Search

In May 2017, a spill from La Zarza pit lake (SW Spain) resulted in the release of approximately 270,000 m3 of extremely acidic waters to the Odiel River. Around 780 × 103 kg of Fe, 170 × 103 kg of Al, 2.15 × 103 kg of As and high amounts of other trace metals and metalloids were spilled. The purpose of this study is to explain the causes, consequences and impacts of the mine spill on the receiving water bodies. To this end, an extensive sampling along the mine site, river and estuary as well as a hydrological model of the pit lake was performed. Around 53 km of the Odiel River's main course, which was already contaminated by acid mine drainage (AMD), were affected. The mine spill resulted in an incremental impact on the Odiel River water quality. Thus, dissolved concentrations of some elements increased in the river up to 450 times; e.g. 435 mg/L of Fe and 0.41 mg/L of As. Due to low pH values (around 2.5), most metals (e.g., Cu, Zn, Mn, Cd) were transported in the dissolved phase to the estuary, exhibiting a conservative behavior and decreasing their concentration only due to dilution. However, dissolved concentrations of Fe, Cr, Pb, Se, Sb, Ti, V and especially As decreased significantly along the river due to Fe precipitation and sorption/coprecipitation processes. At the upper zone of the estuary, a noticeable increment of metal concentrations (up to 77 times) was also recorded. The water balance illustrates the existence of groundwater inputs (at least 16% of total) to the pit lake, due probably to local infiltration of rainwater at the mining zone. The probable existence of an ancient adit connected to the pit lake indicates that potential releases could occur again if adequate prevention measures are not adopted. Image 1 • Around 270,000 m3 of extremely acidic waters were spilled from a pit lake. • An incremental impact after the spill on the already polluted Odiel River and estuary was observed. • Al, Cd, Co, Cu, Mn, Ni, Sc, U and Zn were conservatively transported to the estuary. • Cr, Fe, Se, Pb, Ti, Sb, V and As were removed from water by precipitation/sorption. • The pit lake has not yet reached equilibrium, a new spill could occur in the future. "An accidental discharge (270,000 m3 of acidic and metal-rich waters) from an abandoned pit lake to the Odiel River and its estuary caused a significant additional increase in the contaminant levels". [ABSTRACT FROM AUTHOR]

Bacterial and archaeal community structures and diversity of three different sedimentary environments (BH1A, BH2A and BH3A) in the acid pit lake of a chalcopyrite mine at Touro (Spain) were determined by 16S rRNA gene PCR-DGGE and sequencing of clone libraries. DGGE of bacterial and archaeal amplicons showed that the sediments harbor different communities. Bacterial 16S rRNA gene sequences were assigned to Acidobacteria, Actinobacteria, Cyanobacteria, Planctomycetes, Proteobacteria, Chloroflexi and uncultured bacteria, after clustering into 42 operational taxonomic units (OTUs). OTU 2 represented approximately 37, 42 and 37 % of all sequences from sediments BH1A, BH2A and BH3A, respectively, and was phylogenetically related to uncultured Chloroflexi. Remaining OTUs were phylogenetically related to heterotrophic bacteria, including representatives of Ferrithrix and Acidobacterium genera. Archaeal 16S rRNA gene sequences were clustered into 54 OTUs. Most of the sequences from the BH1A sediment were assigned to Euryarchaeota, whereas those from BH2A sediment were assigned to Crenarchaeota. The majority of the sequences from BH3A sediment were assigned to unclassified Archaea, and showed similarities to uncultured and unclassified environmental clones. No sequences related to Acidithiobacillus and Leptospirillum, commonly associated with acid mine drainage, were detected in this study. [ABSTRACT FROM AUTHOR]

