Assessment of the ecological risk and mobility of arsenic and heavy metals in soils and mine tailings from the Carmina mine site (Asturias, NW Spain).

An evaluation of the pollution, distribution, and mobility of arsenic and heavy metals in spoil heaps and soils surrounding the abandoned Carmina lead-zinc mine (Asturias, northern Spain) was carried out. Fractionation of arsenic was performed by an arsenic-specific sequential extraction method; while, heavy metal fractionations was carried out using the protocol of the Bureau Community of Reference (BCR) (now renamed Standards, Measurements and Testing Programme). Arsenic appeared predominantly associated with amorphous iron oxyhydroxides. Among the heavy metals, lead and zinc showed high availability since significant amounts were extracted in the nonresidual fractions; whereas, chromium, copper and nickel showed very low availability, indicating their lithogenic origins. The results showed that the extractability of heavy metals in soils is influenced mainly by the presence of iron and manganese oxides as well as by pH and Eh. Multiple pollution indices, including the enrichment factor (EF), geoaccumulation index (Igeo), ecological risk index (Er) and potential ecological risk index (PERI), were used to assess the degree of soil pollution in the mine area. All results showed that lead was the key factor causing the pollution and ecological risk in the studied area, and copper, zinc and arsenic also had significant contributions. Notably, the sites at higher risk coincided with those with high availability of arsenic and heavy metals. This study provides an integrative approach that serves as a powerful tool to evaluate the metal pollution status and potential threats to the local environment of abandoned mining areas, and the results are useful for making management decisions in these areas.

Assessment of hydrological, geological, and biological parameters of a river basin impacted by old Hg mining in NW Spain.

Mercury (Hg) is a toxic metal that can cause adverse effects for the health of ecosystems. The Caudal River is one of the main rivers in the Asturias region (NW Spain), whose basin is highly anthropized, hosting several Hg mines, closed in the last century. Arsenic (As) is also found in the mineral paragenesis of the Hg deposits, posing a greater environmental risk. In the mining sites, remaining old facilities and tailings continue to release these elements into the environment. In this work, samples of fluvial sediments and water were taken, both in areas affected by anthropic activity and in pristine areas, in order to establish the background levels for the critical elements. The mineralogical study of the sediments, combined with EDS microanalysis, is useful to identify mineralogical traps such as Fe oxides or clays to retain the As. The As content in all sampled sediments is above the threshold effect levels (TEL), the possible effect range within which adverse effects occasionally occur, according to the Canadian Sediment Quality Guidelines for the Protection of Aquatic Life. This fact is related to a naturally high geochemical background in the basin, due to the existing mineral deposits. The PEL threshold (the probable effect range within which adverse effects frequently occur) is exceeded by more than an order of magnitude in the sediments downstream of the Hg mines. In these points, the As content in the water, exceeding 700 µg L-1 As, is also above the quality standard established in Spanish legislation. As a result, the Caudal River tributaries in the lower part of the basin do not reach a good ecological state, according to the Hydrological Planning Office, and in some cases their state is deficient, showing low richness and high dominance of macroinvertebrates. Although the concentrations decrease with distance from the source, these findings justify the low ecological quality of the affected watercourses.

Surface Microanalysis and Sequential Chemical Extraction as Tools for Reliable Environmental Mobility Assessment of Sb and Other Metals.

Sequential extraction procedures (SEPs) are widely used in environmental studies to infer the chemical and/or mineralogical forms of pollutants of concern in soils and sediments. Although there is no general agreement among the scientific community, these methods have shown some limitations, especially those with a lack of objectivity in their interpretation. In this work, a soil sampling campaign was carried out in an area affected by an abandoned Sb mine. Samples (0-15 cm) were carefully prepared and analyzed by an SEP. They were also studied by conventional mineralogical methods (optical and electronic microscopy, both scanning and transmission, with a coupled energy dispersive X-ray (EDX) spectrometer). When comparing the results obtained from both techniques, some discrepancies are highlighted, with As, Cu, Pb, Sb and Zn as elements of concern. For Sb, Cu, Pb and As the predominant fraction (excluding the residual one) is that associated with organic matter (from 8.54 for Sb to 18.90% for Cu). The fractions of pollutants linked to Fe and/or Mn oxides are quantitatively important for As, Pb and Zn (6.46%, 12.05% and 7.43%, respectively) and almost negligible for Cu and Sb. On the contrary, analyses carried out by EDX at a grain scale pointed out that no detectable quantities of the elements of concern were present on the surface of the organic particles. Sb and Pb were always detectable in Fe oxides (up to 1.84 and 5.76%, respectively). Regarding the role of the clayey fraction, the only disagreement between the employed SEP and the microanalysis is in relation to As. Arsenic bound to clay minerals was found to be an order of magnitude lower than As associated with Fe oxides (0.56% and 6.46%, respectively); in contrast, EDX microanalyses showed similar As contents in both groups. Given the objectiveness of EDX microanalysis, these differences should be considered inaccuracies in the interpretation of the sequential extraction results.

