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.     

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.     

Geology of massive sulphide deposits in the Spanish-Portuguese Pyrite Belt

The Spanish-Portuguese Pyrite Belt covers a large area in the SW part of the Iberian Peninsula from Seville to the westcoast of Portugal. Total reserves of aprox. 1.000 million tons of massive sulphide ores have an average content of 46% S, 42% Fe, and 2–4% Cu+Pb+Zn. The stratiform sulphide deposits and accompanying manganese mineralizations are of synsedimentary-exhalative origin. They occur in a Lower Carboniferous, geosynclinal, volcanic-sedimentary rock sequence, strongly folded during the Hercynian Orogeny. A brief outline of the regional geology of this ore province is given, and the geology of three mining districts is described: Lousal (Portugal), La Zarza and Tharsis (Huelva Province, Spain). A close relationship between sulphide and manganese ores with the submarine, acid alkaline volcanism is emphasized. Solfataric activity is responsible for the formation of sulphides in the final stages of volcanic extrusions. The ore concentration in big deposits (ore-lenses with up to 100 million tons of massive sulphides) has been due to inflows of sulphide muds and/or detrital sulphides into newly formed depressions of a contineously changing seafloor topography due to volcano tectonic movements.     

Geological constraints on massive sulphide genesis in the Iberian Pyrite Belt

The Iberian Pyrite Belt (IPB), SW Iberian Peninsula, Spain and Portugal, one of the most famous and oldest mining districts in the world, includes several major concentrations of massive sulphides, unique on Earth (e.g., Riotinto, Neves Corvo), as well as a large number of smaller deposits of this same type. All these deposits, in spite of their general similarities, show significant differences in geological setting, age, relations to country rocks, hydrothermal alteration, mineralogy and geochemistry. As a consequence of a review of the available data in the IPB, together with new findings on volcanism, hydrothermal alteration and ore mineralogy, we propose a modified genetic scenario, that can account particularly for the diversity of the geological situations in which sulphide deposits occur, as well as for their mineralogical and petrological diversity. It is concluded that there is no direct genetic relationship between felsic volcanic activity and massive sulphide deposition in the IPB, and that most of the massive sulphide bodies, including all of the giant ones, are closely related to hydrothermal vents, being therefore proximal. The available isotopic data yield additional genetic information: (a) Homogeneous lead isotope values indicate a single (or homogenized) metal source; (b) sea and connate water are the fluid reservoirs for hydrothermal input, and (c) bacterial reduction of sulphur is the most probable cause of differences in δ³⁴S between stockwork and massive sulphide mineralizations. Finally, current geodynamic models suggested for the IPB are discussed. It is suggested that an intracontinental, ensialic rift or pull-apart environment is the most probable genetic environment for the IPB mineralizations.     

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.     

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.     

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.     

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.     

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.     

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.     

The Iberian type of volcano-sedimentary massive sulphide deposits

The Iberian Pyrite Belt, located in the SW Iberian Peninsula, contains many Paleozoic giant and supergiant massive sulphide deposits, including the largest individual massive sulphide bodies on Earth. Total ore reserves exceed 1500 Mt, distributed in eight supergiant deposits (>100 Mt) and a number of other smaller deposits, commonly with associated stockwork mineralizations and footwall alteration haloes. Massive sulphide bodies largely consist of pyrite, with subordinated sphalerite, galena and chalcopyrite and many other minor phases, although substantial differences occur between individual deposits, both in mineral abundance and spatial distribution. These deposits are considered to be volcanogenic, roughly similar to volcanic-hosted massive sulphides (VHMS). However, our major conclusion is that the Iberian type of massive sulphides must be considered as a VHMS sub-type transitional to SHMS. This work is an assessment of the geological, geochemical and metallogenic data available up to date, including a number of new results. The following points are stressed; (a) ore deposits are located in three main geological sectors, with the southern one containing most of the giant and supergiant orebodies, whereas the northern one has mainly small to intermediate-sized deposits; (b) ore deposits differ one from another both in textures and mineral composition; (c) Co and Bi minerals are typical, especially in stockwork zones; (d) colloidal and other primary depositional textures are common in many localities; (e) a close relation has been found between ore deposits and some characteristic sedimentary horizons, such as black shales. In contrast, relationships between massive sulphides and cherts or jaspers remains unclear; (f) footwall hydrothermal alterations show a rough zoning, the inner alteration haloes being characterized in places by a high Co/Ni ratio, as well as by mobility of Zr, Y and REE; (g) ¹⁸O and D values indicate that fluids consist of modified seawater, whereas ³⁴S data strongly suggest the participation of bacterial-reduced sulphur, at least during some stages of the massive sulphide genesis, and (h) lead isotopes suggest a single (or homogeneized) metal source, from both the volcanic piles and the underlying Devonian rocks (PQ Group). It is concluded that, although all these features can be compatible with classical VHMS interpretations, it is necessary to sketch a different model to account for the IPB characteristics. A new proposal is presented, based on an alternative association between massive sulphide deposits and volcanism. We consider that most of the IPB massive orebodies, in particular the giant and supergiant ones, were formed during pauses in volcanic activity, when hydrothermal activity was triggered by the ascent and emplacement of late basic magmas. In these conditions, deposits formed which had magmatic activity as the heat source; however, the depositional environment was not strictly volcanogenic, and many evolutionary stages could have occurred in conditions similar to those in sediment-hosted massive sulphides (SHMS). In addition, the greater thickness of the rock pile affected by hydrothermal circulation would account for the enormous size of many of the deposits. Received: 8 September 1998 / Accepted: 4 January 1999     

