Iñaki Yusta

Geochemical and microfaunal proxies to assess environmental quality conditions during the recovery process of a heavily polluted estuary: the Bilbao estuary case (N. Spain).

This study explores the eventual environmental improvement of the Bilbao estuary (northern Spain), from 1997 to 2006, in order to assess current estuarine restoration being undertaken as part of a Revitalization Strategic Plan. The monitoring programme is based on spatial and temporal variation in the distributions of both benthic foraminiferal assemblages and heavy metals contained in surficial sediments from the polluted intertidal flats. The overall pattern shows a decreasing metal concentration; however, reversals to this trend are noticed in the middle estuary. From 2000 to 2003, a significant decrease in heavy metal concentration was observed which is most likely related to the implementation in 2001-2002 of the biological treatment at a central wastewater treatment plant. Although the metal concentration decreased by 85% for some elements, these values still remain considerably high. No significant change occurred between 2003 and 2006 in metal concentrations. During the monitoring period the estuary channel presented environmental conditions close to azoic in 3/4 of its watercourse. Only in the year 2006, the two lowermost estuarine samples exhibited an increase in microfaunal densities. These samples were dominated by pollution-resistant estuarine species. The fact that estuarine sediments quality is recovering very slowly seems to be caused mainly by the resuspension of accumulated contaminants in the sediments due to dredging and working activities in the estuary. Thus, local authorities should consider also the clean up of the pollutants stored in the sediments, not seeking only the achievement of the water quality standards, as these polluted sediments can act as source of contamination.

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

Abstract 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., Concepcion, San Miguel, Aguas Tenidas 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 H 2 O, 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 H 2 O (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.

Mineral Exploration and Alteration Zone Mapping Using Mixture Tuned Matched Filtering Approach on ASTER Data at the Central Part of Dehaj-Sarduiyeh Copper Belt, SE Iran

This paper focuses on mapping jarosite and different types of alteration minerals for mineral exploration, particularly porphyry copper deposits and discriminating alteration zones with high-potential mineralization from those showing low potentials. The study area is situated at the Central Iranian Volcano-Sedimentary Complex, where the large copper deposits like Sarcheshmeh as well as numerous occurrences of copper exist. The visible near infrared and shortwave infrared (VNIR-SWIR) bands of Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) data were used for mineral mapping. The spectra of diagnostic alteration mineral groups, including sericite-illite, pyrophyllite-alunite, kaolinite-dickite, chlorite-calcite-epidote, and jarosite were extracted from VNIR-SWIR bands of the ASTER imagery. These spectra were used for mineral identification through mixture tuned matched filtering (MTMF) algorithm. Results showed that alteration minerals, and the areas containing jarosite were discriminated from the surrounding districts, which illustrate the ASTER ability to provide information on the occurrence of these minerals. Identification of these areas is valuable for mineral exploration, discrimination of strong pyritization, gossans, and the mine tailings. Results also support the role of MTMF as an effective image processing technique for mineral mapping and exploration.

Upper Pleistocene and Holocene palaeoenvironmental records in Cueva Mayor karst (Atapuerca, Spain) from different proxies: Speleothem crystal fabrics, palynology, and archaeology

The Cueva Mayor karst system of Atapuerca, in Northern Spain, hosts a highly significant record of human occupation from the Pleistocene. The climatic context of the human activities during the Pleistocene-Holocene for this inland site has not been well constrained, since existing records of the palaeoclimatic evolution of the Northern Iberian Peninsula are from more distal coastal and high-elevation sites. In this study, we interpret the palaeoenvironmental information recorded on the petrography of a stalagmite and the pollen spectra of the Sierra de Atapuerca karst system during the last 20 kyr. The integration of both types of records has allowed us to define four palaeoenvironmental stages. During the Upper Pleistocene and until 12.8 kyr BP, the climate was cold and dry, toward the end of the interval evolving to wetter and warmer conditions. From 12.8 to 7.7 kyr BP, during the Mesolithic-Neolithic, a major erosion event in both records marks the Pleistocene-Holocene transition. Around 5.9 kyr BP, the Late Neolithic, environmental conditions indicate a climatic optimum with a marked seasonality. The environmental conditions became drier from 4.2 kyr BP until the present, with a decrease in the woodlands. This aridity signal might be amplified by the impact of a more intense human agricultural activity after 3.1 kyr BP, during the Bronze Age.

