The impact of tailings dam spills and clean-up operations on sediment and water quality in river systems: the Rı́os Agrio–Guadiamar,Aznalcóllar,Spain

The Aznalcóllar tailings dam at Boliden Apirsa's Aznalcóllar/Los Frailes Ag–Cu–Pb–Zn mine 45 km west of Seville, Spain, was breached on 25 April 1998, flooding approximately 4600 hectares of land along the Rı́os Agrio and Guadiamar with approximately 5.5 million m³ of acidic water and 1.3×10⁶ m³ of heavy metal-bearing tailings. Most of the deposited tailings and approximately 4.7×10⁶ m³ of contaminated soils were removed to the Aznalcóllar open pit during clean-up work undertaken immediately after the spill until January 1999. Detailed geomorphological and geochemical surveys of the post-clean-up channel, floodplain and valley floor, and sediment and water sampling, were carried out in January and May 1999 at 6 reaches representative of the types of river channel and floodplain environments in the Rı́o Guadiamar catchment affected by the spill. The collected data show that the clean-up operations removed enough spill-deposited sediment to achieve pre-spill metal (Ag, As, Cd, Cu, Pb, Sb, Tl, Zn) concentrations in surface sediment. These concentrations, however, are still elevated above pre-mining concentrations, and emphasise that mining continues to contaminate the Agrio-Guadiamar river system. Dilution by relatively uncontaminated sediment appears to reduce metal concentrations downstream but increases in metal and As concentrations occur downstream, presumably as a result of factors such as sewage and agriculture. River water samples collected in May 1999 have significantly greater dissolved concentrations of metals and As than those from January 1999, probably due to greater sulphide oxidation from residual tailings with concomitant release of metals in the warmer early summer months. These concentrations are reduced downstream, probably by a combination of dilution and removal of metals by mineral precipitation. Single chemical extractions (de-ionised water, CaCl₂ 0.01 mol l⁻¹, CH₃COONH₄ 1 M, CH₃COONa 1 M and ammonium oxalate 0.2 M) on alluvial samples from reaches 1 and 6, the tailings, pre-spill alluvium and marl have shown that the order of sediment-borne contaminant mobility is generally Zn>Cd>Cu>Pb>As. Pb and As are relatively immobile except possibly under reducing conditions. Much of the highly contaminated sediment remaining in the floodplain and channel still contains a large proportion of tailings-related sulphide minerals which are potentially reactive and may continue to release contaminants to the Agrio–Guadiamar river system. Our work emphasises the need for pre-mining geomorphological and geochemical data, and an assessment of potential contributions of contaminants to river systems from other, non-mining sources.     

Monitoring study of the mine pond reclamation of Mina Concepción, Iberian Pyrite Belt (Spain)

Mining of massive (Cu, Pb and Zn) sulphide bodies in the Iberian Pyrite Belt (SW Spain) has generated a great number of abandoned waste deposits such as mine ponds. These represent large accumulations of reactive minerals and subsequently, emission sources of trace elements and formation of acid drainage. Even if they have been restored, monitoring studies are required to evaluate the corrective effects and how they may change over time. This work presents the results of a monitoring study carried out at Mine Concepción mine pond, based on mineralogical (XRD), geochemical (INAA, X-ray fluorescence, ICP-MS) and geophysical (electrical resistivity tomography) techniques. In it, a series of relevant parameters have been well delimited, such as the infilling thickness and its variation and, the position, geometry and absence of water leakages through the base of the mine pond. Additionally, the existence of an internal, remnant flow of acid waters that tends to come out through the pond dyke has been identified. Chemistry of these waters indicates that oxidation processes affecting the Mina Concepción mine tailings are generating acid drainage waters which could potentially release substantial amounts of trace elements to the river Odiel. Thus, giving that not complete sealing is accomplished by the restoration capping and rainfall water infiltrates into the pond materials, at least the sealing of the dyke through which leakages occur should be revised.     

