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The formation of thin mineral films or encrustations floating on the water surface of low-flow or stagnant zones of acid mine drainage (AMD)-affected streams is probably among the most exotic features that can be found in mining areas. However, most fundamental questions about their origin (biotic vs. abiotic), structure, mineralogy, physical stability and metal-retention capacity remain unanswered. This study aims to reveal the factors promoting their formation and to clarify their composition in detail. With this purpose, the major mineral phases were studied with XRD in surface film samples found in different mine sites of the Iberian Pyrite Belt mining district (SW Spain), and the major oxide and trace metal concentrations were measured with XRF and/or ICP-MS. Fe(III) minerals dominated these formations, with mineralogy controlled by the pH (jarosite at pH~2.0, schwertmannite at pH 2.5–3.5, ferrihydrite at pH > 6.0). Other minerals have also been identified in minor proportions, such as brushite or khademite. These mineral formations show an astounding capacity to concentrate, by orders of magnitude (×102 to ×105), many different trace metals present in the underlying aqueous solutions, either as anionic complexes (e.g., U, Th, As, Cr, V, Sb, P) or as divalent metal cations (e.g., Cu, Zn, Cd, Pb). These floating mineral films are usually formed in Fe(II)-rich acidic waters, so their formation necessarily implies the oxidation of Fe(II) to Fe(III) phases. The potential involvement of Fe(II)-oxidizing microorganisms was investigated through 16S rRNA gene amplicon sequencing of water underneath the Fe(III)-rich floating mineral films. The sequenced reads were dominated by Ferrovum (51.7 ± 0.3%), Acidithiobacillus (18.5 ± 0.9%) and Leptospirillum (3.3 ± 0.1%), three well-known Fe(II)-oxidizing genera. These microorganisms are major contributors to the formation of the ferric mineral films, although other genera most likely also play a role in aspects such as Fe(III) sequestration, nucleation or mineral growth. The floating mineral films found in stagnant acidic mine waters represent hotspots of biosphere/hydrosphere/atmosphere interactions of great value for the study of iron biogeochemistry in redox boundaries. This research was funded by the Spanish Ministry of Science and Innovation through grant number CGL2016-74984-R to J.S.-E., the research program TTW by the Dutch Research Council (NWO) under project number 14797 to I.S.-A and the Basque Government (Consolidated Group IT1678-22) to I.Y. and A.M.I.

The most commonly used paleoclimatic proxies in speleothem studies are the carbon and oxygen stable isotopes and the trace elements of calcite. However, assessing the incorporation of other components, such as organic matter, may also be of interest in interpreting and reconstructing the climate during speleothem growth. In this work, the incorporation of humic and fulvic acids derived from overlying soils is proposed as the cause of the red coloration of speleothems from the Goikoetxe Cave (Busturia, Bizkaia). Through the application of petrological studies combined with X-ray fluorescence, UV luminescence, Raman spectroscopy and Fourier-transform infrared spectroscopy (FTIR) analysis, it has been possible to correlate a variation of organic content in the overlying soils and the red coloration, being this stain a main proxy to study and reconstruct the seasonal paleoclimatic parameters during the speleothem formation.

Several isolated studies have tried to understand quartzite from an archaeological perspective by applying two different methodological approaches. The first one is based on non-destructive characterisation, aiming to understand human procurement and management of quartzite, without solid geoarchaeological criteria. The second characterised the material from archaeological sites using only petrographic or geochemical perspectives of a limited sample. Currently, both perspectives are unconnected, creating a methodological gap that needs to be solved to study the procurement and management of quartzite in greater depth. The present study, mainly methodological, will explore the gap between petrographic analysis and non-destructive characterisation. Doing so, we could fill this vacuum of information and generate a solid geoarchaeological basis to characterise not only a sample but complete assemblages. To this end, we analyse the lithic assemblages at El Arteu and El Habario, two Middle-Palaeolithic sites in the Cantabrian Region, northern Spain. We summarise the main results derived from petrographic analysis, but especially we will focus on non-destructive criteria to characterise the lithic surfaces of archaeological quartzite using stereoscope microscopy. This process allows us to understand the complete assemblage but also, through technological characterisation, understand the management of different quartzite petrogenetic types in both sites.

