The modified BCR three-step sequential extraction procedure was used to examine the temporal dynamics of trace elements in soils contaminated by an accidental spill from an opencast mine in south-west Spain. Soils were mainly contaminated with pyritic sludge and acidic wastewater, whereas some soils were affected only by acidic wastewater. The distributions obtained for both some major (Ca, Fe and Mn) and trace elements (As, Cd, Cu, Pb and Zn) in the sludge and soil samples taken at different times after the accident, 1-3 months and 21 months, were compared. Sequential extractions were useful in identifying different sources of contamination, and in obtaining additional information on the solubility of secondary minerals formed by pyrite oxidation. Thus, the effectiveness of the BCR procedure has proved to be a useful tool for predicting short- and long-term mobility of trace elements, even in complex environmental scenarios. The modified BCR three-step sequential extraction procedure has proved a useful prediction tool for short- and long-term mobility of trace elements in contaminated soils.

The water used by 85% of the Asian population originates in Tibetan Plateau. During April and May of 2006, water samples were collected from four major Asian rivers in the Plateau (i.e. the Salween, Mekong, Yangtze River and Yarlung Tsangpo) and analyzed for Cu, Pb, Zn, Ag, Mo, Cd, Co, Cr, Ni, Li, Mn, Al, Fe, Mg and Hg. The results showed that elements such as Mg were rather high in Tibetan rivers, giving a mean electrical conductance of 36 mS/m. In a few locations, the results also showed relatively high concentrations of Al and Fe (>1 mg/L). However, the concentrations of Cu, Zn, Ag, Cd, and Cr were generally low. Contamination with Pb was identified at a few locations in the Salween and Ni at a few sites in the Yangtze River. For the first time, total dissolved metal contents in source water of four major Asian rivers were evaluated at the same time.

After flooding, iron reduction in riverine wetlands may cause the release of large quantities of phosphorus. As phosphorus is an important nutrient causing eutrophication in aquatic systems, it is important to have a tool to predict this potential release. In this study we examined the P release to the soil pore water in soil cores from floodplains in the Netherlands and from less anthropogenically influenced floodplains from Poland. During the inundation experiment, concentrations of P in the pore water rose to 2–90 times the initial concentrations. P release was not directly related to the geographic origin of the soils. An important predictor variable of P release was found in the ratio between the concentration of iron-bound P and amorphous iron. This ratio may provide a practical tool for the selection of new areas for wetland creation, and for impact assessment of plans for riverine wetland restoration and floodwater storage. Mobilisation of phosphorus in floodplain wetland soils can be predicted with easily measurable soil characteristics.

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.

We studied the effectiveness of remediation on microbial endpoints, namely microbial biomass and activity, microbial and plant species richness, of an As-contaminated mine spoil, amended with compost (C) alone and in combination with beringite (B) or zerovalent iron grit (Z), to increase organic matter content and reduce trace elements mobility, and to allow Holcus lanatus and Pinus pinaster growth. Untreated spoil showed the lowest microbial biomass and activity and hydrolase activities, and H. lanatus as sole plant species, whereas the presented aided phytostabilisation option, especially CBZ treatment, significantly increased microbial biomass and activity and allowed colonisation by several plant species, comparable to those of an uncontaminated sandy soil. Microbial species richness was only increased in spoils amended with C alone. No clear correlation occurred between trace element mobility and microbial parameters and plant species richness. Our results indicate that the choice of indicators of soil remediation practices is a bottleneck. Organo-mineral amendment and revegetation of a gold mine spoil increased microbial activity but did not increase microbial species richness.