Contributions of boron isotopes to understanding the hydrogeochemistry of the coastal detritic aquifer of Castellón Plain,Spain

The Castellón Plain alluvial aquifer, Spain, is intensively exploited to meet the demand for agricultural irrigation and industrial water supply. The geochemistry of its groundwater shows complex salinization in the northern and southern parts of the aquifer, with significant pollution from human origin in the central portion. Boron content and B isotope geochemistry are useful for distinguishing between various sources of pollution and their relative importance in different parts of this aquifer. Boron concentrations in the groundwater vary between 0.01 and 0.85 mg/L. In the more saline groundwaters, found at the northern and southern ends of the study area, the presence of B is linked to inputs from seawater and water with a calcium-magnesium sulphate facies, which feed the aquifer and clearly influence the chemistry of its waters. Evidence of B adsorption processes in some samples is shown by the low B/Cl ratios and the high values of δ¹¹B. In the central portion of the aquifer, the high B/Cl ratios and the strongly negative δ¹¹B are related to pollution of human origin.     

Arsenic and metal mobility from Au mine tailings in Rodalquilar (Almería,SE Spain)

In the old mining area of Rodalquilar, mine wastes, soil and sediments were characterized and the results revealed high concentration of Au, Ag, As, Bi, Cu, Fe, Mn, Pb, Se, Sb and Zn in tailings and sediments. The contaminant of greatest environmental concern is As. The mean concentration in the tailings was 679.9, and 345 mg/kg in the sediments of Playazo creek. The groundwater samples from the alluvial aquifer showed high concentration of Al, As, Cd, Fe, Hg, Mn, Ni, Pb, Se, Sb and Zn and very high concentration of chloride and sulfate, which were above the concentration defined in the European standards for drinking water. The presence of As in groundwater may be caused by the oxidation of arsenian pyrite, the possible As desorption from goethite and ferrihydrite and the jarosite dissolution. Groundwater concentrations of Cd, Fe, Mn, and possibly Cu, were associated with low values of Eh, indicating the possible dissolution of oxy-hydroxides of Fe and Mn. The mobility of metals in the column experiments show the release of Al, Fe, Mn, Cr, Cu, Ni, V and Zn in significant concentrations but below the detected values in groundwater. However, As, Cd, Sb, Se Pb and Au, are generally mobilized in concentrations above the detected values in groundwater. The possible mass transfer processes that could explain the presence of the contaminants in the aquifer and the leachates was simulated with the PHREEQC numerical code and revealed the possible dissolution of the following mineral phases: jarosite, natrojarosite, arsenian pyrite, alunite, chlorite, kaolinite and calcite.     

Water qualitiy and distribution of trace elements in the Doñana aquifer (SW Spain)

The variations of groundwater quality in the unconfined zone of the Almonte-Marismas aquifer, upon which Doñana National Park is located, are analysed. Most sampled points are multiple piezometers, allowing for the vertical distribution study of the hydrogeochemical characteristics in the aquifer. Temperature, pH, electrical conductivity, dissolved oxygen and redox potential were determined in the field. A large number of parameters, including major ions and a large amount of minor and trace elements, were analysed. In the southern zone, where aeolian sands crop out, water composition in the shallower part of the aquifer is of the sodium chloride type, with low pH (5.5–6) and mineralization (<200 μS/cm) values. As water circulates through the aquifer, bicarbonate and calcium concentrations increase slightly. In agricultural or urban zones, nitrates and sulphates present their highest contents in the upper part of the aquifer. In zones with low pH levels (around 6), concentration of many trace metals (Al, Co, Cr, Cu, Ni, Zn, etc.) also shows a distribution similar to that of sulphates and nitrates, which indicates its fertilizer-linked origin. In zones with neutral or alkaline pH, regardless of high nitrate content, concentration of the above mentioned metals is very low due to its immobilisation by surface adsorption processes. The distribution of Br contents also shows the effects of agricultural pollution.     