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.     

Chert in the Iberian Pyrite Belt

Since lenses of chert are common within the volcano-sedimentary succession hosting the massive sulphide deposits of the Iberian Pyrite Belt (Spain and Portugal), we examined numerous chert occurrences, both petrographically and geochemically, to test their possible value for massive sulphide exploration. The chert is found at two main lithostratigraphic levels (upper and lower) that are also interpreted as massive-sulphide bearing. In both cases the chert is located at the top of acidic volcanic sequences or in the associated sediments; we have not been able to observe the relationships between massive sulphides and chert, but some of the large orebodies of the Province (Lousal, La Zarza, Tharsis, Planes-San Antonio body of Rio Tinto, Neves) are described as being locally capped by chert facies. Four main types are recognized among the chert and associated facies: (1) red hematitic chert?±?magnetite; (2) radiolarian and/or sedimentary-textured (conglomeratic) chert with hematite and/or Mn oxides; (3) pale sulphidic chert; (4) rhodonite and/or Mn carbonate?±?magnetite facies. In the Spanish part of the Province the radiolarian chert is confined to the upper level; the distribution of the other types appears to be haphazard. The hydrothermal origin of the South Iberian chert is shown by its high Fe-Mn and low Co-Ni-Cu contents. The presence of small positive Ce anomalies indicates a shallow marine environment (shelf or epicontinental sea), which is consistent with the volcanological and sedimentological data. The chert was emplaced below the sea floor through chemical precipitation and/or through alteration and replacement of the country rock, residual traces of which are ghost phenocrysts and high Al, Ti and rare earth contents. Macro- and microscopic relationships indicate that the oxide facies (hematite?±?magnetite) formed first, probably providing a protective insulating cover against the marine environment and enabling an evolution towards sulphide facies; a phase of Mn?carbonate and silicate + quartz?±?chlorite + sulphides appears to be even later. It was not possible, through discrimination, to isolate a chert that could be considered as representing a lateral marker of massive sulphides; moreover, both field observations and geochemical data seem to indicate a relative independence of this siliceous sulphide hydrothermal activity from the hydrothermal activity giving rise to the massive sulphides. Such is also indicated by the lead isotopic signature of the chert, which is appreciably more radiogenic than that of the massive sulphides; the lead enrichment in the sulphidic chert facies indicates the participation of a different source (sediments, sea water) from that of the massive sulphides. The hypothesis of an independent hydrothermal “chert” event can thus be envisaged, wherein the chert reflects submarine low-temperature hydrothermal activity that is most apparent during a “break” within the volcano-sedimentary succession and which may locally have competed with the high-temperature hydrothermal activity giving rise to the massive sulphides. The interest of the chert thus rests in its palaeodynamic significance, as a marker of periods of volcanic quiescence, and in its possible role as a protective insulating cap favourable to the deposition of massive sulphides.     