Agrichemical spills and discharges to soil can cause point-source contamination of surface and ground waters. When high contaminant concentrations inhibit natural attenuation in soils, chemical treatments can be used to promote degradation and allow application of treated soils to agricultural lands. This approach was used to remediate soil containing >650 mg atrazine, >170 mg metolachlor and >18,000 mg nitrate kg⁻¹. Results indicated a decrease in metolachlor concentration to <1 mg kg⁻¹ within 95 days of chemical treatment with zerovalent iron (Fe⁰, 5% w/w) and aluminum sulfate (Al₂(SO₄)₃, 2% w/w) but after one year >150 mg atrazine and >7000 mg nitrate kg⁻¹ remained. Laboratory experiments confirmed that subsequent additions of sucrose (table sugar) to the chemically pretreated soil promoted further reductions in atrazine and nitrate concentrations. Field-scale results showed that adding 5% (w/w) sucrose to windrowed and pretreated soil significantly reduced atrazine (<38 mg kg⁻¹) and nitrate (<2,100 mg kg⁻¹) concentrations and allowed for land application of the treated soil. These results provide evidence that zerovalent iron in combination with Al₂(SO₄)₃ and sucrose can be used for on-site, field-scale treatment of pesticide- and nitrate-contaminated soil.

Acid mine drainage (AMD), a legacy of coal and mineral extraction, contaminates streams with complex mixtures of acid and heavy metals that are usually partitioned between the water column and substrate. Understanding the conditions under which sediments retain toxicity after the water column is cleared is important for predicting the long term success of remediation efforts. We conducted laboratory and field experiments to evaluate the relative contribution of acidity versus metals to the toxicity of AMD contaminated sediment towards aquatic macroinvertebrates. Laboratory bioassays showed that precipitate-coated substrate from AMD-impacted sites were toxic to Ctenodaphnia magna and reduced growth of mayflies (Ephemeroptera: Heptageniidae). Toxicity correlated more with acidity released from the sediment than with metals. After transplantation to a clean stream, the same Al- and Fe-contaminated substrate were not toxic to daphnia and was readily colonized by benthic macroinvertebrates within 5 weeks.

To investigate the consequences of acidification and metal accumulation on the biology of aquatic bryophytes, the acid-tolerant liverwort Scapania undulata (L.) Dum. and the acid-sensitive moss Rhynchostegium riparioides (Hedw.) Cardot were transplanted from one stream to two other streams of differing acidity (pH 5.20 and 6.38). The bryophytes were collected in a circumneutral (pH 6.57) stream in the Vosges Mountains. Metal accumulation was semi-quantitatively measured in shoots by energy dispersive TEM X-ray spectroscopy (EDXS). After 1 month, the two species remained green without alteration signs. Although no marked ultrastructural damage was observed in either species, some cells seemed to be necrotic, with flattened chloroplasts, in R. riparioides. Lipid droplet accumulation was observed in some leaf cells of S.undulata when transplanted to the most acidic stream. Metal was mostly localised in the cell wall, and was only sometimes detected in small vacuoles. Under acidic conditions, R. riparioides showed the highest relative amount of Al and the lowest amount of Fe, whereas the acid-tolerant bryophyte species S. undulata contained more Fe and less Al. The capability to limit the uptake of metals into the cytoplasm varies according to the bryophyte species. This could be an explanation of the tolerance of S. undulata to acidification.

The competing ligand exchange method was used to investigate the competitive binding of Ni(II) by Al(III) and Fe(III) in model aqueous solutions and freshwaters. Graphite furnace atomic absorption spectrometry and adsorptive cathodic stripping voltammetry were used to monitor the rate of uptake of the Ni by Chelex 100 chelating resin and dimethylglyoxime as the competing ligands, respectively. The results have revealed that Ni(II)-humate complexes were more labile in presence of the mixture of Al(III) and Fe(III), compared to the lability of the Ni(II)-humate complexes when only one of the two, Al(III) or Fe(III), was present. The environmental significance of this work is that in model solutions simulating freshwater containing humic substances and the target trace metal Ni(II) and cations, Al(III) and Fe(III), the competitive binding of Ni(II), Al(III) and Fe(III) by humic substances makes Ni(II)-humate complexes labile, releasing free Ni²⁺-aqua complex, which reported to be toxic.

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.