Immobilization of toxic elements in mine residues derived from mining activities in the Iberian Pyrite Belt (SW Spain): Laboratory experiments

In the mining environments of the Iberian Pyrite Belt (IPB), the oxidation of sulphide wastes generates acid drainage with high concentrations of SO₄, metals and metalloids (Acid Mine Drainage, AMD). These acid and extremely contaminated discharges are drained by the fluvial courses of the Huelva province (SW Spain) which deliver high concentrations of potentially toxic elements into the Gulf of Cádiz. In this work, the oxidation process of mine tailings in the IPB, the generation of AMD and the potential use of coal combustion fly ash as a possible alkaline treatment for neutralization of and metal removal from AMD, was studied in non-saturated column experiments. The laboratory column tests were conducted on a mine residue (71.6 wt% pyrite) with artificial rainfall or irrigation. A non-saturated column filled solely with the pyrite residue leached solutions with an acid pH (approx. 2) and high concentrations of SO₄ and metals. These leachates have the same composition as typical AMD, and the oxidation process can be compared with the natural oxidation of mine tailings in the IPB. However, the application of fly ash to the same amount of mine residue in another two non-saturated columns significantly increased the pH and decreased the SO₄ and metal concentrations in the leaching solutions. The improvement in the quality of leachates by fly ash addition in the laboratory was so effective that the leachate reached the pre-potability requirements of water for human consumption under EU regulations. The extrapolation of these experiments to the field is a promising solution for the decontamination of the fluvial courses of the IPB, and therefore, the decrease of pollutant loads discharging to the Gulf of Cádiz.     

Trace elements contamination of agricultural soils affected by sulphide exploitation (Iberian Pyrite Belt,Sw Spain)

Agricultural soils of the Riotinto mining area (Iberian Pyrite Belt) have been studied to assess the degree of pollution by trace elements as a consequence of the extraction and treatment of sulphides. Fifteen soil samples were collected and analysed by ICP-OES and INAA for 51 elements. Chemical analyses showed an As–Cu–Pb–Zn association related with the mineralisation of the Iberian Pyrite Belt. Concentrations were 19–994 mg kg⁻¹ for As, 41–4,890 mg kg⁻¹ for Pb, 95–897 mg kg⁻¹ for Zn and of 27–1,160 mg kg⁻¹ for Cu. Most of the samples displayed concentrations of these elements higher than the 90th percentile of the corresponding geological dominium, which suggests an anthropogenic input besides the bedrock influence. Samples collected from sediments were more contaminated than leptosols because they were polluted by leachates or by mining spills coming from the waste rock piles. The weathering of the bedrock is responsible for high concentrations in Co, Cr and Ni, but an anthropogenic input, such as wind-blown dust, seems to be indicative of the high content of As, Cu, Pb and Zn in leptosols. The metal partitioning patterns show that most trace elements are associated with Fe amorphous oxy-hydroxides, or take part of the residual fraction. According to the results obtained, the following mobility sequence is proposed for major and minor elements: Mn, Pb, Cd, > Zn, Cu > Ni > As > Fe > Cr. The high mobility of Pb, Cu and Zn involve an environmental risk in this area, even in soils where the concentrations are not so high.     

Metal partitioning in sediments and mineralogical controls on the acid mine drainage in Ribeira da Água Forte (Aljustrel,Iberian Pyrite Belt,Southern Portugal)

