Abandoned and flooded mine networks provide underground reservoirs of mine water that can be used as a renewable geothermal energy source. A complete hydrochemical characterization of mine water is required to optimally design the geothermal installation, understand the hydraulic behaviour of the water in the reservoir and prevent undesired effects such as pipe clogging via mineral precipitation. Water pumped from the Barredo-Figaredo mining reservoir (Asturias, NW Spain), which is currently exploited for geothermal use, has been studied and compared to water from a separate, nearby mountain mine and a river that receives mine water discharge and partially infiltrates into the mine workings. Although the hydrochemistry was altered during the flooding process, the deep mine waters are currently near neutral, net alkaline, high metal waters of Na-HCO3 type. Isotopic values suggest that mine waters are closely related to modern meteoric water, and likely correspond to rapid infiltration. Suspended and dissolved solids, and particularly iron content, of mine water results in some scaling and partial clogging of heat exchangers, but water temperature is stable (22ºC) and increases with depth, so, considering the available flow (>100 L s -1 ), the Barredo-Figaredo mining reservoir represents a sustainable, long-term resource for geothermal use.

Sediments contaminated by Hg and As from two historical mining areas have been deposited in the Nalón estuary (Asturias, northern Spain) since 1850. Total mercury (Hg) concentrations in the sediments range from 0.20 μg g to 1.33 μg g, most of it in the form of sulphides. Concentrations of methylmercury (303.20-865.40 pg g) are up to two orders of magnitude lower than the concentration of Hg. Total As concentration (As) is enriched compared to the background level for the area. The relative abundance of As(V) on As(III) in the sediments ranges from 97.6% to 100%, whereas inorganic Hg accounts for more than 99% of the total Hg. The occurrence of the most toxic species, inorganic As(III) and organic methylmercury, seem to be related to redox conditions together with the amounts of sulphur which act as natural barriers which inhibit the biological and chemical speciation processes. Despite the high amounts of Hg and As present in the sediments, their transference to the water column appear to be limited thus converting sediments in an effective sink of both elements. Special attention should be paid to potential variations of the environmental conditions which might increase the element mobility and exchange between sediments and the water column.

Castilla-La Mancha (central Spain) is a region characterized by significant agricultural production aimed at high-quality food products such as wine and olive oil. The quality of agricultural products depends directly on the soil quality. Soil geochemistry, including dispersion maps and the recognition of baselines and anomalies of various origins, is the most important tool to assess soil quality. With this objective, 200 soil samples were taken from agricultural areas distributed among the different geological domains present in the region. Analysis of these samples included evaluation of edaphological parameters (reactivity, electrical conductivity, organic matter content) and the geochemistry of major and trace elements by X-ray fluorescence. The dataset obtained was statistically analyzed for major elements and, in the case of trace elements, was normalized with respect to Al and analyzed using the relative cumulative frequency (RCF) distribution method. Furthermore, the geographic distribution of analytical data was characterized and analyzed using the kriging technique, with a correspondence found between major and trace elements in the different geologic domains of the region as well as with the most important mining areas. The results show an influence of the clay fraction present in the soil, which acts as a repository for trace elements. On the basis of the results, of the possible elements related with clay that could be used for normalization, Al was selected as the most suitable, followed by Fe, Mn, and Ti. Reference values estimated using this methodology were lower than those estimated in previous studies.

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Sediments from the Castilseras reservoir, located downstream on the Valdeazogues River in the Almadén mercury district, were collected to assess the potential contamination status related to metals(oids) associated with river sediment inputs from several decommissioned mines. Metals(oids) concentrations in the reservoir sediments were investigated using different physical and chemical techniques. The results were analyzed by principal component analysis (PCA) to explain the correlations between the sets of variables. The degree of contamination was evaluated using the enrichment factor (EF) and the geoaccumulation index (Igeo). PCA revealed that the silty fraction is the main metals(oids) carrier in the sediments. Among the potentially harmful elements, there is a group (Al, Cr, Cu, Fe, Mn, Ni, and Zn) that cannot be strictly correlated to the mining activity since their concentrations depend on the lithological and edaphological characteristics of the materials. In contrast, As, Co, Hg, Pb, and S showed significant enrichment and contamination, thus suggesting relevant contributions from the decommissioned mines through fluvial sediment inputs. As far as Hg and S are concerned, the high enrichment levels pose a question concerning the potential environmental risk of transfer of the organic forms of Hg (mainly methylmercury) from the bottom sediments to the aquatic food chain.