The precipitation of dissolved aluminum is among the most important geochemical processes affecting the water chemistry and trace metal dynamics of acid mine drainage (AMD). In this study, we focus on the in situ formation of Al precipitates and their subsequent interaction with trace metals, dissolved silica and microbial cells under anoxic conditions (e.g., deep strata of pit lakes, flooded underground mines). In the presence of sulfate (0.1–0.2 M), dissolved aluminum precipitates at pH ~ 4.0 and forms an amorphous, globular hydroxysulfate precipitate with composition corresponding to hydrobasaluminite. This proto-hydrobasaluminite shows an important capacity to incorporate SiO 2 (aq), divalent metal cations (Fe II , Pb II , Be II ), and many anion-forming trace elements (As, Cr, Sb, V, Se, U) by coprecipitation. Removal efficiencies obtained experimentally with freshly formed hydrobasaluminite under anoxic and oxic conditions were consistent with metal profiles obtained in the pit lakes and suggest that the behaviour of many toxic metals is closely linked to the Al particles. Detailed transmission electron microscopy (TEM) shows that hydrobasaluminite may coexist with more crystalline minerals like gibbsite, bayerite and/or allophane, which are present as nanocrystals embedded in the amorphous matrix and appear to form by transformation of the former. Hydrobasaluminite precipitation is favoured by the activity of iron- and sulfate-reducing microbes in the water column and at the sediment/water interface. Our study shows that, at solubility equilibrium, microbial cells often serve as nuclei for Al precipitation. Further, chemical mapping of Al-coated cells by scanning/TEM shows an important incorporation of SiO 2 , Fe 2 + (valence confirmed by electron energy loss spectroscopy) and other metal cations (e.g., Mg 2 + ) in the Al cell coatings as compared to Al particles presumed to form via abiotic precipitation. These Al cell coatings are amorphous to X-rays and their compositions likely result from coprecipitation of SiO 2 and Fe 2 + resulting in Si-rich and Fe(II)-rich hydrobasaluminite. The disparity between field and laboratory data, the serendipitous detection of nontronite-like smectite in precipitates formed in the acidic waters under laboratory conditions, and the apparent saturation with respect to different clay minerals (e.g., kaolinite, halloysite) are all evidences suggesting thermodynamic feasibility of aluminosilicate precursor formation in these systems.

Micromorphological analysis is an invaluable research tool for reconstructing detailed depositional and post-depositional processes of cave infill sequences and for providing paleoenvironmental insight. In this work, we present the results of a micromorphological and mineralogical study of the sedimentary sequence at the Lezetxiki II cave (northern Iberian Peninsula). The cave forms part of the Lezetxiki archaeological complex which has yielded early Middle Palaeolithic tools and archaic human remains. We have identified three main clastic sedimentary processes as being significant at Lezetxiki II: 1) fluviokarst or runoff processes, which are characterised by yellow sandy illite-rich microfacies; 2) infiltration processes, which produce a massive red silty-clay vermiculite-rich microfacies; and 3) inwash processes, which generate a reworked illite and vermiculite rich silty sand microfacies. The most common post-depositional processes observed are calcite precipitation infilling pore spaces, and compression structures derived from specific vertical loading events. In order to improve the chronological framework of the sedimentary sequence at Lezetxiki II, we have revised previous radiometric and relative dating results from faunal and archaeological remains and have dated the lowermost stratigraphic level using single-grain thermally-transferred optically-stimulated luminescence dating. Sedimentation at the Lezetxiki II cave started during Marine Isotope Stage (MIS) 7 through fluviokarst processes. We interpreted that runoff prevailed during MIS 6, while soil infiltration processes became more significant towards the MIS 5 optimum. Gradually, inwash processes prevailed over infiltration until the end of the interglacial phase. During the following glacial phases, runoff and erosion dominated but were subsequently replaced by inwash processes during MIS 1., PALEOGATE project, funded by the Spanish Ministry of Economy and Competitiveness (HAR2014-53536-P) as well as the US14/16 project funded by the University of the Basque Country and Basque Coast Geopark, and Basque Government (IT1029-16-GBV6). We would also like to thank Tim Nicholson for his work in translating and editing different versions of the English text. Additional financial support for this research was provided by Australian Research Council (ARC) Future Fellowship project FT130100195, ARC Discovery Early Career Researcher Award DE160100743

Cueva de la Mora and Guadiana are two acidic mine pit lake in the Iberian Pyrite Belt (south-west Spain) that exhibit depth-related stratification, which is in turn reflected in the bacterial community population the different layers. Here we describe the microbial communities present in samples of sediments located close to the surface and deep within the lakes, which show interesting contrasts to planktonic communities.

