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.

Groundwater contamination evolution in the Guadiamar and Agrio aquifers after the Aznalcóllar spill: assessment and environmental implications.

In 1998, the Agrio and Guadiamar rivers underwent an enormous environmental disaster caused by the rupture of the Aznalcóllar tailings dam and the release of 6 hm(3) of pyrite sludge and acidic water. Both rivers run over recent alluvial materials which form a small-sized aquifer which is however important because underground water feeds the flow of the rivers. This work analyzes the state of groundwater 10 years after the spill. Before the dam failure, this aquifer was already contaminated in the zone nearest to the mine, to which the impact of the spill was added. Contamination levels in the alluvial aquifer of the Agrio River have decreased remarkably. However, they are still important, with acidic pH values and high concentrations of toxic elements (maximum values of 16 mg/L of Zn and 15 mg/L of Al). There are also important levels of contamination in the Guadiamar alluvial area closest to the mine, as well as in specific zones located further south. The concentration of toxic elements is mainly controlled by pH. The evolution of contaminant levels show a sharp decrease after the first years following the spill, followed by a subsequent stabilization. It is necessary to take measures for the recovery of the aquifer because, otherwise, groundwater will continue contributing contaminants into the Agrio and Guadiamar rivers.

Temporal evolution of acid mine drainage (AMD) leachates from the abandoned tharsis mine (Iberian Pyrite Belt, Spain).

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.

Stream-pit lake interactions in an abandoned mining area affected by acid drainage (Iberian Pyrite Belt).

Opencast mining of sulfide ore deposits may lead to the formation of anthropogenic acidic lakes with highly polluted waters. In these systems, it is crucial to understand the hydrological connections between surface and groundwater and their contribution to the pollutant load delivered to the downgradient streams. This study characterizes the interactions between surface and groundwater in an acidic pit lake using different geochemical tracers (i.e., REE and other trace metals). The San Telmo pit lake, located in one of the most pollutant sources of the Iberian Pyrite Belt (IPB), can be considered as a flow-through pit lake except during dry periods, when it behaves as a terminal lake due to lower inputs by surface waters and higher outputs by evaporation. Results based on geochemical tracers indicate that the main inputs to the pit lake come from surface waters, with minor groundwater inputs rich in As, Cr, Cu, Fe and Pb. The contaminant load released from the mining area is very high (e.g., median values of 520 kg/day of Fe and 38 kg/day of Zn), causing the degradation of the fluvial network downstream. Most of released pollutants come from waste dumps located at the W of the mining zone (~50-70% of Al, Cd, Mg, Mn, Ni, SO4 and Zn and > 70% for Cu, Cr, Fe and, V), while the contribution of the water coming out the pit lake and other dumps is much lower. Thus, remediation efforts to improve the area and fluvial courses downstream must focus on the W waste dumps.

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.

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.

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.

Evaluation of the radioactive pollution in the salt-marshes under a phosphogypsum stack system.

Next to the city of Huelva (SW of Spain), around 100 Mt of phosphogypsum (PG) are stored in stacks on the salt-marshes of the Tinto River estuary covering a surface of about 1000 ha. Due to the high content of 238U series natural radionuclides of the PG, its acidic nature (pH about 3), and the fact that PG stacks were disposed without any kind of isolation from the substrate, they could produce a potential radioactive impact into the underlying sediments. The aim of this work is to assess the pollution of the underlying sediments by natural radionuclides coming from the PG stacks. To this end, seven cores were taken, and PG and sediments samples collected at different depths were analysed. The activity concentrations of the main long half-live natural radionuclides of interest were determined by applying both gamma-ray and alpha-particle spectrometry radiometric techniques. The results of this study showed that the first decimeters of salt-marsh sediment act as a "barrier" for the radionuclides coming from the PG stacks decreasing rapidly its activity concentration in depth, affecting mainly sediments located in the first 20 cm below the contact due to mixing processes. While 230Th, 226Ra and 210Pb pollution is mainly restricted to the first 20 cm of sediments, U-isotopes can reach higher depths (up to around 50 cm) by leaching processes due to their lower reactivity and higher concentration in the polluted leachates. The obtained results have high relevance for the design of the perimeter channel which is projected to build in the restoration project, suggesting that should has around 1 m deep under the base of the PG stacks, to ensure the full collection of polluting leachates, and to prevent their release into the estuary of the Tinto River.

