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Acid mine drainage (AMD) generated from coal and sulfide mining has attracted much interest due to the high concentrations of rare earth elements (REE) observed. However, the origin of REE in AMD and particularly the mechanism of enrichment in medium REE remain uncertain. The combined study of Sr and Nd isotopes can be used to trace the processes that control the mobility and fractionation of REE in aquatic systems such as AMD. This work reports for the first time worldwide isotopic data of Sr and Nd in AMDs from sulfide mining (Iberian Pyrite Belt, SW Spain) and compare with those in host rocks. Additionally, leaching experiments have been carried out to simulate the water–rock interactions found in these acidic systems. The results obtained strongly suggest that the origin of REE in AMDs from metal mining may be related to the preferential dissolution of shales and felsic rocks. The suitability of Sr and Nd isotopic signatures to trace the REE source in AMD-affected systems has been proven, it provides a new environmental and geochemical prospecting tool which could be useful in different geological water–rock interaction systems. [ABSTRACT FROM AUTHOR]

Sulfidic mine wastes have the potential to generate acid mine drainage (AMD) and release acid leachates containing high levels of iron, sulfate and potentially toxic elements (PTEs). Soils receiving AMD discharges are generally devoid of vegetation. Only a few metal-tolerant plant species can survive under such adverse soil conditions. This work investigates two plant species, Nicotiana glauca and Euphorbia segetalis, that have successfully colonized an AMD-impacted wetland area in south-western Spain. The uptake of PTEs from the soil by roots and their transfer and accumulation in the above-ground biomass were quantified. Results showed that these pioneer plants grew in patches of neutral soil within the wasteland despite the high concentrations of PTEs in the rhizosphere soil (up to: 613 mg kg−1 As, 18.7 mg kg−1 Cd, 6370 mg kg−1 Cu, 2210 mg kg−1 Pb and 5250 mg kg−1 Zn). The target organs of As, Cu and Pb accumulation were: root > leaf > stem in N. glauca, and root > stem > leaf in E. segetalis. Zinc and Cd showed a significant decrease in roots relative to aerial parts of N. glauca, and Co was preferentially partitioned in stems of N. glauca and leaves of E. segetalis. The soil–plant transfer coefficient values of PTEs in all parts of both plants were well below unity with the only exception of Cd in leaves of N. glauca (1.254), suggesting that roots acted as a barrier limiting the uptake of PTEs by plants. Interestingly, under the same soil conditions, N. glauca absorbed Cd in considerable proportions from soil and accumulated it in its leaves, while E. segetalis was not effective in transferring PTEs from roots shoots except for Co. In conclusion, soil pH and plant-related factors greatly influence the stabilization of PTE in the rhizospheric soil and produce inconsistencies in PTE phytoavailability. The findings of this study provide criteria to assist in natural remediation in other legacy contaminated sites worldwide. [ABSTRACT FROM AUTHOR]

The uncontrolled release of acid mine drainage (AMD) results in the ongoing deterioration of groundwater and surface water, along with harmful impacts on aquatic ecosystems and surrounding habitats. This study employed a bibliometric analysis to examine research activities and trends related to AMD from 1991 to 2021. The analysis demonstrated a consistent growth in AMD research over the years, with a notable surge in the number of publications starting from 2014. Applied Geochemistry and Science of the Total Environment emerged as the top two extensively published journals in the field of AMD research. The USA held a prominent position, achieving the highest h-index (96) and central value (0.36) among 111 countries/territories, with China and Spain following closely behind. The author keyword analysis provides an overview of the main focuses in AMD research. Furthermore, the co-citation reference analysis reveals four primary domains of AMD research. Moreover, the prevention and remediation of AMD, including source prevention and migration control, as well as the hazards posed by heavy metals/metalloids and the mechanisms and techniques employed for their removal, are discussed in detail. [ABSTRACT FROM AUTHOR]

The uncommon association of ammonium sulfates identified in the Pastora abandoned mine is the result of a complex mineral evolution. By means of dissolution-(re)crystallization reactions operating during long periods of time, ammonium minerals "adapt" to local spatiotemporal changes in physico-chemical conditions. We found that during such an evolution, seasonal variations in temperature and humidity, the relative solubility of mineral species, and the presence of organic matter play an important role. In addition, our study shows the existence of "mineral niches" and "mineral seasonality," which can be explained on the basis of the "mineral ecology" concept introduced by Hazen et al. (2015). Our investigation of the formation of hydrated sulfates, particularly of ammonium sulfates, might be of importance for identifying the existence of life in mineral formation environments. [ABSTRACT FROM AUTHOR]

Mining areas and in particular those containing massive sulfides have left a heavy environmental legacy with soils and hydrographic networks highly contaminated with metals and metalloids as for example in the Iberian Pyrite Belt (Huelva, Spain). Here, we present new data on copper (Cu) isotopic composition of waters and solids collected along a continuum Mine (Tharsis)—River (Meca)—Lake (Sancho) in the Iberian Pyrite Belt. Our results show that the isotopic signature of pit lakes is spatially variable, but remains stable over the seasons; this signature seems to be controlled by water–rock interaction processes. The data obtained on the Meca River imply a number of attenuation processes such as decrease in the metal concentration by precipitation of secondary minerals. This is accompanied by preferential retention of the heavy isotope (65Cu) with a possibility of living organisms (e.g., algae) participation. The terminal Sancho lake demonstrated constant isotopic signature over the entire depth of the water column despite sizable variations in Cu concentrations, which can be tentatively explained by a superposition of counter-interacting biotic and abiotic processes of Cu fractionation. Overall, the understanding of the isotopic variations along the hydrological continuum is useful for a better understanding of metal element transfer within mining environments and surrounding surface waters. [ABSTRACT FROM AUTHOR]

Acid mine drainage events have a negative influence on the water quality of fluvial systems affected by coal mining activities. This research focuses on the analysis of these events, revealing hidden correlations among potential factors that contribute to the occurrence of atypical measures and ultimately proposing the basis of an analytical tool capable of automatically capturing the overall behavior of the fluvial system. For this purpose, the hydrological and water quality data collected by an automated station located in a coal mining region in the NW of Spain (Fabero) were analyzed with advanced mathematical methods: statistical Bayesian machine learning (BML) and functional data analysis (FDA). The Bayesian analysis describes a structure fully dedicated to explaining the behavior of the fluvial system and the characterization of the pH, delving into its statistical association with the rest of the variables in the model. FDA allows the definition of several time-dependent correlations between the functional outliers of different variables, namely, the inverse relationship between pH, rainfall, and flow. The results demonstrate that an analytical tool structured around a Bayesian model and functional analysis automatically captures different patterns of the pH in the fluvial system and identifies the underlying anomalies. [ABSTRACT FROM AUTHOR]

The formation of thin mineral films or encrustations floating on the water surface of low-flow or stagnant zones of acid mine drainage (AMD)-affected streams is probably among the most exotic features that can be found in mining areas. However, most fundamental questions about their origin (biotic vs. abiotic), structure, mineralogy, physical stability and metal-retention capacity remain unanswered. This study aims to reveal the factors promoting their formation and to clarify their composition in detail. With this purpose, the major mineral phases were studied with XRD in surface film samples found in different mine sites of the Iberian Pyrite Belt mining district (SW Spain), and the major oxide and trace metal concentrations were measured with XRF and/or ICP-MS. Fe(III) minerals dominated these formations, with mineralogy controlled by the pH (jarosite at pH~2.0, schwertmannite at pH 2.5–3.5, ferrihydrite at pH > 6.0). Other minerals have also been identified in minor proportions, such as brushite or khademite. These mineral formations show an astounding capacity to concentrate, by orders of magnitude (×102 to ×105), many different trace metals present in the underlying aqueous solutions, either as anionic complexes (e.g., U, Th, As, Cr, V, Sb, P) or as divalent metal cations (e.g., Cu, Zn, Cd, Pb). These floating mineral films are usually formed in Fe(II)-rich acidic waters, so their formation necessarily implies the oxidation of Fe(II) to Fe(III) phases. The potential involvement of Fe(II)-oxidizing microorganisms was investigated through 16S rRNA gene amplicon sequencing of water underneath the Fe(III)-rich floating mineral films. The sequenced reads were dominated by Ferrovum (51.7 ± 0.3%), Acidithiobacillus (18.5 ± 0.9%) and Leptospirillum (3.3 ± 0.1%), three well-known Fe(II)-oxidizing genera. These microorganisms are major contributors to the formation of the ferric mineral films, although other genera most likely also play a role in aspects such as Fe(III) sequestration, nucleation or mineral growth. The floating mineral films found in stagnant acidic mine waters represent hotspots of biosphere/hydrosphere/atmosphere interactions of great value for the study of iron biogeochemistry in redox boundaries. [ABSTRACT FROM AUTHOR]

