Ocean acidification impact on the uptake of trace elements by mussels and their biochemical effects.

This study delves into the intricate interplay between ocean acidification (OA), metal bioaccumulation, and cellular responses using mussels (Mytilus galloprovincialis) as bioindicators. For this purpose, environmentally realistic concentrations of isotopically labelled metals (Cd, Cu, Ag, Ce) were added to investigate whether the OA increase would modify metal bioaccumulation and induce adverse effects at the cellular level. The study reveals that while certain elements like Cd and Ag might remain unaffected by OA, the bioavailability of Cu and Ce could potentially escalate, leading to amplified accumulation in marine organisms. The present findings highlight a significant rise in Ce concentrations within different mussel organs under elevated pCO2 conditions, accompanied by an increased isotopic fractionation of Ce (140/142Ce), suggesting a heightened potential for metal accumulation under OA. The results suggested that OA influenced metal accumulation in the gills of mussels. Conversely, metal accumulation in the digestive gland was unaffected by OA. The exposure to both trace metals and OA affects the biochemical responses of M. galloprovincialis, leading to increased metabolic capacity, changes in energy reserves, and alterations in oxidative stress markers, but the specific effects on other biomarkers (e.g., lipid peroxidation, some enzymatic responses or acetylcholinesterase activity) were not uniform, suggesting complex interactions between the stressors and the biochemical pathways in the mussels.

Ecotoxicological risk assessment in soils contaminated by Pb and As 20 years after a mining spill.

This study evaluates the potential toxicity of the soils of the Guadiamar Green Corridor (GGC) affected by the Aznalcóllar mine spill (Andalusia, Spain), one of the most important mining accidents in Europe in recent decades. Twenty years after the accident, although the area is considered to be recovered, residual contamination in soils persists, and the bioavailability of some contaminants, such as As, is showing trends of increasing. Therefore, the potential residual toxicity in 84 soil samples was evaluated by bioassays with lettuce (Latuca sativa L.), earthworms (Eisenia andrei) and determining the microbial activity by basal respiration and metabolic quotient. The selected soils sampled along the GGC were divided into 4 types according to their physicochemical properties. In the closest part of the mine two soil types appear (SS1 and SS2), originally decarbonated and loamy, with a reduction in lettuce root elongation of 57% and 34% compared to the control, as well as a the highest metabolic quotient (23.9 and 18.1 ng CcO2 µg Cmicrob-1 h-1, respectively) with the highest risk of Pb and As toxicity. While, located in the middle and final part of the affected area of the spill (SS3 and SS4), soils presented alkaline pH, finer textures and the lowest metabolic quotient (<9.5 ng CcO2 µg Cmicrob-1 h-1). In addition, due to Pb and As exceeded the Guideline values established in the studied area, the human toxicity risk was determined according to US-EPA methodology. Although the total contents were higher than the Guidelines established, the obtained hazard quotients for both contaminants were less than one, so the risk for human health was discarded. However, monitoring over time of the toxicity risks of the GGC soils would be advisable, especially due to the existence of areas where residual contamination persist, and soil hazard quotient obtained for As in children was higher and close to unity.

Assessment of the toxic effects of mixtures of three lanthanides (Ce, Gd, Lu) to aquatic biota.