Located in the southern half of Spain, Almadén is the world's largest Hg district and mercury has been mined there for over 2000 years. Its slag heaps and old metallurgy plants represent a risk to watercourses that flow through the district and receive the run-off from the mines. This study collected sediment samples along the length of the main watercourses in the mining district. High levels of heavy metals were detected, with Hg levels varying between 1.77 and 255.88 mg kg −1 , Pb levels between 20.59 and 131.07 mg kg −1 and Zn levels between 59.06 and 131.07 mg kg −1 . The dispersion of these heavy metals in rivers as a result of mining activities has caused sediment quality degradation. As such, when measured using reference indexes such as the SeQI and the EF, sediment quality for the entire district is practically poor, due to anthropogenic contributions, with the concomitant threat to the surrounding environment. IntroductionDecommissioned mercury mines represent a significant source of mercury (Hg) and also occasionally of other heavy metals in the environment as a result of the dumping of waste material originating from mines and metallurgy plants with a high concentration of Hg [1][2][3][4][5]. The metallurgical processing of Hg in mining districts has left a legacy of major mining liabilities as a result of the inefficient calcination of the mineral cinnabar. As this is an incomplete process, other types of soluble and insoluble compounds not originally present at the site, such as metacinnabar or mercury salts, are formed during the processing [6,7].The run-offs originating from the mining liabilities have an adverse effect on the ecosystems of the areas surrounding the mercury mines [8][9][10][11]. Stream-bed sediments and bodies of water located downstream from the mercury mines are characterised by significant levels of Hg and heavy metals, which can persist for decades after mining activities cease [5,7,12].The mining district of Almadén, located in south-central Spain, is the world's largest geochemical mercury anomaly, and it has produced one-third of total global production of this element [13]. The district includes a series of deposits with a range of structures and textures that share a relatively simple paragenesis whose dominant mineral is cinnabar, with pyrite present in lesser quantities. The most important mineralisation type, found in the mines of Almadén and El Entredicho, consists of stratabound cinnabar disseminations in Criadero Quartzite (Lower Silurian) [13]. Other type of mineralisation present in the area is composed of cinnabar filling veins and replacements of volcanic rocks that cannot be associated with specific stratigraphic layers [14,15]. Throughout its history, the district has been the site of various mines and metallurgy facilities. In terms of mines, Almadén is by far the largest and it has been the one most heavily mined, followed by El Entredicho, Las Cuevas and Nueva Concepción. In terms of metallurgy plants, some of them exist along the district, but two are the...

The extensive extraction activity of mercury ores in Asturias (northwest Spain), also rich in As and Sb, has impacted the Nalón river estuary. The objective of this research was to assess the historical evolution of As-Hg-Sb accumulation in the salt marsh sediments of this area. For this purpose, sediment cores were collected from two different salt marshes (eastern and western river banks) in the estuarine environment to evaluate the degree of anthropogenic enrichment and the geochronology of As-Hg-Sb accumulation. Core subsampling was performed by cutting 2-cm-thick slices of sediments. The subsamples were then analysed for several physical and chemical parameters. Sedimentation rate was assessed by measuring short-lived radionuclides (excess Pb andCs). Pre-mining levels of As-Hg-Sb were observed at core depths below 50 cm. In the less extended salt marsh (eastern river bank), maximum As-Hg-Sb concentrations of 87.48, 3.66, and 5.75 μg·g, respectively, were found at the core top as a consequence of long-term mining activity in the area. The vertical distribution of As-Hg-Sb was influenced by the single-point contamination sources, whereas grain-size variability and diagenetic remobilisation did not seem affected. Geochronological measurements showed that the depositional fluxes of As-Hg-Sb were influenced by anthropogenic input after 1900, when mining activity in the area was most intense. Hg mining ceased in 1969; however, the corresponding core profiles did not show a drastic decreasing trend in element fluxes, implying that the river drainage basin retains some "memory" of contamination which affects riverine sediments. A preliminary gross estimation of total As-Hg-Sb "trapped" in the Nalón river salt marsh sediments amounted to approximately 18.7, 1.0, and 0.7 t, respectively. These morphological structures suffer erosive processes, thus representing a potential source of these elements associated with sediments; consequently, management conservation and monitoring of salt marshes should be taken into consideration from this environmental point of view.

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