Morphotectonic study of two regions in the Centre-South Segment of Spain: Córdoba and Granada

The morphotectonics of Córdoba and Granada are differentiated using the Rantsman method [53]. Over 40 quantitative geomorphologic indicators are used in the systemic classification. Both areas are included in what are known as the macroblocks no. 1 (Southern) and no. 2 (Sub-Western 2A) of the Iberian Peninsula megablock. The qua ntities of the four lowest order Territorial Units defined for Córdoba/Granada are: mesoblocks (4/4), blocks (9/9), microblocks (15/35) and nanoblocks (64/83). The main lineaments/intersections determined in Córdoba total 16/1041 and in Granada 25/633, A series of seven morphostructural scarps is found in both areas, along with important modifications (inflections) in some river beds. Some of the structures described are seismicity-related. Córdoba displays less activity than Granada. Between the towns of Loja, Beas de Granada, and Lentejí a seismoactive sector (～820 km²) with blocks B2, B3, B5, and B6 forms the area where the deep earthquakes are concentrated.     

Phytoremediation potential of native plants grown in the vicinity of Ahangaran lead–zinc mine (Hamedan,Iran)

This study aims to assess the extent of metal accumulation by plants found in a mining area in Hamedan Province in the central west part of Iran. It also investigates to find suitable plants for phytoextraction and phytostabilization as two phytoremediation strategies. Plants with a high bioconcentration factor (BCF) and low translocation factor (TF) have the potential for phytostabilization while plants with both BCFs and TFs greater than one have the potential to be used for phytoextraction. In this study, shoots and roots of the 12 plant species and the associated soil samples were collected. The collected samples were then analyzed by measurement of total concentrations of trace elements (Pb, Zn, Mn and Fe) using atomic absorption spectrophotometer. Simultaneously, BCF and TF parameters were calculated for each element. Results showed that although samples suitable for phytoextraction of Pb, Zn, Mn and Fe and phytostabilization of Fe were not detected, Scrophularia scoparia was the most suitable for phytostabilization of Pb, Centaurea virgata, Echinophora platyloba and Scariola orientalis had the potential for phytostabilization of Zn and Centaurea virgata and Cirsium congestum were the most efficient in phytostabilization of Mn. Present study showed that native plant species growing on contaminated sites may have the potential for phytoremediation.     

Asbestiform and non-asbestiform morphologies in a talc and vermiculite mine from the province of Córdoba (Argentina): a case study

In this work, a talc and vermiculite mine from the province of Córdoba (Argentina) was investigated with special emphasis on the occurrence of asbestiform and non-asbestiform phases. The meta-ultramafic rock was studied by a multimethodological approach, complementing field studies with petrographic-mineralogical, compositional and morphological analyses. Samples were examined by stereomicroscopy, polarizing light microscopy, SEM–EDS, XRD, DSC-TGA and FTIR. Complementary, compositional and textural analyses were performed with FE-SEM–EDS and EPMA. Talc-rich veins with a laminar and fibrous appearance were at first recognized. However, the fibrous morphology observed both in the field and by microscopy is due to an apparent habit because of the sample orientation. To avoid erroneous interpretations, studies by secondary electron images (SEM) are fundamental to carrying out this type of analysis. Tremolite was identified in different zones of the outcrop; however, only ~40% of the crystals located in the vermiculite zone have dimensions to be considered as asbestiform fibres in the range of respirable particles. In these types of complex deposits affected by superimposed metamorphic, igneous and deformational events, multimethodological approaches are necessary to develop models of occurrence of asbestiform morphologies that may be applicable to other with similar characteristics.     

Sulfur and lead isotope systematics: Implications for the genesis of the Riópar Zn-(Fe-Pb) carbonate-hosted deposit (Prebetic Zone,SE Spain)

