Guadiamar Green Corridor Research Articles

Microbiological indicators as sensitive indicators in the assessment of areas contaminated by heavy metals

Context As one of the world’s largest mining spills, the Aznalcóllar pyrite mine accident in Spain in 1998 resulted in ~45 km2 of agricultural soils polluted by arsenic and heavy metals. The Guadiamar Green Corridor (GGC) helped with soil remediation but residual pollution is still detected 20 years later. Aims Several methodologies based on chemical indicators have been used to assess the recovery of these areas. However, simple microbiological indicators (e.g. microbial activity and biomass, and metabolic quotient (qCO2)) are yet to be uesed. The aim of this study was to evaluate areas contaminated by arsenic and heavy metals using microbiological indicators of soil quality. Methods We used a systematic random sampling design to collect soil samples from two soil groups with different recovery trajectories. We analysed the total and water-soluble concentrations of arsenic (As), lead (Pb), copper (Cu), and zinc (Zn), the main soil properties, and bioassays including microbial activity and biomass, and metabolic quotient or microbial stress (qCO2). Key results Twenty years after the accident, soils with As and Pb concentrations that consistently exceeded regulatory levels had altered soil microbial biomass and functioning. Although overall rates of microbial respiration were not significantly different between polluted soils, microbial biomass was lower and qCO2 was higher in the more polluted than in less polluted soils. Conclusions The metabolic quotient and microbial biomass are sensitive indicators in the monitoring over time of soil polluted by arsenic and heavy metals. Implications Microbial indicators must be considered in the assessment of potential ecotoxicity and in the evaluation of soil biological properties influencing soil recovery in the long term.

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.

Impact of Biochar Amendment on Soil Properties and Organic Matter Composition in Trace Element-Contaminated Soil.

The application of biochar as an organic amendment in polluted soils can facilitate their recovery by reducing the availability of contaminants. In the present work, the effect of biochar application to acid soils contaminated by heavy metal spillage is studied to assess its effect on the quantity and composition of soil organic matter (SOM), with special attention given to soil humic acids (HAs). This effect is poorly known and of great importance, as HA is one of the most active components of SOM. The field experiment was carried out in 12 field plots of fluvisols, with moderate and high contamination by trace elements (called MAS and AS, respectively), that are located in the Guadiamar Green Corridor (SW Spain), which were amended with 8 Mg·ha−1 of olive pit biochar (OB) and rice husk biochar (RB). The results indicate that 22 months after biochar application, a noticeable increase in soil water holding capacity, total organic carbon content, and soil pH were observed. The amounts of oxidisable carbon (C) and extracted HAs in the soils were not altered due to biochar addition. Thermogravimetric analyses of HAs showed an increase in the abundance of the most thermostable OM fraction of the MAS (375–650 °C), whereas the HAs of AS were enriched in the intermediate fraction (200–375 °C). Spectroscopic and chromatographic analyses indicate that the addition of biochar did not alter the composition of the organic fraction of HAs, while Cu, Fe, and as were considerably accumulated at HAs.

Long‐term assessment of remediation treatments applied to an area affected by a mining spill in Spain

AbstractThis study evaluated the effectiveness of remediation treatments in the long‐term (20 years) for one of the largest mine spills in the world, the Aznalcóllar accident. Soil recovery was carried out through the application of various rates of organic (compost and manure) and inorganic amendments (materials rich in iron oxides and calcium carbonate). Different amendment combinations were grouped in four treatments (T1 to T4) and applied in different sectors depending on the soil properties and the degree of initial contamination. To assess the degree of soil recovery, physicochemical properties, total, water‐soluble, and bioavailable concentrations of the main contaminants (Pb, As, Zn, and Cu) were determined over time. Applied treatments increased pH, calcium carbonate, and organic carbon content of soils, reduced electrical conductivity, and decreased mobility of contaminants, indicating that remediation treatments were efficient recovering soils contaminated by potentially harmful elements (PHEs). However, 20 years after the accident, total concentrations of Pb and As still exceed the intervention levels of the current regulations in certain areas. These areas are located in the sectors closest to the mine and where treatments T1 and T2 were applied. In these cases, the added doses of organic amendments, iron oxide–rich soils, and carbonate amendments were not sufficiently effective, so the application of new treatments is recommended to complete the total recovery of the Guadiamar Green Corridor.

