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This study aims to evaluate the role of indigenous microorganisms in the mobilization of potentially toxic elements (PTE) and rare-earth elements (REE), the influence of the bioavailability of carbon sources that might boost microbial leaching, and the generation of neutral/alkaline mine drainage from alkaline tailings. These tailings, with significant concentrations of total organic carbon (TOC), were mainly colonized by bacteria belonging to the genera Sphingomonas, Novosphingobium and Solirubrobacter, and fungi of the genera Alternaria, Sarocladium and Aspergillus. Functionality analysis suggests the capability of these microorganisms to leach PTE and REE. Bio-/leaching tests confirmed the generation of neutral mine drainage, the influence of organic substrate, and the leaching of higher concentrations of PTE and REE due to the production of organic acids and siderophores by indigenous microorganisms. In addition, this study offers some insights into a sustainable alternative for reprocessing PMC alkaline tailings to recover REE., 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 Elsevier B.V. All rights reserved.)

Phthalateacid esters (PAEs) concentration in bottled water and different factors (water pH, storage time, sunlight exposure, and temperature) that affect/control them have become hot topics during recent years. Nevertheless, quite contradictory results and disagreements on the effects of these factors have been published. In an attempt to find some consensus on this topic, a comprehensive study considering the combined effect of long storage times (longer than a year) and the water hydrochemical signature (including water pH, elemental composition and the presence/absence of dissolved CO 2 )was performedusing the four most commonly consumed bottled water brands on the Chilean market. Each water brand was analyzed between 10 or 14 different times, depending on the brand (in total 97 samples were studied). Following the concept ofthe hydrochemical signature typically used in hydrogeology to classify types of waters, the notion of a water phthalate fingerprint was proposed. Finally, concerning the effect of long storage times, this study demonstrates that all the trends (increase, decrease or steady) of the Total PAEs concentration are possible; and these trends are controlled by the specific hydrochemical signatureandphthalate fingerprint of the bottled water., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The Mapocho River's upper basin (Chilean Central Andes) was studied as a proxy of a high-mountainous hydrothermally-altered (HMHA) system comprised by three sub-basins developed over very different rocks and submitted to different anthropic pressure: 1) a natural acid rock drainage (i.e., Yerba Loca), 2) a creek with mining activity in its headwaters and hydrochemically classified as non-affected by acid mine drainage (i.e., San Francisco), and 3) a low metal concentration creek (i.e., Molina). In general terms, the geochemical composition of the clastic sediments was consistent with the geochemistry inferred from the mineralogical study. However, sediments with a smaller grain size showed higher concentrations than the bigger grain size counterparts for elements such as Fe, S, Cu and As. This behavior was particularly evident in the Yerba Loca basin and it was attributed to the seasonal appearance of Fe- and Al-rich precipitates as constituents of the finer sediments. Different methodologies for the calculation of geochemical backgrounds (Tukey's inner fence, TIF; Median + 2*Median Absolute Deviation, MAD; and 95th percentile) were tested. Results suggest that the 95th percentile-method was the most appropriate for this type of mountainous systems. Using the selected methodology, three different geochemical backgrounds were calculated: 1) Yerba Loca basin, 2) Molina basin, and 3) Mapocho Upper basin. When the generated background levels were compared with the Consensus-Based (CB) Sediment Quality Guidelines; Fe, Mn, Zn, Pb, Cu, Cr, Ni and As showed background values that were consistently higher than the values set by the CB Threshold Effect Concentration and, even higher than the CB Probable Effect Concentration for Fe (MUB Background : 6.78 wt% vs CB PEC: 4.00 wt%; and Cu (MUB Bacground : 3387 mg kg -1 vs CB PEC: 149 mg kg -1 ). The present study clearly states the paramount importance of having a solid geochemical background before any attempt of a sediment risk assessment is made at HMHA regions., 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 Elsevier B.V. All rights reserved.)

