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In mining areas in which sulfur-containing ores are exposed, the oxidation of sulfides leads to the formation of acidic mine drainage (AMD) waters. Both traditional and molecular microbial studies have shown that chemolithotrophic sulfur- and iron-oxidizing bacteria are responsible for this activity. The Iberian Pyrite Belt (IPB), located in southwestern Spain represents one of the world’s largest accumulations of mine wastes and AMD waters. Mineralogical and textural characteristics of the IPB ores favor the oxidation and dissolution of pyrite and the subsequent formation of AMD waters. Acidic pit lakes in the IPB are a hotspot for this activity. These pit lakes are former open pit mines where ores have been exposed leading the formation of AMD waters. At present, there are more than 25 of these pit lakes between the provinces of Huelva and Seville (SW Spain). This work reports the physical properties, hydrogeochemical characteristics, and microbial diversity of two pit lakes located in the IPB Nuestra Señora del Carmen (NSC), and Concepción (CN). Both pit lakes are acid (pH 2-4) and showed chemical and thermal stratification with well defined chemoclines. One particular characteristic of NSC is that it has developed a chemocline very close to the surface (2 m depth). Microbial community composition of the water column was analyzed by 16S and 18S rRNA gene cloning and sequencing. The microorganisms detected in NSC are characteristic of acid mine drainage (AMD), including iron oxidizing bacteria (Leptospirillum) and facultative iron reducing bacteria and archaea (Acidithiobacillus ferrooxidans, Actinobacteria, Acidimicrobiales, Ferroplasma) detected in the bottom layer. Diversity in CN was higher than in NSC. Microorganisms known from AMD systems (Acidiphilium, Acidobacteria and Ferrovum) and microorganisms never reported from AMD systems were both identified.

Mineralogical characterization of the precipitates developed in passive systems treating mine-polluted waters is an essential tool to fully understand and control the removal processes taking place in these systems. In 2008, after five years of operation, a section of the permeable reactive barrier (PRB) at Shilbottle, Northumberland, was subjected to a low intrusive/non-destructive solid sampling. These solid samples were mineralogically characterized by XRD, ESEM-EDS, and sequential extractions. In addition to the solid sampling, 44 water samples obtained in the PRB from January 2004 to August 2009 were used to study the mineral stability of some selected phases in these waters. It was observed that the main iron phases in the PRB were those associated with mineral phases typically developed in non-reducing environments (schwertmannite and goethite), while the presence of a significant amount of pyrite was also observed. The low residence time of the water within the PRB (from 10 to 40 h) appears to be the reason for the absence of a more reducing and less acidic environment in the reactive substrate. An increase of residence time in the PRB, by increasing reactive mixture porosity and resizing the PRB, changes in the reactive material employed (smaller limestone grain size and inclusion of zerovalent iron) and changes in the PRB design (isolating top layer and forced homogeneous flow upward through all the reactive material) are proposed for future reconditioning of the system.

This work describes recent research carried out in an extremely acidic (pH 0.61–0.82) and hypersaline (e.g., 134 g/L SO4 2-, 74 g/L Fe, 7.5 g/L Al, 3 g/L Mg, 2 g/L Cu, 1 g/L Zn) leachate which seeps from a pyrite pile in San Telmo mine (Huelva, SW Spain) and forms evaporative pools of ultra-concentrated water in which attractive crystals of Zn-rich melanterite (FeIISO4 7H2O) are formed. Geochemical modeling with the Pitzer method indicates that the acidic brine was near saturation with respect to melanterite (SIMel = 0 ± 0.2). The microbiological investigation has revealed a surprisingly high biomass (1.4 × 106 cells mL−1) and an exotic ecosystem composed of acidophilic, Fe-oxidizing archaea (mainly Ferroplasma spp., representing 52% of the microbial population), and minor numbers of acidophilic bacteria (including Leptospirillum spp. (3.2%), Acidithiobacillus spp. (1.6%), and Alphaproteobacteria (2.8%)). The microbial production of FeIII allows the oxidative dissolution of pyrite and other sulphides, which results in additional inputs of FeII, SO4 2- and acidity to the system. The surfaces of the pyrite crystals show a typical etch-pitted texture, as well as blobs of elemental sulphur, which are both compatible with this indirect, microbially mediated oxidation mechanism. The composition of the acidic leachate seems to result from the combination of several processes which include: (1) formation of melanterite within the pile during relatively dry seasons, (2) subsequent dissolution of melanterite during rainy episodes, (3) microbial oxidation of FeII, (4) sulphide oxidation mediated by FeIII, (5) dissolution of chlorite and other aluminosilicates present in the pile, and (6) cooling and/or evaporation of seepage from the pile and consequent melanterite precipitation.

