Lead isotope systematics of the giant massive sulphide deposits in the Iberian Pyrite Belt

Lead isotope analyses were performed on 26 polymetallic massive sulphide deposits of the Iberian Pyrite Belt, as well as on overlying gossans and associated volcanic rocks. All the massive sulphide deposits (except for Neves-Corvo), and nearly all the volcanic rocks show very similar isotopic compositions grouped around 18.183 (²⁰⁶Pb/²⁰⁴Pb), 15.622 (²⁰⁷Pb/²⁰⁴Pb) and 38.191 (²⁰⁸Pb/²⁰⁴Pb), indicating that most of the ore deposit lead was derived from the same continental crust environment as the associated volcanic rocks. The isotopic compositions are representative of the average south Iberian crust during the Devonian to Early Carboniferous (Dinantian), and their constancy implies a homogenization of the mineralizing fluids before the deposition of the massive sulphides from hydrothermal fluids circulating through interconnected regional fracture systems. This isotopic constancy is incompatible with multiple, small, independent hydrothermal cells of the East Pacific Rise type, and fits much better with a model of hydrothermal convections driven by “magmatic floor heating”. Neves-Corvo is the only south Iberian massive sulphide deposit to have a heterogeneous isotopic composition with, in particular, a highly radiogenic stanniferous ore (²⁰⁶Pb/²⁰⁴Pb of the cassiterite is >18.40). A model of lead mixing with three components is proposed to explain these variations: (1) one derived from the Devonian to Early Carboniferous (Dinantian) continental crust that generated all the other massive ores; (2) an Eohercynian stanniferous mineralization partly remobilized during the formation of the massive sulphides, but independent of them; and (3) a Precambrian continental crust component. The juxtaposition of three different sources places Neves-Corvo in a specific paleogeographic situation that could also explain its mineralogical specificity. The geodynamic context that best explains all the obtained isotopic results is one of an accretionary prism. The fact that lead isotope signatures of the gossans are almost identical to those of the underlying massive sulphides means that this technique could be a useful exploration tool for the Iberian Pyrite Belt.     

PGE distribution in massive sulfide deposits of the Iberian Pyrite Belt

We present the first platinum group elements (PGE) data on seven massive sulfide deposits in the Iberian Pyrite Belt (IPB), one of the world largest massive sulfide provinces. Some of these deposits can contain significant PGE values. The highest PGE values were identified in the Cu-rich stockwork ores of the Aguas Teñidas Este (Σ PGE 350 ppb) and the Neves Corvo (Σ PGE 203 ppb) deposits. Chondrite normalized PGE patterns and Pd/Pt and Pd/Ir ratios in the IPB massive, and stockwork ores are consistent with the leaching of the PGE from the underlying rock sequence.     

Regional oxygen isotope systematics of felsic volcanics; a potential exploration tool for volcanogenic massive sulphide deposits in the Iberian Pyrite Belt

Regional oxygen isotopic sytematics have been performed mainly on the felsic volcanic footwall rocks of the orebodies but also on purple schist characteristic of the hanging wall series, around two giant VMS deposits in the Spanish Iberian Pyrite Belt, Riotinto and La Zarza. As the terranes of the Iberian Pyrite Belt, these two giant deposits have been affected by the Hercynian tectono-metamorphic events, strongly modifying their geometry. About 60 and 40 samples were collected over a 10×4 km² area at Riotinto and a 3×2 km² area at La Zarza, respectively. Whole-rock powders were analysed for oxygen by CO₂-laser fluorination. At both sites, a same type of low-δ¹⁸O anomaly down to +3.6‰, well differentiated from the regional background (up to 20‰), was identified near the orebodies. The lowest δ¹⁸O values (+4 to +11‰) correspond to the chlorite hydrothermal halo, essentially restricted to the feeder zones of the orebody. Intermediate δ¹⁸O values (+9 to +15‰) correspond to the sericite hydrothermal halo, mostly developed laterally to the orebody until 0.5–1 km. The regional background (+16 to +20‰) is represented by spilitised volcanic rocks. A same kind of low anomaly, but with less contrast, was defined in purple schist in the immediate hanging wall of the orebodies. All these results demonstrate that, despite high geometrical modifications of the orebodies related to the Hercynian tectonics, oxygen isotopic anomalies recorded by volcanic host rocks during the emplacement of the mineralising hydrothermal systems are still identified. This strongly suggests that oxygen isotopic systematics could be useful to identify target areas in the Iberian Pyrite Belt, as already demonstrated on other VMS targets in the world.     