This work focuses on the geochemical processes taking place in the acid drainage in the Ribeira da Água Forte, located in the Aljustrel mining area in the Iberian Pyrite Belt. The approach involved water and stream sediment geochemical analyses, as well as other techniques such as sequential extraction, Mössbauer spectroscopy, and X-ray diffraction. Ribeira da Água Forte is a stream that drains the area of the old mine dumps of the Aljustrel mine, which have for decades been a source of acid waters. This stream flows to the north for a little over than 10 km, but mixes with a reduced, organic-rich, high pH waste water from the municipal waste water pools of the village. This water input produces two different results in the chemistry of the stream depending upon the season: (i) in the winter season, effective water mixing takes place, and the flux of acid water from the mine dumps is continuous, resulting in the immediate precipitation of the Fe from the acid waters; (ii) during the summer season, acid drainage is interrupted and only the waste water feeds the stream, resulting in the reductive dissolution of Fe hydroxides and hydroxysulfates in the stream sediments, releasing significant quantities of metals into solution. Throughout the year, water pH stays invariably within 4.0–4.5 for several meters downstream of this mixing zone even when the source waters come from the waste water pools, which have a pH around 8.4. The coupled interplay of dissolution and precipitation of the secondary minerals (hydroxides and sulfates), keeps the system pH between 3.9 and 4.5 all along the stream. In particular, evidence suggests that schwertmannite may be precipitating and later decomposing into Fe hydroxides to sustain the stream water pH at those levels. While Fe content decreases by 50% from solution, the most important trace metals are only slightly attenuated before the solution mixes with the Ribeira do Rôxo stream waters. Concentrations of As are the only ones effectively reduced along the flow path. Partitioning of Cu, Zn and Pb in the contaminated sediments also showed different behavior. Specific/non-specific adsorption is relevant for Cu and Zn in the upstream branch of Ribeira da Água Forte with acid drainage conditions, whereas the mixture with the waste water causes that the association of these metals with oxyhydroxide to be more important. Metals bound to oxyhydroxides are on the order of 60–70% for Pb, 50% for Cu and 30–60% for Zn. Organic matter is only marginally important around the waste water input area showing 2–8% Cu bound to this phase. These results also show that, although the mixing process of both acid and organic-rich waters can suppress and briefly mitigate some adverse effects of acid drainage, the continuing discharge of these waste waters into a dry stream promotes the remobilization of metals fixed in the secondary solid phases in the stream bed back into solution, a situation that can hardly be amended back to its original state.     

Chemical characteristics of groundwater around two massive sulphide deposits in an area of previous mining contamination, Iberian Pyrite Belt, Spain

A detailed chemical study of groundwater was carried out to elucidate the processes controlling the oxidation and dissolution of sulphide minerals at two massive sulphide deposits in the Iberian Pyrite Belt (IPB), i.e. the mined La Zarza deposit and the unmined Masa Valverde deposit. It was found that major-element compositions varied according to the hydrological regime, La Zarza being in a relatively high area with groundwater recharge (and disturbance due to the human factor) and Masa Valverde being in a relatively low area with groundwater discharge. The variations mainly concern pH, Eh, SO₄ and Na concentrations. Metal concentrations were determined (a) by ICP-MS after filtration, and (b) in some cases by voltammetric measurement of Cu, Pb, Zn, Cd and Mn using the Voltammetric In situ Profiling (VIP) System, which allows detection of only the mobile fractions of trace elements (i.e., free metal ions and small labile complexes a few nanometers in size). If one compares the results obtained by each of the two methods, it would appear that the groundwater shows significant enhancement of metal solubility through complexing with organic matter and/or adsorption onto colloids and/or small particles. In areas of sulphide oxidation, however, this solubility enhancement decreases according to Cu>Zn>Cd>Pb. Under very low redox conditions, the attained metal concentrations can be several orders of magnitude (up to 10⁸–10⁹ for Cu and 10²–10³ for Pb) larger than those expected from equilibrium with respect to sulphide minerals as calculated with the EQ3NR geochemical code; Zn concentrations, however, are close to equilibrium with respect to sphalerite. The implication of these results is discussed with respect both to mineral exploration and to environmental issues.     