© 2014 Elsevier Ltd and INQUA. The western Pyrenean area contains extensive karst areas, however, their genesis and development are still mostly unknown. In this work, we make a general description of the karst landscape in different karst areas: 1) Rasa type; 2) Cone-type karst; and 3) Alpine-type karst. The first two types are present in the littoral area, where geomorphological evolution mostly depends on sea level and climatic changes. We focused our study in two karst areas of the littoral cone-type karst. We correlate different caves created from different stable water table levels. Three representative caves are studied in detail, studying their stratigraphic record based on allostratigraphy. Finally we dated the different phases of speleothem formation in the three caves. Using all this information, we defined four stable paleowater table levels, at 50, 150, 220 and 350masl, controlled by sea level changes and isostatic uplift events. The lowest level is the youngest, with an age of c. 1Ma. We discovered that the interior of the three caves display very similar endokarst allostratigraphic sequences, characterized firstly by an erosion phase, a fluvio-karst input, flowstone speleothem formation and finally dripping speleothem formation. The chronological data shows a correlation between these phases and Pleistocene climatic phases; the erosion phase is related to the falling sea level, fluviokarst detrital input is related to cold (glacial) stages and the formation of speleothems is related to the warmest (interglacial) moments and high sea level periods., This research was funded by the University of the Basque Country's projects (UPV/EHU11/21 and UFI11/09). M. Arriolabengoa and M. del Val are funded by predoctoral grants (BFI-2012-289 and BFI-2010-379) from the Basque Government.

The characteristics and provenance of the fine sediment forming the matrix of detrital endokarst fill can vary greatly, and their study provides valuable information about the paleoenvironment and the different sedimentary and diagenetic processes in which it was formed and deposited. This paper applies this study to the case of Lezetxiki II cave (Arrasate, Gipuzkoa). Using X-ray diffraction (XRD), X-ray fluorescence (XRF), and scanning electron microscopy (SEM–EDS) analysis with samples of endokarst sediment, rocks and soils in the surroundings of the cave, the following source areas and sedimentary processes have been identified: 1) allochthonous sedimentation through the fluviokarst processes which eroded soils formed on siliciclastic formations. It is characterised by a high percentage of illite in the sediment and predominated in relatively cold periods in MIS 6 and MIS 2–4; 2) sedimentation through infiltration from karst fissures of the autochthonous soils formed on the limestone substrate (terra rossa). It is characterised by a higher vermiculite content, and prevailed in the warm MIS 5 period and the Holocene; 3) chemical sedimentation, where calcite precipitated in the form of speleothems in warmer and more humid periods; and 4) deposition of microfauna bones in owl pellets.

Visible near infrared and shortwave infrared (VNIR-SWIR, 350 to 2500 nm) reflectance spectra obtained from an analytical spectral device (ASD) have been used to define alteration zones adjacent to porphyry copper deposits (PCDs), in the central part of Kerman magmatic arc, SE Iran. The spectral analysis identified sericite, illite, halloysite, montmorillonite, dickite, kaolinite, pyrophyllite, biotite, chlorite, epidote, calcite, jarosite, and iron oxyhydroxides (e.g. hematite, goethite) of hydrothermal and supergene origin. Identified alteration zones are classified into six principal types namely phyllic, phyllic/propylitic, propylitic, potassic, argillic and advanced argillic. The iron oxide minerals in the oxidized zone were also identified using spectral analysis. Results of spectral analyses of samples are consistent with mineralogical data obtained from X-ray diffraction (XRD) and petrographic studies. Spectroscopic studies by ASD demonstrate that this tool is very useful for semi-quantitative and cost effective identification of different types of alteration mineral assemblages. Furthermore, it can provide a valuable tool for evaluating aerial distribution of alteration minerals while coupled with remote sensing data analysis.

The main aim of the present study was to examine the feasibility of the EO-1 Hyperion data in discriminating and mapping diagnostic alteration minerals around porphyry copper deposits (PCDs), verified by field surveys and laboratory analyses. A partial sub-pixel method, mixture tuned matched filtering (MTMF), was implemented on a pre-processed and calibrated Hyperion dataset. The tested area is situated at the Central Iranian Volcano-Sedimentary Complex, where abundant porphyry copper deposits like Sarcheshmeh, Darrehzar, and Sereidun are located. The characteristic alteration minerals identified by Hyperion data included biotite, muscovite, illite, kaolinite, goethite, hematite, jarosite, pyrophyllite, and chlorite. Discrimination of these minerals especially biotite and iron oxide (hematite and goethite) can provide valuable evidences for PCD exploration projects. Results revealed that Hyperion data prove to be powerful in discriminating and mapping various types of alteration zones while the data were subjected to adequate pre-processing.