Anomaly threshold estimation and data normalization using EDA statistics: application to lithogeochemical exploration in Lower Cretaceous Zn–Pb carbonate-hosted deposits, Northern Spain

Abstract A lithogeochemical survey of Lower Cretaceous sediments (1293 samples) in the Basque–Cantabrian basin (northern Spain) was carried out in order to estimate the mean contents of major oxides and Ba, Co, Cu, Ni, Pb, Rb, S, Sr, V, Zn and Zr in different lithological subsets and to identify anomalies related with Zn–Pb carbonate-hosted mineralization. After a detailed evaluation of different anomaly recognition methods, using both real and synthetic data, the cut-off values used in the Exploratory Data Analysis (EDA) were selected as thresholds. A prior classification of the rocks (based on chemical, mineralogical and petrographical data) guarantees appropriate homogeneous (with respect to major oxides) rock-groups during the evaluation of the data. A data standardization method was developed and applied to the samples collected from the Carranza sector (n=330). Zinc and Pb values for each sample were normalized to the particular threshold and interquartile range of their corresponding rock-type. These normalized values were plotted in geochemical maps. The results reveal the presence of Zn (up to 0.6%) and Pb (max. 1380 ppm) anomalies concentrated in carbonate facies, mainly in limestones, dolostones and dolomitic limestones. Magnesium-rich carbonates host the most significant anomalies. In the Carranza area, the great majority of outliers occur around known Zn–Pb mineral occurrences and are concentrated at the edge of the carbonate platform. In some cases fault control of the anomalies is indicated.

Extreme carbon dioxide concentrations in acidic pit lakes provoked by water/rock interaction.

We quantify the gas pressure and concentration of a gas-charged acidic pit lake in SW Spain. We measured total dissolved gas pressure, carbon dioxide (CO2) concentration, major ion concentration, isotopic composition of dissolved inorganic carbon (δ(13)C(DIC)), and other physicochemical parameters. CO2 is the dominant dissolved gas in this lake and results mainly from carbonate dissolution during the interaction of acidic water with wall rocks, followed by diffusive and advective transport through the water column. The δ(13)C(DIC) values suggest that the biological contribution is comparatively small. Maximum CO2 concentrations higher than 0.1 M (∼5000 mg/L) have been measured, which are only comparable to those found in volcanic crater lakes. The corresponding gas pressures of CO2 alone (pCO2 ∼3.6 bar) imply 60% saturation relative to local pressure at 50 m depth. High CO2 concentrations have been observed in other pit lakes of the region. We recommend gas-specific monitoring in acidic pit lakes and, if necessary, the design of feasible degassing strategies.

Schwertmannite to jarosite conversion in the water column of an acidic mine pit lake

Abstract Ferric precipitates in the water column at the San Telmo acidic mine pit lake in the Iberian Pyrite Belt, southwest Spain, have been studied by scanning electron microscopy, energy dispersive X-ray spectrometry, X-ray diffraction, X-ray fluorescence, inductively coupled plasma mass spectrometry and other complementary techniques. These Fe(III) precipitates were recovered from sediment traps which were left at different depths (25, 35, 40 and 100 m) in the lake for several months. Seasonal variations in the water chemistry were recorded to link the mineralogical findings to vertical and temporal changes in aqueous composition. The results indicate that schwertmannite is the first Fe(III) mineral to crystallize after the oxidation of Fe(II), in agreement with previous studies. Schwertmannite is kinetically favoured in comparison to other Fe(III) minerals, and it buffers the pH at 2.6-3.0. It is metastable, and alters to a (H3O+)- and (K+)-bearing jarosite (containing 58 mol.% H3O+ and 42 mol.% K+ on average) at lower pH (e.g. at pH 2.2-2.5 in the summer season), either in the water column (during settling) and/or in the benthic sediments, in a time period of weeks to months. The extent of hydronium substitution at the alkali site in the jarosite reflects the higher activity of free aqueous protons in solution (10-2.2 to 10-3.0) in comparison to the activities of K+ (10-4.5) and Na+ (10-3.2). Microscopic examination of mixed schwertmannite-jarosite precipitates found in the water column suggest that some textural and compositional features of metastable schwertmannite (e.g. the internal ‘pincushion’ arrangement and incorporation of trace amounts of Mg, Al, As and Pb) are conserved in the jarosite during the early stages of the mineralogical transformation, but many of these relics are lost in the later stages of crystal growth. Despite the hydronium-rich nature of the jarosite solid solution, this material is also an important sink for K+, which decreases in concentration with decreasing pH unlike most of the other major cations in the water column (notably Na+, Mg2+, Ca2+, Al3+, Fe3+, Cu2+, Zn2+). In addition to the release of Fe3+ to the aqueous solution, the conversion of schwertmannite to (H3O+, K+)-bearing jarosite consumes protons and thus may represent an additional pH control at San Telmo and other acidic mine pit lakes of the area.

