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.

Residual pollution and vegetation distribution in amended soils 20 years after a pyrite mine tailings spill (Aznalcóllar, Spain).

The present work assesses the residual pollution in the Guadiamar Green Corridor (SW, Spain) after a long-term aging process (18 years) since the accident of the Aznalcóllar pyrite mine. We have focused on the study of trace elements (Cu, Zn, Cd, As and Pb) in soils, their fractionation and the transference to the surrounding vegetation. The residual polluted areas are characterized by scattered plots with absence of vegetation, presenting high concentrations of trace elements, acidic pH and low organic carbon content. Surrounding these polluted plots, two vegetation gradient belts are clearly identified by changes in plant cover and richness. The inhibition of plant growth in the bare soils is related to the highest mobility of soluble and exchangeable Cu, Zn and Cd forms, which significantly decrease with the distance to the polluted plots. Plant richness and cover show differences between belts; bioaccumulation of trace elements in plants also differs, with a preferential accumulation in roots. Despite the low bioavailability of As and Pb in soils, bioaccumulation factors in plants for these elements are significantly higher in belt 1 in relation to belt 2. High Cu and Cd potential toxic concentrations in aerial parts of vegetation are found, posing a risk for livestock and a potential entrance to the food-chain. On the other hand, Lamarckia aurea (L.) Moench (in belt1) and Trifolium campestre Schreb. (in belt2) were the most dominant species in severely polluted soils. Elevated concentrations of trace elements in the vegetation growing in the area indicate plant adaptation mechanisms to live in these severely polluted soils, which can be used as a good bioindicator of pollution in similar polluted 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 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.