Inorganic polymers in aqueous solutions are being proposed as essential components in new theories concerning nonclassical nucleation and growth of nanominerals relevant to environmental nanogeosciences. The study of those complex natural processes requires multi-technique analytical approaches able to characterize the solutions and their constituents (solutes, oligomers, polymers, clusters and nanominerals) from atomic to micrometric scales. A novel analytical approach involving an electrospray ionization source (ESI) coupled to time-of-flight mass spectrometry (TOF/MS) was developed to identify inorganic polymers in aqueous solution. To this end, the presence of initial Al oligomers and their polymerization processes was studied during a nanomineral aqueous synthesis (hydrobasaluminte, Al 4 SO 4 (OH) 10 ·12-36H 2 O). Ensuring the feasibility and robustness of the methodology as well as the stability of the polymers under study (avoiding undesirable fragmentation), a meticulous study of the ESI-TOF MS working conditions was performed. Precision of the methodology was evaluated obtaining relative standard deviations below 3.3%. For the first time in the study of inorganic polymers in the earth sciences, the mass accuracy error (ppm) has been reported and the use of significant decimal figures of the m/z signal has been taken into account. Complementary to this, a four-step polymer assignment methodology and a database with the Al - and Al-SO 4 2- polymers assigned were created. Several polymers have been assigned for the first time, including Al (SO 4 ) + ·H 2 O, Al 2 O(SO 4 ) 2+ ·H 2 O, Al 5 O 4 (OH) 5 2+ ·2H 2 O, and Al 3 O 5 (OH) 2- ·4H 2 O, among others. The results obtained in the present study help create a foundation to include mass spectrometry as a routine analytical technique to study mineral formation in aqueous solution., (© 2019 John Wiley & Sons, Ltd.)

Mining residues management is one of the greatest challenges for mining companies around the world. The increasing consciousness of the general public and governments about the potential threat that those residues can pose to the environment is demanding consistent and precise methodologies for assessing the potential release of toxic metals. On this regard, the modified BCR ® sequential extraction procedure (SEP) is frequently the chosen assessing protocol. However, this protocol was designed to study soils and sediments with low to moderate metal pollution, and validation of its applicability to mining residues is missing. The present research covers this gap of knowledge by subjecting selected highly polluted mining residues to the modified BCR ® SEP. On the light of these results, it was confirmed that most of the metal bearing minerals in the mining residues were not completely dissolved in the corresponding SEP and, therefore, the application of BCR ® SEP to mining residues systematically leads to an underestimation of metals mobility. The necessary changes to optimize the BCR ® SEP to study mining residues would set a extraction procedure distinctively different from the original; thus it is strongly recommended to use alternative approaches to assess toxic metals mobility in highly polluted mining residues., (Copyright © 2018 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.

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

The Iberian Pyrite Belt (IPB), SW Spain and Portugal, contains about 100 abandoned mine wastes and galleries that release acid mine drainages (AMD) to the Tinto and Odiel rivers. In situ passive remediation technologies are especially suitable to remediate the drainages of these orphan sites. However, traditional remediation systems, designed for coal mines, have been demonstrated inefficient to treat the IPB mine waters. Due to their high acidity and metal loads, large amount of solids precipitate and fast clogging of porosity or passivation (coating) of the reactive grains occurs. To overcome these problems, the dispersed alkaline substrate (DAS) a mixture of fine-grained limestone sand and a coarse inert matrix (e.g., wood shavings) was developed. The small grains provide a large reactive surface and dissolve almost completely before the growing layer of precipitates passivates the substrate. The high porosity retards clogging. However, calcite dissolution only raises pH to values around 6.5, at which the hydroxides of trivalent metals (Al and Fe) precipitate, but it is not high enough to remove divalent metals. Caustic magnesia (MgO) buffers the solution pH between 8.5 and 10. A DAS system replacing limestone with caustic magnesia has been tested to be very efficient to remove divalent metals (Zn, Cd, Mn, Cu, Co, Ni, and Pb) from the water previously treated with calcite.