Long-term trace element assessment after a mine spill: Pollution persistence and bioaccumulation in the trophic web

Trace elements can be toxic when they cannot be easily removed after entering an ecosystem, so a long-term assessment is fundamental to guide ecosystem restoration after catastrophic pollution. In 1998, a pyrite mining accident in Aznalcóllar (south-western Spain) spilled toxic waste over a large area of the Guadiamar river basin, where, after restoration tasks, the Guadiamar Green Corridor was established. Eight years after the mine accident (2005–2006), the ground-dwelling insectivorous lizard Psammodromus algirus registered high trace-element levels within the study area compared to specimens from a nearby unpolluted control site. In 2017, 20 years after the accident, we repeated the sampling for this lizard species and also quantified trace elements in vegetation as well as in arthropod samples in order to identify remnant trace-element accumulation with the aim of assessing the transfer of these elements through the trophic web. We found remnant trace-element contamination in organisms of the polluted site compared to those from the unpolluted site. All trace-element concentrations were higher in arthropods than in plants, suggesting these compounds bioaccumulate through the trophic web. Lizards from the polluted areas had higher As, Cd, and Hg concentrations than did individuals from the unpolluted area. Lizard abundance between sampling periods (2005–06 and 2017) did not vary in unpolluted transects but strongly declined at polluted ones. By contrast, the Normalized Difference Vegetation Index indicated that in the study period, the vegetation was similar at the two sampling sites. These results suggest that, 20 years after the accident, the trace-element pollution could be the cause of a severe demographic decline of the lizard in the polluted area.

Evaluating the provision of ecosystem services to support phytoremediation measures for countering soil contamination. A case‐study of the Guadiamar Green Corridor (SW Spain)

AbstractFrequently, the plants used for the management of contaminated soil are those native to the area of action and provide a range of ecosystem services (ES). However, in many cases the sustainability of the afforestation planning and the provision of ES are not evaluated under scenarios of climate change (CC). In the present research work, we propose a fast‐track methodology for evaluating the potential distribution of forest species and provisioning of carbon sequestration under soil contaminated by trace elements. Furthermore, the effect of CC on the potential distribution was evaluated through the calibration of the Sierra model from MicroLEIS‐DSS. Seven tree species were selected due to their tolerance of soil contaminated by trace elements during the afforestation planning using the vegetation cover maps (1998–2013) of the Guadiamar Green Corridor. Additionally, compilation, standardization, and cluster process of soil database were applied following INSPIRE, EU‐HYDI, and JRC recommendations. Finally, the carbon sequestration rate of vegetation cover has been calculated according to IPCC methodology. The results show the loss of forest aptitude (Eucalyptus, P. pinea, P. alba, Quercus) under scenario of CC and decreasing of the ES provided. The proposed methodology could support the decision making to determine forest species suited for the regulation of contaminated soils and the provision of ES at spatiotemporal scales.

Evolution of the Residual Pollution in Soils after Bioremediation Treatments

This study is focused on one of the most important spills that ever happened in Europe, the Aznalcóllar’s mine spill. The extensive application of phytostabilization in the area led to the implementation of the Guadiamar Green Corridor (GGC). Soil physicochemical properties were analyzed and the total concentration of Pb, As, Zn and Cu was measured by X-ray fluorescence (XRF); bioassay using Lactuca sativa L. was applied to assess potential toxicity. Two decades after the accident, some soils affected by residual contamination continue to appear in the area. According to regulatory levels, Pb and As concentrations are exceeded in around 13%and 70%, respectively, in the uppermost part of the soils (first 10 cm). The change in soil properties after bioremediation treatment positively promoted the reduction in the potential mobility of pollutants by the increase in pH, CaCO3 content and organic carbon. Anyway, the bioassay with Lactuca sativa, indicated that around 25% of the soils showed toxicity by the reduction of the root elongation in relation to the control samples. Our results indicate that monitoring of the GGC is still needed, together with the application of soil recovery measures to reduce the potential toxicity in some sectors of the affected area.

Assessment of sugar beet lime measure efficiency for soil contamination in a Mediterranean Ecosystem. The case study of Guadiamar Green Corridor (SW Spain)

