High-resolution temporal monitoring of rare earth elements in acidic drainages from an abandoned sulphide mine (iberian pyrite belt, Spain).

Rare earth elements (REE) are strategic elements due to their economic importance. However, the studies dedicated to the distribution and behaviour of REE in aquatic systems have been scarce until a few decades ago. This work studies the seasonal variations of REE concentrations in acid mine drainage (AMD) affected water courses and the factors controlling their mobility under different hydrological conditions. To address this issue, a high-resolution sampling was performed for two years in selected sampling sites. REE concentrations were very high (median values of 2.7-3.4 mg/L, maximum of 7.0 mg/L). These values are several orders of magnitude higher than those found in natural waters, highlighting the importance of AMD processes on the release of REE to the hydrosphere. No good correlations were found between pH and REE concentration, while REE correlated positively (r Spearman coefficient of 0.78-0.94) with EC and negatively (r -0.88 to -0.90) with discharge in AMD-affected streams. A conservative behaviour of REE was observed due to the strongly acidic conditions observed in the study area. The waters also showed an enrichment in MREEs over LREEs and HREEs (mean values of GdN/LaN>1.8 and YbN/GdN < 0.7), typical of AMD waters. An asymmetry in the content of LREE and HREE was observed in AMD samples studied, which could be explained by the preferential dissolution of LREE or HREE-enriched minerals within each waste heaps. Multivariate analysis suggests the influence of Mn-rich minerals existent in the study area as a potential source of LREE.

Metal mobility and bioaccessibility from cyanide leaching heaps in a historical mine site.

Unlike acidic sulfide mine wastes, where metal/loid mobility and bioaccessibility has been widely studied, less attention has been paid to alkaline cyanide heap leaching wastes. Thus, the main goal of this study is to evaluate the mobility and bioaccessibility of metal/loids in Fe-rich (up to 55%) mine wastes resulting from historical cyanide leaching activities. Wastes are mainly composed of oxides/oxyhydroxides (i.e. goethite and hematite), oxyhydroxisulfates (i.e. jarosite), sulfates (i.e., gypsum, evaporitic sulfate salts), carbonates (i.e., calcite, siderite) and quartz, with noticeable concentrations of metal/loids (e.g., 1453-6943 mg/kg of As, 5216-15,672 mg/kg; of Pb, 308-1094 mg/kg of Sb, 181-1174 mg/kg of Cu, or 97-1517 mg/kg of Zn). The wastes displayed a high reactivity upon rainfall contact associated to the dissolution of secondary minerals such as carbonates, gypsum, and other sulfates, exceeding the threshold values for hazardous wastes in some heap levels for Se, Cu, Zn, As, and sulfate leading to potential significant risks for aquatic life. High concentrations of Fe, Pb, and Al were released during the simulation of digestive ingestion of waste particles, with average values of 4825 mg/kg of Fe, 1672 mg/kg of Pb, and 807 mg/kg of Al. Mineralogy may control the mobility and bioaccessibility of metal/loids under rainfall events. However, in the case of the bioaccessible fractions different associations may be observed: i) the dissolution of gypsum, jarosite and hematite would mainly release Fe, As, Pb, Cu, Se, Sb and Tl; ii) the dissolution of an un-identified mineral (e.g., aluminosilicate or Mn oxide) would lead to the release of Ni, Co, Al and Mn and iii) the acid attack of silicate materials and goethite would enhance the bioaccessibility of V and Cr. This study highlights the hazardousness of wastes from cyanide heap leaching, and the need to adopt restoration measures in historical mine sites.

Consequences of sea level rise for high metal(loid) loads in the Ría of Huelva estuary sediments.