The Zn-(Fe-Pb) deposits of the Riópar area (Prebetic Zone, SE Spain) are hosted by dolostones that replace Berriasian to Valanginian (Upper Jurassic-Lower Cretaceous) limestones. Mineralization consists of hypogene sphalerite, marcasite and galena, and supergene calamine zones. The hypogene ores are associated with a saddle dolomite gangue. The ore bodies occur as discordant and stratiform lenses, ore-cemented breccias, cm- to mm-wide veins and veinlets, disseminations and stylolite porosity filling within the host dolomites. The main ore controls include stratigraphy and/or lithology, tectonics (faults, fractures and breccias) and availability of metals and sulfur. The morphologies and epigenetic character of the hypogene ore bodies are consistent with the classification of this mineralization as a Mississippi Valley-type (MVT) deposit. The Ga/Ge geothermometer in sphalerite yielded a temperature range of 194–252 °C, which represents the temperature of the source region of the ore solution. This value is comparable to the temperature obtained in the ore deposition site, 159 ± 15 °C from the Δ³⁴S geothermometer in sphalerite galena pairs. This similitude points to a hydrothermal fluid that did not cool down significantly during flow from the fluid reservoir area to the precipitation site. δ³⁴S values of base-metal sulfides (−7.5 to +3.5‰) are consistent with thermochemical reduction of Triassic sulfate (seawater and/or derived from dissolution of evaporites) by interaction with organic compounds (e.g., hydrocarbons, methane), which reduced sulfate to sulfide in the deposition site. The lead isotope ratios (²⁰⁶Pb/²⁰⁴Pb = 18.736–18.762; ²⁰⁷Pb/²⁰⁴Pb = 15.629–15.660; ²⁰⁸Pb/²⁰⁴Pb = 38.496–38.595) of galena suggest that Pb, and probably other metals as Zn, is derived from continental crustal rocks. On the other hand, these relations points to a unique metal source probably derived from the Paleozoic basement rocks. The relationship between bedding-parallel stylolites, dolomitization, sulfide precipitation and Alpine tectonic affecting the MVT ore, suggests a relative timing range for the mineralization in the Riópar area of 95–20 Ma (Upper Cretaceous-Tertiary). The sulfide mineralization and the associated dolomitization are thus explained by the contribution of two fluids that mixed in different proportions during dolomitization and mineralization: i) a fluid probably derived from Cretaceous seawater saturating Mesozoic sediments (Fluid A), characterized by being dilute and initially low temperature, which should have contained organic rich compounds in the ore deposition site (e.g., hydrocarbons and CH₄ dissolved gas); and ii) a high salinity hydrothermal brine (Fluid B) rich in both metals and sulfate, circulated through the Paleozoic basement. During the pre-ore dolomitizing stage the fluid phase was dominated by the diluted fluid (Fluid A > Fluid B), whereas in a later fluid pulse, the proportion of the high salinity fluid increased (Fluid A < Fluid B) which allowed sulfide precipitation. MVT exploration in the Prebetic Zone should focus towards the SW of the Riópar mines, in the vicinity of the Alto Guadalquivir-San Jorge fault.     

Application of the European water framework directive in a Western Mediterranean basin (Málaga,Spain)

The water framework directive (WFD) is applied within the Guadalhorce river basin, a Western Mediterranean basin in the Málaga province (South Spain). Criteria defining different surface and groundwater bodies are described. The basic hydrographic network is constituted of low-mountain and low-altitude Mediterranean mineralized rivers. Heavily modified surface water bodies correspond (1) to areas where dams regulate the main watercourses, (2) to areas downstream of reservoirs, where river flow is reduced, and (3) to the coastal sector of the river where artificial channelling has caused morphological variations. Groundwater bodies are related to carbonate and porous aquifers and, locally, to aquifers influenced by dissolution of evaporites. The main impacts to water bodies are irrigated lands and livestock farming. There are also point sources of pollution, such as wastewater, landfills, golf courses, industrial zones, quarries and petrol stations. In addition, groundwater is frequently pumped for human supply and irrigation. Qualitative status of groundwater bodies was done by chemical analysis of samples from a monitoring network and the quantitative status by examining variations in piezometric levels. Both revealed the existence of water bodies at risk of not meeting the environmental objectives of the WFD. The main indicators of pollution are nitrates related to agricultural activities, and total organic carbon (TOC), PO₄³⁻ and NH₄⁺ in relation to wastewater.     

Evaluation of geothermal flow at the springs in Aragón (Spain), and its relation to geologic structure

The geothermal flow which emerges by convection at the springs in Aragón is evaluated, and compared with the theoretical heat flow which permeates the surface of the region by conduction. The geological materials through which the convection takes place are defined (geothermal formations), and the areas where thermal convection appears most intensely are related.