Contamination has been identified as one of the main threats for soil conservation worldwide. Availability of high-quality information on soil contamination, its impacts and effects is still required at global level. Well documented case studies provide valuable information to understand long-term trends associated with management of contaminated soils. The temporal evolution of contamination and associated factors have been studied in the Guadiamar river basin, after a mine waste spillage of about 6 hm3 of acidic waters and toxic sludge enriched with trace elements. An extensive database has been compiled, harmonized and standardized from the numerous and heterogeneous sectorial studies and monitoring carried out in the area since 1998, and has been used for spatio-temporal analysis of the effectiveness of individual and mixed soil remediation measures as a pilot case for data exploitation. Database variables consider six ecosystem compartments (soil, water, sediment, air, plant and animal biomass), management (remediation measures applied over time and space), land use and cover, and present and predicted climate. The pilot developed for remediation effectiveness considered 11 different treatments, including mixed addition of compost, red clays and sugar beet lime (SBL). Harmonization and Standardization processes were carried out according to EU-HYDI, INSPIRE and ENVASSO recommendations. However, correlation and regression analyses were applied to standardize pH and Cd values from our case study with R Software. According to the land use, high doses of SBL with other soil amendments don't provide high benefits for the reduction of Cadmium pseudototal. The created database provided a relevant resource of information for the management of the Guadiamar area and other similar cases. Also, the present methodology and harmonized data-based will be useful for soil contamination assessment across Europe allowing the development of decision support tools and decision making for the selection of effective and available remediation strategies.

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.

Effect of soil organic matter on antimony bioavailability after the remediation process

We evaluated the long-term (18 year) and short-term (4 weeks) changes of Sb in contaminated soil with SOM increase under remediation process. In the Aznalcóllar mine accident (1998) contaminated area, the remediation measurement implemented the Guadiamar Green Corridor, where residual pollution is still detected. Soils of the re-vegetated area (O2) with high pH and high SOM content, moderately re-vegetated area (O1) and unvegetated area (C) were sampled. Soil pH, CEC, SOM amount and soil Sb forms were evaluated. Soil Sb was measured as total, soluble, exchangeable, EDTA extractable, acid oxalate extractable, and pyro-phosphate extractable fractions. Further, the short-term effect of artificial organic matter addition was also evaluated with incubation study by adding compost to the sampled soil from C, O1 and O2 areas. After 4 weeks of incubation, soil chemical properties and Sb forms were evaluated. In re-vegetated area (O2), soil total Sb was two times lower than in unvegetated area (C); however, soluble, exchangeable, and EDTA extractable Sb were 2–8 times higher. The mobile/bioavailable Sb increase was also observed after 4 weeks of incubation with the addition of compost. Soluble, exchangeable, and EDTA extractable Sb was increased 2–4 times by compost addition. By the linear regression analysis, the significantly related factors for soluble, exchangeable, and EDTA extractable Sb values were pH, CEC, and SOM, respectively. Soluble Sb increase was mainly related to pH rise. Exchangeable Sb should be bound by SOM-metal complex and increased with CEC. EDTA extractable fraction should be increased with increase of SOM as SOM-Fe associated Sb complex. From these results, it was shown that increase of SOM under natural conditions or application of organic amendment under remediation process should increase availability of Sb to plants.

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.

Natural remediation of an unremediated soil twelve years after a mine accident: Trace element mobility and plant composition

The long-term influence of a mine spill in soil was studied 12 years after the Aznalcóllar accident. Soils where the pyritic sludge was not removed, a fenced plot established for research purposes (2000 m2) and soils where the process of remediation was accomplished successfully were sampled and studied in detail. Soils were characterized at different depths, down to 100 cm depth, determining chemical parameters and total concentrations of major and trace elements. Moreover plants colonizing remediated (RE) and non remediated (NRE) soils were also analysed attending their potential risk for herbivores. Strong acidification was observed in the NRE soil except in surface (0–10 cm). The progressive colonization of natural vegetation, more than 90% of the fenced plot covered by plants, could facilitate this increased pH values in the top soil (pH 6). In the NRE soil, the successive oxidation and hydrolysis of sulphide in the deposited sludge on the surface after the accident resulted in a re-dissolution of the most mobile element (Cd, Cu and Zn) and a penetration to deeper layers. Trace element concentrations in plants growing in the NRE soil showed normal contents for higher plants and tolerable for livestock. Nitrogen and mineral nutrients were of the same order in both soils, and also normal for high plants and adequate for animal nutrition. Despite of the natural remediation of the NRE soil, results demonstrate that the remediation tasks carried out in all the area, the Guadiamar Green Corridor at present, were necessary to avoid the leaching of the most mobile elements and minimize the risk of contamination of groundwater sources, many of them close to the Doñana National Park.