The geochemistry of the Ría de Huelva estuary (Spain) has been widely studied owing to its unique conditions due to mixing of acid mine drainage (AMD), river water and seawater, which have been aggravated by the existence of an adjacent phosphate fertilizer plant and its associated phosphogypsum stack. To better understand the complex geochemistry of the overall estuarine system, we make use of (1) measured concentrations of relevant trace elements (rare earth elements (REEs) and metal(loid)s) in the sediments and waters of the estuary and (2) geochemical modeling which combines mixing and adsorption processes. Our study sheds light on the elemental distribution in the sediments and water in the water-mixing area. As seawater neutralizes the acidity of the river water (pH increases to 6.2) colloids of Fe- and Al-oxyhydroxysulphates (schwertmannite and basaluminite, respectively) precipitate as concentrations of aqueous Fe and Al increase. These phases have a high adsorption capacity and play a critical role in the geochemistry of the aquatic system by retaining Cu, Pb, Cr, As, P, REEs and smaller amounts of Zn, Co, Ni and Mn. The geochemical model reproduces the behaviour of the aqueous REEs, requiring high S/L ratios at pH ≥ 3.5 and participation of sediments and colloids in the reactions to match the field data. The evaluation of the effect of the adjacent phosphogypsum stack on the estuarine geochemistry shows that the stack has a notorious impact on the geochemistry of the surrounding estuarine environment owing to the release of high quantities of phosphate. [ABSTRACT FROM AUTHOR]

The Iberian Pyritic Belt (IPB) is one of the most important metallogenic provinces, which hosts massive sulfides and extends over 230 km from Canal Caveira-Lousal in Portugal to Gerena (near Seville) in Spain. It has 88 active and inactive mines only in the Spanish part and near 30 in Portugal that generate Acid Mine Drainage (AMD) pollution to the main river basins, Corona, Roxo (Portugal), Odiel, Tinto, Guadiamar (Spain) and Chanza-Guadiana (Portugal/Spain) and consequenty to the 35 acidic sampling sites, 14 in Portugal and 21 in Spain, selected for this unique study. The physico-chemical parameters of waters (EC, Eh, pH, Al, As, Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn, SO 4 2−), acidic diatoms (%Pinacid) and diatom diversity (N°sps) were determined in the laboratory. Then, the results were integrated in a database with 16 variables and 35 sampling points to be statistically analyzed by factor and cluster analysis. In the first, for the 35 sampling sites, it showed a clear inexistence of ecological barriers, exposing how could distantly sampling points be paired together. The last, allowed the pollution–biota interaction models formulation governed by 2 factors: 1-Unrestored Mining Surfaces and 2-WFD (Water Framework Directive) exceeding limits. Dispersion diagram showed that although the unrestored mining surface increases, starting from a certain concentration of contaminants, salts begin to precipitate: the AMD process increases but the WFD does not. There are numerous works in the scientific literature aimed to define diatom-hydro-geo-chemistry interrelationships, but none that covers an entire metallogenetic province where ecological barriers could exist, conditioning the diatom species and groups evolution and distribution in an acidic (pH: 1.90–4.43) environment. [Display omitted] • Hydro-geo-chemical-biota relationships in an all metallogenetic province. • Pollution degree in rivers and AMD affected fluvial network. • Factor and cluster analysis towards statistical models of interdependence. [ABSTRACT FROM AUTHOR]

Uncrewed Aerial Systems (UAS) and satellites are used for monitoring and assessing the quality of surface waters. Combining both sensors in a joint tool may scale local water quality retrieval models to regional and global scales by translating UAS-based models to satellite imagery. The main objective of this study is to examine whether Sentinel-2 (S2) data can complement UAS data, specifically from the MicaSense RedEdge MX-Dual sensor, for inland water quality monitoring in mining environments affected by acid mine drainage (AMD). For this purpose, a comparison between UAS reflectance maps and atmospherically corrected S2 imagery was performed. S2 data were processed with Case 2 Regional Coast Colour (C2RCC) and Case 2 Regional Coast Colour for Complex waters (C2X) atmospheric correction (AC) processors. The correlation between the UAS data and the atmospherically corrected S2 data was evaluated on a band-by-band and a pixel-by-pixel basis, and the compatibility of the spectral data was analyzed through statistical methods. The results showed C2RCC and C2X performed better for acidic greenish-blue and non-acidic greenish-brown water bodies concerning the UAS data than for acidic dark reddish-brown waters. However, significant differences in reflectance between the UAS sensor and both S2 AC processors have been detected. The poor agreement between sensors should be considered when combining data from both instruments since these could have further consequences in developing multi-scale models. [ABSTRACT FROM AUTHOR]

Acid mine drainage (AMD) systems are extremely acidic and are metal-rich formations inhabited by relatively low-complexity communities of acidophiles whose enzymes remain mostly uncharacterized. Indeed, enzymes from only a few AMD sites have been studied. The low number of available cultured representatives and genome sequences of acidophiles inhabiting AMDs makes it difficult to assess the potential of these environments for enzyme bioprospecting. In this study, using naïve and in silico metagenomic approaches, we retrieved 16 esterases from the α/β-hydrolase fold superfamily with the closest match from uncultured acidophilic Acidobacteria, Actinobacteria (Acidithrix, Acidimicrobium , and Ferrimicrobium), Acidiphilium , and other Proteobacteria inhabiting the Los Rueldos site, which is a unique AMD formation in northwestern Spain with a pH of ∼2. Within this set, only two polypeptides showed high homology (99.4%), while for the rest, the pairwise identities ranged between 4 and 44.9%, suggesting that the diversity of active polypeptides was dominated not by a particular type of protein or highly similar clusters of proteins, but by diverse non-redundant sequences. The enzymes exhibited amino acid sequence identities ranging from 39 to 99% relative to homologous proteins in public databases, including those from other AMDs, thus indicating the potential novelty of proteins associated with a specialized acidophilic community. Ten of the 16 hydrolases were successfully expressed in Escherichia coli. The pH for optimal activity ranged from 7.0 to 9.0, with the enzymes retaining 33–68% of their activities at pH 5.5, which was consistent with the relative frequencies of acid residues (from 54 to 67%). The enzymes were the most active at 30–65°C, retaining 20–61% of their activity under the thermal conditions characterizing Los Rueldos (13.8 ± 0.6°C). The analysis of the substrate specificity revealed the capacity of six hydrolases to efficiently degrade (up to 1,652 ± 75 U/g at pH 8.0 and 30°C) acrylic- and terephthalic-like [including bis(2-hydroxyethyl)-terephthalate, BHET] esters, and these enzymes could potentially be of use for developing plastic degradation strategies yet to be explored. Our assessment uncovers the novelty and potential biotechnological interest of enzymes present in the microbial populations that inhibit the Los Rueldos AMD system. [ABSTRACT FROM AUTHOR]

Odiel river basin is located in the Iberian Pyritic Belt (IPB) and mostly of its tributaries are severely affected by acid mine drainage (AMD). It is originated when pyritic minerals from abandoned mines, especially mineral residues from waste rock dams, get in contact with air and water. Fifteen sampling points were chosen to analyze interactions between diatom communities and water hydrogeochemistry. Considering physicochemical characteristics, sampling points were assigned as highly, moderately, and unpolluted by AMD. No correlation was observed between ecological diversity indexes and physico-chemical parameters. However, a dependency relationship between diatom species distribution and specific pH, conductivity, redox potential, sulfate, and metal concentrations was observed. Cluster analysis based on Pearson correlation and rs values of the non-parametric Spearman correlation allowed to identify Pinnularia acidophila, Pinnularia subcapitata var. elongata, and Eunotia exigua as the main bioindicators of AMD-polluted Odiel streams. Finally, a principal component analysis led to associate the most abundant diatoms species to specific physico-chemical parameters. [ABSTRACT FROM AUTHOR]

This work focuses on the physical-chemical characterization of a mining effluent affected by acid mine drainage (AMD) from its source to the confluence in the Odiel river, one of the most polluted rivers by AMD worldwide, in order to understand the reactions involved in the modifications in the chemical characteristics of water and precipitates resulting from water–rock–atmosphere interaction in an environment highly affected by mining activity without corrective measures. The channel starts in an open pit lake through one of the Concepción Mine main galleries, located in the Iberian Pyrite Belt, about 10 km northwest of Rio Tinto mining complex (southwest Spain). This gallery intercepts one of the largest and oldest underground mining work locations called "gallery Carmen", allowing the exit of AMD affected waters. This channel is the first AMD polluting source in the Odiel basin. Thus, at the end of the rainy season, we conducted water sampling along this channel, from its source to its mouth, to further analyse its characterization and interpret the cause–effect relationships through the application of Fuzzy Logic and classical statistics tools. The interdependent relationship between the measured physicochemical parameters are set in order to propose a model, capable of describing the evolution of contaminants in response to the processes and reactions taking place within the affected channel and the Odiel river. The present work concluded the existence of natural attenuation processes for the mining channel, despite the entrances of other drainages in the AMD channel with different hydrochemical characteristics imposing modifications on it. This indicates that these media have a high vulnerability to external stimuli. [ABSTRACT FROM AUTHOR]