Antithetic behaviour of gold in the volcanogenic massive sulphide deposits of the Iberian Pyrite Belt

Detailed mineralogical and geochemical studies of the volcanogenic sulphide mineralization in the Spanish part of the Iberian Pyrite Belt (IPB) define two geochemical, mineralogical and spatial gold associations: (1) the Tharsis-Sotiel-Migollas type in which the gold is enriched with (Co?±?Bi) in the stockworks and interaction zones at the base of the massive sulphide mound; and (2) the Rio Tinto-Aznalcóllar-La Zarza type in which the gold is enriched in facies with a polymetallic (Zn?+?Ag?±?As?±?Tl?±?Hg) signature in a distal position or blocked beneath the massive sulphides. The first type is localized within a domain covering the southern half of the belt which is characterized by an abundance of sedimentary facies. The paragenesis shows that the gold association formed at high temperature (>300?°C) during the initial phases of massive sulphide genesis; the gold, which occurs in patches of very auriferous electrum (Au?>?75?wt.%), was transported by chloride complexes. The second type is found in the northern domain of the belt where volcanic facies are predominant. The paragenesis shows that the gold association formed at lower temperature (<280?°C) late in the massive sulphide genesis. This gold was transported by bisulphide complexes [Au(HS)₂ ^?] and is contained in Ag- and Hg-rich electrum (up to 61.0 and 30.5?wt.% respectively) and/or auriferous arsenopyrite (mean of 280?ppm Au), two mineral expressions that are able to coexist. It would appear that sulphur activity and oxygen fugacity were important factors in controlling the distribution of gold between the two host minerals and also in determining the Ag content of the electrum. This antithetic behaviour of the gold in the IPB reflects differences in the gold mineralizing fluids that may be due to the geologic environment; i.e. either dominantly sedimentary and acting as a mechanical barrier for gold bearing fluids, or dominantly volcanic and more open to seawater circulation. The fact that possible complications can occur during massive sulphide genesis, in response to the source and evolution of the fluids, raises the question of whether one or two gold influxes are involved. For example, the two gold associations could derive from a single gold influx, with remobilization and redistribution of the gold from the early (Co?±?Bi) facies giving rise to the later gold paragenesis of the (Zn?+?Ag?±?As?±?Tl?±?Hg) facies; this would not have occurred or would have been limited at the Tharsis-Sotiel-Migollas type orebodies. Alternatively, the two gold associations could reflect two separate evolutionary processes distinguished by the gold appearing either early or late in the hydrothermal fluids. Knowing the gold association of a massive sulphide deposit is an advantage when exploring for potential host facies.     

Supergene features and evolution of gossans capping massive sulphide deposits in the Iberian Pyrite Belt

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?).     

Magmatism in the Iberian Pyrite Belt: petrological constraints on a metallogenic model

Igneous formations associated with massive sulphide deposits in the Iberian Pyrite Belt (IPB) are essentially composed of basic lavas and dolerites, and dacitic to rhyolitic volcanites; intermediate lavas are subordinate. The basic rocks show variable geochemical characteristics: lavas and dolerites comparable to recent within-plate alkaline basalts seem restricted to the western and southern parts of the IPB, whereas basic rocks comparable to continental tholeiites or arc-related basalts occur across the whole belt. The felsic rocks are classified as calc-alkaline and belong to the “low-Al₂O₃ and high-Yb type”. At given SiO₂, Al₂O₃ and TiO₂ contents, they show variable Zr, Nb, and HREE contents. Heavy-rare-earth element fractionation decreases from the dacites to the rhyolites ([Gd/Yb]_N ∼ 1), whereas the negative Eu-anomaly becomes more pronounced. The characteristics of the rhyolites are typical of sulphide-fertile volcanic packages. Trace-element modelling suggests that the felsic rocks evolved from a dacitic parent magma through fractional crystallization of hornblende and plagioclase. Partial melting of an amphibolite protolith, which appears as the most probable model for the origin of this dacitic magma, requires a high T/P gradient in the crust. The occurrence of alkaline basalts and continental tholeiites is consistent with formation of the IPB in a tensional tectonic setting. However, the associated island-arc tholeiites suggest a location in a domain of plate convergence. Emplacement in a fore-arc basin over a recently accreted crustal segment is envisaged as a possible hypothesis to account for the geological and petrological constraints. A high geothermal gradient and eruption in a submarine tensional basin could have been two key ingredients for the development of massive sulphide deposits within the IPB.