Recovery of the Bird Community after a Mine Spill and Landscape Restoration of a Mediterranean River

AbstractIn Mediterranean areas, river systems are key for maintaining regional biodiversity by providing a high diversity of habitats. We studied bird community recovery for 9 years (2001–2009) during landscape restoration and Guadiamar Green Corridor establishment in the area affected by the Aznalcóllar mine spill (SW Spain, 1998). One year following plant restoration (3 years after the spill), values for α‐ and β‐bird species diversity were high, sooner than reported for similar restoration processes elsewhere. Species richness, ecological diversity, and abundance increased only slightly in the following 8 years. Overlap between communities in sequential years, measured by similarity indexes, increased throughout the study period to about 70% during final survey years, and most breeding bird species present before the accident again inhabit the area. Only 5 years after the mine accident, bird communities in the restored site were similar in species richness, abundance, and diversity to an unaffected reference site; redundancy analysis demonstrated that bird communities were also similar between the reference river and the Guadiamar. Despite the severity of the mine accident, our results suggest a swift recovery of the bird community. We attribute this success to the rapid restoration of habitat availability and the resilience of the birds. This long‐term study contributes to our limited knowledge of bird species response to habitat restoration following toxic spills in Mediterranean habitats.

Recovering the Reptile Community after the Mine‐Tailing Accident of Aznalcóllar (Southwestern Spain)

Abstract Ecosystem restoration requires that habitat requirements of all species be considered. Among animal communities in Mediterranean ecosystems, reptiles, as ectothermic vertebrates, need refuges for avoidance of extreme environmental temperatures, concealment from predators, and oviposition sites. In 1998, a massive amount of tailings broke out of the holding pond of the Aznalcóllar mine (southwestern Spain) and polluted the Guadiamar river valley. After the accident, a soil‐ and vegetation restoration program began, and the Guadiamar Green Corridor was created to connect two huge natural areas, Doñana National Park and the Sierra Morena. Within this corridor, the reptile community remained dramatically impoverished, probably because of elimination of all natural refuges during the soil restoration program. To test this hypothesis, we set an array of artificial refuges (logs) in a large experimental plot. During the 5 years of the experiment (2002–2006), the area managed with artificial refuges exhibited a better and faster recovery of the reptile community in species richness and individual abundance than did the control area with no artificial refuges. Moreover, reptile colonization of the Guadiamar Green Corridor was transverse rather than lineal—that is, it did not act as a corridor for reptiles, at least in the first stages of colonization. This suggests that landscape restoration programs should not neglect refuge availability, a limiting resource for reptile species.

Nutritional Status of Mediterranean Trees Growing in a Contaminated and Remediated Area

Soil contamination may contribute to forest decline, by altering nutrient cycling and acquisition by plants. This may hamper the establishment of a woody plant cover in contaminated areas, thus limiting the success of a restoration program. We studied the nutritional status of planted saplings of Holm oak (Quercus ilex subsp. ballota (Desf.) Samp.), white poplar (Populus alba L.), and wild olive tree (Olea europaea var. sylvestris Brot.) in the Guadiamar Green Corridor (SW Spain) and compared it with established adult trees. Soils in this area were affected by a mine-spill in 1998 and a subsequent restoration program. The spill resulted in soil acidification, due to pyrite oxidation, and deposited high concentrations of some trace elements. In some sites, we detected a phosphorus deficiency in the leaves of Q. ilex and O. europaea saplings, as indicated by a high N:P ratio (>16). For O. europaea, soil contamination explained 40% of the variability in leaf P and was negatively related to chlorophyll content. Soil pH was a significant factor predicting the variability of several nutrients, including Mg, P, and S. The uptake of Mg and S by P. alba was greater in acidic soils. The monitoring of soil pH is recommended since long-term effects of soil acidification may negatively affect the nutritional status of the trees.

Application of the mean individual biomass (MIB) of ground beetles (Coleoptera, Carabidae) to assess the recovery process of the Guadiamar Green Corridor (southern Iberian Peninsula)

This research is part of the Guadiamar River Basin (S Iberian Peninsula) Recovery Monitoring Programme. The main aim of this Program is to establish whether the management of the area affected by the Aznalcollar mining accident (1998) has indeed led to a regeneration process and to select applicable parameters for the future following program. The Carabidae Family was selected to analyse these questions since it is one of the most effective bio-indicator taxa belonging to the soil fauna. Previous research carried out in different areas from Europe suggested that the mean individual biomass (MIB) of ground beetles could be used as a suitable measure to assess the environment stage. This paper analyses the progress made by the ground beetles community 6 years after the disaster and aims to validate the usefulness of MIB as a means of assessing the recovery process of the Guadiamar Green Corridor. To evaluate changes in the research area over time, correlation and classification analysis have been performed. Indices commonly used in population dynamics were calculated in addition to the MIB. Results allow us to infer two conclusions: (I) The area as a whole is undergoing a significant recovery process. However, this process has not yet reached the expected levels of a non-affected basin in the southern Iberian Peninsula. (II) The application of the MIB index of Carabid beetles could be a useful tool to assess long-term environmental changes. However, this proposal requires further validation.