Silver and copper as pollution tracers in Neogene to Holocene estuarine sediments from southwestern Spain.

Estuaries are very sensitive ecosystems to human activities and the natural evolution of their drainage basins located upstream. Pollution derived from human activities, such as historical mining or recent industrial wastes, can significantly affect their environmental quality. This paper analyzes the silver and copper contents of four cores extracted in two estuaries of SW Spain. Its chronology and vertical evolution allow to differentiate the effects of several pollution episodes (natural, Roman, 19th-20th centuries) on its different sedimentary environments in the last 6 million years. Possible future applications are included in the fields of environmental management or even education.

Natural attenuation processes in two water reservoirs receiving acid mine drainage.

Characteristics of water profiles and sulphide formation processes in sediments were studied in two water reservoirs affected by acid mine drainage in order to investigate the mechanisms controlling the physical and chemical processes that, under favourable conditions, act to reduce the toxicity, mobility and concentration of metals and metalloids in the water column. Water columns and pore-waters from sediments were analysed for Fe species, trace elements (As, Cd, Co, Cu, Mn, Ni, Pb, Zn, Cr), sulphide, sulphate and bicarbonate. Inorganic reduced sulphur compounds (acid volatile sulphur, pyrite sulphur and elemental sulphur) and reactive Fe were determined in the sediments. A sequential extraction was also performed. Both reservoirs behave like holomictic and monomictic lakes, with a summer thermal stratification that disappears during winter. pH values between 4 and 7 can be observed along the water columns. Pore-water concentrations of up to 25 mg/l of Fe, 4 mg/l of Al, 1.3 mg/l of Zn, 170 microg/l of Pb, 11 microg/l of As, etc. have been found. The results suggest that toxic elements such as Cu, Zn, Co, Pb, Cr, As, etc. are mainly found in the bioavailable fraction which is the most hazardous for the environment. The calculated degree of sulphidization (DOS) and degree of pyritization (DOP) values indicates that removal of trace elements from anoxic pore-waters occurs by coprecipitation and/or adsorption on newly formed Fe sulphides (framboidal pyrite), attenuating the contamination. However oxidation of the sediments during turnover periods also occurs, which releases toxic elements back into the water column.

Pollution evaluation on the salt-marshes under the phosphogypsum stacks of Huelva due to deep leachates.

In the salth-marshes of the Tinto River (Huelva estuary, SW Spain), are stored in stacks around 100 Mt of PG, covering a surface of 1000 ha without any type of isolation, which produce an important impact in the surrounding environment. On the other hand, this ecosystem it is affected by acid mine drainage (AMD) from sulphide mines located upstream the Tinto River. The aim of this study is to evaluate the deep pollution of the underlain salt-marsh sediments due to leachates from the PG stacks. For that purpose, 7 cores were collected from zones 2 and 3 of the stacks, and PG and salt-marsh sediments samples from different depths were analyzed. The physicochemical parameters, mineralogy, granulometry and the concentration of the main elements of interest were determined in the samples. Most analysed salt-marsh sediments are not affected by PG stacks pollution, because sediments act as a "barrier" for the leachates from the PG, concentrating the contaminants in the first decimetres (0.5 m) under PG-sediments contact, and the deep infiltration is very limited. The obtained results suggest that the perimeter channel which is projected to build in the restauration project, should has a depth of 1 m below the level of the PG stacks for assuring the complete collection of leachates from the stacks, and avoid their liberation into the Tinto River estuary.

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.

Acid mine drainage pollution in the Tinto and Odiel rivers (Iberian Pyrite Belt, SW Spain) and bioavailability of the transported metals to the Huelva Estuary.