Mine Water for the Generation and Storage of Renewable Energy: A Hybrid Hydro-Wind System.

Mine water is normally considered as waste that has to be managed. However, new applications are increasingly being sought for the water that floods mining voids, especially in relation to its use as an energy resource. The worldwide energy market, within the current transition framework, is searching for creative approaches to produce and store clean energy. In particular, underground pumped hydroelectric energy storage systems (UPHS) constitute efficient and flexible alternatives to deal with intermittent renewable energy sources. In this work, a UPHS is designed using the mine water and the voids of a closed coal mine in Asturias (North-west Spain) as a lower reservoir. Moreover, this system is combined with a wind energy generation facility and the efficiency of the hybrid system is evaluated. With an investment cost of EUR 193 M, a 40 MW UPHES joined to a 60 MW wind farm would generate benefits of about EUR 54 M in 40 years. The reduction in CO2 emissions (29,000 equivalent tons per year) and the social benefits in a traditional mining area are other intangible advantages of this system.

Arsenic in Soils Affected by Mining: Microscopic Studies vs. Sequential Chemical Extraction.

Soil samples from three inactive mines, corresponding to different Arsenic-bearing mineralization types, were collected and studied. The aim was to determine the influence of mine wastes mineralogy/geochemistry and texture in As mobility and to compare results from sequential chemical extraction and microscopic techniques (optical and electron) at a grain scale. Arsenic in soils is found mainly associated to the residual fraction, indicating that mechanical As dispersion is mainly responsible for As soil pollution. The use of objective microscopic techniques (i.e., Scanning Electron Microscopy-Energy Dispersive Spectroscopy -SEM-EDS-, High Resolution Transmission Electron Microscopy -HR-TEM) has pointed out that the selected sequential extraction method overestimates the role of Mn amorphous oxy-hydroxides and organic matter in As retention while underestimating the mechanism of As adsorption onto clay particle surfaces.

Assessment of the toxicity toward Vibrio fischeri in sediments of a mining impacted estuary in the north of Spain.

This study has been carried out on the Nalón estuary, a mining impacted estuarine contaminated by metals(oid), to evaluate how the metals(oids) concentrations in the sediments contributes to the toxicity and, therefore, supposes a potential risk for the biota. For this purpose, a total of 14 surface sediment samples were collected and analysed by different techniques. Estuary sediments showed a maximum high concentration of As (68.10 µg g-1), Hg (1.33 µg g-1) and Pb (189.60 µg g-1), exceeding the NOAA Effects Range Low. Likewise, these three elements were one of the most bioavailable in the sediments according to the toxicity characteristic leaching procedure performed, reaching average values of 14.28% for As, 12.81% for Hg and 9.23% for Pb. The bioavailable concentrations of As and Hg significantly correlated with toxicity (R > 0.92), suggesting that both were the main contributors to the toxicity of the sediments. Toxicity values detected (avg. 499 TU g-1) were similar to those showed by other sites considered contaminated in the Cantabrian coastline, confirming its status as a contaminated area. The location of the highest toxicity values in the estuary was restricted to the port areas where the fine sediments that act of sink of metals(oids) are mainly deposited. This result is very important if re-mobilization of sediments take place in these areas related to dredging or other human activities.

Arsenic partitioning among particle-size fractions of mine wastes and stream sediments from cinnabar mining districts.

Tailings from abandoned mercury mines represent an important pollution source by metals and metalloids. Mercury mining in Asturias (north-western Spain) has been carried out since Roman times until the 1970s. Specific and non-specific arsenic minerals are present in the paragenesis of the Hg ore deposit. As a result of intensive mining operations, waste materials contain high concentrations of As, which can be geochemically dispersed throughout surrounding areas. Arsenic accumulation, mobility and availability in soils and sediments are strongly affected by the association of As with solid phases and granular size composition. The objective of this study was to examine phase associations of As in the fine grain size subsamples of mine wastes (La Soterraña mine site) and stream sediments heavily affected by acid mine drainage (Los Rueldos mine site). An arsenic-selective sequential procedure, which categorizes As content into seven phase associations, was applied. In spite of a higher As accumulation in the finest particle-size subsamples, As fractionation did not seem to depend on grain size since similar distribution profiles were obtained for the studied granulometric fractions. The presence of As was relatively low in the most mobile forms in both sites. As was predominantly linked to short-range ordered Fe oxyhydroxides, coprecipitated with Fe and partially with Al oxyhydroxides and associated with structural material in mine waste samples. As incorporated into short-range ordered Fe oxyhydroxides was the predominant fraction at sediment samples, representing more than 80% of total As.