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Resumen (translated by E. Pascual) Las formaciones ígneas asociadas con los depósitos de sulfuros masivos de la Faja Pirítica Ibérica (IPB) se componen esencialmente de doleritas y lavas básicas y de rocas volcánicas dacíticas a riolíticas; las lavas intermedias son poco abundantes. Las rocas básicas muestran caracteres geoquímicos variables: lavas y doleritas comparables a basaltos alcalinos intraplaca recientes parecen hasta ahora restringidos a las partes W y S de la IPB, mientras que rocas básicas de caracteres comparables a las de toleítas continentales o basaltos relacionados con arcos aparecen en toda la zona. Las rocas ácidas se clasifican como calcoalcalinas del tipo “low-Al₂O₃, high-Yb”. Para un contenido dado en SiO₂, Al₂O₃ y TiO₂, muestran contenidos variables en Zr, Nb y REE. El contenido en tierras raras pesadas decrece de dacitas a riolitas ([Gd/Yb]_N ∼ 1), al tiempo que la anomalía de Eu se hace más pronunciada. La modelización de elementos trazas sugiere que las rocas evolucionaron a partir de un magma parental dacítico mediante cristalización fraccionada de hornblenda y plagioclasa. La fusión parcial de un protolito anfibolítico, que parece el modelo más plausible para el origen del magma dacítico, requiere un elevado gradiente T/P en la corteza. La existencia de basaltos alcalinos y de toleítas continentales es congruente con la formación de la IPB en un entorno tectónico distensivo. El emplazamiento en una cuenca “fore-arc”, en un segmento cortical de reciente acreción, se contempla como una hipótesis posible para explicar los caracteres geológicos y petrológicos. Un alto gradiente térmico, junto con la erupción en una cuenca submarina extensional, pueden haber sido los dos ingredientes clave en el desarrollo de los depósitos de sulfuros masivos en la IPB.

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Received: 3 March 1996 / Accepted: 7 April 1997     

The Iberian Pyrite Belt: a mineralized system dismembered by voluminous high-level sills

The Iberian Pyrite Belt is a world-ranking massive sulphide province in which a reassessment of the palaeovolcanology has dramatically changed understanding of the source of metals and mechanism of ore formation. In the northern sector, the deposits are hosted by a sill–sediment complex in which more than 90% of the sills post-date the sulphide sheets. Because of a very high sill/sediment ratio, these late intrusions dominate the host succession and have severely disrupted the post-mineralization configuration thus obscuring the true genetic relationships. For example, some oxide deposits have been separated by hectometric sills from sulphide deposits they originally capped, creating seemingly totally independent mineralizing systems. In addition, stratiform sulphide sheets without underlying stockworks are not necessarily allochthonous. An early timing for the mineralization with respect to volcanism means that metals had to be predominantly sourced from the sedimentary basin and the continental crust below the volcanogenic sequence.     

The volcanic-hosted massive sulphide deposits of the Iberian Pyrite Belt Review and preface to the Thematic Issue