Stratigraphy of the tectonically imbricated lithological succession of the Neves Corvo mine area,Iberian Pyrite Belt,Portugal

Biostratigraphic research, based on palynomorphs and ammonoids, of the tectonically imbricated lithological succession of the Neves Corvo mine, in the Portuguese part of the Iberian Pyrite Belt, has yielded ages for all formerly recognised lithostratigraphic units. These can be assembled in three main lithological sequences: (1) detrital sandy/shale substrate (Phyllite-Quartzite Formation) of late Famennian age; (2) Volcano-Sedimentary Complex, divided into a lower and an upper suite, in which one basic, three dolerite sills and four felsic volcanic units and a mineralised package of massive sulphides are identified with ages which range from the late Famennian to the late Visean; (3) flysch succession (Mértola Formation) composed of shale and greywacke dated as late Visean to early Serpukhovian. Precise biostratigraphic dating of the sedimentrary host rocks of massive sulphide mineralisation constrains the age of the latter to the late Strunian (354.8–354.0 Ma). Three stratigraphic hiatuses, corresponding to early/middle Strunian, Tournaisian and early Visean respectively and a south-westward progressive unconformity were also recognised. Sequences 1 and 2 are related to extensional episodes while sequence 3 marks the beginning of compressive tectonic inversion which gave rise to south-westward flysch progradation in close relation to a foreland basin development. Our results lead to the reinterpretation of the tectonic structure of the Neves Corvo mine, with implications for the interpretation of the regional basin dynamics and metal exploration.Editorial handling: F. Tornos     

Geochemistry and mineralogy of surface pyritic tailings impoundments at two mining sites of the Iberian Pyrite Belt (SW Spain)

Two pyritic tailings impoundments located in two mining areas of the Iberian Pyrite Belt (Cueva de la Mora and Minas de Ríotinto-Zarandas) were selected to asses their potential environmental impact. Mineralogical (XRD diffraction study), physico-chemical characterization (colour, particle size, pH, acid–base account, total Fe, As, Cu, Pb and Zn) as well as a speciation study (by means of a seven-step sequential extraction procedure) were performed in superficial (0–20 cm) tailings samples. Arsenic and metal contents in soils around the tailings impoundments were also studied. Zarandas dam, a reclaimed impoundment, which has been limed, partially topsoiled and planted, has supported and allowed the growth of pine trees and other plants for many years. The surface of this impoundment can be considered very acid but nonacid forming. Although total As and metal concentrations were relatively high, it is not possible to conclude that the Zarandas tailings have polluted the surrounding soils. Tailings in Cueva de la Mora showed high total and easily mobilizable concentration of toxic elements. The net neutralization potential was strongly negative as a consequence of the acid generation caused by the sulphide oxidation, the presence of secondary acid-generating minerals and the absence of neutralizing materials. Coquimbite and rhomboclase efflorescences formed during the Mediterranean dry summers on the surface of this impoundment contained very high levels of soluble As, Cu and Zn that were easily dissolved and released to the running water in the first rains of autumn.     

Interaction of acid mine drainage with waters and sediments at the Corona stream, Lousal mine (Iberian Pyrite Belt, Southern Portugal)

This study investigates the geochemical characteristics of the acid mine drainage discharged from the abandoned mine adits and tailing piles in the vicinity of the Lousal mine and evaluates the extent of pollution on water and on the stream sediments of the Corona stream. Atmospheric precipitation interacting with sulphide minerals in exposed tailings produces runoff water with pH values as low as 1.9–2.9 and high concentrations of (9,249–20,700 mg l⁻¹), Fe (959–4,830 mg l⁻¹) and Al (136–624 mg l⁻¹). The acidic effluents and mixed stream water carry elevated Cu, Pb, Zn, Cd and As concentrations that exceed the water quality standards. However, the severity of contamination generally decreases 4 km downstream of the source due to mixing with fresh waters, which causes the dilution of dissolved toxic metals and neutralization of acidity. Some natural attenuation of the contaminants also occurs due to the general reduced solubility of most trace metals, which may be removed from solution, by either co-precipitation or adsorption to the iron and aluminium precipitates.     