The Tinto and Odiel rivers (SW Spain) drain from a vast sulfide mining district and join at a 20-km-long estuary that enters the Atlantic Ocean. In this work, the contents of rare earth elements (REE) and fractionation in Neogene–Holocene sediment cores from La Fontanilla cove (Tinto estuary) were studied. The sediments were collected from a depth of 18 m at different distances from the recent river flow and were analyzed for new information on the temporal development of the REE load in the sediment column. Results show that the ∑ REE is higher in the finer sediments and during periods of mining activity from prehistoric to recent times. Marine influence appears to increase the light REE (LREE) relative to the heavy REE (HREE). The REE patterns of these estuarine sediments show convex curvatures in the MREE relative to the LREE and HREE, indicating the presence of acid-mixing processes between the fluvial waters affected by acid mine drainage (AMD) and seawater, as well as the precipitation of poorly crystalline mineral phases. Significant positive Eu anomalies were found in ebb-tide channels and marsh deposits, which can reflect the mineralogical composition and/or a strong localized salinity gradient combined with organic matter degradation. Sedimentological characteristics of the deposits appear to play the main role in accumulation and fractionation of the REE. [ABSTRACT FROM AUTHOR]

Few studies have assessed mining-associated water pollution using spectral characteristics. We used high-resolution multispectral data acquired by unmanned aerial drones combined with in situ chemical data to assess water quality parameters in 12 relatively small water bodies located in the Tharsis complex, an abandoned mining area in the Iberian pyrite belt (SW Spain). The spectral bands of Micasense RedEdge-MX Dual and spectral band combinations were used jointly with physicochemical data to estimate water quality parameters and develop reliable empirical models using regression analysis. Physicochemical parameters including pH, ORP, EC, Al, Cu, Fe, Mn, S, Si, and Zn were estimated with high accuracy levels (0.81 < R2 < 0.99, 4 < RMSE% < 75, 0.01 < MAPE < 0.97). In contrast, the observed and modelled values for Ba, Ca, and Mg did not agree well (0.42 < R2 < 0.70). The best-fitted models were used to generate spatial distribution maps, providing information on water quality patterns. This study demonstrated that using empirical models to generate spatial distribution maps can be an effective and easy way to monitor acid mine drainage. [ABSTRACT FROM AUTHOR]

Production of acid mine drainage may occur during mining operations and may continue for many years after closure. In some cases, especially when host rock is capable of reacting with acidic drainage, metal concentrations may decrease over time and distance. Seasonal variations in water flow rate also play an important role in metals concentration both in surface and groundwater. The present study evaluates the contamination of an abandoned pyrite mining area (Wieściszowice, SW Poland) and the temporal variation of the water contamination in selected locations of 2 sampling campaigns (2000 and 2015). The mining surrounding Rudawy Janowickie Mountains range is well known for the rich mining history and is considered as one of the oldest in Europe. The Wieściszowice pyrite mine was exploited for several hundreds of years and processed Fe and Cu sulfides, and sulfur. This mine was closed in 1925 because of the high competition of pyrites from Spain. Results show clearly that water samples collected in the mining area are mainly Ca–SO4 and acid/high metal, while spring water and surface water samples, representing the local geochemical background, are Ca–HCO3 and neutral-low metal. The analysis of data shows an improvement in water quality from 2000 to 2015 as well as a decreasing of water risk assessment for human use. This improvement can be related to the fact that 2015 was a very dry year, with over 60% less flow than in 2000, leading to less water contamination. [ABSTRACT FROM AUTHOR]

The Iberian Pyrite Belt in southwest Spain hosts some of the largest and diverse extreme acidic environments with textural variation across rapidly changing biogeochemical gradients at multiple scales. After almost three decades of studies, mostly focused on molecular evolution and metagenomics, there is an increasing awareness of the multidisciplinary potential of these types of settings, especially for astrobiology. Since modern automatized exploration on extraterrestrial surfaces is essentially based on the morphological recognition of biosignatures, a macroscopic characterization of such sedimentary extreme environments and how they look is crucial to identify life properties, but it is a perspective that most molecular approaches frequently miss. Although acid mine drainage (AMD) systems are toxic and contaminated, they offer at the same time the bioengineering tools for natural remediation strategies. This work presents a biosedimentological characterization of the clastic iron stromatolites in the Tintillo river. They occur as laminated terraced iron formations that are the most distinctive sedimentary facies at the Tintillo river, which is polluted by AMD. Iron stromatolites originate from fluvial abiotic factors that interact with biological zonation. The authigenic precipitation of schwertmannite and jarosite results from microbial–mineral interactions between mineral and organic matrices. The Tintillo iron stromatolites are composed of bacterial filaments and diatoms as Nitzschia aurariae, Pinnularia aljustrelica, Stauroneis kriegeri, and Fragilaria sp. Furthermore, the active biosorption and bioleaching of sulfur are suggested by the black and white coloration of microbial filaments inside stromatolites. AMD systems are hazardous due to physical, chemical, and biological agents, but they also provide biogeochemical sources with which to infer past geochemical conditions on Earth and inform exploration efforts on extraterrestrial surfaces in the future. [ABSTRACT FROM AUTHOR]

This paper proposes the use of wetlands as a phytoremediation strategy for areas of mining and maritime influence in the southeast of Spain. Potentially toxic elements (PTEs) tolerant and salinity-resistant macrophytes (Phragmites australis, Juncus effusus and Iris pseudacorus) have been used. The experiment is carried out in an aerobic artificial wetland using representative sediments affected by mining activities in the study area. Selected species were placed in pots containing substrates made with different mixtures of topsoil and/or peat, mining residues (black or yellow sand). After six months, rhizosphere, root and aerial parts were collected. A transfer study of As, Pb, Zn and Cu is performed, determining contents in rhizosphere and plant (aerial and underground part). From these data, the TF and BCF were calculated for each plant in 15 different substrates. The work is complemented by an initial study of scanning electron microscopy (SEM–EDX) of plants. The obtained results indicate a tolerance of the metallophytes to these PTEs, which may favour the obtaining of a naturalized habitat that acts as an effective protective barrier to the ecosystem, that is easy to maintain and that avoid the risk of transfer to the trophic chain. The use of these species can be a complement to the chemical stabilization proposed for the whole area and carried out in experimental plots. Because they are perennial plants, it is necessary to continue with the experiments and obtain results in a longer period of time that allows to evaluate yield and stabilization. [ABSTRACT FROM AUTHOR]

The Huelva estuary is formed by the common mouths of the Odiel and Tinto Rivers, and inside this ecosystem is the biosphere reserve of the Odiel saltmarshes. This ecosystem has been historically affected by acid mine drainage (AMD) and by releases of pollutants from five phosphoric acid industrial plants and phosphogypsum (PG) waste stacks located in the area. This study carried out a comprehensive assessment of the environmental impact of the biosphere reserve of the Odiel saltmarshes. To this end, it was necessary to find a suitable sedimentary background (Piedras River in our case). To quantify this impact, several pollution indexes were used. According to the values reached by the indexes, this impact was classified as "serious" pollution for most trace elements, excepting the deepest layers, and "low-moderate" pollution for the 238 U-series radionuclides, while no pollution for the 232 Th-series and 40 K radionuclides was found as expected., 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 © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Water is one of the receptors media more affected by the environmental impacts, especially caused by mining sulfides exploitation. Acid mine drainage (AMD) is the main problem associated with these mining operations, producing extremely high impacts, and in many cases irreversible, still remaining nowadays. Diatoms, are the taxonomic algal group most used in environmental studies, to assess the water quality of rivers. From a monitoring perspective, the diagnosis of AMD contamination through the use of diatoms has proved to be an effective ecological tool to assess the impact and select the preventive and corrective measures more adequate to treat these impacted sites. In the present work, the existing relationships between biological and physicochemical indicators of acid mine drainage processes (AMD) in all the reservoirs affected by AMD in the Iberian Pyrite Belt (IPB) were studied through the use of fuzzy logic and data mining techniques that in contrast to the classic statistical treatments. The fuzzy rules show the relationship between biological and physical-chemical indicators, demonstrating the presence of a perfect correlation in all cases; thus, the numbers of species and pH have the same behavior, and inverse to that presented by the percentage of Pinnularia and the metallic charge and sulfates. These techniques improve the work considerably and make easier the knowledge of the involved processes, allowing a better discrimination of the diatoms responses to the stimuli caused by the hydrochemical changes imposed by the processes affecting water quality. [ABSTRACT FROM AUTHOR]