The Iberian Pyrite Belt (IPB) has, over the past decade, been an area of renewed mining activity and scientific research that has resulted in a wealth of new data and new geological and metallogenic concepts that are succinctly presented in this Thematic Issue. The reason for this interest in the IPB, which forms part of the Hercynian orogenic belt, is that its Late Devonian to Middle Carboniferous rocks host a huge quantity of volcanic-hosted massive sulphide (VMS) mineralization (1700 Mt of sulphides, totalling 14.6 Mt Cu, 13.0 Mt Pb, 34.9 Mt Zn, 46100 t Ag and 880 t Au). The mineralization and its environment display a number of typical signatures that can be related to the mineralogy and zoning of the sulphide orebodies, to the lead isotopes of the mineralization, to the geochemical and mineralogical variations in the hydrothermal alteration halos surrounding the orebodies, to the geochemical characteristics of the bimodal volcanics hosting the VMS, to the complex structural evolution during the Hercynian orogeny, to the presence of palaeofaults and synsedimentary structures that acted as channels and discharge traps for the metalliferous fluids, and to the gossans developed over VMS. Discriminant geological criteria have been deduced for each domain which can be helpful in mineral exploration, complementing the more traditional prospecting techniques. Although the question of the IPB's geodynamic setting is still under debate, any interpretation must now take into account some incontrovertible constraints: for example, the geochemical characteristics of a large part of the basic lavas are comparable to those of mantle-derived basalts emplaced in extensional tectonic settings, and the associated acidic rocks were produced by melting of a basic crustal protolith at low- to medium-pressures and a steep geothermal gradient, thus, the sulphide-bearing volcano-sedimentary sequence differs strongly from recent arc-related series. It is considered here that the tectonic setting was extensional and epicontinental and that it developed during the Hercynian plate convergence, that culminated in thin-skinned deformation and accretion of the South Portuguese terrane to the Iberian Paleozoic continental block.

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Resumen (translated by E. Pascual) Durante la década pasada, la Faja Pirítica Ibérica (FPI) ha sido un área de actividad minera e investigación cientifica renovadas, lo que ha conducido a la obtención de nuevos datos y conceptos geológicos y metalogénicos, que se exponen sucintamente en este Número Especial. La razón de este interés en la FPI, que forma parte del cinturón orogénico hercínico, es que sus rocas, cuyas edades abarcan desde el Devónico tardío al Carbonífero Medio, albergan una enorme cantidad de mineralizaciones de sulfuros masivos ligados a vulcanismo (1700 millones de toneladas de sulfuros, que totalizan 14,6 Mt de Cu, 13,0 Mt de Pb, 34,9 Mt de Zn, 46100 toneladas de Ag y 880 toneladas de Au). Las mineralizaciones y su entorno muestran signaturas que se pueden relacionar con la mineralogía y la zonación de las masas de sulfuros, con los isótopos de plomo de la mineralización, con las variaciones en los halos de alteración hidrotermal alrededor de las mineralizaciones, con los caracteres geoquímicos de las rocas volcánicas bimodales que albergan los sulfuros masivos, con la compleja evolución tectónica del conjunto durante la orogenia hercínica, con la existencia de paleofallas y estructuras sinsedimentarias que actuaron como canales y trampas de descarga para los fluidos metalíferos y los gossans que se desarrollaron sobre los sulfuros. Se han deducido criterios geológicos discriminantes para cada área de conocimiento, que pueden ser útiles para la exploración minera, complementando las técnicas más tradicionales de prospección. Aunque la cuestión del entorno geodinámico de la FPI todavía es materia de debate, cualquier interpretación tiene que tener ahora en cuenta algunas restricciones incontrovertibles: por ejemplo, los caracteres geoquímicos de una gran parte de las rocas básicas son comparables a los de basaltos derivados del manto y emplazados en entornos tectónicos extensionales, y las rocas ácidas asociadas se produjeron a partir de un protolito cortical básico, a presiones bajas o intermedias y asociadas a un abrupto gradiente térmico. Por consiguiente, la secuencia vulcanosedimentaria que contiene los sulfuros masivos difiere claramente de las series recientes relacionadas con entornos de arco. Consideramos aquí que el entorno tectónico fue extensional y epicontinental y que tuvo lugar durante la convergencia de placas hercínica, que culminó en deformación “thin-skinned” y acreción del terreno constituído por la Zona Sudportuguesa al bloque continental paleozoico ibérico.

