An integrated chemical and mineralogical characterization approach was applied to smelter wastes collected from 50-year-old dump sites in Argentina. Characterization included pseudo-total element concentrations, acid generation/neutralization potential, sequential extractions, pH-dependent leaching kinetics, and mineralogical analysis of all residues. These analyses provided detailed information on the reactivity of the minerals in the waste material and associated metal release. Cadmium and Zn were the elements of greatest environmental concern due to their high mobility. On average, the release of Zn and Cd in pH-dependent leaching essays reached 17.6% (up to 5.24 mg g-1) and 52.7% (up to 0.02 mg g-1) of the pseudo-total content, respectively. Moreover, Cd and Zn were also the metals that showed the higher proportions of labile fractions associated to the adsorbed and exchangeable fraction (60-92% for Cd and 19-38% for Zn). Since Cd and Zn concentrations in the residue are not high enough to form their own minerals, a large proportion of these elements would be weakly adsorbed on Fe oxyhydroxides. In contrast, the low release of Cu, Pb and Fe would be associated with these elements being incorporated into the crystalline structure of insoluble or very poorly soluble minerals. Lead is incorporated into plumbojarosite and anglesite. Copper was mainly in association with Fe oxyhydroxides and may also have been incorporated into the plumbojarosite structure. The latter could act as a sink especially for Pb under the acidic conditions of the smelter residue. Despite the elevated concentrations of Pb observed in the residue, it showed a very low mobility (≈0.1%), indicating that it is mostly stabilized. Nevertheless, the smelter residue is a continuous source of metals requiring remediation.

Iron phosphate-based coating and iron silicate-based coating were used to inhibit the oxidation of sulfide minerals in rainy and submerged environments. The inhibiting effectiveness of coating agents on the oxidation of iron sulfide minerals was investigated using pyrite and rock samples resulting from acid drainage. The film formed with both surface-coating agents was identified by pyrite surface analysis. It was also confirmed that the formation of coatings varies depending on the crystallographic orientation. The inhibitory effects under rainy and submerged conditions were investigated using column experiments. Submerged conditions accelerated deterioration compared to that under rainy conditions. Iron phosphate coating had a significantly better oxidation-inhibitory effect (84.86-98.70%) than iron silicate coating (56.80-92.36%), and at a concentration of 300 mM, H+ elution was inhibited by more than 90% throughout the experiment. Furthermore, methods for effective film formation were investigated in terms of producing Fe3+; (1) application of coating agents mixed with oxidant (H2O2), (2) application of coating agent after the use of the oxidant. In a rainy environment, applying iron phosphate-based coating using the sequential method showed oxidation inhibition effects for cycles 1-9, whereas applying the mixed material showed effects for cycles 9-13. The use of a surface-coating agent after applying an oxidant did not inhibit oxidation. The surface coating agent and the oxidizing agent should be applied as a mixture to form a film.

Contaminated groundwater is a serious problem in developed countries. The abandonment of industrial waste may lead to acid drainage affecting groundwater and severely impacting the environment and urban infrastructure. We examined the hydrogeology and hydrochemistry of an urban area in Almozara (Zaragoza, Spain); built over an old industrial zone, with pyrite roasting waste deposits, there were acid drainage problems in underground car parks. Drilling and piezometer construction, and groundwater samples revealed the existence of a perched aquifer within old sulfide mill tailings, where the building basements interrupted groundwater flow, leading to a water stagnation zone that reached extreme acidity values (pH < 2). A groundwater flow reactive transport model was developed using PHAST to reproduce flow and groundwater chemistry, in order to be used as a predictive tool for guiding remediation actions. The model reproduced the measured groundwater chemistry by simulating the kinetically controlled pyrite and portlandite dissolution. The model predicts that an extreme acidity front (pH < 2), coincident with the Fe (III) pyrite oxidation mechanism taking dominance, is propagating by 30 m/year if constant flow is assumed. The incomplete dissolution of residual pyrite (up to 18 % dissolved) predicted by the model indicates that the acid drainage is limited by the flow regime rather than sulfide availability. The installation of additional water collectors between the recharge source and the stagnation zone has been proposed, together with periodic pumping of the stagnation zone. The study findings are expected to serve as a useful background for the assessment of acid drainage in urban areas, since urbanization of old industrial land is rapidly increasing worldwide.