Ría of Huelva, located in southwestern Spain, is a highly metal(loid)-contaminated estuary system where sediments are exceeding action limits in an increasing order for Cd, Zn, Pb, Cu, and As. With a predicted sea level rise over the next 50 years, the estuary will be subject to flooding with brackish water or seawater. To evaluate the risk of metal(loid) mobilization under future climate scenarios, different locations along the estuary were sampled at different depths. Samples were flooded with river water, brackish water, and seawater under different short- and long-term laboratory setups. Potential metal(loid) mobilization showed that water quality standards for As, Pb, Zn, Ni, Cu, and Cd could be exceeded upon seawater flooding. However, metal(loid) mobilization was not predictable solely based on sediment loads. The driving factors for cation and anion mobility were identified to be mainly pH under low salinity and competitive desorption under high salinity conditions. Further drivers such as wave movement or labile C input in C-limited systems were found to enhance metal(loid) mobilization. Long-term flooding of intact sediment cores revealed that sea level rise will have different effects on the estuary system depending on duration of flooding. Short-term flooding in the near future will first affect alkaline sediments and enhance currently low cation mobilization, while anion mobilization due to reductive Fe dissolution will remain high. Once acidic sediments further inland are flooded with seawater, highest contaminant mobilization can be expected as high salinity will further enhance already high cation mobilization under acidic pH. Long-term flooding with seawater will neutralize the sediment pH and limit cation mobilization compared to acidic pH. However, the contaminant load stored in the estuary is so high that, extrapolating data obtained, mobilization could last for >1000 years, e.g. for As, Pb, and Al.

Potential release and bioaccessibility of metal/loids from mine wastes deposited in historical abandoned sulfide mines.

This study deals with the potential release of metal/loids from sulfide mine wastes upon weathering and the health risks associated with their accidental ingestion. To address this, a complete chemical and mineralogical characterization of a variety of sulfide mine wastes was performed alongside a determination of metal/loid bioaccessibility through leaching tests simulating human digestive and lung fluids. The mine wastes consisted predominantly of Fe (35-55% of Fe2O3) and exhibited high concentrations of trace metalloids such as As (382-4310 mg/kg), Pb (205-15,974 mg/kg), Cu (78-1083 mg/kg), Zn (274-1863 mg/kg), or Sb (520-1816 mg/kg). Most wastes with high concentrations of soluble compounds are considered hazardous according to the European regulations due to the exceedance of threshold values for As, Pb, Cr, Cu, Sb, sulfates, and Zn determined by standardized tests. In general terms, the absorption of waste-hosted metals through both digestive and respiratory routes was low compared to the total metal contents of the wastes, with values below 8% of the total concentration in wastes for most metal/loids including Cu, Zn, As, Cd, Tl, or U. However, some metals exhibited a significantly higher absorption potential, especially through the respiratory route, reaching values of up to 17% for Cr and 75% for Pb, highlighting the strong bioaccessibility of Pb in certain sulfide wastes. Despite the high metal/loid concentrations observed in the studied wastes, a health risk assessment indicated that some non-carcinogenic effects could be observed in children only following the accidental digestion of Pb.

Thallium distribution in an estuary affected by acid mine drainage (AMD): The Ría de Huelva estuary (SW Spain).

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 TlCl0 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.

Natural radioactivity and element characterization in pit lakes in Northern Sweden.

Northern Sweden has been the object of intense metal mining in the last decades producing several water-filled open-pits, or pit lakes. Most of these pit lakes have been limed to maintain a good water quality and to prevent generation of acidic water that could leach the exposed rocks and release metals into water. The aim of this work was to examine the concentration of stable elements and naturally occurring radionuclides in water and sediment samples from pit lakes originating from non-uranium mining activities in Northern Sweden. Surface water and surface sediments were collected from 27 pit lakes in Northern Sweden. Water quality parameters, concentration of stable elements and radionuclides were measured by a water probe, ICP-MS and XRF, and alpha and gamma spectrometry, respectively. Furthermore, a multivariate statistical analysis (PCA) was performed on the water samples and sediments. In general, the quality of the surface water was good, but some lakes had low pH values (2.5-5.7), and high concentrations of Fe (up to 200 mg/L) and other metals (e.g. Zn, Cu). When relating the metal concentrations in sediments in pit lakes with the concentration found in natural lakes, some sites had relatively high levels of Cu, As, Cr and Pb. The activity concentration of 210Po, and U and Th isotopes in water and sediment samples were at environmental levels, as was the ambient dose equivalent rate at these sites (range 0.08-0.14 µSv/h).