The objective of this study was to determine to what extent the attenuation or loss of andic soil properties caused by land use change – from forest (FOR, average C content 118.2 ± 23.7 g kg−1) to agricultural land (AGR, average C content 55.7 ± 16.7 g kg−1) use – is reflected in soil organic matter (SOM) at the molecular level. For this, NaOH-extractable SOM of A horizons from 17 soils developed on amphibolitic parent material in NW Spain was studied by pyrolysis gas chromatography spectrometry (Py-GC/MS). We also included two buried andic A horizons (PAL, 2200 cal yr BP in age) on the same parent material, as a reference for the molecular composition of SOM from soils without recent litter additions. Organic matter of PAL soils had a composition largely different from that of superficial soils (FOR and AGR), with an important relative contribution of microbial polysaccharides and N-compounds, and an absence of compounds that characterize fresh plant litter (e.g. lignins). In the superficial soils, the relative contribution of lignin-derived compounds was greater in AGR than in FOR soils. Differences were also observed in the relative contribution of aliphatic compounds, FOR soils being enriched in this type of components compared with AGR soils. The results indicated that land use change from FOR to AGR, which was accompanied by a decrease in total SOM, resulted in an enrichment in primary SOM. The smaller relative abundance of primary SOM derivatives in andic FOR soils indicates that these compounds were quickly degraded in Andisols. [ABSTRACT FROM AUTHOR]

Examines the phosphate and sulfate sorption capacities of several Spanish Spodosols with albic horizon. Molar ratios of organic carbon; Characteristics of soil used in the study; Identification of the infrared spectra of untreated soil samples from spodic horizons.

Abstract: The potential of soils as a sink of atmospheric carbon and the implications related to mitigate greenhouse-gas emissions are well recognized. The raising of tree crops on agricultural soils can augment soil-carbon sequestration more than do other agricultural uses such as corn crops. Thus, 6 plots with different durations of use as poplar plantation (5, 10, 20, 30, 50, and 100 years) were studied in comparison with 6 adjacent plots with corn crop. The carbon pool in poplar-plantation soils was positively correlated to the time of use at the three soil depths studied (0–20, 20–50, and 50–100cm), the mean annual increase being 1.16Mg C ha−1 year−1. Poplar-plantation soils also increased the total carbon content in a more effective way because the duration of use was also correlated with the most recalcitrant carbon forms. Therefore, land-use change from corn crops to poplar-plantation soils is economically profitable as well as positive both for the total organic-carbon pool as well as for the efficiency of carbon sequestration by the increase of non-oxidizable forms in the soil. [Copyright &y& Elsevier]

Abstract: The rhizosphere is a narrow zone of soil influenced by plant root and their exudates and its extent varies with soil type, plant species, age and many other factors. The rhizosphere microenvironment therefore has different characteristics from those of bulk soils. In the present study, the physicochemical parameters, exchangeable micronutrients (extracted with 1M NH4Cl), available micronutrients (extracted with Mehlich-III: Fe, Mn, Cu, and Zn), toxic metals (Cr, Pb, Ni, Cd), the Fe associated with the organic matter (extracted with Na-pyrophosphate) and the poorly crystalline Fe (extracted with 0.2M oxalic acid) were studied in the bulk soil and in the rhizosphere of the spontaneous vegetation growing at an abandoned copper mine. The natural vegetation colonising the mine dump included two species of Ericaceae (Erica cinerea, Calluna vulgaris) and Salix atrocinerea, whereas only the first two grew on the mine slope. The results showed that plants influence the physicochemical conditions of the rhizosphere, although not all in the same way. Thus the pH of the rhizosphere of the ericaceous species was extremely low, approximately 2–3units lower than the pH of the bulk soil, whereas the pH of the Salix rhizosphere remained close to the respective bulk soil, which has a pH of 6.6. Furthermore, the concentration of organic matter was higher in the rhizosphere than in the bulk soil. In general the same pattern was observed for the most labile fractions of the micronutrients and toxic metals, with higher concentrations in the rhizosphere than in the bulk soil. However, there were clear differences between the ericaceous species and Salix, which prevents general conclusions being reached about the processes to which trace metals are submitted in the rhizosphere. On the other hand, although the elements under study are included in the term trace metals, they display different geochemical behaviour. Thus the exchangeable fraction was clearly correlated with the TOC for all micronutrients except Cu, presumably because the organic matter selectively adsorbs this element, thereby reducing its mobility. Finally, as regards the potential toxicity, only the concentrations of Cu and Fe surpassed the limits above which phytotoxicity may occur, while toxic metals were present at very low concentrations. [Copyright &y& Elsevier]