Factors affecting the distribution of potentially toxic elements in surface soils around an industrialized area of northwestern Greece

In order to investigate the factors influencing the distribution of 32 potentially toxic elements in the Ptolemais–Kozani basin, northwestern Greece, 38 soil samples were collected and analyzed. Concentrations of Al, Ca, Fe, K, Mg, Mn, Na, P, Ti, Ba, Co, Cr, Cu, La, Li, Ni, Pb, Sc, Sr, V, Y, and Zn were determined by ICP-AES and concentrations of As, Bi, Cd, Cs, Mo, Rb, Sb, Th, Tl, and U by ICP-MS. Bivariate analysis, principal component analysis, and geostatistical analysis were employed to investigate the factors influencing the distribution of the elements determined in the study area. The results indicate that the distribution of the majority of elements determined, especially for Cr, Ni, and associated elements, is greatly influenced by the geology and geomorphology of the study area. Principal component analysis has yielded four factors that explain over 77% of the total variance in the data. These factors are as follows: lithophilic elements that are associated with Al silicates minerals of K (factor I: 29.4%), ultramafic rocks (factor II: 20.5%), elements that are coprecipitated with Fe and Mn oxides (factor III: 18.0%), and anthropogenic activities (factor IV: 9.3%). The anthropogenic activities that influence the distribution of several potentially toxic elements (i.e., Cd, Cu, Pb, Zn) are agricultural practices and the deposition of fly ash in the vicinity of the local power stations.     

Use of sequential extraction procedure for assessing the environmental impact at regional scale of the São Domingos Mine (Iberian Pyrite Belt)

São Domingos is one of the most emblematic Portuguese mining districts in the Iberian Pyrite Belt (IPB). The beginning of mining exploitation in the area has been dated back to pre-Roman times, remaining in activity until 1966 when it was definitely halted. The intense mining labours are reflected in the presence of a huge amount of sulphide-mining wastes and downstream production of acid mine drainage (AMD). The mining wastes in the area are highly heterogeneous, and numerous different types may be recognized, including slags, iron oxides, smelting ashes, brittle and blocks of pyrite, leaching tank refuses, industrial landfill and other residues coming from ore extraction (gossan wastes and country rocks). The chemical speciation of potentially toxic elements (As, Cd, Cr, Cu, Fe, Mn, Pb, S, Sb and Zn) in all mine wastes from São Domingos was determined by modified BCR-sequential extraction procedure (European Community Bureau of Reference) and combined with the mass/volume proportions of each waste to quantify the potential risk of this mining district at regional scale. Analytical recoveries by sequential extraction, with respect to a pseudo-total metal content digestion, were generally acceptable (100 ± 17%). The oxidizable fraction corresponds with metals bound to sulphides and released easily under oxidizing conditions in AMD production processes. This is the most polluting fraction for the environment in this type of residues. Part of this fraction is retained by precipitation of soluble secondary minerals in warm periods, moving to the bio-available fraction that is dissolved in rainy periods. Just considering the bio-available fraction, all mine wastes from São Domingos may leach up to 172514 ton of Fe, 10564 ton of S, 6644 ton of Pb, 2610 ton of Zn, 1126 ton of Mn, 1032 ton of Cu, 183 ton of Cr, 109 ton of As, 34 ton of Sb and 0.9 ton of Cd. The process of precipitation and re-dissolution of efflorescent salts formed directly by oxidation of the oxidizable fraction is seasonally repeated, which causes an annual self-feeding and releasing of the bio-available fraction. Thus, the present study shows the pollutant potential of this IPB mining district and explains the spoiled state of the fluvial courses in the region.     

Application of multivariate statistical methods to indicate the origin and geochemical behavior of potentially hazardous elements in sediment around the Sarcheshmeh copper mine,SE Iran