Geochemical behaviour and transport of technology critical metals (TCMs) by the Tinto River (SW Spain) to the Atlantic Ocean.

This paper addresses the behaviour of several technology critical metals (TCMs), i.e., rare earth elements (REEs), Y, Sc, Ga and Tl, in the Tinto River (SW Spain), quantifying their fluxes to the Atlantic Ocean and unravelling the governing geochemical processes controlling their solubility. To accomplish this goal, a high-resolution (2-24 h) sampling was performed during the hydrological year 2017/18. Mean dissolved concentrations of 380 µg/L of REE, 99 µg/L of Y, 15 µg/L of Sc, 9.2 µg/L of Ga and 4.8 µg/L of Tl were found. Most TCMs followed a behaviour similar to that of sulphate and base metals throughout the year, exhibiting a quasi-conservative behaviour due to acidic conditions. However, dissolved Tl concentrations seem to be strongly controlled by Tl incorporation onto secondary minerals and diatoms deposited on the riverbed, especially during the dry season. The remobilization of riverbed sediments led to the transport of significant amounts of TCMs associated with particulate matter, especially Al oxy-hydroxy-sulphates or Al-silicates rather than Fe precipitates (except for Tl and Ga). Around 5.8 t of REE, 1.3 t of Y, 248 kg of Sc, 139 kg of Ga and 138 kg of Tl were delivered annually in their dissolved forms by the Tinto River to the Atlantic Ocean, which constitutes around 0.09% of the dissolved global flux into the oceans of Y, 0.02% of the REE flux, 0.01% of the Ga flux and 0.001% of the Sc flux.

Distribution and availability of rare earth elements and trace elements in the estuarine waters of the Ría of Huelva (SW Spain).

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.

Rare earth elements in a historical mining district (south-west Spain): Hydrogeochemical behaviour and seasonal variability.

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.

Metal partitioning and speciation in a mining-impacted estuary by traditional and passive sampling methods.

This study deals with the metal partitioning and bioavailability of metal/loids in the estuary Ria of Huelva (SW Spain) which is strongly affected by historical mining and industrial activities. To address this issue, traditional (i.e., grab samples) and passive sampling (i.e., diffusive gradient in thin films, DGTs) was carried out in the outer part of the estuary during different tidal cycles in order to determine the dissolved and particulate metal/loid concentrations. The dissolved concentrations exceeded, by several orders of magnitude, those reported in other estuaries worldwide that are affected by anthropogenic activities. A spatial pattern was observed in the metal distribution; a decrease seaward was recorded for some of the elements associated with mining (e.g., Cu, Zn, and Cd), the opposite tendency is observed for others associated with harbor emissions (e.g., Sn, Ni, or Pb). A different metal/loid partitioning pattern was also observed; Fe, and to a lesser extent Pb and Sn, were chiefly found in the particulate matter, while the rest of the elements were mainly found in the dissolved form. The bioavailability of the metal/loids was studied by speciation using both geochemical modeling and DGTs; while concentrations in DGTs supported metal/loid speciation for Zn, Cd, Mn, Co, As, and Sb according to their affinity to form strong or weak complexes, some discrepancies were observed for other elements such as Cu, V, Fe, and Pb, which are prone to forming strong complexes. The main reason behind the unexpectedly high Fe and Pb DGTs concentrations may be associated with their presence in the colloidal particles passing through the DGT. There was a strong positive correlation between dissolved and DGT concentrations for Cd and Mn, and to a lesser extent for Fe and Cu, highlighting the direct relationship between the concentrations in water and availability to living organisms in the estuary.

Seasonal variability of extremely metal rich acid mine drainages from the Tharsis mines (SW Spain).

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.

Assessing the quality of potentially reclaimed mine soils: Environmental implications for the construction of a nearby water reservoir.

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 CaCO3/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.

Hydrogeochemical behavior of an anthropogenic mine aquifer: Implications for potential remediation measures.