Abstract: Concentrations of the isomers of the organochlorine pesticide hexachlorocyclohexane (HCH) were determined in 252 surface soil samples collected within a sampling network covering agricultural areas in Galicia (NW Spain). The concentration of total HCH (sum of α+β+γ+δ) ranged between 4 and 2305ngg−¹ (dry weight), with the α-HCH and γ-HCH isomers predominating (<1–1404ngg−¹ and <1–569ngg−¹, respectively). The distribution of the pesticide residues was very heterogeneous, with the largest concentrations present in one of the studied areas (the province of A Coruña). The distribution of HCH was not found to be related to any soil property (organic matter, pH, clays, and metals). Multivariate statistical analysis of the data revealed that three populations of samples with a defined composition of HCH, can be related to the source of HCH: technical HCH (α/γ>3), lindane (99% γ-HCH), or both. The existence of a third population consisting almost exclusively of α-HCH suggests that background contamination of anthropogenic origin dates from several decades ago. The detailed analysis of these populations enabled the possible temporal scale of the application of these pesticides to be deduced. [Copyright &y& Elsevier]

This research reports the effects of pH increase on contaminant mobility in acid mine drainage from the Iberian Pyrite Belt by seawater mixing in the laboratory, simulating the processes occurring in the Estuary of Huelva (SW Iberian Peninsula). Concentrations of Al, Fe, As, Cu and REY in mixing solutions significantly decreased with increasing pH. Schwertmannite precipitation at pH 2.5-4.0 led to the total removal of Fe(III) and As. Subsequently, iron-depleted solutions began to be controlled by precipitation of basaluminite at pH 4.5-6.0, which acted as a sink for Al, Cu and REY. Nevertheless, as the pH rises, schwertmannite becomes unstable and releases back to solution the previously retained As. Moreover, other elements (S, Zn, Cd, Ni and Co) behaved conservatively in mixing solutions with no participation in precipitation processes. Some toxic elements finally end up to the Atlantic Ocean contributing to the total pollutant loads and environmentally threatening the coastal areas., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

This study investigates the behavior of Tl in the Ría de Huelva (SW Spain), one of the most metal polluted estuaries in the world. Dissolved Tl concentration displayed a general decrease across the estuary during the dry season (DS); from 5.0 to 0.34 μg/L in the Tinto and Odiel estuaries, respectively, to 0.02 μg/L in the channel where the rivers join. A slighter decrease was observed during the wet season (WS) (from 0.72 to 0.14 μg/L to 0.02 μg/L) due to the dilution effect of rainfalls in the watersheds. These values are 3 orders of magnitude higher than those reported in other estuaries worldwide. Different increases in Tl concentrations with salinity were observed in the upper reaches of the Tinto and Odiel estuaries, attributed to desorption processes from particulate matter. Chemical and mineralogical evidences of particulate matter, point at Fe minerals (i.e., jarosite) as main drivers of Tl particulate transport in the estuary. Unlike other estuaries worldwide, where a fast sorption process onto particulate matter commonly takes place, Tl is mainly desorbed from particulate matter in the Tinto and Odiel estuaries. Thus, Tl may be released back from jarositic particulate matter across the salinity gradient due to the increasing proportion of unreactive TlCl 0 and K + ions, which compete for adsorption sites with Tl + at increasing salinities. A mixing model based on conservative elements revealed a 6-fold increase in Tl concentrations related to desorption processes. However, mining spills like that occurred in May 2017 may contribute to enhance dissolved and particulate Tl concentrations in the estuary as well as to magnify these desorption processes (up to around 1100% of Tl release), highlighting the impact of the mine spill on the remobilization of Tl from the suspended matter to the water column., (Published by Elsevier Ltd.)