This paper consists of the evaluation in regards to the ecotoxicological effectiveness of a treatment applied to a coal mining waste. The treatment consisted of separating the particles based on gravimetric concentration in spirals, generating three fractions: heavy, intermediate, and light, with high, moderate, and low pyrite content, respectively. The intermediate fraction represents the larger disposal volume of the waste on soils. To evaluate the effectiveness of the treatment, metal determination and bioassays Eisenia andrei, Folsomia candida, Lactuca sativa, Daphnia similis, and Raphidocelis subcapitata were applied to the intermediary fraction. To evaluate the toxicity to aquatic organisms, elutriates were generated from the unprocessed waste and the intermediate fraction. The intermediate fraction showed a decrease of metal concentrations compared to the untreated waste. Metal concentrations in the intermediate fraction were below the Brazilian thresholds for soil quality. Avoidance bioassay with E. andrei and germination tests of L. sativa showed no significant effects. The bioassay with F. candida indicated a significant reduction in reproduction at the highest doses used (24% and 50%). Bioassays with D. similis and R. subcapitata revealed a reduction in toxicity of the intermediate fraction compared to the untreated waste. However, the toxicity levels of the intermediate fraction to aquatic organisms still require attention, especially in regards to pH that played a crucial role in the toxicity. Finally, the results suggest that the treatment performed on the coal waste was efficient, even though significant toxicity have still been detected in the treated waste and additional steps are still required for adequate final disposal.

The fate of suspended solids in aqueous systems enriched with copper (Cu) and arsenic (As) is still poorly understood, especially in mildly acidic streams with natural turbidity. This study integrated field, laboratory, and modeling to determine how turbidity, particle size distribution, and the partition of Cu and As interact in two model river confluences in an Andean watershed (upper Elqui, North-Central Chile). The mildly acidic Toro River (40.4 mgL-1; CuTOTAL>8 mgL-1) was diluted and neutralized at two consecutive confluences, resulting in dissolved As and Cu lower than 0.04 and 0.1 mgL-1, respectively. On-site laser scattering measurements showed that the size of suspended sediments was dominated by ultrafine (d<6 μm) and fine (6200 μm) were not observed, contrasting with other reactive Andean confluences that work as natural coagulation-flocculation reactors. Laboratory mixing experiments with filtered endmembers followed closely the trends observed in the field measurements. SEM observations and thermodynamic calculations, suggested that As-rich amorphous Fe minerals dominated the fine suspended solid inflow (d<15 μm) from the Toro River, while XRD did not reveal significant amounts of crystalline forms of Fe, As, or Cu minerals. Despite fresh precipitates that further associated dissolved As and Cu, the particles from the Toro River grew only slightly after the confluences, thus limiting particle settling potential and a significant metal-(loid)s removal. Consequently, the seasonal variation in the size and chemical nature of suspended solids in acid drainage inflows control the distinct physical and chemical fates of As and Cu after neutralization, as well as hydrodynamic or hydraulic conditions likely also constrain sediment deposition. The combined monitoring of chemical parameters and particle size distributions is a simple and cost-effective method to obtain information about the behavior of metal(loid)s and sediments.

Acid and metalliferous drainage (AMD) is a major environmental issue resulting largely from exposure to weathering of mine wastes containing pyrite (FeS2). At-source strategies to reduce the rate of formation of AMD have potential to be more cost-effective and sustainable than post-generation downstream treatments. The objective of this study was to examine the efficacy of geochemical and microbial treatments for at-source control through pyrite surface passivation. Six kinetic leach columns (KLCs), using a mine waste containing 3.8 wt% pyrite, were subjected to various treatments: 1) untreated, 2) blended calcite, and applications of 3) calcite-saturated water, 4) lime-saturated water followed by calcite-saturated water, 5) biosolids extract water (providing a source of organic carbon to promote microbial growth) and 6) biosolids extract in calcite-saturated water. The untreated KLC leachate pH was on average 5.7 for the first 12 weeks, followed by a gradual decrease to pH 4.5 at week 52. This slow pH decrease is attributed to neutralisation released upon Mg-siderite dissolution. The leachate pH from all treated KLCs was near-neutral at the end of the tests. Pyrite was surface-passivated and leaching supressed by all treatments except for calcite-saturated water. Leaching of Mn and Zn from the untreated waste identified the potential for adverse environmental impact. No evidence was found for surface passivation of Zn- or Mn-containing minerals in the treated KLCs. Blended calcite addition and lime-saturated water followed by calcite-saturated water were most effective at reducing release of Zn and Mn, likely due to precipitation as hydroxides/carbonates.