The Tinto and Odiel rivers are seriously affected by acid mine drainage (AMD) from the long-term mining activities in Iberian Pyrite Belt (IPB). As a consequence, the Huelva estuary is heavily contaminated by metals and metalloids. This study presents an estimation of the seasonal variation, and the dissolved contaminant load transported by both rivers from February 2002 to September 2004. Besides, toxicity and bioaccumulation tests with the sediments of the estuary have been conducted in order to measure the mobility of the toxic metals. Results show that the Tinto and Odiel rivers transport enormous quantities of dissolved metals to the estuary: 7900 t yr(-1) of Iron (Fe), 5800 t yr(-1) Aluminium (Al), 3500 t yr(-1) Zinc (Zn), 1700 t yr(-1) Copper (Cu), 1600 t yr(-1) Manganese (Mn) and minor quantities of other metals and metalloids. These values represent 37% of the global gross flux of dissolved Zn transported by rivers in to the ocean, and 15% of the global gross flux of dissolved Cu. These metals and metalloids usually sink in the estuarine sediments due to pH and salinity changes. The increase of salinity in the estuary favours the adsorption and trapping of metals. For this reason, the mobility and bioavailability of metals such as Zn, Cd and Cu is higher in sediments located in the area of fresh water influence that in sediments located in the marine influenced area of the estuary, showing a higher percentage of fractionation and bioaccumulation of these metals in the station influenced by the fresh water environment.

A geochemical approach to the restoration plans for the Odiel River basin (SW Spain), a watershed deeply polluted by acid mine drainage.

The Odiel River Basin (SW Spain) drains the central part of the Iberian Pyrite Belt (IPB), a world-class example of sulfide mining district and concomitantly of acid mine drainage (AMD) pollution. The severe AMD pollution and the incipient state of remediation strategies implemented in this region, coupled with the proximity of the deadline for compliance with the European Water Framework Directive (WFD), urge to develop a restoration and water resources management strategy. Furthermore, despite the presence of some reservoirs with acid waters in the Odiel basin, the construction of the Alcolea water reservoir has already started. On the basis of the positive results obtained after more than 10 years of developing a specific passive remediation technology (dispersed alkaline substrate (DAS)) for the highly polluted AMD of this region, a restoration strategy is proposed. The implementation of 13 DAS treatment plants in selected acid discharges along the Odiel and Oraque sub-basins and other restoration measurements of two acidic creeks is proposed as essential to obtain a good water quality in the future Alcolea reservoir. This restoration strategy is also suggested as an economically and environmentally sustainable approach to the extreme metal pollution affecting the waters of the region and could be considered the starting point for the future compliance with the WFD in the Odiel River Basin.

Acid mine drainage in the Iberian Pyrite Belt: 1. Hydrochemical characteristics and pollutant load of the Tinto and Odiel rivers.

Acid mine drainage in the Iberian Pyrite Belt is probably the worst case in the world of surface water pollution associated with mining of sulphide mineral deposits. The Iberian Pyrite Belt is located in SW Iberian Peninsula, and it has been mined during the last 4,500 years. The central and eastern part of the Iberian Pyrite Belt is drained by the Tinto and Odiel rivers, which receive most of the acidic leachates from the mining areas. As a result, the main channels of the Tinto and Odiel rivers are very rich in metals and highly acidic until reaching the Atlantic Ocean. A significant amount of the pollutant load transported by these two rivers is delivered during the rainy season, as is usual in rivers of Mediterranean climate regions. Therefore, in order to have an accurate estimation of the pollutant loads transported by the Tinto and Odiel rivers, a systematic sampling on a weekly basis and a high temporal resolution sampling of floods events were both performed. Results obtained show that metal fluxes are strongly dependent on the study period, highlighting the importance of inter-annual studies involving dry and wet years.

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.

Biologically-induced precipitation of sphalerite-wurtzite nanoparticles by sulfate-reducing bacteria: implications for acid mine drainage treatment.

Several experiments were conducted to evaluate zinc-tolerance of sulfate-reducing bacteria (SRB) obtained from three environmental samples, two inocula from sulfide-mining districts and another inoculum from a wastewater treatment plant. The populations of SRB resisted zinc concentrations of 260 mg/L for 42 days in a sulfate-rich medium. During the experiments, sulfate was reduced to sulfide and concentrations in solution decreased. Zinc concentrations also decreased from 260 mg/L to values below detection limit. Both decreases were consistent with the precipitation of newly-formed sphalerite and wurtzite, two polymorphs of ZnS, forming <2.5-µm-diameter spherical aggregates identified by microscopy and synchrotron-µ-XRD. Sulfate and zinc are present in high concentrations in acid mine drainage (AMD) even after passive treatments based on limestone dissolution. The implementation of a SRB-based zinc removal step in these systems could completely reduce the mobility of all metals, which would improve the quality of stream sediments, water and soils in AMD-affected landscapes.