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.

Twelve massive sulphide deposits from the Iberian Pyrite Belt (IPB) show well-preserved iron caps, some of which were mined during the last century to recover precious metals (e.g., Tharsis, Rio Tinto, San Miguel). Field observations and correlation assays between the distinct mineral sequences at different deposits suggest that all the gossans were developed under similar conditions and have undergone the same geological events. All the gossans have a mushroom-like morphology in sharp contact with the underlying massive sulphide orebodies. In most cases these are located over an apparent supergene enrichment zone rich in secondary sulphides. Some gossans extend into tongues of alluvial heterolithic breccias consisting of eroded transported gossans displaced as far as several hundred meters away from their sources. The distribution of major minerals throughout the gossan profiles (goethite, hematite, quartz and jarosite) and the statistical analysis of the geochemical data distinguish three separate zones, with gradual contacts roughly parallel to the current topography: (1) the lower zone dominated by goethite and subordinate jarosite, with significant enrichment in S, As, P, Pb, Sn, Sb, Ag and Au; (2) the middle or principal zone dominated by goethite and lacking jarosite, which is depleted in S, and As, as well as heavy and precious metals; and (3) the upper zone near the surface, mainly composed of hematite and quartz with only weak anomalies in P, Pb and Sn. The origin and variations occurred in the profiles are explained by a three-stage process. This involves an initial acidic stage of gossan development centred on the oxidation of sulphides that lead to the formation of the first Fe-rich oxyhydroxides and sulphates (mainly goethite and jarosite, respectively). Over time, a progressive stage of maturity is reached progressively downwards through the gossan profile due to the intensification of the oxidation and leaching processes. The ongoing gossan formation produced alteration and reprecipitation of pre-existing oxyhydroxides, the loss of the majority of the previously sorbed heavy metals, and a major dilution of trace elements especially in the zones near the surface. The main results of this stage of formation are the production of heavy metal-depleted oxyhydroxides, most commonly goethite and hematite, and the disappearance of jarosite. Subsequently, local uplift of the gossanous rocks by neotectonic movements facilitated the rejuvenation of the oxidation of the ores. This final stage complicated the previously developed zonation with the formation of jarosite in mature areas. Possible major breaks in this gossan development ocurred in Messinian times (7–8 Ma) and at the beginning of the Early Quaternary (1–2 Ma?).

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 Herrerias, 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.

Este documento corresponde a una versión PREPINT (versión enviada originalmente a la revista, previa a las modificaciones sugeridas por los revisores). El artículo final ha sido publicado originalmente por la revista Ore Geology Review de la Editorial Elsevier. La URL del mismo es: http://dx.doi.org/10.1016/j.oregeorev.2015.10.005, This is a PREPRINT version (pre-refereeing process version). The final article has been published in Ore Geology Review by Elsevier. The URL is: http://dx.doi.org/10.1016/j.oregeorev.2015.10.005, Geological evidence and mineralogical, fluid inclusion temperature and geochemistry data suggest that the Mazarrón Zn-Pb-Cu-Ag-Fe deposit is a volcanic-hosted epithermal deposit. It is hosted by dacites with advanced argillic alteration, argillic alteration, propylitic alteration and silicification halos. K-Ar dating of illite from the argillic alteration gives an age of 9.7 ± 1.2 Ma, which suggests that mineralization took place very close to the volcanism. The fluid inclusion study in the ore veins shows epithermal temperatures (between 190 and 260ºC), but moderate salinities, between 12 and 18 wt. % NaCl eq), compatible with mixing between surface waters and polygenic deep hydrothermal fluids. Two mineralization types are identified: iron sulfide mineral association and polymetallic mineral association (sphalerite-galena-chalcopyrite-fahlore bearing). According to isotopic data, the first mineralization was mainly formed by interaction between basinal fluids that leached Triassic sulfates (+ surface waters), and C-bearing reduced deep waters. This interaction developed a Thermochemical Sulfate Reduction (TSR) supporting extreme and geologically unusual fractionation, with a range up to +30‰ δ34S, and reaching +53‰ δ34S. The second mineralization event is compatible with the irruption of a magmatic fluid discharge. Although this study suggests that Mazarron could be classified as an intermediate sulfidation deposit, the genetic model includes processes such as TSR that are not typical features of volcanic-hosted epithermal deposits., Universidad de Granada. Departamento de Mineralogía y Petrología, Instituto Andaluz de Ciencias de la Tierra (UGR-CSIC), Universidad del País Vasco. Departamento de Mineralogía y Petrología, Scottish Universities Environmental Research Centre (SUERC), Universidad de Granada. Departamento de Didáctica de las Ciencias Experimentales, Grupo de Investigación Mineralogía, Petrología y Yacimientos Minerales (GIMPY) (RNM131) de la Junta de Andalucía., Grupo de Investigación Didáctica de las Ciencias Experimentales y de la Sostenibilidad (HUM613)de la Junta de Andalucía, This research has been supported by the Project of ExcellenceP05-RNM-0736 (founded by Consejería de Innovación, Ciencia y Empresa, Junta de Andalucia, Spain) and the Spanish projectCGL-2006-02594-BTE (founded by Ministry of Science and Innovation/Ministry of Education and Science and Fondo Europeo de Desarrollo Regional, FEDER).