Lanthanide (LNs) release into the environment is expected to greatly increase in the coming years due to a high demand for new technologies. However there is a gap in the ecological risk assessment of these metals because most of the ecotoxicological studies have been performed with only one element, although they are usually found in nature as a group. This research evaluated the effects of mixtures of three lanthanides, cerium (Ce), gadolinium (Gd), and lutetium (Lu), representative of the light, middle and heavy rare earth elements, respectively, on seven aquatic species (A. fischeri, R. subcapitata, C. vulgaris, B. calyciflorus, H. incongruens, D. magna and D. rerio). Lanthanide content decreased over time in all toxicity test media and it was observed that LN sedimentation starts at the beginning of the tests with a steep decline of the available LN amount. Potential toxic effects of LNs were observed only in five species of the seven studied, predominantly in the unicellular organism (A. fischeri) and in the organisms belonging to the lower trophic levels (R. subcapitata and B. calyciflorus). The multi-toxicity approach performed in this study showed synergistic effects in tests performed with the bacteria A. fischeri and the algae R. subcapitata, and antagonistic effects for the rotifer B. calyciflorus. Although predicting the response of aquatic organisms exposed to multi-elements is not an easy task and can be masked by potential interactions with other compounds or even by nutrient removal. The variation in toxic action among species observed in this study reveals that lanthanide interaction in toxicity mechanisms should not be discarded, and supports that further studies with LN mixtures are required to properly understand their toxic behaviour in nature ecosystems.

Assessment of baseline ecotoxicity of sediments from a prospective mining area enriched in light rare earth elements.

Rare earth elements (REEs) disperse from indigenous rocks to the environment, thus making sediments one of the major sinks and sources of metal pollution. The emerging use of REEs and the subsequent opening of new mining areas may contribute to their release into surrounding ecosystems. For this reason, this study was performed in a natural area with geological material abundant in ferrocarbonatites and light REE. The aim of this work was to assess the natural REE availability and (eco)toxicity in freshwater sediments. Sediments showed high REE concentrations in samples with fine grain size fractions, and low in organic-rich sediments. The enrichment in LREE was mostly from rocks and the obtained enrichment factors (EF) confirmed that the sediments are not anthropogenically polluted. To assess REE availability and ecotoxicity, four toxicity tests were performed. REEs measured as the dissolved concentration in the test media were very low compared to the potentially available total REE in sediments and showed positive or negative correlations with fine or coarse grain sizes, respectively, and positive correlations with the content in Mg, Fe and Al. In tests performed in media supplemented with salts, the availability of REEs decreased considerably. Only some toxic effects could be linked to the REE contents in the ostracodtox and luminotox tests. However, measurement of toxicity could be influenced by the sediment properties and lead to a potential overestimation of ecotoxicity if only REE are regarded. Our study reveals that the physicochemical properties of sediments are a key factor controlling both REE availability and toxicity, whereas the determination of REE effects from toxicity tests using liquid media with salt addition will decrease REE availability and could mask toxic effects. Our findings provide new knowledge about REE behaviour in sediments and are a starting point for understanding potential REE pollution around prospective mining areas.

Evaluation of remediation techniques in soils affected by residual contamination with heavy metals and arsenic.

Residual soil pollution from the Aznalcóllar mine spill is still a problem in some parts of the affected area, today converted in the Guadiamar Green Corridor. Dispersed spots of polluted soils, identified by the absence of vegetation, are characterized by soil acid pH and high concentrations of As, Pb, Cu and Zn. Ex situ remediation techniques were performed with unrecovered soil samples. Landfarming, Composting and Biopiles techniques were tested in order to immobilize pollutants, to improve soil properties and to promote vegetation recovery. The effectiveness of these techniques was assessed by toxicity bioassays: Lactuca sativa L. root elongation test, Vibrio fischeri bioluminescence reduction test, soil induced respiration test, and Eisenia andrei survival and metal bioaccumulation tests. Landfarming and Composting were not effective techniques, mainly due to the poor improvement of soil properties which maintained high soluble concentrations of Zn and Cu after treatments. Biopile technique, using adjacent recovered soils in the area, was the most effective action in the reduction of soil toxicity; the improvement of soil properties and the reduction in pollutants solubility were key to improve the response of the tested organisms. Therefore, the mixture of recovered soils with polluted soils in the areas affected by residual contamination is considered a more suitable technique to reduce the residual pollution and to promote the complete soil recovery in the Guadiamar Green Corridor.

Long-term toxicity assessment of soils in a recovered area affected by a mining spill.