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

As acid mine drainage (AMD) remediation is increasingly faced by governments and mining industries worldwide, the generation of metal-rich solid residues from the treatments plants is concomitantly raising. A proper environmental management of these metal-rich wastes requires a detailed characterization of the metal mobility as well as an assessment of this new residues stability. The European standard leaching test EN 12457-2, the US EPA TCLP test and the BCR sequential extraction procedure were selected to address the environmental assessment of dispersed alkaline substrate (DAS) residues generated in AMD passive treatment systems. Significant discrepancies were observed in the hazardousness classification of the residues according to the TCLP or EN 12457-2 test. Furthermore, the absence of some important metals (like Fe or Al) in the regulatory limits employed in both leaching tests severely restricts their applicability for metal-rich wastes. The results obtained in the BCR sequential extraction suggest an important influence of the landfill environmental conditions on the metals released from the wastes. To ensure a complete stability of the pollutants in the studied DAS-wastes the contact with water or any other leaching solutions must be avoided and a dry environment needs to be provided in the landfill disposal selected., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Acid mine drainage (AMD) from the Iberian Pyrite Belt has high acidity and metal concentrations. Earlier pilot experiments, based on limestone sand dispersed in wood shavings (dispersed alkaline substrate; DAS) have been shown to be an efficient treatment option. However, complete metal removal was not achieved, principally due to the high ferrous iron concentration in the inflow AMD. In order to oxidize and remove iron, a natural Fe-oxidizing lagoon (NFOL) was added prior to treatment with limestone-DAS. The NFOL comprises several pre-existing Fe-stromatolite terraces and cascades, and a lagoon with a volume of 100 m(3) built near the mine shaft. Downstream of the NFOL, the limestone-DAS treatment consists of two reactive tanks of 3 m(3) each filled with limestone-DAS reactive substrate, connected in series with two decantation ponds of 6 m(3) each and several oxidation cascades. The AMD emerging from the mine shaft displayed a pH near 3, a net acidity of 1800 mg/L as CaCO(3) equivalents, and mean concentrations of 440 mg/L Zn; 275 mg/L Fe (99% Fe(II)); 3600 mg/L SO(4); 250 mg/L Ca; 100 mg/L Al; 15 mg/L Mn; 5 mg/L Cu; and 0.1-1 mg/L As, Pb, Cr, Cd, Co, and Ni. The oxidation induced in the NFOL enhanced ferric iron concentration, showing an average of 65% oxidation and 38% retention during the monitoring period. The whole system removed a mean of 1350 mg/L net acidity as CaCO(3) equivalents (71% of inflow); corresponding to 100% of Fe, Al, Cu, Pb and As, and 6% of Zn., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Several experiments were conducted to evaluate zinc-tolerance of sulfate-reducing bacteria (SRB) obtained from three environmental samples, two inocula from sulfide-mining districts and another inoculum from a wastewater treatment plant. The populations of SRB resisted zinc concentrations of 260 mg/L for 42 days in a sulfate-rich medium. During the experiments, sulfate was reduced to sulfide and concentrations in solution decreased. Zinc concentrations also decreased from 260 mg/L to values below detection limit. Both decreases were consistent with the precipitation of newly-formed sphalerite and wurtzite, two polymorphs of ZnS, forming <2.5-μm-diameter spherical aggregates identified by microscopy and synchrotron-μ-XRD. Sulfate and zinc are present in high concentrations in acid mine drainage (AMD) even after passive treatments based on limestone dissolution. The implementation of a SRB-based zinc removal step in these systems could completely reduce the mobility of all metals, which would improve the quality of stream sediments, water and soils in AMD-affected landscapes., (Copyright © 2012 Elsevier B.V. All rights reserved.)