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Received: 4 April 1996 / Accepted: 10 April 1997     

Geology and genesis of the Aznalcóllar massive sulphide deposits, Iberian Pyrite Belt, Spain

The Aznalcóllar mining district is located on the eastern edge of the Iberian Pyrite Belt (IPB) containing complex geologic features that may help to understand the geology and metallogeny of the whole IPB. The district includes several ore deposits with total reserves of up to 130 Mt of massive sulphides. Average grades are approximately 3.6% Zn, 2% Pb, 0.4% Cu and 65?ppm Ag. Mined Cu-rich stockwork mineralizations consist of 30?Mt with an average grade of 0.6% Cu. Outcropping lithologies in the Aznalcóllar district include detrital and volcanic rocks of the three main stratigraphic units identified in the IPB: Phyllite-Quartzite Group (PQ), Volcano-Sedimentary Complex (VSC) and Culm Group. Two sequences can be distinguished within the VSC. The Southern sequence (SS) is mainly detritic and includes unusual features, such as basaltic pillow-lavas and shallow-water limestone levels, the latter located in its uppermost part. In contrast, the Aznalcóllar-Los Frailes sequence (AFS) contains abundant volcanics, related to the two main felsic volcanic episodies in the IPB. These distinct stratigraphic features each show a different palaegeographic evolution during Upper Devonian and Lower Carboniferous. Massive sulphides occur in association with black shales overlying the first felsic volcanic package (V_A1) Palynomorph data obtained from this black shale horizon indicate a Strunian age for massive sulphides, and consequently an Upper Devonian age for the V_A1 cycle. Field and textural relationships of volcanics suggest an evolution from a subaerial pyroclastic environment (V_A1) to hydroclastic subvolcanic conditions for the V_A2. This evolution can be related to compartmentalizing and increasing depth of the sedimentary basin, which may also be inferred from changes in the associated sediments, including black shales and massive sulphides. Despite changes in the character of volcanism, the same dacitic to rhyolitic composition is found in both pyroclastic and subvolcanic igneous series. The main igneous process controlling chemical variation of volcanics is fractional crystallization of plagioclase (+accessories). This process took place in shallow, sub-surface reservoirs giving rise to a compositional range of rocks that covers the total variation range of felsic rocks in the IPB. The Hercynian orogeny produced a complex structural evolution with a major, ductile deformation phase (F₁), and development of folds that evolved to thrusts by short flank lamination. These thrusts caused tectonic repetition of massive and stockwork orebodies. In Aznalcóllar, some of the stockwork mineralization overthrusts massive sulphides. These structures are cut by large brittle overthrusts and by late wrench faults. The original geometric features of massive sulphide deposits correspond to large blankets with very variable thicknesses (10 to 100?m), systematically associated with stockworks. Footwall rock alteration exhibits a zonation, with an inner chloritic zone and a peripheral sericitic zone. Silicification, sulphidization and carbonatization processes also occur. Hydrothermal alteration is considered a multi-stage process, geochemically characterized by Fe, Mg and Co enrichment and intense leaching of alkalies and Ca. REE, Zr, Y and Hf are also mobilized in the inner chloritic zones. Three ore types occur, both in stockworks and massive sulphides, named pyritic, polymetallic and Cu-pyritic. Of these, Cu-pyritic is more common in stockworks, whereas polymetallic is prevalent in massive sulphides. Zoning of sulphide masses roughly sketches a typical VHMS pattern, but many alternating polymetallic and barren pyritic zones are probably related to tectonics. Although the paragenesis is complex, several successive mineral associations can be distinguished, namely: framboidal pyritic, high-temperature pyritic (300?°C), colloform pyritic, polymetallic and a late, Cu-rich high-temperature association (350?°C). Fluid inclusion data suggest that hydrothermal fluids changed continuously in temperature and salinity, both in time and space. Highest Th and salinities correspond to inner stockworks zones and later fluids. Statistic population analysis of fluid inclusion data points to three stages of hydrothermal activity, at low (<200?°C), intermediate (200–300?°C) and high temperatures (300–400?°C). ³⁴S values in massive sulphides are lower than in stockwork mineralization suggesting a moderate bacterial activity, favoured by the euxinoid environment prevailing during black shale deposition. The intimate relation between massive sulphides and black shales points to an origin of massive sulphides by precipitation and replacement within black shale sediments. These would have acted both as physical and chemical barriers during sulphide deposition. Hydrothermal activity started during black shale deposition, triggered by a rise in thermal gradient due to the ascent of basic magmas. We suggest a three-stage genetic model: (1) low temperature, diffuse fluid flow, producing pyrite-bearing lenses and disseminations interbedded with black shales; locally, channelized high-T fluid flow occurs; (2) hydrothermal cyclic activity at a low to intermediate temperature, producing most of the pyritic and polymetallic ores, and (3) a late high-temperature phase, yielding Cu-rich and Bi-bearing mineralization, mainly in the stockwork zone.     