Short-wave infrared reflectance (SWIR) spectra obtained from a Portable Infrared Mineral Analyser (PIMA) were applied to map acidic mine soils at San Miguel massive sulphide deposit, Iberian Pyrite Belt, Spain. Field spectral measurements and laboratory analysis were performed on samples from 58 stations from two very polluted grounds. These analyses identified secondary and tertiary Fe-rich sulphate–hydrate minerals associated with the alteration of sulphide-bearing mine wastes and other associated infrared active minerals. The spectral absorption features for the pure salt types found in these areas allowed the preparation of a specific reference library for automatic mineral identification. Using this approach three separate zones around the sources of contamination have been discriminated: a “proximal” zone dominated by rozenite + hexahydrite, a “transitional” zone dominated by copiapite + coquimbite and a “distal” zone of hydronium–jarosite. An additional zone of “gypsum” was also recognized locally at the areas, where, last decade the neutralization of the acid soils with limestones was attempted. In addition to discriminating distinct mineralogical zones quantitative spectral data allowed contoured mineral maps to be produced that are comparable with the estimated mineralogical data obtained from conventional methods, such as XRD and field observations. These maps demonstrate that sulphate minerals were firstly formed by oxidation of the pyrite-rich ores followed by dissolution and precipitation involving a combination of oxidation, dehydration, and neutralization reactions. The study shows the potential of SWIR spectral analysis to identify and understand the distribution of efflorescent salts and other products of pyrite decomposition and provides a methodology to assist the research and monitoring of sources of environmental contamination.

The Reocin Zn-Pb deposit, 30 km southwest of Santander, Spain, occurs within Lower Cretaceous dolomitized Urgonian limestones on the southern flank of the Santillana syncline. The Reocin deposit is one of the largest known strata-bound, carbonate-hosted, zinc-lead deposits in Europe. The total metal endowment of the deposit, including past production and remaining reserves, is 62 Mt of ore grading 8.7 percent Zn and 1.0 percent Pb. The epigenetic mineralization consists of sphalerite and galena, with lesser marcasite and trace pyrite with dolomite as gangue. Microprobe analyses of different generations of dolomite revealed nonstoichiometric compositions with various amounts of iron (up to 14 mol % of FeCO3). Replacement of host dolomite, open-space filling of fractures, and cementation of breccias derived from dissolution collapse are the principal types of ore occurrence. Detailed cross-section mapping indicates a stratigraphic and structural control on the deposit. A stratiform morphology is present in the western part of the orebody (Capa Sur), whereas mineralization in the eastern part is highly discordant but strata bound (Barrendera). Stratigraphic studies demonstrate that synsedimentary tectonic activity, related to the rifting of the North Atlantic (Bay of Biscay), was responsible for variation in sedimentation, presence of unconformities (including paleokarsts), local platform emergence and dolomitization along the N60 fault trend. In the Reocin area, two stages of dolomitization are recognized. The first stage is a pervasive dolomitization of the limestone country rocks that was controlled by faulting and locally affected the upper part of the Aptian and the complete Albian sequence. The second dolomitization event occurred after erosion and was controlled by karstic cavities. This later dolomitization was accompanied by ore deposition and, locally, filling of dolomite sands and clastic sediments in karstic cavities. The circulation of hydrothermal fluids responsible for sulfide deposition and the infilling of karst cavities were broadly contemporaneous, indicating a post-Albian age. Vitrinite reflectance data are consistent with previously measured fluid inclusion temperatures and indicate temperatures of ore deposition that were less than 100°C. Carbon and oxygen isotopic data from samples of regional limestone, host-rock dolostone and ore-stage dolomite suggest an early hydrothermal alteration of limestone to dolostone. This initial dolomitization was followed by a second period of dolomite formation produced by the mixing of basinal metal-rich fluids with local modified seawater. Both dolomitization events occurred under similar conditions from fluids exhibiting characteristics of basinal brines. The δ 34S values of sulfides are between –1.8 and +8.5 per mil, which is consistent with thermochemical sulfate reduction involving organic matter as the main source of reduced sulfur. Galena lead isotope compositions are among the most radiogenic values reported for Zn-Pb occurrences in Europe, and they are distinct from values reported for galena from other Basque-Cantabrian deposits. This suggests that a significant part of the lead was scavenged from the local underlying Asturian sediments. The stratigraphic and structural setting, timing of epigenetic mineralization, mineralogy, and isotopic geochemistry of sulfide and gangue minerals of the Reocin deposit are consistent with the features of most of Mississippi Valley-type ore deposits.