Acid mine drainage (AMD) due to the mining of sulfide deposits is one of the most important causes of water pollution worldwide. Remediation measures, especially in historical abandoned mines, require a deep knowledge of the geochemical characteristics of AMD effluents and metal fluxes, considering their high spatial and temporal evolution, and the existence of point and diffuse sources with a different response to rainfall events. This study investigates the temporal variations and hydrogeochemical processes affecting the composition of main AMD sources from the Tharsis mines (SW Spain), one of most important historical metal mining districts in the world. To address this, a fortnightly-monthly sampling was performed during two years in the main AMD sources and streams within the mine site covering different hydrological conditions. A seasonal pattern was observed linked to hydrological variations; higher pollutant concentrations were observed during the dry season (maximum values of 4,6 g/L of Al, 11,8 g/L of Fe, and 67 g/L of sulfate) and lower ones were observed during the rainy periods. Stream samples exhibited a negative correlation between electrical conductivity (EC) and flow, while positive values were observed in AMD sources, where groundwater fluxes were predominant. High flow also seems to be the main driver of Pb fluxes from AMD sources, as the concentration of Pb in waters increased notably during these events. The precipitation of secondary Fe minerals may limit the mobility of As and V, being retained in the proximity of mine sites. The concentration of Zn in waters seems to be controlled by the original grade in the metal deposit from which the waste is generated, together with the age of these wastes. The pollutant load delivered by the Tharsis mines to the surrounding water courses is very high; e.g., mean of 733 ton/yr of Al or 2757 ton/yr of Fe, deteriorating the streams and reservoirs downstream., (Copyright © 2021 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

This paper tries to analyse the technical and economic performance of a full-scale passive Disperse Alkaline Substrate (DAS) treatment plant steadily operating for 28 months (840 days) to treat extremely acidic and metal rich mine waters in the Iberian Pyrite Belt (SW Spain). For the first time, an economic evaluation of this technology and its comparison with other passive treatments is reported. During this period, around 56,000 m 3 of mine waters have been treated, without significant clogging or exhaustion of the alkaline substrate. The efficiency of the system is demonstrated by a significant decrease in the average net acidity (from 2005 to -43 mg/L as CaCO 3 equivalent) and the total elimination of Al, Cu, REY, Zn, As, Cr, Mo, V, Cd, Pb, Co and other trace metals. Water quality of the treated output discharge meets the threshold values for irrigation and drinking standards, except for Fe, Mn and sulphate. The accumulation of elements of economic interest in the waste (e.g., 32 t of Fe, 6.1 t of Al, 0.8 t of Cu, 0.8 t of Zn, 39.4 kg of REE, 20 kg of Co or 1 kg of Sc), easily extractable with diluted acids, may turn a hazardous waste into a valuable resource. The benefits associated with the revalorization of this metal-rich waste could reach a total of 27478 USD, but is more reliably estimated to be around 8243 USD due to technologic limitations. This benefit would help to defray the maintenance costs (8428 €) and make DAS an economically self-sustainable treatment. The annual treatment cost for DAS was 0.27 €/m 3 , being the lowest value found among other reported conventional passive schemes, and from 8 to 12 times lower compared to active technologies. The results obtained prove that the DAS technology is the most technically and economically sustainable way to decontaminate acid and metal-rich mine waters in abandoned mines., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The optimization of the dispersed alkaline substrate (DAS) technology was investigated to achieve the treatment of highly acidic and polluted effluents from a phosphogypsum pile in an orphan site of SW Spain. This phosphogypsum disposal area is located on the Tinto river marsh soils, where it acts as a source of pollution for the estuarine environment, releasing high concentrations of metal(loid)s and radionuclides, which degrade the surrounding waters. The methodology consists of flowing the leachates through columns loaded with a combination of a fine-grained alkaline reagent scattered in a non-reactive matrix to raise the water pH while decreasing the solubility of dissolved contaminants. Seven columns were built, one for each of the alkaline reagent used: limestone, barium carbonate, biomass ash, fly ash, MgO, Mg(OH) 2 , and Ca(OH) 2 . The Ca(OH) 2 -DAS and MgO-DAS treatment systems showed the highest effectiveness, reaching near-total removal for PO 4 , F, Fe, Zn, Cu, Al, Cr, and U with initial reagent mass:treated volume ratios of 36.3 g/L and 7.57 g/L, respectively. Total As removal was only achieved in the Ca(OH) 2 -DAS treatment. Phosphate precipitation was the main mechanism responsible for pollutants removal. Geochemical modeling using PHREEQC code and mineralogical evidence confirmed the precipitation of these minerals. This study forms the basis of an effective and environmentally sustainable treatment system for phosphogypsum leachates to reduce the impact of the fertilizer industry worldwide., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Metal pollution in estuaries represents a serious environmental challenge, especially in areas affected by industrial and mining activities. This study investigates the metal partitioning and availability of rare earth elements (REE), Y and other trace metals (Ag, Tl, U and Cs) in the Ria of Huelva estuary (SW Spain), strongly affected by mining and industrial activities. A 30 h monitoring campaign was performed collecting periodic water samples and deploying diffusive gradient in thin films (DGTs) devices to determine the main factors controlling metal availability. The dissolved concentrations of U (3118-3952 ng/L) and Cs (284-392 ng/L) were in the same order of magnitude than those reported in other estuaries and coastal waters worldwide, however, REE (26-380 ng/L), Y (15-109 ng/L), Ag (14-307 ng/L) and Tl (29-631 ng/L) concentrations exceeded these values for the same salinities. Unlike most metals (i.e. Ag, Tl, U, Cs), which were mainly found in the dissolved form (87-100% of total), REE and Y were found in the particulate phase (22-36% of total). Metal lability was mainly related to the concentration in the water column following this order: U>REE>Y>Ag>Tl. A similar binding mechanism was observed for Tl and Cd, due to its chemical affinity. This relationship between chemical properties and absorption by DGT-resin was also observed for REE (and Y), Rb and Sr, which may cause bioaccumulation upon persistent exposure, considering the ability of these metals to cross the biological membranes. The lability of metals predicted by geochemical codes did not coincide with absorption of labile metals by DGTs due probably to the instability of complexes in contact with the DGT membranes, the inability of metals to form thermodynamically stable complexes or the absorption of colloids. From this work it can be concluded that DGT passive sampling should complement traditional sampling to monitor metal availability in aquatic environments., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