This study characterizes the hydrogeochemical behavior of one of the most pollutant sources in the Iberian Pyrite Belt, namely, the Poderosa adit outflow. This artificial spring arises from an anthropogenic mine aquifer with a similar hydrogeological behavior to karstic systems, where the infiltration area is an endorheic zone and the aquifer shows allogenic recharge. Recent mining has markedly increased the contaminant levels. The pollutant load released from the adit to the receiving water body is very high, with average loads of 280 kg/day of Fe, 47 kg/day of Al, 17 kg/day of Cu and so on. However, a high variability is observed related to hydrological and geochemical factors, especially during intense rainy episodes. Thus, the pollutant load during these events suffers a dramatic increase, i.e., from ~100-200 kg/day of Fe during base flow to almost 2200 kg/day during the flow peak. These data highlight the importance of short but intense rainy events on metal fluxes from mining areas, which has been previously reported in surface waters but scarcely reported in mine adits, with expected lower response times to rainfall. The pollutant load released by non-point sources, i.e., spoil heaps, is lower than that released from the adit most of the year, although it increased noticeably during intense rainy events. Some remediation measures were adopted during the 1990s without a suitable hydrogeological characterization and were shown to be ineffective. On the basis of the obtained results, potential restoration measures are discussed.

Mobility of rare earth elements, yttrium and scandium from a phosphogypsum stack: Environmental and economic implications.

This paper investigates the mobility and fluxes of REE, Y and Sc under weathering conditions from an anomalously metal-rich phosphogypsum stack in SW Spain. The interactions of the phosphogypsum stack with rainfall and organic matter-rich solutions, simulating the weathering processes observed due to its location on salt-marshes, were simulated by leaching tests (e.g. EN 12457-2 and TCLP). Despite the high concentration of REE, Y and Sc contained in the phosphogypsum stack, their mobility during the leaching tests was very low; <0.66% and 1.8% of the total content of these elements were released during both tests. Chemical and mineralogical evidences suggest that phosphate minerals may act as sources of REE and Y in the phosphogypsum stack while fluoride minerals may act as sinks, controlling their mobility. REE fractionation processes were identified in the phosphogypsum stack; a depletion of LREE in the saturated zone was identified due probably to the dissolution of secondary LREE phosphates previously formed during apatite dissolution in the industrial process. Thus, the vadose zone of the stack would preserve the original REE signature of phosphate rocks. On the other hand, an enrichment of MREE in relation to HREE of edge outflows is observed due to the higher influence of estuarine waters on the leaching process of the phosphogypsum stack. Despite the low mobility of REE, Y and Sc in the phosphogypsum, around 104kg/yr of REE and 40kg/yr of Y and Sc are released from the stack to the estuary, which may imply an environmental concern. The information obtained in this study could be used to optimize extraction methods aimed to recover REE, Y and Sc from phosphogypsum, mitigating the pollution to the environment.

Oxycline formation induced by Fe(II) oxidation in a water reservoir affected by acid mine drainage modeled using a 2D hydrodynamic and water quality model - CE-QUAL-W2.

The Sancho reservoir is an acid mine drainage (AMD)-contaminated reservoir located in the Huelva province (SW Spain) with a pH close to 3.5. The water is only used for a refrigeration system of a paper mill. The Sancho reservoir is holomictic with one mixing period per year in the winter. During this mixing period, oxygenated water reaches the sediment, while under stratified conditions (the rest of the year) hypoxic conditions develop at the hypolimnion. A CE-QUAL-W2 model was calibrated for the Sancho Reservoir to predict the thermocline and oxycline formation, as well as the salinity, ammonium, nitrate, phosphorous, algal, chlorophyll-a, and iron concentrations. The version 3.7 of the model does not allow simulating the oxidation of Fe(II) in the water column, which limits the oxygen consumption of the organic matter oxidation. However, to evaluate the impact of Fe(II) oxidation on the oxycline formation, Fe(II) has been introduced into the model based on its relationship with labile dissolved organic matter (LDOM). The results show that Fe oxidation is the main factor responsible for the oxygen depletion in the hypolimnion of the Sancho Reservoir. The limiting factors for green algal growth have also been studied. The model predicted that ammonium, nitrate, and phosphate were not limiting factors for green algal growth. Light appeared to be one of the limiting factors for algal growth, while chlorophyll-a and dissolved oxygen concentrations could not be fully described. We hypothesize that dissolved CO2 is one of the limiting nutrients due to losses by the high acidity of the water column. The sensitivity tests carried out support this hypothesis. Two different remediation scenarios have been tested with the calibrated model: 1) an AMD passive treatment plant installed at the river, which removes completely Fe, and 2) different depth water extractions. If no Fe was introduced into the reservoir, water quality would significantly improve in only two years. Deeper extractions (3m above the bottom) would also improve the water quality by decreasing the hypoxic zone. However, extractions at the epilimnion would increase the amount of hypoxic water in the reservoir.