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Resumen En el presente trabajo se evalúa el flujo geotérmico que emerge por convección en los principales manantiales de aguas termales de Aragón (España), comparándolo con el flujo geotérmico que penetra en la corteza terrestre por conducción. Se definen las formaciones geotérmicas y se estudian las áreas en las que se concentra de forma preferente ese flujo termal por convección.

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Résumé Le flux géothermique qui émerge par convection à la source Aragon est évalué, et comparé avec le flux de chaleur théorique par conduction. Le matériel géologique dans lequel la convection prend place est défnit (formations géothermiques) et les zones qui manifestent les plus importantes convections thermiques sont relatés.

     

Nitrates as indicators of aquifer interconnection. Application to the Campo de Dalías (SE – Spain)

 Relatively high concentrations of NO₃ usually have their origin in processes of organic pollution and excessive use of inorganic fertilizers. In the case of agricultural areas, these activities may generate great quantities of nitrates. This fact has enabled us to use the nitrate ion to characterize an exploited aquifer unit of a very complex aquifer system, as is the case for the Campo de Dalías aquifer system (SE Spain). The shallow boreholes, which draw water from intensively cultivated superficial formations, yield waters with a high NO₃ content. When the boreholes are deeper and penetrate low-permeability formations in the superficial layers, the waters contain little NO₃; similar to what happens in areas of recharge where agricultural activities are absent. In addition, using longitudinal sections, it is possible to demonstrate the possible existence of connections between superficial and deep aquifers using NO₃ as a tracer. Similarly one can locate those sectors responsible for contamination caused by the poorly lined boreholes themselves, when they perforate more than one aquifer in a multiple aquifer formation. Received: 22 December 1998 · Accepted: 20 March 1999     

First lead isotopic data for cinnabar in the Almadén district (Spain): implications for the genesis of the mercury deposits

The Almadén district constitutes the largest and probably the most intriguing mercury concentration in the world. Two types of mineralization are recognized: 1) stratabound, of Lower Silurian age, well represented by the large Almadén deposit; and 2) fully discordant mercury deposits of minor importance in terms of size, and exemplified by the deposit of Las Cuevas. The latter ones can be found at different positions along the Almadén stratigraphic column. Both types of deposits are always associated with the so-called frailesca rocks (diatremes of alkali basaltic composition). This paper reports the first lead isotope compositions of cinnabar in the district. Whole samples and stepwise leaching cinnabar aliquots display relatively homogeneous isotopic compositions (²⁰⁶Pb/²⁰⁴Pb = 18.112–18.460; ²⁰⁷Pb/²⁰⁴Pb = 15.635–15.705; ²⁰⁸Pb/²⁰⁴Pb = 38.531–38.826). Taken together with Jébrak et al.s (2002) pyrite lead isotope results, the new cinnabar isotopic data define a steep array trend on the ²⁰⁷Pb/²⁰⁴Pb– ²⁰⁶Pb/²⁰⁴Pb diagram, indicating a mixed contribution of lead and probably mercury from different sedimentary sources in the Almadén basin. The Almadén Hg deposits are related to a contemporaneous mafic magmatism that might have provided part of the mercury. Hydrothermal leaching of organic matter from sedimentary rocks and formation of Hg organic complexes enhanced metal solubility, promoting transport from and within the volcanic units.Editorial handling: M. Chiaradia     

Magnetic properties of surface sediments as proxies of recent anthropogenic pollution in the Anllóns riverbed (NW Spain)