This work deals with the distribution of rare earth elements (REE) in the abandoned Tharsis mines under different hydrological conditions. High concentrations of REE were observed; mean value of 1747 μg/L. The highest concentrations of REE were recorded during the dry period (DP, mean of 2220 μg/L) due to high evaporation and strong water-rock interactions. However, some sampling points showed the highest REE concentrations during the wet period (WP) due to the washing out of large dumps during intense rainfall. The concentration of REE shows a positive correlation with electrical conductivity (EC) and a negative correlation with pH because more acidic conditions enhance dissolution of minerals. However, the highest concentrations of REE occurred in samples with intermediate levels of metal pollution and EC values. The highest correlations of middle REE (MREE) and heavy REE (HREE) occurred with elements related to hydrothermal mineralisation of Mn and Ni, associated with sulphide deposits. The normalised patterns of the AMD sources showed an enrichment of MREE over light REE (LREE) and HREE in all samples. The use of REE patterns as geochemical tracers confirmed the conservative behaviour of REE in the fluvial network, that is, they are not affected by the precipitation of mineral phases. The quantification of REE released from AMD sources to water bodies reveals that, although the highest concentrations occur during the DP, the main load of REE occurs during the WP, due to the highest discharges, with 6.62 kg/day of LREE, 1.12 kg/day of MREE, and 0.54 kg/day of HREE., Competing Interests: Declaration of competing interest None., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The Tharsis mine is presently abandoned, but the past intense exploitation has left large dumps and other sulphide-rich mining wastes in the area generating acid mine drainages (AMD). The main goal of this work is to study the effect of hydrogeochemical processes, hydrological regime and the waste typology on the physicochemical parameters and dissolved concentrations of pollutants in a deeply AMD-affected zone. Extreme leachates are produced in the area, reaching even negative pH and concentrations of up to 2.2 g/L of As and 194 g/L of Fe. The results of the comparison of ore grades of sulphide deposits with dissolved concentrations in waters shows that Pb is the least mobile element in dissolution probably due to the precipitation of Pb secondary minerals and/or its coprecipitation on Fe oxyhydroxysulphates. Arsenic, Cr, and V are also coprecipitated with Fe minerals. Seasonal patterns in metal contents were identified: elements coming from the host rocks, such as Al, Mn and Ni, show their maximum values in the dry period, when dilution with freshwater is lower and the interaction of water-rock processes and evaporation is higher. On the other hand, As, Cr, Fe, Pb and V show minimum concentrations in the dry period due to intense Fe oxyhydroxysulphate precipitation. In this sense, large sulphide rich waste heaps would be a temporal sink of these elements (i.e. Pb, As, Cr and V) in the dry period, and a significant source upon intense rainfalls., Competing Interests: Declaration of competing interest None., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Introduction: Type 1 Diabetes Mellitus (T1DM) is the second leading chronic disease and the most common endocrine-metabolic disorder in childhood. The study objective was to estimate the direct cost of T1DM in pediatric patients in Andalusia., Methodology: A descriptive, observational, multicenter study was conducted during six consecutive months of 2017-2018 on a sample of 220 patients from 6 hospitals in Andalusia. Variables collected included demographic characteristics, metabolic control parameters, glucose levels, use of continuous monitoring systems, mean HbA 1c levels, episodes of severe hypoglycemia and ketoacidosis, comorbidities and complications, as well as direct healthcare costs, including costs of drugs, materials, laboratory tests, and supplemental tests, as well as those derived from both inpatient and outpatient care., Results: The study sample consisted of 178 patients. Mean age at diagnosis was 6 years, and mean disease duration was 4.69 (0.29 SD) years. Mean HbA 1c level was 7.06%, and 25% of patients had values higher than 7.5%. The estimated annual cost per patient was € 4,720.4. Cost derived from use of insulins (€ 2,212.9) and materials for insulin administration and blood glucose monitoring (€ 1,518) accounted for greatest proportion of cost (79.1%). No association was found between metabolic control, comorbidities, or complications and cost of disease., Conclusion: This study has shown a direct cost associated to T1DM in Andalusian children of approximately € 4,700 per patient., (Copyright © 2019 SEEN y SED. Publicado por Elsevier España, S.L.U. All rights reserved.)

