The effect of the earthworm Lumbricus terrestris L. on metal availability in two mining soils was assessed by means of chemical extraction methods and a pot experiment using crop plants. Results from single and sequential extractions showed that L. terrestris had a slight effect on metal fractionation in the studied soils: only metals bound to the soil organic matter were significantly increased in some cases. However, we found that L. terrestris significantly increased root, shoot and total Pb and Zn concentrations in maize and barley for the soil with the highest concentrations of total and available metals. Specifically, shoot Pb concentration was increased by a factor of 7.5 and 3.9 for maize and barley, respectively, while shoot Zn concentration was increased by a factor of 3.7 and 1.7 for maize and barley, respectively. Our results demonstrated that earthworm activity increases the bioavailability of metals in soils.

Sediment samples collected from large harbours and public slipways on the island of Malta have been analysed for geochemically important metals (Al, Ca, Fe, Mn) and contaminant metals (As, Cd, Co, Cr, Cu, Ni, Pb, Sn, Zn) following fractionation (<63μm) and digestion in aqua regia. Absolute and Al-normalised concentrations of contaminant metals exhibited relatively little dispersion both among different samples from the same location and between samples from different locations, notable exceptions including lower concentrations of Cr and Sn on the slipways than in the harbours. Sources of contaminant metals are attributed to diffuse and specific waste inputs from urban surroundings and boating and shipping activities. Overall, concentrations are similar to those reported for other large harbours in urban settings where equivalent sample fractionation-digestion has been performed. Relative to various sediment quality guidelines, Pb is predicted to exert the greatest threat to the marine environment of Malta.

Coal is one of the major sources of fuel for electricity production and will continue to be used for many more decades. Thus, it is important to study the effects of disposal of coal burning byproducts including fly ash into the environment. In this study, the solubility of cations and anions from the fly ash in water is discussed. Also, the fractionation of different metals from fly ash in water is studied to understand which fraction of the metals would likely be mobilized. The results from these studies suggested that the metals in the fly ash are bound mostly to carbonate, organic, and residual fractions. Also, when water solubility data are modeled with a geochemical model (Visual MINTEQ), the saturation index predictions suggested that brucite (Mg(OH)2) and calcite (CaCO3) could potentially precipitate and mineralize the atmospheric CO2. Such mineralization process could potentially reduce the leaching of toxic metals from fly ash. Results from this study will be helpful in understanding the fate of different metals from fly ash land disposal environments.

The behavior of metals in sediments after their disposal to land has important implications for the environmental management. The sediment from the Carska Bara (Serbia) was polluted with adequate metal salts in order to reach severe contamination based on the pseudo-total metal content of Pb, Cd, Ni, Zn, Cu, and Cr according to the corresponding Dutch standards and Canadian guidelines. The toxicity and fate of the metal in sediment depend on its chemical form, and therefore, quantification of the different forms of a metal is more meaningful than the estimation of its total concentration. In this study, fractionation of metals in sediment has been investigated to determine its speciation and ecotoxic potential, as well as evaluation of metal potential toxicity based on the simultaneously extracted metals (SEMs) and acid volatile sulfides (AVSs) analysis at the beginning of the experiment and after 5 weeks of sediment aging. The investigations suggest that Cd, Pb, and Zn have a tendency to associate with labile fraction, the most mobile and most dangerous fraction for the environment. Risk assessment code revealed their high risk. Copper and chromium showed low to medium risk to the aquatic environment. Nickel showed no risk to the aquatic environment. This was the case at the beginning and after 5 weeks of aging. Aging yielded an increased mobility of all metals based on the increased proportion in mobile fractions. The Σ[SEM i ]/[AVS] ratio was found to be >1 both at the beginning and after 5 weeks of aging, with the ratio showing an increase with time. This ratio indicates the potential availability/toxicity and, according to the US EPA criteria, the samples belong to the group with probable negative effect. If particular metals are considered, only the Σ[SEM i ]/[AVS] ratio for zinc was >1 at the beginning. After 5 weeks, the ratio was >1 for zinc, lead, and copper. Comparison of the results of sequential extraction and the results of SEM and AVS analysis showed good agreement for lead and zinc.

