Elemental mercury (Hg0) is a metal with a number of atypical properties, which has resulted in its use in myriad anthropogenic processes. However, these same properties have also led to severe local subsurface contamination at many places where it has been used. As such, we studied the influence of various parameters on Hg(II) sorption onto pyrite (pH, time, Hg(II) concentration), a potential subsurface reactive barrier. Batch sorption studies revealed that total Hg(II) removal increases with both pH and time. X-ray absorption spectroscopy analysis showed that a transformation in the coordination environment at low pH occurred during aging over 2 weeks, to form an ordered monolayer of monodentate Hg–Cl complexes on pyrite. In column studies packed with pure quartz sand, the transport of Hg(II) was significantly retarded by the presence of a thin pyrite-sand reactive barrier, although dissolved oxygen inhibited Hg(II) sorption onto pyrite in the column. Pyrite may be an effective subsurface reactive barrier for Hg in groundwater.

The aim of the study was to determine whether the application of superphosphate fertiliser to soils contaminated with mine wastes can inhibit metal and metalloid mobility (Cu, Pb, Zn, Cd, Fe, Mn, As, Sb) in the long term. Contaminated soils contained sulfide- and sulfate-rich waste materials from the Broken Hill and Mt Isa mining centres. Results of long-term (10 months) column experiments demonstrate that fertiliser amendment had highly variable effects on the degree of metal and metalloid mobilisation and capture. Rapid release of metals from a sulfate-rich soil showed that phosphate amendment was ineffective in stabilising highly soluble metal-bearing phases. In a sulfide-rich soil with abundant organic matter, complexing of metals with soluble organic acids led to pronounced metal (mainly Cd, Cu and Zn) release from fertiliser-amended soils. The abundance of pyrite, as well as the addition of fertiliser, caused persistent acid production over time, which prevented the formation of insoluble metal phosphate phases and instead fostered an increased mobility of both metals and metalloids (As, Cd, Cu, Sb, Zn). By contrast, fertiliser application to a sulfide-rich soil with low organic carbon content and a sufficient acid buffering capacity to maintain near-neutral pH resulted in the immobilisation of Pb in the form of newly precipitated Pb phosphate phases. Thus, phosphate stabilisation was ineffective in suppressing metal and metalloid mobility from soils that were rich in organic matter, contained abundant pyrite and had a low acid buffering capacity. Phosphate stabilisation appears to be more effective for the in situ treatment of sulfide-rich soils that are distinctly enriched in Pb and contain insignificant concentrations of organic matter and other metals and metalloids.

In this work, the determination of moving averages is proposed as a method for quantifying metal, arsenic, and sulfate discharges into a water course undergoing acid mine drainage processes which flows into a public water supply dam in the Iberian Pyrite Belt. The analysis of the results obtained by applying moving averages shows that the highest metal and sulfate concentrations occur in October, coinciding with the first rainfall and the sponging of mine dumps, with November and December being the months when the highest contributions to the Andevalo Dam take place. The discharge of acid mine waters with its corresponding metal load into the Andevalo Dam means, for a single hydrological year, more than 6,000 t of sulfates, almost 600 t of iron, and 1 t of As, of special relevance for the hydrochemical quality of the stored waters. When they arrive at the dam, these metals precipitate, since the water pH is near 7, and remain latent in the bottom sediment as long as the chemical makeup of the dam water does not change.

Traditionally, the Guadiamar River (Seville, Southwest Spain) has received pollution from two different sources, in its upper section, from a pyrite exploitation (Los Frailes mine) and, in its lower section, from untreated urban and industrial wastes and from intensive agricultural activities. In 1998, the accidental spillage of about 6 million m3 of acid water and sludge from mine tailings to Guadiamar River worsened the pollution of an already contaminated area. The main polluting agents of the spillage were heavy metals. The total concentration of a metal provides scarce information about the effects on environmental processes or about the toxicity of the sediment samples. A more sophisticated fractionation of the sediment samples based on a species distribution can help to understand the behaviour and fate of the metals. This article describes a distribution study of the metals Al, Cd, Cu, Fe, Mn, Pb and Zn by fractionation analysis of sediments from eleven sample sites alongside the Guadiamar Riverbed. The samples were collected in summer 2002, four years after the spillage and after the area had been cleaned. Sequential extraction analysis resulted in the definition of four fraction categories: exchangeable metal (the most available fraction), reducible metal (bound to hydrous oxides of Fe and Mn), oxidizable metal (bound to organic matter and sulphides) and a residual fraction (bound to minerals). Significant increases in the available fraction of several potentially toxic metal ions like Cd, Mn and Zn were found. The distribution pattern was variable along the River. At the site closest to the mineworks, the soluble forms of Cd, Mn and Zn were significantly more abundant that those downstream. Cu and Pb were present in the reducible fraction while Fe was present associated in the residual fraction.