Environmental context: Natural weathering of rocks may release technology critical elements (TCEs) to the environment, and anthropogenic activities can noticeably increase TCE release rates. We investigated acid mine drainage outflows from an underground sulfide mine in south-west Spain, reporting TCE concentrations orders of magnitude higher than those observed in natural waters. The findings improve our knowledge on mobility of TCEs in different geological settings. Extensive extraction of technology critical elements (TCEs) from the lithosphere and their use results in a growing dispersion and remobilisation of these elements within the environmental compartments. We investigated the concentration and mobility of different TCEs (rare earth elements (REEs), Sc, Y, Ga and Tl) in acid mine drainage (AMD) outflows from a massive sulfide underground mine in south-west Spain for around 2 years. High levels of TCEs were observed; average concentrations of 8.2 mg L−1 of REEs, 1.5 mg L−1 of Y, 80 µg L−1 of Ga, 53 µg L−1 of Sc and 42 µg L−1 of Tl were reported, several orders of magnitude higher than those observed in natural waters. The TCEs source in the study site is primarily accessory minerals in the host rocks, although the contribution of Ga and Tl by sulfides cannot be discarded. A seasonal variability in TCEs is observed in AMD waters, although their maximum concentrations do not coincide with those of sulfide-related elements. TCEs seem not to be controlled by the precipitation of secondary minerals, but by the intensity of chemical weathering inside the mined zone. A positive correlation between REEs and the Si/Na+K ratio seems to indicate that these elements are linked to resistant minerals to weathering. Environmental context. Natural weathering of rocks may release technology critical elements (TCEs) to the environment, and anthropogenic activities can noticeably increase TCE release rates. We investigated acid mine drainage outflows from an underground sulfide mine in south-west Spain, reporting TCE concentrations orders of magnitude higher than those observed in natural waters. The findings improve our knowledge on mobility of TCEs in different geological settings. [ABSTRACT FROM AUTHOR]

High altitude (alpine) lakes are efficient sentinels of environmental processes, including local pollution and long-range atmospheric transfer, because these lakes are highly vulnerable to ongoing climate changes and increasing anthropogenic pressure. Towards improving the knowledge of trace element geochemistry in the water column of alpine lakes, we assessed 64 physico-chemical parameters, including macro- and micronutrients, major and trace element concentrations in the water column of 18 lakes in the Pyrenees, located along the border between France and Spain. Lake depth, morphology, retention time and watershed rock lithology did not exhibit sizable impact on major and trace element concentrations in the water column. However, acidic (pH = 4.7 ± 0.2) lakes were distinctly different from circumneutral lakes (pH = 6.8 ± 0.5) as they exhibited >10 times higher concentrations of SO 4 2− and trace metals (Fe, Mn, Zn, Cd, Pb, Co, Ni, Be, Al, Ga and REEs). While some of these elements clearly mark the presence of sulphide-rich minerals within the watershed (Fe, Zn, Cd and Pb), the increased mobility of lithogenic elements (Be, Al, Ga and REEs) in acidic lakes may reflect the leaching of these elements from silicate dust derived from atmospheric deposits or surrounding granites. At the same time, compared to circumneutral lakes, acidic lake water displayed lower concentrations of dissolved oxyanions (As, Mo, V, B and W) and elevated SO 4 2− concentrations. The latter could lead to efficient Ba removal from the water column. The exploitation of metal ores within the watershed of three lakes clearly impacted high Zn and Cd concentrations observed in their water column, despite two of these lakes not being acidic. We conclude that local impacts have a greater effect on the water column than long-range atmospheric inputs and that dissolved trace element concentration measurements can be used for revealing sulphide-rich minerals or acid mine drainage within the lakes' watershed. [Display omitted] • Dissolved major and trace elements in water column of 18 alpine lakes. • Solute sensitivity to local lithological context and long-range atmospheric input. • Sulphide mineral weathering controls trace metals in the water column. • Acidic, sulphate-rich waters are rich in trace metals and trivalent lithogenic elements. • Oxyanions are depleted in acidic lakes due to adsorption on mineral particles. [ABSTRACT FROM AUTHOR]

Rare earth elements (REE) are strategic elements due to their economic importance. However, the studies dedicated to the distribution and behaviour of REE in aquatic systems have been scarce until a few decades ago. This work studies the seasonal variations of REE concentrations in acid mine drainage (AMD) affected water courses and the factors controlling their mobility under different hydrological conditions. To address this issue, a high-resolution sampling was performed for two years in selected sampling sites. REE concentrations were very high (median values of 2.7–3.4 mg/L, maximum of 7.0 mg/L). These values are several orders of magnitude higher than those found in natural waters, highlighting the importance of AMD processes on the release of REE to the hydrosphere. No good correlations were found between pH and REE concentration, while REE correlated positively (r Spearman coefficient of 0.78–0.94) with EC and negatively (r −0.88 to −0.90) with discharge in AMD-affected streams. A conservative behaviour of REE was observed due to the strongly acidic conditions observed in the study area. The waters also showed an enrichment in MREEs over LREEs and HREEs (mean values of Gd N /La N >1.8 and Yb N /Gd N < 0.7), typical of AMD waters. An asymmetry in the content of LREE and HREE was observed in AMD samples studied, which could be explained by the preferential dissolution of LREE or HREE-enriched minerals within each waste heaps. Multivariate analysis suggests the influence of Mn-rich minerals existent in the study area as a potential source of LREE. [Display omitted] • A high-resolution of Rare Earth Elements (REE) samples was performed from acid mine drainage (AMD) sources and streams for two years • High concentration of REE (up to 7 mg/L) were recorded in the mining area • REE concentrations correlate negatively with flow rates in streams and poor in AMD sources • REE behaved conservatively due to their acidic conditions • Most samples exhibited a Heavy REE enrichment over Light REE, while some samples showed Light REE/Heavy REE rate close to 1 [ABSTRACT FROM AUTHOR]

At the mouth of the Odiel River, within the Natural Area "Marismas del Odiel", there has been for years a collection of waste from different mining sites. In the present work, an approach has been made to the problem that this supposes, quantifying the pollutants that are poured into the estuary from the mineral collection located on the banks of the river. The study carried out has been able to determine high metal concentrations, comparable with any rubble from the upstream mines, with pH value of 1.66, lower than many other areas affected by acid mine drainage in the same river, and even with concentrations of Fe and As higher than those provided by the rest of the mining facilities of the Odiel basin. This can make us understand the serious situation of the Natural Park, where a great variety of birds and plants of special ecological interest are located. [ABSTRACT FROM AUTHOR]

In the salth-marshes of the Tinto River (Huelva estuary, SW Spain), are stored in stacks around 100 Mt of PG, covering a surface of 1000 ha without any type of isolation, which produce an important impact in the surrounding environment. On the other hand, this ecosystem it is affected by acid mine drainage (AMD) from sulphide mines located upstream the Tinto River. The aim of this study is to evaluate the deep pollution of the underlain salt-marsh sediments due to leachates from the PG stacks. For that purpose, 7 cores were collected from zones 2 and 3 of the stacks, and PG and salt-marsh sediments samples from different depths were analyzed. The physicochemical parameters, mineralogy, granulometry and the concentration of the main elements of interest were determined in the samples. Most analysed salt-marsh sediments are not affected by PG stacks pollution, because sediments act as a "barrier" for the leachates from the PG, concentrating the contaminants in the first decimetres (0.5 m) under PG-sediments contact, and the deep infiltration is very limited. The obtained results suggest that the perimeter channel which is projected to build in the restauration project, should has a depth of 1 m below the level of the PG stacks for assuring the complete collection of leachates from the stacks, and avoid their liberation into the Tinto River estuary. Image 1 • Salt-marsh sediments act as a "barrier" for leachates from the phosphogypsum stacks. • Pollutants reach only the first 0.5 m of salt-marsh sediments under the stacks. • P is a good tracer of the pollution coming from PG piles. • Very useful results for the design of the restauration project of the PG stacks. [ABSTRACT FROM AUTHOR]