A study of surface sediments from the Anllóns riverbed (northwestern Spain) was conducted to assess the use of their magnetic properties as proxies of recent trace element contamination (i.e., As, Zn, Pb, Cr, Ni and Cu). Thermomagnetic curves, hysteresis parameters, specific magnetic susceptibility χ, frequency-dependent magnetic susceptibility κ _FD%, magnetic remanence and saturation isothermal remanent magnetization ratios (i.e., S and SIRM/χ) reveal the presence of mostly fine-grained magnetite and maghemite in these samples. The Tomlinson Pollution Load Index (PLI), as well as the magnetic parameters χ, κ _FD%, SIRM/χ and S-ratios, vary more or less in agreement to each other when they are sequentially arranged throughout a 30-km-long transect that goes from the town of Carballo to the river mouth in Ponteceso. From that profile, it is possible to identify an anomaly of χ that lies between two small peaks of the PLI and seems to define a contaminated area probably linked to a diffuse low-impact source of pollution. There is also a conspicuous peak of the PLI that is likely associated to a nearby gold mine. The variations of the κ _FD%’s along the transect are the ones that best reflect the changes in the PLI values, regardless of the level of contamination. This result suggests that adsorption is the main mechanism of trace elements removal by Fe oxides in these samples. Direct signal analyses, used to decompose the isothermal remanent magnetization curves, reveal the presence of four magnetic fractions, with varying relative concentrations all over the profile, namely single-domain magnetite, close to the superparamagnetic threshold (SD/SP) and/or maghemite (\(\log B_{1/2}\) ca 1.2), single-domain magnetite (\(\log B_{1/2}\) ca 2), hematite (\(\log B_{1/2}\) ca 2.5) and goethite (\(\log B_{1/2}\) ca 3.5). Integrating all the available information, it was sketched out a likely sequence of events that included magnetic minerals neoformation in parent soils, their subsequent chemical transformations and the contamination episodes that affected the region.     

Estimation of potential pollution from mine tailings in the San Pedro River (1993–2005), Mexico–US border

The San Pedro River (SPR) is located in northern Sonora (Mexico) and southeastern Arizona (USA). SPR is a transboundary river that develops along the Sonora (Mexico) and Arizona (USA) border, and is considered the main source of water for a variety of users (human settlements, agriculture, livestock, and industry). The SPR originates in the historic Cananea mining area, which hosts some of the most important copper mineralizations in Mexico. Acid mine drainage derived from mine tailings is currently reaching a tributary of the SPR near Cananea City, resulting in the contamination of the SPR with heavy metals and sulfates in water and sediments. This study documents the accumulation and distribution of heavy metals in surface water along a segment of the SPR from 1993 to 2005. Total concentrations of Cd, Cu, Fe, Mn, Pb, and Zn in surface waters are above maximum permissible levels in sampling sites near mine tailing deposits. Nevertheless, a significant decrease in the Fe and SO₄ ²⁻ in surface water (SO₄ ²⁻: 7,180–460.39 mg/L; Fe: 1,600–9.51 mg/L) as well as a gradual decrease in the heavy and transition metal content were observed during the period from 1994 to 2005. Approximately 2.3 km downstream of the mine tailings, the heavy metal content of the water drops quickly following an increase in pH values due to the discharging of wastewater into the river. The attenuation of the heavy metal content in surface waters is related to stream sediment precipitation (accompanied by metal coprecipitation and sorption) and water dilution. Determining the heavy metal concentration led to the conclusion that the Cananea mining area and the San Pedro River are ecosystems that are impacted by the mining industry and by untreated wastewater discharges arising from the city of Cananea (Sonora, Mexico).     

Climate shifts vs. edaphic humidity and the difficulty of palaeoreconstructions – a malacological study on stable isotopes in Quaternary dune sequences of Fuerteventura

Dune palaeosurface sequences on the Eastern Canary Islands were investigated for stable isotope records in gastropod shells of the genus Theba. Due to the ecology of the taxon and the special oceanic insularity of the study site, we assume that δ¹⁸O_shell signals in our case mainly reflect shifts in δ¹⁸O signals of sea surface water. We found that a rapid decrease in δ¹⁸O_shell signals is associated with significant changes in gastropod associations. We suggest that these faunal changes were caused by strong (hot) winds at the end of glacial phases, that were described previously by Moreno et al. In addition, we assume that rapid declines in δ¹⁸O_shell signals due to marine transgressions were followed by geomorphologically stable phases, dominated by dust enrichment. Such palaeosurfaces correlate with maxima of gastropod biodiversity and with more negative δ¹³C_shell signals indicating a higher proportion of C3 plants. Based on our results, we also assume that these silty palaeosurfaces were associated with increased soil moisture conditions due to a higher water storage capacity of the finer substrate, independent of climatic moisture conditions.