Multivariate statistical techniques, i.e., correlation coefficient analysis, principal components analysis (PCA), and hierarchical cluster analysis (CA), were applied to the total and water-soluble concentrations of potentially hazardous metals in sediments associated with the Sarcheshmeh mine, one of the largest Oligo-Miocene porphyry copper deposits in the world. The samples were analyzed for hazardous metal concentration levels by inductively coupled plasma mass spectrometry method. Results indicate that the contaminant metals As, Cd, Cu, Mo, S, Sb, Sn, Se, Pb, and Zn were positively correlated with the total concentrations. These hazardous metals also have strong association in the PCA and CA results. Different anthropic versus natural sources of contaminant metals were distinguished by using CA method. Water-soluble fraction of hazardous metals showed that the hydro-geochemical behavior of these metals in sediments is different considerably. Elements such as Cd, Co, Cr, Cu, Fe, Mn, Ni, S, and Zn are readily water soluble from contaminated samples, especially from evaporative mineral phases, while the release of As, Mo, Sb, and Pb into the water is limited by adsorption processes. Results obtained from the application of multivariate techniques on the water-soluble fraction data set show that the hazardous metals are categorized into three groups including (1) Ni, S, Co, Cu, Cr, and Fe; (2) Se, Mn, Cd, and Zn; and (3) Sb, As, Mo, and Sn. This classification describes the hydro-geochemical behavior of hazardous metals in water–sediment environments of the Sarcheshmeh porphyry copper mine and can be used as a basis in remedial and treatment strategies.     

Mineralogical evolution of the Las Cruces gossan cap (Iberian Pyrite Belt): From subaerial to underground conditions

The Las Cruces VMS deposit is located at the eastern corner of the Iberian Pyrite Belt (SW Spain) and is overlain by the Neogene–Quaternary sediments of the Guadalquivir foreland Basin. The deposit is currently exploited from an open pit by Cobre Las Cruces S.A., being the supergene Cu-enriched zone the present mined resource. The Las Cruces orebody is composed of a polymetallic massive sulfide orebody, a Cu-rich stockwork and an overlying supergene profile that includes a Cu-rich secondary ore (initial reserves of 17.6 Mt @ 6.2% Cu) and a gossan cap (initial reserves of 3.6 Mt @ 3.3% Pb, 2.5 g/t Au, and 56.3 g/t Ag).The mineralogy of the Las Cruces weathering profile has been studied in this work. Textural relationships, mineral chemistry, deposition order of the minerals and genesis of the Las Cruces gossan are described and discussed in detail. A complex mineral assemblage composed by the following minerals has been determined: carbonates such as siderite, calcite and cerussite; Fe-sulfides including pyrite, marcasite, greigite and pyrrhotite; Pb–Sb sulfides and sulfosalts like galena, stibnite, fulöppite, plagionite, boulangerite, plumosite, and the jordanite–geocronite series, Ag–Hg–Sb sulfides and sulfosalts including miargyrite, pyrargyrite, sternbergite, acanthite, freibergite, cinnabar, Ag–Au–Hg amalgams; and Bi–Pb–Bi sulfides and sulfosalts such as bismuthinite, galenobismutite, others unidentified Bi–Pb-sulfosalts, native Bi and unidentified Fe–Pb–Sb-sulfosalts. Remains of the former oxidized assemblage appear as relicts comprised of hematite and goethite.Combining paragenetic information, textures and mineral chemistry it has been possible to derive a sequence of events for the Las Cruces gossan generation and subsequent evolution. In that sense, the small amount of Fe-oxyhydroxides and their relict textures replaced by carbonates and sulfides suggest that the gossan was generated under changing physico-chemical conditions. It is proposed that the Las Cruces current gossan represents the modified residue of a former gossan mineralization where prolonged weathering led to dissolution and leaching out of highly mobile elements and oxidation of the primary sulfides. Later, the gossan was subject to seawater-gossan interaction and then buried beneath a carbonated-rich cover. The basinal fluids-gossan interaction and the equilibration of fluids with the carbonated sediments brought to the carbonatization and sulfidation of the gossan, and thus to the generation of Fe-carbonates and Pb–Sb-sulfides.The Las Cruces mineral system likely represents a new category within the weathering class of ore deposits.     

