These processes were simulated by PHREEQC, which confirms that the acidification trend will continue, causing pH values to reach 2.5 if AMD pressure persists., (Copyright © 2015 Elsevier B.V. All rights reserved.)

High ammonium (NH4), arsenic (As) and boron (B) concentrations are found in aquifers worldwide and are often related to human activities. However, natural processes can also lead to groundwater quality problems. High NH4, As and B concentrations have been identified in the confined, deep portion of the Niebla-Posadas aquifer, which is near the Cobre Las Cruces (CLC) mining complex. The mine has implemented a Drainage and Reinjection System comprising two rings of wells around the open pit mine, were the internal ring drains and the external ring is used for water reinjection into the aquifer. Differentiating geogenic and anthropogenic sources and processes is therefore crucial to ensuring good management of groundwater in this sensitive area where groundwater is extensively used for agriculture, industry, mining and human supply. No NH4, As and B are found in the recharge area, but their concentrations increase with depth, salinity and residence time of water in the aquifer. The increased salinity down-flow is interpreted as the result of natural mixing between infiltrated meteoric water and the remains of connate waters (up to 8%) trapped within the pores. Ammonium and boron are interpreted as the result of marine solid organic matter degradation by the sulfate dissolved in the recharge water. The light δ(15)NNH4 values confirm that its origin is linked to marine organic matter. High arsenic concentrations in groundwater are interpreted as being derived from reductive dissolution of As-bearing goethite by dissolved organic matter. The lack of correlation between dissolved Fe and As is explained by the massive precipitation of siderite, which is abundantly found in the mineralization. Therefore, the presence of high arsenic, ammonium and boron concentrations is attributed to natural processes. Ammonium, arsenic, boron and salinity define three zones of groundwater quality: the first zone is close to the recharge area and contains water of sufficient quality for human drinking; the second zone is downflow and contains groundwater suitable for continuous irrigation but not drinkable due to high ammonium concentrations; and the third zone contains groundwater of elevated salinity (up to 5940 μS cm(-1)) and is not useable due to high ammonium, arsenic and boron concentrations., (Copyright © 2015 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.)

Clay minerals are reputed sorbents for Cs-137 and can be used as a low-permeability material to prevent groundwater flow. Therefore, clay barriers are employed to seal Cs-137 polluted areas and nuclear waste repositories. This work is motivated by cases where groundwater flow cannot be impeded. A permeable and reactive barrier to retain Cs-137 was tested. The trapping mechanism is based on the sorption of cesium on illite-containing clay. The permeability of the reactive material is provided by mixing clay on a matrix of wood shavings. Column tests combined with reactive transport modeling were performed to check both reactivity and permeability. Hydraulic conductivity of the mixture (10(-4) m/s) was sufficient to ensure an adequate hydraulic performance of an eventual barrier excavated in most aquifers. A number of column experiments confirmed Cs retention under different flow rates and inflow solutions. A 1D reactive transport model based on a cation-exchange mechanism was built. It was calibrated with batch experiments for high concentrations of NH4+ and K+ (the main competitors of Cs in the exchange positions). The model predicted satisfactorily the results of the column experiments. Once validated, it was used to investigate the performance and duration of a 2 m thick barrier under different scenarios (flow, clay content, Cs-137 and K concentration)., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Soil aquifer treatment is widely applied to improve the quality of treated wastewater in its reuse as alternative source of water. To gain a deeper understanding of the fate of thereby introduced organic micropollutants, the attenuation of 28 compounds was investigated in column experiments using two large scale column systems in duplicate. The influence of increasing proportions of solid organic matter (0.04% vs. 0.17%) and decreasing redox potentials (denitrification vs. iron reduction) was studied by introducing a layer of compost. Secondary effluent from a wastewater treatment plant was used as water matrix for simulating soil aquifer treatment. For neutral and anionic compounds, sorption generally increases with the compound hydrophobicity and the solid organic matter in the column system. Organic cations showed the highest attenuation. Among them, breakthroughs were only registered for the cationic beta-blockers atenolol and metoprolol. An enhanced degradation in the columns with organic infiltration layer was observed for the majority of the compounds, suggesting an improved degradation for higher levels of biodegradable dissolved organic carbon. Solely the degradation of sulfamethoxazole could clearly be attributed to redox effects (when reaching iron reducing conditions). The study provides valuable insights into the attenuation potential for a wide spectrum of organic micropollutants under realistic soil aquifer treatment conditions. Furthermore, the introduction of the compost layer generally showed positive effects on the removal of compounds preferentially degraded under reducing conditions and also increases the residence times in the soil aquifer treatment system via sorption., (Copyright © 2015 Elsevier Ltd. All rights reserved.)