Industrial by-products and wastes from Portugal and Spain were tested for the first time as carbon sources/electron donors for sulphate-reducing bacteria. Cultures in mineral medium supplemented with the tested substrates were monitored, and sulphate reduction efficiency is discussed in light of substrates compositions, dosages and corresponding chemical oxygen demand/[SO42−] ratios. The results reveal the ability of those substrates to feed SRB and confirm that testing doses targeting ratios of 1.5 and values close to this was a good strategy to optimize sulphate reduction activity. As expected, this activity was faster for substrates that have in their composition simple compounds (such as low-chain alcohols and organic acids) and/or compounds that can be rapidly degraded (such as sugars), though it also occurred in a longer-term perspective with substrates composed mainly of slowly degradable compounds (such as cellulose and lignin). Thus, this work demonstrates the potential of new substrates and respective required doses to feed SRB bioreactors in long-term passive bioremediation processes or faster more active processes. That is, it opens the way for the use of such substrates in the treatment of sulphate-rich waters, as the acid mine drainage generated in some mines on the Iberian Pyrite Belt region, and it encourages further experiments to evaluate the use of SRB-based processes to treat the industrial wastewaters successfully tested in this work themselves, specially the olive mill wastewater which is still a problem for many small olive oil producers. [ABSTRACT FROM AUTHOR]

Water pollution by metals and, in particular, acid mine drainage (AMD) is one of the most severe environmental problems to be faced by society. In this sense, treatment by membrane processes is a promising alternative, highlighting membrane distillation (MD) features to overcome the limitations of conventional processes. In this work, water gap MD (WGMD) and air gap MD (AGMD) were tested under different feed temperatures and organic matter concentrations, using 0.45 μm polytetrafluoroethylene (PTFE) membranes and real AMD from Tinto River, which is located in SW Spain. For both MD modes, high permeate fluxes (up to 16.80 L h−1 m−2 for WGMD and 10.16 L h−1 m−2 for AGMD) were reached and over 99% rejection was obtained for electrical conductivity, ions and metals (Na+, K+, Ca2+, Mg2+, F−, Cl−, NO 3− , SO 4 2−, Cu, Fe, Zn, Cd, Co, Mn, Ni). In addition, specific thermal energy consumption (STEC) per unit of permeate water was calculated to obtain MD heat requirements. Furthermore, MD efficiency in terms of heat recovery was estimated by gained output ratio (GOR) between useful and total heat of the system. On that basis, MD and specifically the WGMD mode, showed great potential for the sustainable treatment of AMD. Image 1 • Air and water gap membrane distillation (MD) were tested with acid mine drainage. • Influence of different feed temperatures and humic acid concentrations were studied. • Quantitative rejection of ions and metals was obtained for all experiments conducted. • Water gap MD showed greater performances of permeate flux and energy efficiency. [ABSTRACT FROM AUTHOR]

In May 2017, a spill from La Zarza pit lake (SW Spain) resulted in the release of approximately 270,000 m3 of extremely acidic waters to the Odiel River. Around 780 × 103 kg of Fe, 170 × 103 kg of Al, 2.15 × 103 kg of As and high amounts of other trace metals and metalloids were spilled. The purpose of this study is to explain the causes, consequences and impacts of the mine spill on the receiving water bodies. To this end, an extensive sampling along the mine site, river and estuary as well as a hydrological model of the pit lake was performed. Around 53 km of the Odiel River's main course, which was already contaminated by acid mine drainage (AMD), were affected. The mine spill resulted in an incremental impact on the Odiel River water quality. Thus, dissolved concentrations of some elements increased in the river up to 450 times; e.g. 435 mg/L of Fe and 0.41 mg/L of As. Due to low pH values (around 2.5), most metals (e.g., Cu, Zn, Mn, Cd) were transported in the dissolved phase to the estuary, exhibiting a conservative behavior and decreasing their concentration only due to dilution. However, dissolved concentrations of Fe, Cr, Pb, Se, Sb, Ti, V and especially As decreased significantly along the river due to Fe precipitation and sorption/coprecipitation processes. At the upper zone of the estuary, a noticeable increment of metal concentrations (up to 77 times) was also recorded. The water balance illustrates the existence of groundwater inputs (at least 16% of total) to the pit lake, due probably to local infiltration of rainwater at the mining zone. The probable existence of an ancient adit connected to the pit lake indicates that potential releases could occur again if adequate prevention measures are not adopted. Image 1 • Around 270,000 m3 of extremely acidic waters were spilled from a pit lake. • An incremental impact after the spill on the already polluted Odiel River and estuary was observed. • Al, Cd, Co, Cu, Mn, Ni, Sc, U and Zn were conservatively transported to the estuary. • Cr, Fe, Se, Pb, Ti, Sb, V and As were removed from water by precipitation/sorption. • The pit lake has not yet reached equilibrium, a new spill could occur in the future. "An accidental discharge (270,000 m3 of acidic and metal-rich waters) from an abandoned pit lake to the Odiel River and its estuary caused a significant additional increase in the contaminant levels". [ABSTRACT FROM AUTHOR]

Abstract The mining activities performed in the Iberian Pyrite Belt (south of Spain) have generated since long-time acid mining drainage (AMD) inputs to the Odiel River and its tributaries. These inputs are continuing nowadays, with origin mostly in the abandoned mines that cover the area, provoking a steady-state situation where the river waters present very low pH and very high concentrations of different heavy metals. In this work, the behavior of several natural radionuclides (210Po, Th- and U-isotopes) in water and sediment samples collected in the Odiel River and its tributaries have been analyzed and their levels determined looking for assessing the radiological environmental impact of the AMD. Highlights • Radioactive NORM impact associated to acid mining drainage (AMD) have been analyzed. • Enhanced U and Th concentrations are present in waters affected by AMD. • Very high 234U/238U activity ratios have been also observed in the affected waters. [ABSTRACT FROM AUTHOR]

Abstract The Río Tinto mining area provides ideal conditions for studying the role of colloidal particles in concentrating. All the elements are present in higher concentrations respect to their content in common natural waters. 234U/238U activity ratio ranges between 2.286 ± 0.149 and 2.531 ± 0.151. Concentration of Fe and Al are in the order of 104–103 mg/L; Co, Zn and Cu values are three times lower than Fe and Al, but still much greater than in natural waters; U reaches values up to 40.73 μg/L. To evaluate the partitioning of these elements into the colloidal fraction, ultrafiltration (UF) experiments were made. A permeation model describing the relationship between concentration of the elements or isotopes in the permeate solution and the concentration factor (CF) was calculated. Experiments were carried out using CF from 1.5 to 25.0. The behaviour of investigated heavy metals and U can be predicted by a permeation model that provides similar permeation coefficient (P c) for all of them (P c = 0.95–0.97 for 50 kDa, P c = 0.86–0.88 for 10 kDa, and P c = 0.80–0.86 for 3 kDa). Retention for all the investigated elements occurs, resulting in up to 23% of the element associated to the 3 kDa colloidal fraction. The increase in U and heavy metals concentrations in the retentate fraction with the increasing CF is due to the retention of the colloidal fraction. The colloidal abundance of related metals increased with decreasing membrane MWCO even though the difference is small between 3 and 10 kDa fraction for some metals Characterization of colloidal material is needed to better understand the state of play in this context. Highlights • Partitioning of U and selected heavy metals in dissolved and colloidal fractions in AMD conditions were examined. • UF with distinct MWCO was used and a permeation model to quantify the behaviour of U and selected metals was applied. • Metal concentrations much higher than those in natural waters were found and high 234U/238U in the water samples were observed. • Little colloidal metals in the size fraction 3–10 kDa are present, likely due to the strong acidic conditions. • Low concentrations of colloidal U in the study area were measured. [ABSTRACT FROM AUTHOR]

[Display omitted] • Durability of concrete affected by acid mine drainage environment. • Relationt between tensile and compressive strength. A new formulation. • Reduction of compressive strength (9%) and tensile strength (24%) in six months. • An increase in porosity, air permeability and a reduction in the modulus of elasticity. Although not many studies have analysed the effects of acid mine drainage (AMD) on the durability of concrete, it is clear that such an aggressive environment affects the different mechanical parameters of this material. AMD is an environmental problem that affects the five continents and is especially widespread in the south western part of the Iberian Peninsula, in an area known as the Iberian Pyrite Belt. In this work, the effect of AMD on tensile and compressive strength of concrete has been evaluated, analysing the evolution of these two fundamental parameters on this structural material. For this purpose, a series of concrete samples were subjected to a controlled AMD environment in the laboratory, using water with pH 2.8 collected from the Tharsis Mine (SW Spain). The concrete samples were prepared in accordance with the parameters required by various international standards. The samples were subjected to the aggressive environment by AMD for two periods of time (3 and 6 months), after which they were subjected to non-destructive testing and destructive testing until breaking the samples by means of compression and tensile (indirect tensile test). In addition, Emission Scanning Electron Microscopy studies were performed on samples before AMD influence and on samples affected by AMD for six months. The obtained results using the ultrasonic equipment showed a decrease in concrete quality, an increase in porosity and permeability, the reduction of modulus of elasticity that reaches 8.5% after six months, as well as the appearance of microcracks. The destructive the tests showed that tensile strength is much more affected than the compressive strength: the tensile strength went from 4.31 MPa to 3.27 MPa (24%) after six months, while the compressive strength went from 48.22 MPa to 43.83 MPa (9%) in the same period of time. This different evolution means that the formulas used in international standards that relating compressive strength to tensile strength need to be modified by means of a correction factor. [ABSTRACT FROM AUTHOR]