Spatial and multivariate analysis of geochemical data from metavolcanic rocks in the Ben Nevis area, Ontario

A study of the lithogeochemistry of metavolcanics in the Ben Nevis area of Ontario, Canada has shown that factor analysis methods can distinguish lithogeochemical trends related to different geological processes, most notably, the principal compositional variation related to the volcanic stratigraphy and zones of carbonate alteration associated with the presence of sulphides and gold. Auto- and cross-correlation functions have been estimated for the two-dimensional distribution of various elements in the area. These functions allow computation of spatial factors in which patterns of multivariate relationships are dependent upon the spatial auto- and cross-correlation of the components. Because of the anisotropy of primary compositions of the volcanics, some spatial factor patterns are difficult to interpret. Isotropically distributed variables such as CO ₂ are delineated clearly in spatial factor maps. For anisotropically distributed variables (SiO ₂ ), as the neighborhood becomes smaller, the spacial factor maps becomes better. Interpretation of spatial factors requires computation of the corresponding amplitude vectors from the eigenvalue solution. This vector reflects relative amplitudes by which the variables follow the spatial factors. Instability of some eigenvalue solutions requires that caution be used in interpreting the resulting factor patterns. A measure of the predictive power of the spatial factors can be determined from autocorrelation coefficients and squared multiple correlation coefficients that indicate which variables are significant in any given factor. The spatial factor approach utilizes spatial relationships of variables in conjunction with systematic variation of variables representing geological processes. This approach can yield potential exploration targets based on the spatial continuity of alteration haloes that reflect mineralization.List of symbols c _i Scalar factor that minimizes the discrepancy between andU _i - D Radius of circular neighborhood used for estimating auto- and cross-correlation coefficients - d Distance for which transition matrixU is estimated - d _ij Distance between observed valuesi andj - E Expected value - E _i Row vector of residuals in the standardized model - F(d _ij) Quadratic function of distanced _ij F(d _ij)=a+bd _ij+cd _ij ² - L Diagonal matrix of the eigenvalues ofU - _i Eigenvalue of the matrixU;ith diagonal element ofL - N Number of observations - p Number of variables - Q Total predictive power ofU - R Correlation matrix of the variables - R _0j Variance-covariance signal matrix of the standardized variables at origin;j is the index related tod andD (e.g.,j=1 ford=500 m,D=1000 m) - R _1j Matrix of auto- and cross-correlation coefficients evaluated at a given distance within the neighborhood - R _m ² Multiple correlation coefficient squared for themth variable - S _i Column vectori of the signal values - s _k ² Residual variance for variablek - T _i Amplitude vector corresponding toV _i;ith row ofT=V ^–1 - T Total variation in the system - U Nonsymmetric transition matrix formed by post-multiplyingR ₀₁ ^–1 byR _ij - U _i Componenti of the matrixU, corresponding to theith eigenvectorV _i;U _i= _iV_iT_i - U* _i ComponentU _i multiplied byc _i - U _ij Sum of componentsU _i+U _j - V _i Eigenvector of the matrixU;ith column ofV withUV=VL - w Weighting factor; equal to the ratio of two eigenvalues - X _i Random variable at pointi - x _i Value of random variable at pointi - y _i Residual ofx _i - Z _i Row vectori for the standardized variables - z _i Standardized value of variable     

Mineralogy and environmental relevance of AMD-precipitates from the Tharsis mines,Iberian Pyrite Belt (SW,Spain)

This paper documents the solid phases associated to acid mine drainage (AMD) at the Tharsis mines (SW Spain). It provides an inventory of the AMD-precipitates, describing their main modes of occurrence and mineral assemblages. Results indicate that iron, aluminum and magnesium sulfates predominate in the assemblages. They occur as efflorescences composed of complex mixtures of metallic salts, and as ochres (jarosite combined with goethite). Also, their distributions illustrate two hydrochemical environments: the open pits, which reflect a proximal secondary paragenesis; and the downstream river banks (Meca River), which represent a more evolved paragenesis, resulting from the evolution of AMD produced throughout the system. These environments can be differentiated by composition and variety of minerals, which is considerably lower along the Meca River.The newly-formed minerals have monitoring significance and proved capable of participating in cycles of retention–liberation of hydrogen ions, sulfate, and metals. In a semi-arid climate, the importance of the AMD-precipitates as environmental indicators is stressed. They may help to understand the response of the system to the episodic rainfall events that occur after prolonged dry periods.     