Pollutant flows from a phosphogypsum disposal area to an estuarine environment: An insight from geochemical signatures.

Phosphogypsum wastes from phosphate fertilizer industries are stockpiled in stacks with high contamination potential. An assessment of the environmental impact, including the use of geochemical tracers such as rare earth elements (REE) and Cl/Br ratios, was carried out in the phosphogypsum stack located at the Estuary of Huelva (SW Spain). Inside the pile, highly polluted acid pore-waters flows up to the edge of the stack, emerging as small fluvial courses, known as edge outflows, which discharge directly into the estuary. The disposal area is divided into four zones; two unrestored zones with surface ponds of industrial process water and two a priori already-restored zones. However, an extensive sampling of edge outflows conducted in the perimeter of the four zones demonstrates the high potential of contamination of the whole stack, including those zones that were supposedly restored. These solutions are characterized by a pH of 1.9 and concentrations of 6100 mg/L for P, 1970 mg/L for S, 600 mg/L for F, 200mg/L for NH4(+), 100mg/L for Fe, 10-30 mg/L for Zn, As and U, and 1-10mg/L for Cr, Cu and Cd. Preliminary restoration actions and those planned for the future prioritize removal of ponded process water and cover of the phosphogypsum with artificial topsoil. These actions presuppose that the ponded process water percolates through the porous medium towards the edge up to reach the estuary. However, geochemical tracers rule out this connection and point to an estuarine origin for these leachates, suggesting a possible tidal-induced leaching of the waste pile in depth. These findings would explain the ineffectiveness of preliminary restoration measures and should be considered for the development of new action plans.

Influence of releases from a fresh water reservoir on the hydrochemistry of the Tinto River (SW Spain).

The Tinto River is an extreme case of pollution by acid mine drainage (AMD), with pH values below 3 and high sulphate, metal and metalloid concentrations along its main course. This study evaluates the impact of releases from a freshwater reservoir on the Tinto River, identifying the metal transport mechanisms. This information is needed to understand the water quality evolution in the long term, and involves the comprehension of interactions between AMD sources, freshwaters, particulate matter and sediments. This work proposes a methodology for quantifying the proportions in which the different sources are contributing. The method is based on the mass balance of solutes and accounts for the uncertainty of end-members. The impact of the releases from the Corumbel Reservoir on the hydrochemistry of the Tinto River was significant, accounting up to a 92% of river discharge. These releases provoked a sharp decrease in dissolved metal concentrations, especially for Fe (approximately 1000 fold) due to dilution and precipitation. Cadmium, Zn, Cu, Co, Ni and Al suffered a dilution to a 12-16 fold decrease while Ca, Sr, Na, Pb and Si were less affected (2-4 folds decrease). However, these releases also gave rise to an increase in particulate transport, mainly Fe, As, Cr, Ba, Pb and Ti, due to sediment remobilisation and Fe precipitation. Aluminium, Li, K, Si, Al, Ni and Sr, together with Cu were present in the particulate phase during the discharge peak. The proposed 2-component mixing model revealed the existence of non-conservative behaviour for Al, Ca, Li, Mn, Ni and Si as a consequence of the interactions between the acidic Tinto waters and the clay-rich reservoir sediments during the bottom outlet opening. These results were improved by a 3-component mixing model, introducing a new end-member to account the chemical dissolution of clay-rich sediments by acidic Tinto waters.