The fate of copper (Cu) in rivers impacted by acid drainage remains poorly studied in waters with comparatively low Al and Fe concentrations. This work addresses the role of confluences in controlling the physical and chemical fate of Cu in a system with total molar ratio Cu/Al > 0.2 and Cu/Fe > 0.15. Two consecutive confluences were studied in the upper Mapocho watershed, a densely populated basin with intensive mining located in the Chilean Andes. The inflow had acidic conditions with seasonal variations and Cu up to 9 mg L-1. Lability measurements with diffusive gradient in thin films showed that Cu entered as a dissolved labile form. However, downstream from the confluences a higher pH shifted Cu toward nonlabile compounds and solid phases enriched with Cu. Measurements of x-ray absorption spectroscopy of freshly formed particles showed that composition was dominated by sorbed Cu and Cu(OH)2(s) precipitates, with a higher proportion of sorbed Cu downstream from confluences when pH < 5. Particle size distributions (PSD) measured in field showed that downstream from the confluences the total volume and average diameter of the suspended particles grew progressively, with estimated mean settling velocities increasing from 0.3 to 4.2 cm s-1. As a result, 7-30% of the influent Cu was removed from the river flow. These results highlight that shifts in chemical partition and PSDs in river confluences and the hydrodynamic environments at the river reach level control the mobility of Cu in systems with high Cu/Al and Cu/Fe.

Neutralisation of acid drainage creates metal-rich precipitates that may impact receiving water bodies. This study assessed the fate of over seven years of acid drainage discharges on the sediments of the lower River Murray (Australia), including the potential for periodic water anoxia to enhance risk via reductive dissolution of amorphous (Fe, Mn and co-precipitated and bound metal) oxide phases. With the exception of one site with restricted water exchange, elevated reducible/reactive metal(oid) (Fe, Ni, As, Co, Zn) concentrations were only observed in the localised wetland-riparian area within approximately 100 m of the discharges. Only a minor exceedance of national sediment quality guideline values occurred for Ni. In the main river channel, elevated reactive metal (Fe, Mn, Ni, Zn) concentrations were also only observed less than approximately 100 m from the drainage discharge point. This appears due to (a) rapid neutralisation of pH leading to metal precipitation and deposition in the localised discharge area, and/or (b) dilution of any metal precipitates entering the main channel with natural river sediments, and/or (c) flushing of precipitates downstream during higher flow conditions. The influence of deoxygenation on metal release was profound with large increases in the concentration of dissolved Fe, Mn, Zn, Ni, and As in the overlying water during laboratory experimental simulations. However, given in situ sediment metal contamination is very localised, it appears on a river reach scale that the acid drainage precipitates will not significantly contribute, over and above, the background release of these metals during these conditions.

A global warming-induced transition from glacial to periglacial processes has been identified in mountainous regions around the world. Degrading permafrost in pristine periglacial environments can produce acid rock drainage (ARD) and cause severe ecological damage in areas underlain by sulfide-bearing bedrock. Limnological and paleolimnological approaches were used to assess and compare ARDs generated by rock glaciers, a typical landform of the mountain permafrost domain, and their effects on alpine headwater lakes with similar morphometric features and underlying bedrock geology, but characterized by different intensities of frost action in their catchments during the year. We argue that ARD and its effects on lakes are more severe in the alpine periglacial belt with mean annual air temperatures (MAAT) between -2°C and +3°C, where groundwater persists in the liquid phase for most of the year, in contrast to ARD in the periglacial belt where frost action dominates (MAAT < -2°C). The findings clearly suggest that the ambient air temperature is an important factor affecting the ARD production in alpine periglacial environments. Applying the paleoecological analysis of morphological abnormalities in chironomids through the past millennium, we tested and rejected the hypothesis that unfavorable conditions for aquatic life in the ARD-stressed lakes are largely related to the temperature increase over recent decades, responsible for the enhanced release of ARD contaminants. Our results indicate that the ARDs generated in the catchments are of a long-lasting nature and the frequency of chironomid morphological deformities was significantly higher during the Little Ice Age (LIA) than during pre- or post-LIA periods, suggesting that lower water temperatures may increase the adverse impacts of ARD on aquatic invertebrates. This highlights that temperature-mediated modulations of the metabolism and life cycle of aquatic organisms should be considered when reconstructing long-term trends in the ecotoxicological state of lakes.

Huelva Estuary is a transition zone where REE-rich acidic waters interact with saline-alkaline seawater. This mixing process influences the geochemical and mineralogical characteristics of particulate and dissolved fractions. The Tinto River has >11,000μgL-1 dissolved REE (pH=1.66), whereas seawater only reaches 8.75·10-2μgL-1 dissolved REE (pH=7.87). REE-normalized patterns in \"pH<6 solutions\" are parallel and show similarities, diminishing their concentration as pH increases. Sequential extraction performed on the generated precipitates of mixed solutions indicates that most REE are associated to the residual phase. In a second order, REE are associated with soluble salts at pH3 and 3.5 whereas in sediments generated at pH4 and 5, they are distributed in salts (1° extraction), poorly crystallized Fe-bearing minerals (schwertmannite, 3° extraction) and well crystallized Fe-bearing minerals (goethite - hematite, 4° extraction). Finally, precipitated REE are highest at pH6 newly formed minerals with a release to solution in higher pH.