Exploratory and spatial data analysis (EDA–SDA) for determining regional background levels and anomalies of potentially toxic elements in soils from Catorce–Matehuala, Mexico

The threshold between geochemical background and anomalies can be influenced by the methodology selected for its estimation. Environmental evaluations, particularly those conducted in mineralized areas, must consider this when trying to determinate the natural geochemical status of a study area, quantifying human impacts, or establishing soil restoration values for contaminated sites. Some methods in environmental geochemistry incorporate the premise that anomalies (natural or anthropogenic) and background data are characterized by their own probabilistic distributions. One of these methods uses exploratory data analysis (EDA) on regional geochemical data sets coupled with a geographic information system (GIS) to spatially understand the processes that influence the geochemical landscape in a technique that can be called a spatial data analysis (SDA). This EDA–SDA methodology was used to establish the regional background range from the area of Catorce–Matehuala in north-central Mexico. Probability plots of the data, particularly for those areas affected by human activities, show that the regional geochemical background population is composed of smaller subpopulations associated with factors such as soil type and parent material. This paper demonstrates that the EDA–SDA method offers more certainty in defining thresholds between geochemical background and anomaly than a numeric technique, making it a useful tool for regional geochemical landscape analysis and environmental geochemistry studies.     

Geology and geophysics as successful tools in the discovery of the Lagoa Salgada Orebody (Sado Tertiary Basin – Iberian Pyrite Belt), Grândola, Portugal

Gravimetry was the main exploration method used in this high risk area to the north of the Grândola fault, in the Iberian Pyrite Belt (IPB). It showed several targets, among which the Valverde-Lagoa Salgada area stood out. Here, in August 1992, a polymetallic massive sulphide orebody was found, named Lagoa Salgada. According to the geological characteristics of the area and to the nature of the surveyed targets, other exploration techniques were used, namely: geology, magnetometry, resistivity, electrical sounding, magneto-telluric, seismic and mechanical drilling. The deposit was found under a Tertiary cover, 128?m in depth, complete with a 15?m thick gossan, caused by paleoalteration, with a supergene enrichment zone. This gossan gave way to massive sulphides, with intersections, at times, exceeding 60?m. They are limited towards the footwall by an important fault with strong associated kaolinization, which is interpreted as a reverse fault, placed on the inverse limb of an anticlinal structure. Throughout the deposit, the chemical composition of the mineralization showed great variation reaching significant values of Zn, Pb, Sn, Cu, As, Hg, Sb, Cd, Au and Ag. In the initial phase the deposit has an estimated tonnage of 5?Mt. It is related to a large gravity anomaly with the general orientation NW-SE, which was investigated by 15 boreholes made by the Instituto Geológico e Mineiro. The drilling cut an important volcanic centre of an acid to intermediate nature, around which intense hydrothermal activity was associated with contemporaneous sulphide mineralization. The gravity anomaly has two nuclei, a NW and a central one, about 450?m apart, where a pyrite orebody with polymetallic sulphides and stockwork sulphide mineralization are developed. This discovery led to an extensive exploration project that confirmed the mining potentialities of the NW sector of the IPB, to the north of Grândola fault, where previously no polymetallic sulphide occurrences were known.     

Contamination risk assessment of fresh groundwater using the distribution and chemical speciation of some potentially toxic elements in Calabar (southern Nigeria)