A passive treatment plant, located in the Iberian Pyrite Belt (Huelva, Southwest Spain), was designed for acid mine drainage remediation. Since its installation, the improvement of water quality in terms of hydrochemical composition has been demonstrated successfully. However, according to the Water Framework Directive, the treated effluent must have ecological values for potential living. The freshwater clam Corbicula fluminea was chosen to carry out bioassessments (survival, biomarker responses, and metal bioaccumulation in soft tissue) with effluents from the mining site, as well as, products from the passive treatment plant in order to determine the level of quality of that water from the biological point of view in toxicity tests. Results discarded mortality as endpoint for biomonitoring purposes. Only the lipid peroxidation of the cell membrane evidenced significant responses, even in correlation with the pollution degree of each effluent. Regarding bioaccumulation, some elements displayed a strong relationship (Fe, Cu, Co, and Zn) between concentrations in the environment and in the tissue. As final conclusion, the usage of the Asian clam was validated as biomonitor tool in short term exposure to acid mine drainage, and, as early warning responses (72 h), the chosen parameters would be lipid peroxidation and bioaccumulation of a specific set of elements (Fe, Cu, Co, Zn). Ecological water quality levels reached by the passive treatment plant were in agreement with the efficiency of hydrochemical improvements., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The cementation complex of Las Viñas (SW Spain) is a partially reclaimed abandoned mine site located in the drainage basin of a water reservoir currently under construction. The aim of this investigation was to analyze these mine soils to evaluate their potential environmental impact, especially on the final reservoir water quality. Results evidence the extremely high acidity of soils (pH of 3.4 and maximum potential acidity of 47 kg CaCO 3 /ton), with high concentrations of trace elements, especially As, Pb and Cu. Sequential extraction data reveal the potential release of significant quantities of Mn, Cd, Cu and other easily-soluble trace elements by rainfalls. The weathering and transport of soils to the bottom sediments of the planned reservoir could lead to the release of significant quantities of toxic trace elements to the water column if anoxic (mainly As, Sb, Cr, Ni, Cu and Pb) or oxic (mainly Hg, Pb, V, Cu and As) conditions are found in the sediments. The acidity and metals released from these soils could jeopardize the quality of the reservoir waters. Remediation measures must be therefore adopted, focused on the cleanup and liming of soils in order to promote colonization and vegetation succession, thus avoiding soil erosion and limiting metal release to the hydrosphere. This study proposes the use of different low-cost materials to improve the soil quality, limiting the metal transfer to the planned reservoir water. The information contained in this study could be of great importance in other watersheds affected by abandoned mine sites., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Water resources management and restoration strategies, and subsequently ecological and human life quality, are highly influenced by the presence of short and long term cycles affecting the intensity of a targeted pollution. On this respect, a typical acid mine drainage (AMD) groundwater from a sulfide mining district with dry Mediterranean climate (Iberian Pyrite Belt, SW Spain) was studied to unravel the effect of long term weather changes in water flow rate and metal pollutants concentration. Three well differentiated polluting stages were observed and the specific geochemical, mineralogical and hydrological processes involved (pyrite and enclosing rocks dissolution, evaporitic salts precipitation-redisolution and pluviometric long term fluctuations) were discussed. Evidencing the importance of including longer background monitoring stage in AMD management and restoration strategies, the present study strongly advise a minimum 5-years period of AMD continuous monitoring previous to the design of any AMD remediation system in regions with dry Mediterranean climate., (Copyright © 2015 Elsevier B.V. All rights reserved.)