Nineteen soil samples (SE Spain) with very different chemical physical properties and developed over different parent materials were contaminated by adding increments of an acidic solution from oxidised pyrite tailings. The quantities of Cu, Zn, Cd and Pb precipitated by the soil samples were directly and significantly related to the pH-buffering capacity. However, when the contamination caused the pH to fall below 3.0 the soil tended to release a fraction of the element adsorbed, which increased as the pH decreased. The quantity of each precipitated element at which the action value for each element is reached, was also directly related to the pH-buffering capacity. Nevertheless, in carbonate-rich soils, the precipitated Cu and Zn maintained a relatively high level of bioavailability, while Cd reached a critical level with a content exceeding 25 mg kg⁻¹, regardless of the pH-buffering capacity.

The concentrations of As and Zn in 100 georeferenced soils uniformly distributed throughout the area affected by the spill from the Aznalcóllar mine (April 1998) were analysed at three depths (0-10, 10-30, and 30-50 cm) and on four dates (autumn-winter 1998, 1999, 2001, and 2004). For an estimate of the geochemical background, 30 unaffected soils near the edge of the spill were also analysed at the same depths. The soils were contaminated before the spill and, the accident seriously increased the concentration of As and Zn in the first 10 cm of almost all the affected soils. After the enormous efforts of cleaning up the tailings, around 45% of the soils had a concentration higher than 100 mg As kg⁻¹ dry soil, and some 35% had a concentration higher than 1,000 mg Zn kg⁻¹ dry soil. Both As and Zn penetrated between 10 and 30 cm in 25% and 45% of the soils, respectively, but reached 30 cm in only 12% of the soils. The remediation actions, especially the tilling and homogenisation of the uppermost 25 cm of the all soils, caused the As and Zn concentrations to decline in the soils, but this change was not very effective from the standpoint of pollution. Thus, 6 years after the spill, the uppermost 10 cm of 30% of the soils continued to have an As concentration higher than 100 mg As kg⁻¹, while the Zn concentration diminished considerably on the surface due to its greater mobility, accumulating between 10 and 30 cm in depth, where 20% of the soils continued to register more than 1,000 mg Zn kg⁻¹ dry soil.

Pyrite, FeS₂, is the most common sulfide mineral. The aim of this work was to assess the oxidative ability of H₂O₂ in presence of natural pyrite by employing reactive black 5, acid red GR, and cationic red X-GRL as model pollutants. The effects of H₂O₂ dosage, pyrite loading, and initial pH on reaction were investigated. The results reveal that natural pyrite-promoted H₂O₂ has a great activity in the decoloration of azo dyes. About 85 % of reactive black 5 and acid red GR can be removed within 10 min when 0.3 mM H₂O₂ and 0.3 g/L pyrite are used with initial pH values ranging from 6.32 to 6.96. The discoloration efficiencies are demonstrated to be less sensitive to the initial solution pH value. Approximately 90 % of discoloration for reactive black 5 and acid red GR can be achieved when initial pH value ranges from 2 to 10. Ion leaching experiments show that high levels of ferrous iron and sulfate can be detected when natural pyrite is added to dye solution alone. To gain an understanding of the reaction mechanism and the role of natural pyrite takes in these processes, techniques including scanning electron microscope, X-ray diffraction, and X-ray photoelectron were employed to characterize the solid sample and ion leaching experiments were also carried out. Results indicate that the determined high levels of ions have resulted from the dissolution of FeSO₄·H₂O formed on the surface of pyrite and the homogeneous Fenton reaction initiated by ferrous iron in presence of H₂O₂ is mainly responsible for the observed fast color removal rate.

The present research reproduces the chemical and microbiological reactions that occur naturally when a metal sulfide is discharged onto a natural soil, with special emphasis on iron cycle. The role of indigenous microbiota from an extremely acidic site on both weathering and attenuation processes related to the iron mobilization has been studied and the iron cycle has been reproduced at laboratory scale. In the first stage, the weathering phase, a residual sulfide mineral was bioleached using a mixed culture of iron-oxidizing bacteria isolated from the own substrate. The acid liquor obtained (pH 2), with a high metal concentration (160 mM in total iron), was filtered and neutralized. Solids obtained from the two sources (from the weathering process and after the neutralization stage) were characterized by X-ray and scanning electron microscope/energy dispersive X-ray spectroscopy, resulting ferric iron precipitates such as jarosites, goethites, and ferrihydrites with different crystalline properties. The contribution of ferric iron-reducing bacteria on the attenuation of high-content iron effluents was also studied. Mixed cultures of ferric iron-reducing bacteria, isolated from those acidic substrates, were active in reducing soluble ferric iron (60 mM in concentration), and a 66% of bioreduction was reached after 15 days. Dissimilatory ferric iron reduction has been achieved with adapted cultures at pH values from 7 to 4.

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.