The computer program PHREEQC was used to determined the distribution, chemical speciation and mineral saturation indices in a fresh groundwater environment with limited mining activities in the adjoining areas. The aim was mainly to determine the potential risk of a coastal plain aquifer contamination by some potentially toxic elements. The results show that the elements Ba, Cd, Cu, Fe, Mn, Ni, Rb, Sr, and Zn are distributed as free metal ions. Arsenic is in the neutral form of H₃AsO₃ ^o, while three species of aluminium [Al³⁺, AlOH₂, Al(OH)₂ ⁺] dominate. The major species of uranium include UO₂CO₃, UO₂²⁺+, UO₂⁺, and UO₂OH⁺, respectively, in order of abundance. The groundwater is saturated with respect to alunite [KAl₃ (SO₄)₂ (OH)₆], basaluminite [Al₄ (OH)₁₀ SO₄], boehmite [Al(OH)], Cu metal (Cu), cuprous ferrite (CuFeO₂), diaspore [AlO(OH)], gibbsite [Al(OH)₃], goethite (FeOOH), hematite (Fe₂O₃), magnetite (Fe₃O₄) and uraninite (UO₂). Most of the species are not mobile under the prevailing pH (3.3 to 5.9) and Eh (7 to 158 mV) conditions. The mobile ones are very low in concentration and will be immobilized by precipitation of mineral phases. The study concludes that presently these species do not pose any risk to the aquifer.     

Hydrothermal alteration of felsic volcanic rocks associated with massive sulphide deposition in the northern Iberian Pyrite Belt (SW Spain)

Massive sulphide deposits of the northern Iberian Pyrite Belt (IPB) are mainly hosted by felsic volcanic rocks of rhyolitic to dacitic composition. Beneath most of the massive ores of this area (e.g., Concepción, San Miguel, Aguas Teñidas Este or San Telmo deposits) there is usually a wide hydrothermal alteration halo associated with stockwork-type mineralization. Within these alteration envelopes there are two principal rock types: (1) chlorite-rich rocks, linked to the inner and more intensely altered zones and dominantly comprising chlorite+pyrite+quartz+sericite (+carbonate+rutile+zircon+chalcopyrite), and (2) sericite-rich rocks, more common in the peripheral zones and showing a dominant paragenesis of sericite+quartz+pyrite+chlorite (+carbonate+rutile+zircon+sphalerite). Mass-balance calculations comparing altered and least-altered felsic volcanic rocks suggest that sericitization was accompanied by moderate enrichment in Mg, Fe and H₂O, with depletion in Si, Na and K, and a slight net mass loss of about 3%. Chloritization shows an overall pattern which is similar to that of the sericitic alteration, but with large gains in Fe, Mg and H₂O (and minor enrichment in Si, S and Mn), and a significant loss of Na and K and a minor loss of Ca and Rb. However, chloritization has involved a much larger net mass change (mass gain of about 28%). Only a few elements such as Nb, Y, Zr, Ti, P and LREE appear to have remained inert during hydrothermal alteration, whilst Ti and Al have undergone very minor mobilization. The results point to the severity of the physico-chemical conditions that prevailed during the waxing stage of the ore-forming hydrothermal systems. Further, mineralogical and geochemical studies of the altered footwall rocks in the studied deposits indicate that hydrothermal ore-bearing fluids reacted with host rocks in a multi-stage process which produced a succession of mineralogical and chemical changes as the temperature increased.     

Ordinary kriging and indicator kriging in the cartography of trace elements contamination in São Domingos mining site (Alentejo, Portugal)

The abandoned pyrite mine of São Domingos, in the southeast Portugal is still an acid mine drainage generator and a source for trace elements pollution. This study aims to evaluate and map the soils and sediments chemical pollution. With this purpose three test sites located in the vicinities of the mine were sampled for soils, sediments and mining waste materials. The samples were analysed for pH, organic carbon, iron oxides and total content of As, Cu, Cr, Hg, Pb, Sb, U, Zn, Mn, S, Fe Al, Ca, K, Mg and P. The hyperspectral image of the test sites was acquired using the aero transported sensor HymapTM. Chemical analysis and hyperspectral images data were processed to estimate the contamination maps by multivariate data analysis, ordinary kriging, cokriging and indicator kriging methodologies.The test sites located downstream the mine open pit, are highly contaminated mainly in As, Hg, Pb and Sb, but no contamination was found in the third test site, upstream the mining site. The acid mining drainage seems to be the main spreading agent of chemical contaminants mostly originating from the mine waste materials. Factorial analysis and the geostatistical methodologies allowed several approaches for the contamination cartography of mining areas.