Purpose: Geochemical and mineralogical studies of soils potentially polluted by trace elements are basic to find the source of pollution, to understand the behavior of the contaminants in the environment, and to propose remediation and reclamation actions. This work reviews the role of the Mineralogy and Geochemistry to assess the hazard of soil contamination by trace elements in mining areas, focusing on three different case studies carried out in the Andalusian community (South Spain), with a Mediterranean temperate climate.Materials and methods: Two significant mining districts were selected for this work: the Linares-La Carolina (Pb-Zn ores) and the Riotinto (Iberian Pyrite Belt, IPB) mining areas. Another case study was the Guadiamar basin, which soil was polluted by the spill produced in 1998 by the breakage of a mine tailing impoundment in Aznalcóllar mines (IPB). Soils, mine waste, and secondary precipitates were studied to approach the source of the pollution and the fate of the contaminants. Chemical composition (major and trace elements), soil parameters, and mineralogy of all materials selected were studied. In addition, the bioavailability of trace elements was determined by different methods.Results and discussion: Pyrite and secondary phases are the main sources of pollution in the Riotinto area. Their stability is a key factor in the release of trace elements. The availability of trace elements in soils was lower in unpolluted leptosols than in contaminated orchards. In Linares-La Carolina, a severe pollution by Pb and a high availability (10-70% extracted with EDTA) were found. In Guadiamar basin, the residual pyrite sludge continues releasing trace elements to soil. Cd and Zn were mobile at pH < 6 and As at pH > 8, and Pb was quite immobile. Cd, Zn, and Pb can be coprecipitated by carbonates while As is mainly adsorbed by clays and iron oxyhydroxides.Conclusions: The geochemical studies of soils polluted by mining activities allow to evaluate the availability of trace elements and their retention in soils. Therefore, geochemical and mineralogical studies are necessary for the assessment of soil pollution and remediation actions. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

[Display omitted] • Preferential leaching evidence of REE-rich minerals has been observed. • REE-rich minerals (phosphates and carbonates) seem to be REE source in the AMD. • Ce and Eu anomalies are inherited in leachate from rock, serving as REE source tracer. • REE fractionation during water–rock interaction produces MREE-enriched patterns. • Shales and igneous rocks show the highest REE release rate in the IPB. Acid mine drainage (AMD) is a worldwide pollution problem of watersheds. In addition to toxic metal(oid)s and acidity, many elements of economic interest are released into the environment, which make AMD a potential strategic secondary source of these elements such as rare earth elements (REE). Despite the importance of these metals, their origin in AMD is still uncertain. Recent hypotheses suggest preferential leaching of REE-enriched minerals as a possible source. Leaching tests with H 2 SO 4 have been developed to simulate the interaction under AMD formation conditions with sulfide bodies and host rocks from two representative mining areas in the Iberian Pyrite Belt: the Perrrunal and Poderosa mines (SW of Spain). The REE patterns and Ce and Eu anomalies of the rock leachates have confirmed the geochemical relationship between the AMD and certain country rocks (felsic and mafic volcanics, and shales). A detailed chemical and mineralogical study has confirmed the existence of a diversity of minerals with high concentrations of REE. Thus, the minerals with the highest REE contents are also those with the fast dissolution kinetics under acid conditions: REE phosphates (monazite and xenotime type) and carbonates (parisite type). Finally, petrographic evidence of the selective leaching of these minerals clearly supports these minerals as the main source of REE in the AMD. [ABSTRACT FROM AUTHOR]

This works investigates the origin, behavior and fate of Tl in acid mine drainage (AMD) affected areas at catchment scale, following the path from rocks to the ocean. To address this issue, comprehensive data set of Tl in rocks, waters, secondary minerals, plants and other environmental compartments is presented, using the Iberian Pyrite Belt (SW Spain) as representative example. The content of Tl in host rocks (mean of 0.51 mg/kg) exhibits moderate positive correlations with elements such as K and Rb, whereas no correlations were observed in sulfides (27 mg/kg) between Tl, Fe and other metal/loids commonly found in these minerals, such as As, Pb, Cd, Cu or Zn. During sulfide oxidation processes, Tl is mobilized from sulfides, as evidenced by the depletion of Tl in gossans (1.8 mg/kg), and host rock minerals, leading to a Tl enrichment in AMD leachates (mean of 242 μg/L), with concentrations of up to 8.3 mg/L, several orders of magnitude higher than those reported in natural waters. The precipitation of secondary minerals, with large surface areas, may be a sink for Tl, especially in jarosite minerals (8.4 mg/kg). Thallium can be also removed during the treatment of AMD in alkaline passive treatment systems due mainly to sorption processes onto Fe and Al secondary minerals (i.e., schwertmannite and basaluminite, respectively). Mean Tl contents of 13 mg/kg have been observed in wastes dumped in abandoned mines of the IPB, mainly spoil heaps, slags, roasted pyrite, heap leaching wastes and tailings. However, there is no clear relationship between Tl content and the type of mining wastes. These wastes can suffer weathering, leading to an enrichment of Tl in soils. Previous studies reported that <25% of total Tl is easily extractable, being mainly adsorbed to crystalline Fe oxides in acidic soils and Al oxides in neutral-alkaline soils. Despite this, Tl may be translocated by plants. The translocation of Tl in plants of the IPB has not been properly addressed, however previous studies in other areas showed a low phytoavailability of Tl compared to Cd and Zn, although Tl translocation appears to be strongly controlled by plant species or by differences in Tl speciation. The weathering of rocks, mine wastes and soils may lead to the release of notable amounts of both dissolved and particulate Tl to the hydrosphere. In acidic conditions, Tl seems to be mainly transported by the dissolved phase in AMD-affected streams and rivers, with <15% being transported by the particulate matter. This latter Tl transport may be associated to its incorporation into diatoms and Fe minerals such as jarosite after replacement of Tl+ by H+ in their structure. Subsequent release by desorption processes from jarosite and diatoms in acidic conditions can occur. This process has also been observed in estuaries affected by AMD, thus, Tl transported by jarosite minerals in the particulate matter and diatoms are released back to the estuarine waters across the salinity gradient due to the increasing proportion of unreactive TlCl0 and K+ ions, which compete for adsorption sites in jarosite with Tl+. Thus, enhanced transport of Tl to the oceans is observed in AMD-affected systems. [Display omitted] • The origin, behavior and fate of Tl in mineralized catchment was investigated. • Tl in rocks, waters, secondary minerals, plants and other reservoirs was analyzed. • High Tl concentrations in acid mine drainage due to intense sulfide oxidation. • Tl mobility controlled by the precipitation of secondary minerals and sorption. • Sorption competition between Tl+ and K+ controls Tl mobility in estuaries. [ABSTRACT FROM AUTHOR]

Summary The Odiel watershed drains materials belonging to the Iberian Pyrite Belt, where significant massive sulfide deposits have been mined historically. As a result, a huge amount of sulfide-rich wastes are deposited in the watershed, which suffer from oxidation, releasing acidic lixiviates with high sulfate and metal concentrations. In order to reliably estimate the metal loadings along the watershed a complete series of discharge and hydrochemical data are essential. A hydrological model was performed with SWAT (Soil and Water Assessment Tool) to solve the scarcity of gauge stations along the watershed. The model was calibrated and validated from daily discharge data (from 1980 to 2010) at the outlet of the watershed, river inputs into an existent reservoir, and a flow gauge station close to the northern area of the watershed. Discharge data obtained from the hydrological model, together with analytical data, allowed the estimation of the dissolved pollutant load delivered annually by the Odiel River (e.g. 9140 t of Al, 2760 t of Zn). The pollutant load is influenced strongly by the rainfall regime, and can even double during extremely rainy years. Around 50% of total pollution comes from the Riotinto Mining District, so the treatment of Riotinto lixiviates reaching the Odiel watershed would reduce the AMD (Acid Mine Drainages) in a remarkable way, improving the water quality downstream, especially in the reservoir of Alcolea, currently under construction. The information obtained in this study will allow the optimization of remediation efforts in the watershed, in order to improve its water quality. [ABSTRACT FROM AUTHOR]