This study examines some relevant limnological and hydrogeochemical characteristics of 22 mine pit lakes of the Iberian Pyrite Belt (IPB). The studied pit lakes include some of the largest and historically most important mines of the IPB (including Corta Atalaya and Cerro Colorado in Riotinto, Filon Norte, Filon Centro and Filon Sur in Tharsis, Aznalcollar, or San Telmo) and many other of minor size. As a whole, these lakes constitute, at present, a large volume of highly acidic and metal-polluted water. Some of these pit lakes are very recent (e.g., Corta Atalaya, 2.5 a; Los Frailes, 6 a) and present a continuous hydrological and geochemical evolution, although many others were abandoned decades ago and show nearly constant water volume. Depth profiles obtained in several pit lakes (e.g., San Telmo, Confesionarios, Cueva de la Mora, Concepcion) indicate that many of them have developed meromixis and show, at present, a permanent thermal and chemical stratification with a well defined chemocline separating an anoxic, Fe(II)-rich monimolimnion, and a well mixed, oxygenated and Fe(III)-rich mixolimnion. In the upper layer, the bacterial oxidation of Fe(II) competes with photoreductive processes which take place in the surface water, thus provoking diel cycles of Fe(II) concentration. The observed water chemistry reflects the oxidation and dissolution of pyrite and other sulphides and gangue aluminosilicates from the country rock. The pit lakes of the IPB cover a wide range of water compositions, from circumneutral and relatively low-metal (e.g., Los Frailes, pH 7.2, 0.07 mg/L Fe, 3.8 mg/L Mn, 30 mg/L Zn), to extremely acidic and metal(loid)-rich (e.g., Corta Atalaya, pH 1.2, 36.7 g/L Fe, 6.7 g/L Zn, 1.3 g/L Cu, 159 mg/L As). Most pit lakes, however, are comprised within the pH range of 2.2–3.6 and appear to be strongly buffered by the hydrolysis and precipitation of Fe(III) in the form of schwertmannite, which forms colloids that can sorb trace elements from the aqueous phase.

The oxidation of Fe(II) in acidic mine waters emerging from the portals of abandoned mines (Lomero, Esperanza, Tharsis and Poderosa) of the Iberian Pyrite Belt (IPB) massive sulphide province, has been investigated. Field and laboratory studies have been performed in mine effluents with different iron concentrations (290 to 1940 mg/L Fe(II)) and pH (1.9–3.1) to calculate: (1) the reaction rates at which dissolved Fe(II) is oxidised to Fe(III) in the mine portals, (2) the hourly variations of these oxidation rates, and (3) the rate at which Fe(III) is subsequently hydrolyzed and precipitated as schwertmannite. The calculated field rates, between 5.5 × 10 − 6 and 4 × 10 − 7 mol L − 1 s − 1 , are characteristic of bacterial oxidation. A marked difference has been recognized between the different mine sites depending on the biomass density. The oxidation rates measured in the mine portals with dense biofilms of acidic slime streamers (Tharsis and Esperanza), are notably faster than those measured in the mine sites where streamers are not present (Lomero mine portal). Among the sites with the highest density of biofilms, pH also appears to control the oxidation rate, with the effluents of lowest pH (Poderosa mine, pH 1.9) showing slower rates than those with higher pH (Tharsis and Esperanza, pH 2.7–3.0). The oxidation kinetics of Fe(II) appears to be zero-order and highly dependent on the water temperature ( T ). Consequently, iron-oxidation rates vary significantly along the day, being minimum at the early morning and sunset (with T ∼ 15–25 °C), and maximum at midday (with T ∼ 25–35 °C). Laboratory oxidation studies performed with samples of these mine effluents have confirmed the influence of T , pH, dissolved oxygen content and biofilm presence/absence on the oxidation rate of Fe(II). Precipitation of Fe(III) takes place at pH 2.7–3.1 and rates ranging from 1.7 × 10 − 6 to 10 − 7 mol L − 1 s − 1 , also showing a daily cycle.