Bismuth and cobalt minerals as indicators of stringer zones to massive sulphide deposits, Iberian Pyrite Belt

The stringer zones and commonly the interaction zone at the base of the massive sulphide mounds in the Iberian Pyrite Belt contain bismuth and cobalt minerals that are not found in the overlying massive sulphides. These are fairly rare cobalt sulphoarsenides (cobaltite, alloclasite, galucodot) that were formed at the beginning of the massive sulphide genesis, and fairly common bismuth sulphides (bismuthinite, hammarite, wittichenite, cosalite, kobellite, joseite, etc.), including species rare at world scale (nuffieldite, giessenite, jaskolskiite) that were deposited from last stage high-temperature (> 300 °C) copper-bearing fluids containing Bi (Te, Se). The last stage fluids precipitated chalcopyrite containing Cu, Bi, Te, (Se) sulphosalts at the base of the sulphide mound to form a high cupriferous zone. Their interaction with the massive sulphides is reflected by the formation of an exchange zone, a few metres thick, showing chalcopyrite disease textures, at the base of the mound; this zone forms the upper limit of potentially economic copper enrichment and of bismuth minerals. Gold is undoubtedly in part, if not totally, related to this last phase. The bismuth concentrations being equivalent in the massive sulphides and the stringers, the presence of bismuth minerals in the stringer zones results from high-temperature conditions combined with a rarity of galena, which impedes absorption of available Bi. The distribution of these bismuth minerals provides a basic mineralogical zoning in the stringer zone, with a deep, low-aS₂ zone containing native bismuth and tellurides and a shallow, higher-aS₂ zone in contact with the massive ore sensu stricto and containing complex bismuth sulphides. These results make it possible to distinguish between sulphide veinlets belonging to stockwork zones of massive orebodies and veinlets of an ambiguous nature, and provide mineralogical criteria for the proximity of copper-rich zones. They enrich the very complex mineralogy of the Iberian Pyrite Belt.     

Genesis of proterozoic iron-formation: sulphur isotope evidence

Seven units of carbonaceous shale or sulphide-facies iron-formation have been sampled. They are associated with Proterozoic iron-formations that range in age from ~ 1.9 to ~2.5 Ga: Sokoman and Gunflint (Canada), Riverton (United States), Penge (South Africa) and Brockman (Australia). Sulphur isotope ratios have been determined on the sulphides removed from these shales by both physical and chemical means.The mean δ³⁴S composition of the seven units varies between ?4.9%. and +6.6%. and the sample variance is low within each unit. These distributions are more characteristic of hydrothermal sulphide than sulphide produced by biogenic reduction. This hydrothermal sulphide is believed to have originated from high temperature reduction of seawater sulphate and from magmatic sulphide. A model is suggested whereby this sulphide was exhaled into stratified anoxic/oxic basins. The sulphide and associated base metals were deposited in the reduced sediments beneath the anoxic waters, while some iron and manganese was deposited on oxygenated shelves.The data support, but do not prove, a hydrothermal exhalative origin for lower Proterozoic iron-formation.     

Source and evolution of ore-forming hydrothermal fluids in the northern Iberian Pyrite Belt massive sulphide deposits (SW Spain): evidence from fluid inclusions and stable isotopes