Residual pollution in the Guadiamar Green Corridor still remains after Aználcollar mine spill in 1998. The polluted areas are identified by the absence of vegetation, soil acidic pH and high concentrations of As, Pb, Zn and Cu. Soil toxicity was assessed by lettuce root elongation and induced soil respiration bioassays. In bare soils, total As and Pb concentrations and water-extractable levels for As, Zn and Cu exceeded the toxicity guidelines. Pollutants responsible for toxicity were different depending on the tested organism, with arsenic being most toxic for lettuce and the metal mixture to soil respiration. Soil properties, such as pH or organic carbon content, are key factors to control metal availability and toxicity in the area. According to our results, there is a risk of pollution to living organisms and the soil quality criteria established in the area should be revised to reduce the risk of toxicity.

Influence of soil properties on the bioaccumulation and effects of arsenic in the earthworm Eisenia andrei.

This study aimed at assessing the influence of soil properties on the uptake and toxicity effects of arsenic in the earthworm Eisenia andrei exposed for 4 weeks to seven natural soils spiked with different arsenic concentrations. Water-soluble soil concentrations (AsW) and internal As concentrations in the earthworms (AsE) were greatly different between soils. These two variables were highly correlated and were key factors in earthworm toxicity response. AsW was explained by some soil properties, such as the pH, calcium carbonate content, ionic strength, texture or oxide forms. Toxicity showed a clear variation between soils, in some cases without achieving 50 % adverse effect at the highest As concentration added (600 mg kg(-1)). Nevertheless, soil properties did not show, in general, a high relation with studied toxicity endpoints, although the high correlation with AsW could greatly reduce indirectly As bioavailability and toxicity risk for earthworms. Obtained results suggest that soil properties should be part of the criteria to establishing thresholds for contaminated soils because they will be key in controlling As availability and thus result in different degrees of toxicity.

Effect of soil properties on the toxicity of Pb: assessment of the appropriateness of guideline values.

Soil contamination with lead is a worldwide problem. Pb can cause adverse effects, but its mobility and availability in the terrestrial environment are strongly controlled by soil properties. The present study investigated the influence of different soil properties on the solubility of lead in laboratory spiked soils, and its toxicity in three bioassays, including Lactuca sativa root elongation and Vibrio fischeri illumination tests applied to aqueous extracts and basal soil respiration assays. Final aim was to compare soil-dependent toxicity with guideline values. The L. sativa bioassay proved to be more sensitive to Pb toxicity than the V. fischeri and soil respiration tests. Toxicity was significantly correlated with soil properties, with soil pH, carbonate and organic carbon content being the most important factors. Therefore, these variables should be considered when defining guideline values.

Long-term contamination in a recovered area affected by a mining spill.

Soil pollution from the spill of Aznalcóllar mine (S Spain) was monitored by analysing polluted soils in 1998, 1999, and 2004. Following the methodology used in previous studies, in 2013 we conducted a new sampling and analysis of the soils affected by the spill and the data were compared with those of 2004. The results confirm that the pH tended to rise and concentration of pollutants tended to diminish over time. In 2013, the total concentration of pollutants was within the normal range for uncontaminated soils and close to the background concentration of the soils prior to the spill; while the soluble concentration of pollutants was clearly below the toxic level. These results indicate that remediation measures implemented have been effective. However, the removal of tailings (first remediation measure applied) was deficient and in many places the tailings were mixed with the soil. The high concentration of sulphides and metal(loid)s in the tailings gave rise to spots with very acidic and highly polluted soils devoid of vegetation. In 2013, fifteen years after the spill, these spots of bare soils remain a major source of pollution from which pollutants are scattered through the solid and liquid phases of runoff water, requiring action to immobilize pollutants and encourage the restoration of vegetation on these soils. In this type of pollution in a Mediterranean environment, the complete removal of tailings is more important than the speed at which they are removed.