During 20 months of proper operation the full scale passive treatment in Mina Esperanza (SW Spain) produced around 100 mg/L of ferric iron in the aeration cascades, removing an average net acidity up to 1500 mg/L as CaCO(3) and not having any significant clogging problem. Complete Al, As, Cd, Cr, Cu, Ti and V removal from the water was accomplished through almost the entire operation time while Fe removal ranged between 170 and 620 mg/L. The system operated at a mean inflow rate of 43 m(3)/day achieving an acid load reduction of 597 g·(m(2) day)(-1), more than 10 times higher than the generally accepted 40 g·(m(2) day)(-1) value commonly used as a passive treatment system designing criteria. The high performance achieved by the passive treatment system at Mina Esperanza demonstrates that this innovative treatment design is a simple, efficient and long lasting remediation option to treat highly polluted acid mine drainage., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Calculations of critical loads of acidity within Europe have shown Galicia to be one of the regions in Spain with the highest risk of soil acidification by deposition of atmospheric pollutants. We used the simple mass balance method (SMB) to derive critical loads of sulphur and nitrogen for forest soils in Galicia using available site-specific information. Exceedance of acidic deposition was calculated using the deposition levels of N and S registered in 2001. Most forest ecosystems analysed can support acid loads of more than 2000 eq N ha(-1) year(-1). The lowest critical loads of acidity (1483 eq ha(-1) year(-1)) occurred in coniferous forest stands growing on shallow soils developed on slates, in the interior zone. The highest critical load values (9386 eq ha(-1) year(-1)) were observed in coniferous stands in zones with elevated precipitation rates, in the littoral area. The critical load for acidity was exceeded in 5% of the forest soils. Such exceedances were mainly caused by deposition of nitrogen compounds. The contribution of sulphur deposition to acid exceedance was important in the surroundings of the city of A Coruña. Analysis of rainfall bulk composition revealed that N deposition in Galicia was mainly due to ammonium emissions, probably derived from agricultural and cattle breeding activities.

The trace elements present at highest concentrations were Cr and Zn, which probably originated from the dumping of effluent from a tanning factory. High proportions of these two elements were associated with the residual fraction. Biodeposits and sediments showed high concentrations of Cd and Pb in the reactive fraction, with a high proportion of the concentration in the reactive fraction being associated with carbonates. Nickel showed a higher degree of pyritization than the previous elements, although most of the Ni was associated with the residual and reactive fractions. Arsenic, Hg and Cu showed high degrees of pyritization, particularly below a depth of 5 cm. The results demonstrate that those elements with a high degree of pyritization may be released into the water through oxidation of the metal sulphides that they form when in suspension in oxic sea water, with the subsequent risk of increased bioavailability to benthic fauna.

The composition of interstitial water collected from a salt marsh in NW Spain showed clear seasonal and spatial variations associated with redox cycles of Fe and S. In the summer, salinity increased in all soils as a consequence of the increase in evapotranspiration. The pH and concentrations of heavy metals also differed with season, but not all environments showed the same variations. Soils not colonized by plants had the highest pH and lowest heavy metal concentrations in the summer. These results support the idea that higher temperatures lead to an increase in the activity of sulfate-reducing bacteria, which in turn leads to an increase in alkalinity and concentration of sulfides in the water. Trace metals tend to precipitate with sulfides under these conditions and are removed from the interstitial water. In contrast, in the soils colonized by Spartina maritima, the oxidation of metal sulfides during the summer led to a decrease in pH and an increase in the metal concentrations in the interstitial water. The results obtained concur with those found for seasonal variations in metal sulfides in soils from the same salt marsh.