The province of Huelva is one of the areas most affected by acid mine drainage (AMD) in the world, which can produce big enhancements and fractionations in the waters affected by AMD. There are very few studies on this issue, and none on polonium-210. Twenty-two water reservoirs were sampled, and the 210 Po was measured in both dissolution and particulate phases. The 210 Po concentrations in the waters were in the same order of magnitude to those ones for unperturbed systems, although the data published to particulate matter are very scarce. A mean value and standard uncertainty for 210 Po of 0.25 ± 0.03 mBq L −1 in the dissolved matter, and 62 ± 9 mBq g −1 in the particulate matter can be established as base line for the reservoirs of the Huelva area. The distribution coefficients (k d ) range from 10 4 to 10 6 L kg −1 , in agreement to the found ones by other authors for the case of neutral waters, but being the lowest values for the more acidic reservoirs. It has been also found that 210 Po has a high tendency to be associated to the particulate matter for neutral-alkaline waters, however, under extreme acid conditions (pH < 3), increases the Po tendency to be associated to the dissolved phase. Therefore, the main conclusion obtained in this work is that AMD has no a significant influence on the total activity concentration of 210 Po in the waters of reservoirs, but the acidity has a clear influence on its distribution between both dissolved and the particulate phases. [ABSTRACT FROM AUTHOR]

The Sancho Reservoir in SW Spain has been impacted by acid mine drainage (AMD) since the Tharsis mine stopped activity in 1998. As a result, the reservoir exhibits low pH (~ 3.5) and high aqueous concentrations of sulfate, aluminum, iron and trace metals. Thus far, removal of contaminants by sediment burial has not been as effective as expected in improving water quality within the reservoir. To inform potential remediation strategies, a 1-D, non-steady-state reactive transport model with a comprehensive set of equilibrium and kinetic biogeochemical reactions is used to simulate the fate of trace metals and acidity in sediments affected by AMD. Two realizations of the model account for the spatial heterogeneity of bottom water oxygenation. A “permanently oxic” model represents shallow sediments above the thermocline, while a “holomictic” model represents the deeper sediments where bottom water oxygen levels oscillate between completely anoxic and oxic as a result of water-column overturn. The model is calibrated against an extensive dataset on the depth distributions of pore water and solid phase species. Model results imply that, under permanently oxic conditions, the sediments act as a sink for acidity (H + ) and aqueous Al, Zn, Cu, Co and Ni, but act as a source of aqueous Mn, Fe and As. The latter are released to the overlying water as a result of Mn and Fe (oxy)hydroxide reductive dissolution in the sediments. Below the thermocline, when bottom waters become anoxic, metal sulfides precipitate in the sediment. When the bottom waters subsequently become oxic, the metal sulfides are oxidized along the downward-penetrating oxygen front and the associated metals are released to the overlying water. On the order of 35% of the sediment pools of sulfide-bound Zn, Cu, Co and Ni, and ~ 25% of FeS are thus reoxidized. However, overall the sediments act as a net sink for the pollutants considered in the model. On an annual basis, about 10% of the total elemental masses of S, Al, Zn and Cu present in the water column of the reservoir are removed by burial in the sediments, but only ~ 2% for Co and Ni. For Fe, Mn and As, the corresponding values are 80, 70 and 98% respectively. The model predicts that, if AMD input to the reservoir were to completely cease, the sediments would reach a new steady state with negligible release of aqueous contaminants to the overlying water column within a few years. [ABSTRACT FROM AUTHOR]

Sulphide mine waste extensively contaminates the Odiel River (southwest Spain), releasing sulphuric acid into the water body. Acidic water in this river precipitates and dissolves variably hydrated iron sulphate in a complex geological pattern controlled by climate. Local abrupt changes in the water pH in the vicinity of highly contaminated tributaries can be mapped by means of imaging spectroscopy using hyperspectral remote sensing (HyMap) data. Also, increased pH through mixing of acidic river water with marine water can be detected when the river reaches the area influenced by sea tides. Mapping the quality of water with hyperspectral data is confounded by vegetation, either dry or wet, rooted or floating. The spectral features of acidic water measured with a field spectrometer revealed the spectral influence of green vegetation, similar to the influence of the depth and transparency of water. Careful mapping of such parameters with HyMap data must therefore precede any spectral evaluation of water related to acidity in a river course. The spectral features detectable by HyMap data and associated with pH changes caused by contamination in river water by iron sulphide mine waste, and their controls, are described and references established for routine monitoring through hyperspectral image processing. [ABSTRACT FROM AUTHOR]

This study investigates the behavior of Tl in the Ría de Huelva (SW Spain), one of the most metal polluted estuaries in the world. Dissolved Tl concentration displayed a general decrease across the estuary during the dry season (DS); from 5.0 to 0.34 μg/L in the Tinto and Odiel estuaries, respectively, to 0.02 μg/L in the channel where the rivers join. A slighter decrease was observed during the wet season (WS) (from 0.72 to 0.14 μg/L to 0.02 μg/L) due to the dilution effect of rainfalls in the watersheds. These values are 3 orders of magnitude higher than those reported in other estuaries worldwide. Different increases in Tl concentrations with salinity were observed in the upper reaches of the Tinto and Odiel estuaries, attributed to desorption processes from particulate matter. Chemical and mineralogical evidences of particulate matter, point at Fe minerals (i.e. , jarosite) as main drivers of Tl particulate transport in the estuary. Unlike other estuaries worldwide, where a fast sorption process onto particulate matter commonly takes place, Tl is mainly desorbed from particulate matter in the Tinto and Odiel estuaries. Thus, Tl may be released back from jarositic particulate matter across the salinity gradient due to the increasing proportion of unreactive TlCl0 and K+ ions, which compete for adsorption sites with Tl+ at increasing salinities. A mixing model based on conservative elements revealed a 6-fold increase in Tl concentrations related to desorption processes. However, mining spills like that occurred in May 2017 may contribute to enhance dissolved and particulate Tl concentrations in the estuary as well as to magnify these desorption processes (up to around 1100% of Tl release), highlighting the impact of the mine spill on the remobilization of Tl from the suspended matter to the water column. [Display omitted] • Tl partitioning was investigated in a metal-impacted estuary. • Dissolved concentrations of 5.0–0.34 μg/L of Tl were reported in estuarine waters. • Tl concentrations 3 orders of magnitude higher than in other estuaries worldwide. • Competition between Tl+ and K+ ions for sorption sites control Tl mobility. • A mixing model revealed 6-fold increase in dissolved Tl concentration by desorption. [ABSTRACT FROM AUTHOR]

The present work aims to propose a methodology for quantifying the sources of acid mine drainage (AMD) and to characterize the magnitude of the affected areas in the Iberian Pyrite Belt (SW Spain). Such an approach allows the creation of a support tool for managing land and natural resources valorization, which may be easily applied in similar mining regions. The motivation and usefulness of this work can be realized by focusing on two main emerging strategic issues: (1) water resources management, with the example of Alcolea dam that will receive water from affected areas in the Iberian Pyrite Belt; and (2) mineral resources valorization, especially, regarding copper exploration due to increasing market prices. The used methodology included the following general steps: it started with an inventory of the mines in the Iberian Pyrite Belt, followed by field cartography campaigns and finally the quantification of affected areas and contaminant discharges. The results of the present work serve to confirm and quantify the magnitude of the AMD pollution in the Pyrite Belt. A total affected area of about 4,847 ha was estimated. Taking into account this figure and combining it with the annual average precipitation (650 L/m) results in an estimation of 31,503,680 m/year of discharging water affected by the presence of sulphides. In this scenario, a total annual contribution of 260,056 tonnes/year was obtained for sulphates, which means more than 712 tonnes a day. In the case of arsenic, a toxic element, the total annual contribution is more than 20 tonnes, or close to 55 kg/day. Regarding copper, this economically interesting metal translates into total contributions of 10,364 tonnes/year in the generating medium. This gave more than 28 tonnes/day, which today sits at 8,200 dollars/tonne. This result suggests that solutions aimed at recovering this resource should be searched. It may represent a financial return at the same time that it would mean overcome environmental liabilities. [ABSTRACT FROM AUTHOR]

Highlights: [•] This paper describes solid phases associated to AMD in a massive sulfide deposit. [•] The study was performed in Tharsis mines, in the Iberian Pyrite Belt. [•] The AMD-precipitates are dominated by efflorescent sulfate minerals. [•] There are two mineralogical environments differentiated by composition and variety. [•] The open pits reflect a proximal paragenesis; the Meca River reflects a distal one. [Copyright &y& Elsevier]