Quantifying, assessing and removing the extreme gas load from meromictic Guadiana pit lake, Southwest Spain

High gas charges in deep waters of lakes can represent a hazard to the lives of human beings and animals in the surrounding. As this danger was feared, we quantified the amount of dissolved gas in Guadiana pit lake (Las Herrerías, Huelva; southwest Spain) and documented the temporal evolution over a period of two years. Gas pressure due to dissolved gases, such as carbon dioxide, methane and nitrogen was measured. Based on these data, we assessed the risk and the associated danger of limnic eruptions from the lake and concluded that the present situation cannot be considered safe. By deploying a vertical pipe, the updraft of degassing water was tested and demonstrated: the pilot plant provided enough energy to drive a self-sustained flow. Such a system could be implemented to remove the extreme gas pressure from the deep water. Measurements of discharges could be extrapolated to indicate the size for an efficient plant for the gas removal. The construction of such a system would be technically and economically viable. A reintroduction of degassed water into the monimolimnion would be advisable.

Low-crystallinity products of trace-metal precipitation in neutralized pit-lake waters without ferric and aluminous adsorbent: Geochemical modelling and mineralogical analysis

Abstract The removal of dissolved trace metals during neutralization of acid mine drainage has usually been described and modelled as a progressive, pH-dependent sorption onto standard ferric or aluminous adsorbent. In the absence of adsorbent mineral surfaces, trace metals tend to form amorphous to lowcrystallinity compounds which are often difficult to characterize. Here, we study the behaviour of the more soluble metals (Cu2+, Zn2+, Mn2+, Co2+, Ni2+, Cd2+) in the absence of ferric and aluminous adsorbent by neutralization experiments with waters from two acidic pit lakes. The objectives of our study were to identify the mineral products formed by trace-metal precipitation and the pH ranges at which these metals are removed from the solutions. Both geochemical modelling and detailed mineralogical and chemical analyses (XRD, SEM, TEM, XRF, ICP-AES) were undertaken to characterize the products. The schwertmannite and hydrobasaluminite colloids formed in the initial neutralization stages were removed from the waters at pH 3.5 and 5.1, respectively. These two minerals had previously adsorbed the Cr3+ and Pb2+ initially present in the solutions. The Cu precipitates were amorphous to X-rays, though chemical and modelling data suggest that Cu probably precipitated as a precursor of brochantite (Cu4(SO4)(OH)6·2H2O) at pH >6.0, together with minor quantities of other Cu hydroxysulfates (langite, antlerite) and Cu(OH)2. At higher pH, other divalent metals (Zn2+, Mn2+) precipitated as silicates, carbonates and/or (possibly) minor oxides and (oxy)hydroxides. The high concentration of aqueous SiO2 in the solutions allowed Zn to precipitate as willemite (Zn2SiO4) at pH >7.0. Similarly, the presence of inorganic carbon (originally as CO2 (aq.)) greatly influenced the nature of the corresponding precipitate of Mn. This metal was initially present as Mn2+ and experienced a partly oxidative precipitation forming, in combination with Mg2+, the hydroxyl carbonate desautelsite (Mg6Mn2(CO3)(OH)16·4H2O) at pH 9.0-10.0. The formation of Mn3+/ Mn4+ oxides and hydroxides (hausmannite, manganite, birnessite) could not be demonstrated, although geochemical calculations support their subordinate formation. Other metallic cations such as Co2+, Ni2+ and Cd2+ did not form discrete mineral phases but were totally removed by sorption onto and/or incorporation into the cited Zn and Mn compounds. The discrepancies between theoretical and demonstrated mineralogy and the significance of these minerals for future pit-lake remediation initiatives are discussed.