A fluid inclusion and stable isotopic study has been undertaken on some massive sulphide deposits (Aguas Teñidas Este, Concepción, San Miguel, San Telmo and Cueva de la Mora) located in the northern Iberian Pyrite Belt. The isotopic analyses were mainly performed on quartz, chlorite, carbonate and whole rock samples from the stockworks and altered footwall zones of the deposits, and also on some fluid inclusion waters. Homogenization temperatures of fluid inclusions in quartz mostly range from 120 to 280 °C. Salinity of most fluid inclusions ranges from 2 to 14 wt% NaCl equiv. A few cases with T _h=80–110 °C and salinity of 16–24 wt% NaCl equiv., have been also recognized. In addition, fluid inclusions from the Soloviejo Mn–Fe-jaspers (160–190 °C and ˜6 wt% NaCl equiv.) and some Late to Post-Hercynian quartz veins (130–270 °C and ˜4 wt% NaCl equiv.) were also studied. Isotopic results indicate that fluids in equilibrium with measured quartz (d ¹⁸O _fluid ˜–2 to 4‰), chlorites (d ¹⁸O _fluid ˜8–14‰, dD _fluid ˜–45 to –27‰), whole rocks (d ¹⁸O _fluid ˜4–7‰, dD _fluid ˜–15 to –10‰), and carbonates (d ¹⁸O _ankerite ˜14.5–16‰, d ¹³C _fluid =–11 to –5‰) evolved isotopically during the lifetime of the hydrothermal systems, following a waxing/waning cycle at different temperatures and water/rock ratios. The results (fluid inclusions, d ¹⁸O, dD and d ¹³C values) point to a highly evolved seawater, along with a variable (but significant) contribution of other fluid reservoirs such as magmatic and/or deep metamorphic waters, as the most probable sources for the ore-forming fluids. These fluids interacted with the underlying volcanic and sedimentary rocks during convective circulation through the upper crust.     

A reappraisal of the structure of the Spanish segment of the Iberian Pyrite Belt

The major structural features of the Iberian Pyrite Belt are described in terms of geometry, deformation mechanisms, scale, timing, kinematics and the mutual relationships among the various architectural elements. The result of such an analysis allows this zone to be considered as a S-verging, thin-skinned, fold and thrust belt propagating southwards over a mid-crustal basal detachment. This was the response in the footwall of the suture to the major phase of Hercynian oblique collision between the South Portuguese Plate and the Ossa-Morena Zone of the Iberian Autochthon. This thin-skinned event inverted a previous extensional structure acquired during the initial stages of the collisional process and intimately linked to the formation of the ore deposits that make this region a world-class metallogenic province.     

Synchronous deposition of massive sulphide deposits in the Iberian Pyrite Belt: New data from Las Herrerías and La Torerera ore-bodies

Two small to medium sized massive sulphide deposits, Las Herrerías and La Torerera, located in the Iberian Pyrite Belt (IPB) are examined from a geological and palynostratigraphic perspective. The palynological assemblages are assignable to the Retispora lepidophyta–Verrucosisporites nitidus (LN) miospore Biozone (Latest Devonian: Latest Famennian/Strunian) of Western Europe. This age permits correlation with some of the main massive sulphide deposits dated so far in the region (viz., Tharsis, Aznalcóllar, Sotiel-Coronada or Neves-Corvo), and validates once again the hypothesis that a single mineralizing event was responsible for the genesis of most of the IPB’s massive sulphide deposits. The present study confirms that palynostratigraphy is an invaluable high-resolution biostratigraphic tool in the IPB, applicable to dating, correlation and ore-exploration.     

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.     

The effect of Rayleigh degassing of magma on sulphur isotope composition: a quantitative evaluation

The effect of Rayleigh distillation by outgassing of SO₂ and H₂O on the isotopic composition of sulphur remaining in silicate melts is quantitatively modelled. A threshold mole fraction of sulphur in the sulphide component of the melts is reckoned as being critically important in shifting the δ³⁴S value of degassed melts with respect to the original magmas. During the outgassing, melts above the threshold are depleted in ³⁴S, whereas melts below the threshold are enriched in ³⁴S. In particular, the outgassing of SO₂ above the sulphide threshold can produce large negative δ³⁴S values in the degassed melts, whereas the outgassing of H₂S below the threshold will strongly drive the δ³⁴S value of the melts in the positive direction. The correlation between δ³⁴S value and sulphur content of total sulphur in the solidified rocks is indicative of the Rayleigh-type degassing.     