The geochemical evolution of two acid mine effluents in Tharsis and La Zarza-Perrunal mines (Iberian Pyrite Belt, Huelva, Spain) has been investigated. In origin, these waters present a low pH (2.2 and 3.1) and high concentrations of dissolved sulphate and metals (Fe, Al, Mn, Cu, Zn, As, Cd, Co, Cr, Ni). However, the natural evolution of these acidic waters (which includes the bacterial oxidation of Fe(II) and the subsequent precipitation of Fe(III) minerals) represents an efficient mechanism of attenuation. This self-mitigating process is evidenced by the formation of schwertmannite, which retains most of the iron load and, by sorption, toxic trace elements like As. The later mixing with pristine waters rises the pH and favours the total precipitation of Fe(III) at pH 3.5 and, subsequently, Al compounds at pH 4.5, along with the sorption of trace metals (Mn, Zn, Cu, Cd, Co, Ni) until chemical equilibrium at circumneutral conditions is achieved.

This work reports the physical properties and water chemistry of 64 AMD discharges from 25 different mines in the IPB draining to the Odiel river watershed, which have been investigated during the hydrologic year 2003–2004. These AMD solutions vary largely in flow rate and chemical composition both spatially (between the different mine sites, suggesting a strong geologic control on AMD chemistry) and seasonally (due to marked hydrologic variations), and include cases with very low pH (mostly in the range 1.4–4), and extreme sulphate (up to 44 g/L SO 4 2 - ) and metal content (e.g., up to 7.7 g/L Fe, 2.6 g/L Al, or 1.4 g/L Zn). Different hydrogeochemical facies of AMD (namely, Fe(II)/anoxic, Fe(III)/suboxic, and aluminous/oxic) are recognized in the field, as a response to the continuous oxidation and hydrolysis of dissolved Fe. Relevant geochemical aspects of these AMD environments are discussed, including: (i) the redox chemistry of the Fe(II)/Fe(III) couple, (ii) the reaction rates for bacterially catalyzed oxidation of Fe(II) and hydrolysis of Fe(III), (iii) the role played by dissolved Fe and Al in the acidity and chemical buffering of the AMD systems, and (iv) the solubility and trace metal retention capacity of the Fe oxyhydroxysulphate and hydrated sulphate minerals commonly associated with AMD. In addition, the mineralogy and chemistry of the Fe precipitates (schwertmannite, jarosite, goethite, ferrihydrite), Al phases (e.g., basaluminite) and Mg–Fe–Al efflorescent SO4 salts (e.g., epsomite, hexahydrite, copiapite, halotrichite, rozenite, coquimbite) present in the AMD-generating mine sites, have also been studied. The mineralogy of the Fe precipitates is well correlated with the water pH (with jarosite at pH ∼ 2, schwertmannite at pH 2–4, basaluminite at pH 4–5, and ferrihydrite at pH > 6). Schwertmannite appears to be the most important mineral phase, both in controlling the Fe solubility at pH 2–4, and as sorbent of trace elements (As, Cu, Zn), which favours natural attenuation. Finally, a basin-scale environmental perspective is given in order to evaluate the impact of AMD on the water quality, including calculation of metal loadings transported by AMD from the most important mine districts in the province.

Iron terraces that form in acidic mine drainage settings are unique and extreme geomicrobiological systems that can provide highly relevant information about the interaction between microbes and their surrounding aqueous environments. These singular systems can represent, additionally, potential models for the study of ancient geological formations (e.g., banded iron formations, stromatolites) and/or for the cycling of iron on Mars. This work describes geochemical, mineralogical, morphological, and microbiological evidence obtained in the highly acidic and Fe-rich Tintillo River (Riotinto mines, Huelva, SW Spain), which can be used to speculate about the origin and nature of the terraced iron formations (TIFs) that are being currently formed in acid mine drainage environments. The size (up to 36 m long and 1 m thick) and continuity (strong development over 3.5 km) of the iron terraces offer a unique opportunity to study the different organic (mainly microbial) and inorganic processes involved in the construction of these characteristic, travertine-like, sedimentary structures. Evidence presented in this study suggests that both types of processes appear to be controlling factors in the formation and internal arrangement of the TIFs, although no defi nitive evidence has been found to support the prevalence of any of these mechanisms with respect to another. The photosynthetic production of dissolved oxygen by eukaryotic microorganisms (green algae, euglenophytes, and diatoms) and the Fe-oxidizing metabolism of acidophilic prokaryotes are critical factors for the formation of TIFs, whereas abiotic parameters, such as water composition, fl ow rate and velocity, or stream channel geometry, also appear to be essential variables.