During 20 months of proper operation the full scale passive treatment in Mina Esperanza (SW Spain) produced around 100 mg/L of ferric iron in the aeration cascades, removing an average net acidity up to 1500 mg/L as CaCO(3) and not having any significant clogging problem. Complete Al, As, Cd, Cr, Cu, Ti and V removal from the water was accomplished through almost the entire operation time while Fe removal ranged between 170 and 620 mg/L. The system operated at a mean inflow rate of 43 m(3)/day achieving an acid load reduction of 597 g·(m(2) day)(-1), more than 10 times higher than the generally accepted 40 g·(m(2) day)(-1) value commonly used as a passive treatment system designing criteria. The high performance achieved by the passive treatment system at Mina Esperanza demonstrates that this innovative treatment design is a simple, efficient and long lasting remediation option to treat highly polluted acid mine drainage., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Metal contamination from acid mine drainage (AMD) is a serious problem in the southwest of the Iberian Peninsula, where the Iberian Pyrite Belt is located. This zone contains original sulfide reserves of about 1700Mt distributed among more than 50 massive sulfide deposits. Weathering of these minerals releases to the waters significant quantities of toxic elements, which severely affect the sediments and surface waters of the region. The main goal of this paper is to evaluate the toxicity and the potential risk associated with the mining areas using Microtox test and different factors which assess the degree of contamination of the sediments and waters. For this, a natural stream polluted by AMD-discharge from an abandoned mine has been studied. The results show that elevated concentrations of Cu, As and Zn involve an important potential risk on the aquatic environment, associated both with sediments and waters. Microtox test informs that the sediments are extremely or very toxic, mainly related to concentrations of Fe, As, Cr, Al, Cd, Cu and Zn. Pollution is mainly transferred to the sediments increasing their potential toxicity. A natural creek affected by AMD can store a huge amount of pollution in its sediments while exhibiting a not very low water pH and low water metal concentration., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Synchrotron radiation-induced micro-X-ray analysis were applied to characterize the newly formed phases that precipitate in a passive treatment system using magnesium oxide to remove high concentrations of zinc (ca. 440 mg/L) and other minor metals from neutral pretreated waters in the Iberian Pyrite Belt (SW Iberian Peninsula). Micro-X-ray fluorescence (μ-XRF) maps of polished samples were used to find spatial correlations among metals, pinpointing zones of interest where micro-X-ray diffraction (μ-XRD) data were exploited to identify the mineral phases responsible for metal retention. This coupled technique identified hydrozincite (Zn(5)(CO(3))(2)(OH)(6)) and minor loseyite ((Mn,Zn)(7)(CO(3))(2)(OH)(10)) as the mineral sinks for Zn and also other potentially toxic elements such as Co and Ni. Although hydrozincite retains traces of Mn, this metal is mainly retained by precipitation of loseyite. The precipitation of zinc hydroxy-carbonates and their ability to uptake other metals (Mn, Co, and Ni) is hence of potential interest not only for the treatment of contaminated waters but also for the generation of a solid waste that could be exploited as a new Zn economic resource.

Three laboratory column experiments were performed to test the suitability of two different MgO-rich reagents for removal of Mn and Al from the out-flowing waters of Shilbottle passive treatment system (Northumberland, UK). The input water was doped with 100 mg/L Zn in order to extrapolate results to waters in sulphide mining districts. One column was filled with a Dispersed Alkaline Substrate (DAS) containing 12.5% (v/v) caustic magnesia precipitator dust (CMPD) from Spain mixed with wood shavings, two columns were filled with DAS containing wood shavings and 12.5% or 25% (v/v), respectively, of dolomitic lime precipitator dust (DLPD) from Thrislington, UK. The two columns containing 12.5% of CMPD or DLPD completely removed the contaminants from the inflow water during the first 6 weeks of the experiment (mean removal of 88 mg/L Al, 96 mg/L Zn and 37 mg/L Mn), operating at an acidity load of 140 g acidity/m(2)day. At this moment, a substantial increase of the Al and Mn water concentration in the out-flowing waters of Shilbottle occurred (430 g acidity/m(2)day), leading to passivation of the reactive material and to the development of preferential flow paths within less than another 6 weeks, probably mainly due to Al precipitates. Al should be removed prior to MgO treatment., (Copyright 2010 Elsevier B.V. All rights reserved.)