Surface water monitoring in the mercury mining district of Asturias (Spain).

Systematic monitoring of surface waters in the area of abandoned mine sites constitutes an essential step in the characterisation of pollution from historic mine sites. The analytical data collected throughout a hydrologic period can be used for hydrological modelling and also to select appropriate preventive and/or corrective measures in order to avoid pollution of watercourses. Caudal River drains the main abandoned Hg mine sites (located in Mieres and Pola de Lena districts) in Central Asturias (NW Spain). This paper describes a systematic monitoring of physical and chemical parameters in eighteen selected sampling points within the Caudal River catchment. At each sampling station, water flow, pH, specific conductance, dissolved oxygen, salinity, temperature, redox potential and turbidity were controlled "in situ" and major and trace elements were analysed in the laboratory. In the Hg-mineralised areas, As is present in the form of As-rich pyrite, realgar and occasionally arsenopyrite. Mine drainage and leachates from spoil heaps exhibit in some cases acidic conditions and high As contents, and they are incorporated to Caudal River tributaries. Multivariate statistical analysis aids to the interpretation of the spatial and temporary variations found in the sampled areas, as part of a methodology applicable to different environmental and geological studies.

Atmospheric monitoring at abandoned mercury mine sites in Asturias (NW Spain).

Mercury concentrations are usually significant in historic Hg mining districts all over the world, so the atmospheric environment is potentially affected. In Asturias, northern Spain, past mining operations have left a legacy of ruins and Hg-rich wastes, soils and sediments in abandoned sites. Total Hg concentrations in the ambient air of these abandoned mine sites have been investigated to evaluate the impact of the Hg emissions. This paper presents the synthesis of current knowledge about atmospheric Hg contents in the area of the abandoned Hg mining and smelting works at 'La Peña-El Terronal' and La Soterraña, located in Mieres and Pola de Lena districts, respectively, both within the Caudal River basin. It was found that average atmospheric Hg concentrations are higher than the background level in the area (0.1 microg Nm(-3)), reaching up to 203.7 microg Nm(-3) at 0.2 m above the ground level, close to the old smelting chimney at El Terronal mine site. Data suggest that past Hg mining activities have big influences on the increased Hg concentrations around abandoned sites and that atmospheric transfer is a major pathway for Hg cycling in these environments.

Environmental impact of toxic metals and metalloids from the Muñón Cimero mercury-mining area (Asturias, Spain).

This paper presents the results of the sampling surveys carried out in order to evaluate the environmental problems associated to La Soterraña, an abandoned Hg mine in Asturias, north of Spain. In particular, this paper overviews the impact of mining and metallurgical activities on terrestrial and aquatic environments. The wastes generated during the mining activity (ore extraction and processing) and later accumulated on the ground, contain great amount of sulphides, becoming potentially acid-generating. Consequently, the mobility of heavy metals and other ecotoxic elements is enhanced. Wastes are generally located close to watercourses and on very steep hillsides, where they are exposed to oxidative weathering, posing a significant risk due to the release of ecotoxic elements to the environment. Background levels were determined at sites, which had not been directly affected by mercury mining. A multielemental geochemical study of mining wastes, soils, stream sediments, water and air samples collected in the area of influence of the old mining and metallurgical works was carried out. Total Hg and As concentrations in soils reach values up to 502 and 19,940 mg kg(-1), respectively, 500 and 2000 times higher than the local background levels. The effects of mining seem to be intense both in waters and stream sediments, as well as in the local atmosphere, whose Hg content is 10 times higher than the background level in the area. Therefore, the target carcinogenic risk was exceeded for As and Hg in La Soterraña site.

Physicochemical characterization and mercury speciation of particle-size soil fractions from an abandoned mining area in Mieres, Asturias (Spain).

Soils from old cinnabar mining areas usually exhibit high Hg contents, whose mobility depends on soil parameters and environmental conditions. This paper presents the study of the Hg speciation in soil samples from an abandoned Hg mine and metallurgical plant in Mieres (Asturias, Spain), in relation to their mineralogical and chemical composition and their particle-size distribution. A characterization of samples was made by X-Ray Diffraction Spectrometry, Scanning Electron Microscopy and Atomic Absorption and Emission Spectroscopy analyses. A sequential extraction method was applied to establish Hg mobility in the samples and their grain-size subsamples. The highest Hg mobility was found in well-developed soils, as a consequence of the adsorption processes by iron and manganese oxides, whereas in those more contaminated soils, a higher proportion of Hg was leached in the non-mobile fraction. A higher Hg mobility was found in the finest grain-size subsamples, probably due to the accumulation of clay minerals and oxides in these ranges.

