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.

Metal contamination of freshwater bodies resulting from mining activities or deactivated mines is a common problem worldwide such as in Portugal. Braçal (galena ore) and Palhal (pyrrhotite, chalcopyrite, galena, sphalerite, and pyrite ore), located in a riverside position, are both examples of deactivated mining areas lacking implemented recovery plans since their shutdown in the early mid-1900s. In both mining areas, effluents still flow into two rivers. The purpose of this work was to evaluate the potential hazard posed by the mining effluents to freshwater communities. Therefore, short- and long-term ecotoxicological tests were performed on elutriates from river sediments collected at each site using standard test organisms that cover different functional levels (Vibrio fischeri, Pseudokirchneriella subcapitata, Lemna minor, and Daphnia sp.). The results show that elutriates from the sediments of Palhal were very toxic to all tested species, while in contrast, elutriates from Braçal showed generally no toxicity for the tested species. Our study highlights the usefulness of using an ecotoxicological approach to help in the prioritization/scoring of the most critical areas impacted by deactivated mines. This ecotoxicological test battery can provide important information about the ecological status of each concerning site before investing in the application of time-consuming and costly methods defined by the Water Framework Directive or can stand as a meaningful complementary analysis.

Sediment cores were analysed from four coastal wetland sites within the Minas Basin, Bay of Fundy to compare mercury speciation and sediment characteristics. The coastal wetland sediments were low in total mercury (mean = 17.4 ± 9.9 ng g−1); however, MeHg concentration was 92 times higher (mean of 249 pg g−1) than intertidal mudflat sediment (mean of 2.7 pg g−1). Total mercury concentrations in intertidal mudflat cores were also low (0.5–23.7 ng g−1) and correlated (Pearson correlation = 0.98; p < 0.01) with % organic carbon; with low concentrations of MeHg present only below depths of 6 cm (mean = 2.7 ± 1.0 pg g−1). Total mercury concentrations were negatively correlated (correlation = 0.56, p < 0.05) with inorganic sulphur (acid volatile sulphides (AVS) and pyrite) while MeHg concentrations were inversely correlated (Pearson correlation = −0.68; p < 0.05) with the pyrite content but not with AVS. Methyl mercury concentrations were not significantly correlated with organic carbon content in the wetland sediments, and mercury-in-biomass enrichment factors were lower (total mercury mean 1.5 ± 1.9 and MeHg mean = 3.6 ± 4.8) than published measurements from mercury polluted sites. Modelling estimates found on average 4.4 times more total mercury mass in the intertidal mudflat sediments relative to vegetated wetlands. A negative relationship was observed between MeHg concentrations (below 20 cm depth) and modelled tidal inundation. The mineral fraction within wetland sediments contained 96.2% of the total mercury mass; however, the highest concentrations of mercury species were in root biomass. This research confirms that vegetated coastal wetlands are key areas for formation of bioavailable methyl mercury, and mercury distribution is tied to organic carbon and sulphur speciation.

On 1998, a settling pond of a pyrite mine in Aznalcóllar (SW Spain) broke open, spilling some 3.6 × 10⁶ m³ of water and 0.9 × 10⁶ m³ of toxic tailings into the Agrio and Guadiamar river basin 40 km downstream, nearly to Doñana National Park. The soils throughout the basin were studied for arsenic pollution. Almost all the arsenic penetrated the soils in the solid phase (tailings) in variable amounts, mainly as a result of the different soil structure. The chemical oxidation of the tailings was the main cause of the pollution in these soils. A study of the relationships between the main soil characteristics and arsenic extracted with different reagents (water, CaCl₂, acetic acid, oxalic–oxalate and EDTA) indicates a direct relationship with the total arsenic concentration. The highest amount of arsenic was extracted by oxalic–oxalate (24%–36% of the total arsenic), indicating the binding with the iron oxides.