The paradigm of Circular Mining in the world: the Iberian Pyrite Belt as a potential scenario of interaction

Water is one of the receptors most affected by the impacts caused, especially in the case of mining sulphides and, to a lesser extent, of coal. Acid Mine Drainage (AMD) is the main problem associated with these mining operations, producing extremely high impacts, and in many cases irreversible impacts, until now. A new concept of mining can make this activity compatible with the environmental preservation and also to the recovery of the environment affected by the old mining operations that today are in the process of reopening. This new concept implicates the paradigm of Circular Mining as a derivative of the concept of Circular Economy, considered as a strategy that aims to reduce both the entry of materials and the production of virgin waste, closing the “loops” or economic and ecological flows of resources. The present work discusses the paradigm of Circular Mining, focused on the Iberian Pyrite Belt, one of the most paradigmatic metallogenetic regions in the world. Based on some examples, expeditious calculations show the possibility of recovering base metals as well as strategic elements from acid mine drainage, thus obtaining important economic assets.     

Trondhjemites,tonalites and diorites in the South Portuguese Zone and their relations to the vulcanites and mineral deposits of the Iberian Pyrite Belt

In the South Portuguese Zone close associations of diorites, tonalites and trondhjemites occur north of the Pyrite Belt. The period of their emplacement is Pre-Carboniferous and not, as has generally been assumed, Variscanpostorogen. The trondhjemitic intrusive suite and the Lower Carboniferous spilite-keratophyre association are related through their comagmatic derivation. Both series share sodium dominance, low concentrations of large-ion lithophile elements, indicators of a water-rich original magma and a deficient scorification of the element potential, which was acummulated in the sulphide and manganese deposits of the Pyrite Belt through post-volcanic hydrothermal processes. The mineralogically and geochemically primitive composition of both plutomtes and vulcanites, their mode of eruption from acid to basic facies as well as their position in the orogenic process indicate that they represent products of a successively proceeding partial melting of subducting oceanic crust. The trondhjemitic intrusives are the initialites in the magmatic-orogenic development.

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Zusammenfassung In der Südportugiesischen Zone treten nördlich des Pyritgürtels enge Vergesellschaftungen von Dioriten, Tonaliten und Trondhjemiten auf. Der Zeitraum ihrer Platznahme ist päkarbonisch und nicht, wie bisher allgemein angenommen, variszisch-postorogen. Die trondhjemitische Intrusivsequenz und die unterkarbonische Spilit-Keratophyr-Assoziation sind in weiten Bereichen durch komagmatische Herkunft verbunden. Gemeinsamkeiten beider Abfolgen sind ihre Na-Dominanz, die niedrigen Gehalte an gro\ionigen Elementen, die Anzeichen für ein wasserreiches Ausgangsmagma und die mangelhafte Verschlackung des Elementpotentials, das in den Sulfid- und Manganlagerstätten des Pyritgürtels während postvulkanischer, hydrothermaler Proze\e angereichert wurde. Die mineralogisch wie geochemisch primitive Zusammensetzung sowohl der Plutonite wie der Vulkanite, ihr Eruptionsmodus von saurer zu basischer Fazies sowie ihre Position im orogenen Ablauf deuten darauf hin, da\ sie die Produkte einer sukzessiv fortschreitenden Aufschmelzung subduzierender, ozeanischer Kruste darstellen. Die trondhjemitischen Intrusiva sind die Initialite innerhalb der magmatisch-orogenen Entwicklung.

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Résumé Dans la zone sud du Portugal, il existe, au nord de la ceinture pyriteuse, des associations étroites de diorites, de tonalites et de trondhjémites. Leur mise en place date de la période pré-carbonifère et non, comme on l'avait généralement admis jusqu'à présent, de la période varisque post-orogénique. Le faisceau intrusif trondhjémitique et l'association spilite-kératophyre du Carbonifère inférieur sont liés par une origine comagmatique. Les points communs des deux successions sont leur dominante sodique, les faibles teneurs en éléments à gros ions, les indices d'un magma de départ aquifère et la scorification réduite du potentiel d'éléments qui, dans les gisements de sulfure et de manganèse de la ceinture pyriteuse a été enrichi par des processus post-volcaniques et hydrothermaux. La composition primitive, tant minéralogique que géochimique, de la plutonite comme de la vulcanite, leur mode d'éruption qui va du type acide au type basique, ainsi que leur position dans le processus orogénique indiquent qu'il s'agit de produits successifs de la fusion partielle d'une croûte océanique en voie de subduction. Les intrusions trondhjémitiques représentent le stade initial dans l'évolution orogéno-magmatique.

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