• The extreme conditions of these PG stacks hide an unexpected microbial diversity. • The prokaryotic profile includes acidophilic bacteria found in AMD environments. • Archaea, cyanobacteria, and sulfate-reducing bacteria are practically absent. • The high presence of microalgae in the piezometer denotes seawater influence. • The eukaryotic population in the PG is different from that of the AMD environments. • PG new strains might have unique potential biotechnological applications. Around 100 Mt of phosphogypsum (PG) have been deposited in large stacks on the salt marshes of the Tinto River estuary in Huelva (SW Spain), covering about 1000 ha. These stacks contain extremely acidic water (pH < 2) with high concentrations of pollutants which can cause emissions into their surroundings, generating important environmental concerns. Despite many chemical, geological or hydrological studies have been conducted to characterize the PG stacks of Huelva, the microbial community inhabiting this extreme environment remains unexplored. Using a 16S/18S-rRNA-high throughput sequencing approach, we have uncovered the main taxonomic groups able to live in the acidic metal-contaminated water, which is in direct contact with the PG, demonstrating for the first time the existence of a huge diversity of microbial species in these extreme conditions. In addition, the physicochemical characteristics of the water sampled have been analyzed. These studies have revealed that the most abundant bacteria found in two different leachate samples of the PG stacks belong to the genera Acidiphilium, Pseudomonas, Leptosprillum, Acidithrix, or Acidithiobacillus , typically found in acid mine drainage (AMD) environments, which in total represent around 50% of the total bacterial community. Biodiversity of eukaryotes in PG water is lower than that of prokaryotes, especially in the water collected from the perimeter channel that surrounds the PG stacks, where the pH reaches a value of 1.5 and the activity concentrations exceed 300 Bq L−1 for 238U or 20 Bq L−1 for 210Po, values which are from four to five orders of magnitude higher than those usually found in unperturbed surface waters. Even so, an unexpected diversity of algae, fungi, and ciliates have been found in the PG stacks of Huelva, where chlorophyte microalgae and basidiomycetes fungi are the most abundant eukaryotes. Additional bioinformatics tools have been used to perform a functional analysis and predict the most common metabolic pathways in the PG microbiota. The obtained data indicate that the extreme conditions of these PG stacks hide an unexpected microbial diversity, which can play an important role in the dynamics of the contaminating compounds of the PG and provide new strains with unique biotechnological applications. [ABSTRACT FROM AUTHOR]

Bacterial and archaeal community structures and diversity of three different sedimentary environments (BH1A, BH2A and BH3A) in the acid pit lake of a chalcopyrite mine at Touro (Spain) were determined by 16S rRNA gene PCR-DGGE and sequencing of clone libraries. DGGE of bacterial and archaeal amplicons showed that the sediments harbor different communities. Bacterial 16S rRNA gene sequences were assigned to Acidobacteria, Actinobacteria, Cyanobacteria, Planctomycetes, Proteobacteria, Chloroflexi and uncultured bacteria, after clustering into 42 operational taxonomic units (OTUs). OTU 2 represented approximately 37, 42 and 37 % of all sequences from sediments BH1A, BH2A and BH3A, respectively, and was phylogenetically related to uncultured Chloroflexi. Remaining OTUs were phylogenetically related to heterotrophic bacteria, including representatives of Ferrithrix and Acidobacterium genera. Archaeal 16S rRNA gene sequences were clustered into 54 OTUs. Most of the sequences from the BH1A sediment were assigned to Euryarchaeota, whereas those from BH2A sediment were assigned to Crenarchaeota. The majority of the sequences from BH3A sediment were assigned to unclassified Archaea, and showed similarities to uncultured and unclassified environmental clones. No sequences related to Acidithiobacillus and Leptospirillum, commonly associated with acid mine drainage, were detected in this study. [ABSTRACT FROM AUTHOR]

The abandoned mining districts of the Iberian Pyrite Belt (IPB, SW Spain) are an extreme source of pollution by acid mine drainage (AMD) to the Tinto and Odiel rivers. The pollutant flux transported by the Odiel River during a high stage period was assessed using concentration–discharge relationships and concentration–conductivity relationships, for the hydrological year 2009/10 (which was especially wet). Both correlations were high (R2 >0.80) for most of the elements studied. The two methods for flux calculation gave similar results with differences generally lower than 10%. The dissolved contaminant flux transported by the Odiel River just before its mouth mainly includes sulphate (257,534±13,464t/yr), Al (13,259±1071t/yr), Zn (4265±242t/yr), Mn (2532±146t/yr) and Cu (1738±136t/yr), and minor amounts of other elements. These findings confirm that, up to our knowledge, the Odiel River can be considered to be the largest contributor of mining-related pollutants to the world's oceans. [ABSTRACT FROM AUTHOR]

In the Iberian Pyrite Belt (IPB), the process of acid mine drainage (AMD) is anthropogenic in origin. The impact of AMD pollution processes is characterised in 23 dams in the IPB. Based on the pH values, three groups are established: group 1 (pH <3), group 2 (pH 3-5) and group 3 (pH >5). Group 1 has the lowest pH values, with all of them lower than 3 and a minimum value of 1.9. The pH values are higher in the other groups, with lower values in group 2 (between 2.34 and 6.15) and higher in group 3 (between 4.36 and 7.58). Conductivity is higher in group 1 (varying between 1,005 and 12,280 μScm), while it takes intermediate values in group 2 (between 139 and 2,652 μScm), and group 3 is the lowest (between 80 and 750 μScm). Among the ions analysed, the concentration of sulphates stands out due to its magnitude, which is always greater than that of the other ions in the three groups. It is in group 1 that it reaches the highest values, with 6,200 mg/L, while it is lower in the others. Applying variable cluster analysis shows that in group 1, pH exercises control over the dissolution of most of the metals. It is also sulphates that control the value for conductivity. In group 2, precipitation is the main variable that controls the dissolution of ions, with the influence of pH being lower. In group 3, it is observed that in pH control metals, conductivity is controlled by sulphates. [ABSTRACT FROM AUTHOR]

Abstract: A detailed study of two adjacent mine tailings impoundments comparing mineralogical and geochemical analyses of the solids with geochemical analysis of the pore-water and -gas was carried out in the Monte Romero sulfide mining district (Iberian Pyrite Belt, SW Spain). Since 1978, both facilities have been exposed to weathering in a semi-arid climate with dry-warm and wet-rainy seasons. In these impoundments, sulfide oxidation releases sulfate and contaminants to the pore-water that are transported and concentrated by evaporation in the top surface of the tailings, causing precipitation of soluble iron sulfate salts in dry seasons. These salts act as temporary sinks for minor elements such as Cd, Co, Zn, Ni, Cu and Mn, which are again released during rainfall events in wet seasons. Stored flotation tailings have an average pyrite content of 30wt.% although average amounts up to 80% are present in the upper 50cm of one of the impoundments. According to the results of the current study, this difference is key to control the oxidation model in both tailings. In the impoundment containing 30wt.% of pyrite, pore-water pH increases in wet periods to 3.1 average by rainwater dilution, causing supersaturation and precipitation of secondary Fe(III) phases such as jarosite, goethite and schwertmannite. Consequently, this impoundment shows a 20–25cm thick yellowish oxidation layer in the top part. In contrast, in the impoundment containing 80wt.% of pyrite in the top part extremely acidic pore-waters (pH<0.5) are present in both dry and wet seasons, and no precipitation of secondary Fe(III) phases occurs in the oxidation zone. The absence of secondary precipitates explains the apparent unweathered aspect of these tailings, in spite of its much higher remobilization of contaminants to the surface runoff or groundwaters. [Copyright &y& Elsevier]

Abstract: The Tinto River estuary is one of the most contaminated coastal systems in the world due to the high amounts of pollutants this acidic river transports. The tidal influence and the fluvial discharges control the water mixing, which include a salt-induced process (that is typical of all estuaries) and an acid neutralization process (pH-induced mixing). These processes affect the geochemical behavior of uranium, which has a non-conservative pattern. Despite the high concentrations of dissolved uranium in the Tinto River, 234U/238U shows that uranium stems mostly from seawater (between 80 and 100%). Riverine uranium is adsorbed onto both Fe and Al precipitates when the acidic river water is mixed with seawater. Distribution coefficients (Kd) show that dissolved and particulate uranium are controlled by adsorption–desorption processes and the formation of carbonate complexes, both depending on pH. At low pH, uranium tends to be dissolved, and the adsorption by suspended particles is low. As the pH increases, the adsorption processes onto Fe and Al particles are more intense, increasing particulate uranium which reaches a maximum at pH 5.5, where the uranium solubility minimum occurs. At higher pH values, dissolved uranium increases by carbonate complexation. [Copyright &y& Elsevier]