This paper investigates the changes in bioavailable phosphorus (P) within the hyporheic zone of a groundwater-dominated chalk stream. In this study, tangential flow fractionation is used to investigate P associations with different size fractions in the hyporheic zone, groundwater and surface water. P speciation is similar for the river and the chalk aquifer beneath the hyporheic zone, with ‘dissolved’ P (<10 kDa) accounting for ~90% of the P in the river and >90% in the deep groundwaters. Within the hyporheic zone, the proportion of ‘colloidal’ (<0.45 μm and >10 kDa) and ‘particulate’ (>0.45 μm) P is higher than in either the groundwater or the surface water, accounting for ~30% of total P. Our results suggest that zones of interaction within the sand and gravel deposits directly beneath and adjacent to river systems generate colloidal and particulate forms of fulvic-like organic material and regulate bioavailable forms of P, perhaps through co-precipitation with CaCO3. While chalk aquifers provide some degree of protection to surface water ecosystems through physiochemical processes of P removal, where flow is maintained by groundwater, ecologically significant P concentrations (20–30 μg/L) are still present in the groundwater and are an important source of bioavailable P during baseflow conditions. The nutrient storage capacity of the hyporheic zone and the water residence times of this dynamic system are largely unknown and warrant further investigation.

In recent years, elevated arsenic concentrations in groundwater used for drinking water supplies have been recognised in the Madrid Tertiary detrital aquifer. Although only natural causes have been suggested as the source of arsenic, this study aims to highlight that the anthropogenic contribution cannot be disregarded. During the sub-catchment's areas sampling, we found many geographical sites where natural arsenopyrite [FeAsS] originally encapsulated in pegmatite bodies and quartz veins, was artificially outcropped and dumped out, since mining wastes were scattered and exposed to weathering. Several mineral and ground specimens were collected to analyse its mineralogical and chemical composition by X-Ray Diffraction (XRD) and X-Ray Fluorescence (XRF) spectrometry and by Environmental Scanning Electron Microscope (ESEM). Both, the abundant existence of secondary phases, such as scorodite [FeAsO₄⋅2H₂O] and jarosite [KFe₃(SO₄)₂(OH)₆], much more soluble than arsenopyrite, and the lixiviation experiments of arsenopyrite in acidic media to simulate acid mine drainage (AMD) conditions, usually found in old mining districts, point to a potential risk of arsenic contamination of surface water bodies, which operate as recharged waters of the aquifer in the studied area. The elemental determination of heavy metals present in ground samples by XRF analyses, reaching up to 1,173 mg kg⁻¹ of copper, 347 mg kg⁻¹ of lead and 113,702 mg kg⁻¹ of arsenic; and the physicochemical and arsenic fractionation studies of soil samples, led us to classify the soil as Spolic Technosol (Toxic). The contamination of the area due to old mining activities could release arsenic to Madrid water supplies; accordingly, additional decontamination studies should be performed.

PURPOSE: The objective of this paper is to assess the impact of long-term electroplating industrial activities on heavy metal contamination in agricultural soils and potential health risks for local residents. METHODS: Water, soil, and rice samples were collected from sites upstream (control) and downstream of the electroplating wastewater outlet. The concentrations of heavy metals were determined by an atomic absorption spectrophotometer. Fractionation and risk assessment code (RAC) were used to evaluate the environmental risks of heavy metals in soils. The health risk index (HRI) and hazard index (HI) were calculated to assess potential health risks to local populations through rice consumption. RESULTS: Hazardous levels of Cu, Cr, and Ni were observed in water and paddy soils at sites near the plant. According to the RAC analysis, the soils showed a high risk for Ni and a medium risk for Cu and Cr at certain sites. The rice samples were primarily contaminated with Ni, followed by Cr and Cu. HRI values >1 were not found for any heavy metal. However, HI values for adults and children were 2.075 and 1.808, respectively. CONCLUSION: Water, paddy soil, and rice from the studied area have been contaminated by Cu, Cr, and Ni. The contamination of these elements is related to the electroplating wastewater. Although no single metal poses health risks for local residents through rice consumption, the combination of several metals may threaten the health of local residents. Cu and Ni are the key components contributing to the potential health risks.

BACKGROUND AND SCOPE: Effect-directed analysis is increasingly used for the identification of key toxicants in environmental samples and there is a growing need for in vivo biotests as diagnostic tools. Within this study, we performed an in vivo sediment contact test, applicable on both native field samples and their extracts or fractions, in order to be able to compare the results from both field and laboratory studies. MATERIAL AND METHODS: A sediment contact test with the prosobranch snail, Potamopyrgus antipodarum, was carried out on extracts and fractions of field sediments from three European river basins. The results were compared with previous results of the native field samples. RESULTS: In contrast to the native sediments, the extracts of the samples led to an overall decrease in reproduction. Even the chosen reference sites had an adverse effect on the snails' reproduction. It appeared that a higher bioavailability in the organic extracts, together with a changing composition of compounds could have lead to this change in effects. The fractionation of the extracts partly led to a more differentiated picture, but the resolution was not high enough to see any distinct effects on the snails' reproduction. DISCUSSION AND CONCLUSION: Our results highlight the importance of the use of in vivo biotests and point out the relevance of bioavailability in native sediments. For further fractionation studies, a more realistic extraction procedure, together with a higher resolution fractionation, would be appropriate in order to separate individual bioavailable compounds more efficient.