Distribution and mobility of mercury in soils from an old mining area in Mieres, Asturias (Spain).

Mercury content in soils near abandoned mine wastes in the mercury mining area of Mieres (Asturias, Spain) is highly elevated as a result of the long period of mining and abundant Hg production. In this work, an evaluation of Hg concentration, distribution, and mobility in three soil samples from the immediate vicinity of a chimney used for vapour evacuation during pyrometallurgical treatment of the ore was carried out. For that purpose, total Hg contents were determined for the original samples and their grain-size subsamples. The study of mercury mobility in the original samples and in the different particle-size subsamples was made by the application of a sequential extraction method. Results showed that Hg concentration in soils decreases directly with the distance from the chimney and the dispersion of Hg is not influenced by the topographic height of the site tested. The sample collected in the base of the chimney exhibited appreciable amounts of mobile Hg. In general, a higher Hg concentration was found for the finest particle-size subsamples. Hg mobility was found to be higher for quite developed soils. The sample collected downstream from the chimney showed a significant Hg mobile content as a result of a more intensive weathering. An increase of Hg mobility at decreasing particle size was found in all three analysed samples.

Geochemical fingerprints and controls in the sediments of an urban river: River Manzanares, Madrid (Spain).

The geochemical fingerprint of sediment retrieved from the banks of the River Manzanares as it passes through the City of Madrid is presented here. The river collects the effluent water from several Waste Water Treatment (WWT) plants in and around the city, such that, at low flows, up to 60% of the flow has been treated. A total of 18 bank-sediment cores were collected along the course of the river, down to its confluence with the Jarama river, to the south-east of Madrid. Trace and major elements in each sample were extracted following a double protocol: (a) "Total" digestion with HNO3, HClO4 and HF; (b) "Weak" digestion with sodium acetate buffered to pH=5 with acetic acid, under constant stirring. The digests thus obtained were subsequently analysed by ICP-AES, except for Hg which was extracted with aqua regia and sodium chloride-hydroxylamine sulfate, and analysed by Cold Vapour-AAS. X-ray diffraction was additionally employed to determine the mineralogical composition of the samples. Uni- and multivariate analyses of the chemical data reveal the influence of Madrid on the geochemistry of Manzanares' sediments, clearly manifested by a marked increase in the concentration of typically "urban" elements Ag, Cr, Cu, Pb and Zn, downstream of the intersection of the river with the city's perimeter. The highest concentrations of these elements appear to be associated with illegal or accidental dumping of waste materials, and with the uncontrolled incorporation of untreated urban runoff to the river. The natural matrix of the sediment is characterised by fairly constant concentrations of Ce, La and Y, whereas changes in the lithology intersected by the river cause corresponding variations in Ca-Mg and Al-Na contents. In the final stretch of the river, the presence of carbonate materials seems to exert a strong geochemical control on the amount of Zn and, to a lesser extent, Cu immobilised in the sediments. This fact suggests that a variable but significant proportion of both elements may be susceptible to reincorporation in the aqueous phase under realistic environmental conditions.

Untreated abandoned mercury mining works in a scenic area of Asturias (Spain).

Mercury mining was a large and thriving industry during the last century in Asturias (NW Spain). At Brañalamosa, mining activity introduced significant quantities of wastes in spoil heaps located close to the mining operations. In these mining wastes, in addition to mercury, high concentrations of other potentially dangerous elements like As have been found. As a consequence, pollution and dereliction of the local environment occurred. This paper focuses on the environmental impact of these old mining operations and describes a preliminary assessment of the extent of contamination. This includes analytical data from systematic sampling of soils, stream sediments, wastes from spoil heaps, water and herbaceous plants in areas affected by mining activities. The potential risk that spoil materials imply for human health and the environment is documented on the basis of the application of EPA Risk Assessment methodology.

Investigation of trace element sources from an industrialized area (Avilés, northern Spain) using multivariate statistical methods.

In the industrialized urban area of Avilés (Spain), pooled soil samples from grassland sites were taken after careful sampling design and then investigated for their content of trace elements. A combination of statistic and geostatistic techniques proved to be a reliable tool in the interpretation of the analytical results. Geochemical groups and areas influenced mainly by anthropogenic activities were distinguished by means of classic multivariate methods (factor analysis and cluster analysis) and innovative geostatistical tools (Fourier spectral analysis). The constitution of the groups is supported by the linked results of methods sequentially distributed in order to extract as much information as possible from the original data.