Xonotlite, ideally Ca6Si6O17(OH)2, occurs as a major phase in the leucocratic dyke complex that intruded the Ronda peridotites, near the village of Carratraca, Malaga, Spain. Xonotlite occurs as acicular grains in veins parallel to the dykes, as tabular grains along the reaction zone between the serpentinite host-rock and the leucocratic dykes, and as acicular grains replacing hydrogrossular in the matrix of the dykes. It is associated with albite, pectolite and hydrogrossular. Electron-microprobe analyses give a formula (Ca6.05)(Si5.96Al0.01)O17(OH)2 for the acicular and tabular xonotlite, and (Ca6.11)(Si5.92Al0.03)O17(OH)2 for xonotlite replacing hydrogrossular. X-ray powder-diffraction patterns of xonotlite show the presence of two polytypes: M2a2b2c and Ma2b2c. This unusual association (xonotlite, hydrogrossular, pectolite) was produced by the rodingitization of the leucocratic dykes during the serpentinization of the ultramafic massif at low-temperature conditions, 300° to 350°C; it was associated with the production of lizardite in the surrounding serpentinites.

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.

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 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.

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.

The Cap de Creus pegmatite field exhibits a well-defined regional zonation of four types of granitic pegmatite: barren K-feldspar-rich pegmatites (type I), beryl–columbite-subtype pegmatites (type II), beryl–columbite–phosphate-subtype pegmatites (type III) and albite-type pegmatites (type IV). There is an increase in the albite content, relative to K-feldspar, with increasing pegmatite evolution. Type-I microcline-rich pegmatites have low contents of albite, whereas in type IV, albite is the only feldspar. The K/Rb value in K-feldspar decreases progressively from type-I to type-III pegmatites. In addition, there is a progressive enrichment in P, Rb, Cs, Y, Sr, Ga, Ce, W and Sn from type-I to type-IV pegmatites. Concentrations of Pb and Zr decrease in K-feldspar from type-I to type-III pegmatites. K-feldspar from the Cap de Creus pegmatites exhibits higher contents in Ba, Rb, Cs, Nb, Y, Sn, V and Cr than albite. Albite is richer in Sr, Zr, Cu, As, Ce and Ga. Pb, Zn, W, Co and Ni have similar affinity for K-feldspar and albite. Muscovite exhibits similar geochemical evolution to K-feldspar. These progressive trends suggest a common origin for all of the Cap de Creus pegmatites by fractionation of the same parental magma. The high P content of feldspars, up to 1.67 wt.% P 2 O 5 in K-feldspar and 1.75 wt.% in albite, indicates buildup in this element from the earliest stages of pegmatite crystallization. Trace-element variation in feldspars and muscovite reflects enrichments in the melt; a higher content correlates with characteristic minerals of these elements. In particular, the phosphorus content of albite is proposed as a useful mineralogical guide to niobium–tantalum-rich oxide mineralization.