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

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

A case study of the internal structures of gossans and weathering processes in the Iberian Pyrite Belt using magnetic fabrics and paleomagnetic dating

In the Rio Tinto district of the Iberian Pryrite Belt of South Spain, the weathering of massive sulfide bodies form iron caps, i.e., true gossans and their subsequent alteration and re-sedimentation has resulted in iron terraces, i.e., displaced gossans. To study the stucture and evolution of both types of gossans, magnetic investigations have been carried out with two foci: (1) the characterisation and spatial distribution of magnetic fabrics in different mineralised settings, including massive sulfides, gossans, and terraces, and (2) paleomagnetic dating. Hematite has been identified as the suceptibility carrier in all sites and magnetic fabric investigation of four gossans reveals a vertical variation from top to bottom, with: (1) a horizontal foliation refered to as “mature” fabric in the uppermost part of the primary gossans, (2) highly inclined or vertical foliation interpreted as “immature” fabric between the uppermost and lowermost parts, and (3) a vertical foliation interpreted to be inherited from Hercynian deformation in the lowermost part of the profiles. In terraces, a horizontal foliation dominates and is interpreted to be a “sedimentary” fabric. Rock magnetic studies of gossan samples have identified goethite as the magnetic remanence carrier for the low-temperature component, showing either a single direction close to the present Earth field (PEF) direction or random directions. Maghemite, hematite, and occasionally magnetite are the remanence carriers for the stable high-temperature component that is characterized by non PEF directions with both normal and reversed magnetic polarities. No reliable conclusion can be yet be drawn on the timing of terrace magnetization due to the small number of samples. In gossans, the polarity is reversed in the upper part and normal in the lower part. This vertical distribution with a negative reversal test suggests remanence formation during two distinct periods. Remanence in the upper parts of the gossans is older than in the lower parts, indicating that the alteration proceeded from top to bottom of the profiles. In the upper part, the older age and the horizontal “mature” fabric is interpreted to be a high maturation stage of massive sulfides’ alteration. In the lower part, the age is younger and the inherited “imature” vertical Hercynian fabric indicates a weak maturation stage. These two distinct periods may reflect changes of paleoclimate, erosion, and/or tectonic motion.     

Distinctive features of Late Palaeozoic massive sulphide deposits in South China

More than 20 sediment-hosted massive sulphide deposits occur in Late Palaeozoic basins in South China. These deposits are accompanied by a certain amount of volcanic rocks in the host sequence and are economically important for their Cu, Pb, Zn, Au and Ag reserves. The deposits and their host strata were commonly intruded by Mesozoic granitoids. Remobilisation of sedimentary ores and magmatic hydrothermal overprinting processes resulted in the coexistence of massive sulphides with vein-, skarn- and porphyry-type orebodies in the same region or within a single deposit. The ore-containing basins occur in different tectonic settings. The Lower Yangtze basin occurs on a passive continental margin, where the deposits are high in Cu and Au with minor Pb and Zn and recoverable Ag, Co and Mo. The ores have a lower concentration of radiogenic lead, and δ³⁴S values close to zero. Fluid inclusions are highly saline and Na-rich. Fluids and metals of the Lower Yangtze Region are interpreted to have been derived essentially from deep sources including the Precambrian basement. By contrast, basins of the Nanling Region formed in an intracontinental setting developed on a folded Caledonian basement. These deposits are higher in Pb, Zn, Sn and W, as well as Cu, with recoverable Ag, Sb, Hg, U, Bi, Tl and Mo. The ores are characterised by a higher concentration of radiogenic lead and a wide variation of δ³⁴S composition. Fluid inclusions have lower salinities and higher K⁺/Na⁺ ratios. Fluids are considered to have been sourced substantially from seawater by convection. Metals for the Nanling deposits were essentially derived from the Caledonian basement by leaching. The contrast in ore composition between these two regions appears to have been controlled by differences in basement composition of the ore-forming basins.     

Gold mineralisations in the SW Iberian Pyrite Belt

The occurrence and distribution of gold in the massive sulfide orebodies of the upper Palaeozoic volcano-sedimentary environment of the SW Iberian Pyrite Belt have long been assumed to be quite uniform. Recent investigations in several working mines indicate that the gold content of the ores varies between ore types, and is controlled by physico-chemical and time factors during deposition. Above-average gold grades occur in the following ore types: lead-zinc-rich ores, situated laterally and on top of the massive sulfide lenses; copper-rich siliceous basal ore facies; footwall stringer sulfides; and gangue-rich massive sulfides (siliceous, carbonate-rich, baryte bearing, or carbonaceous matrix). Exploration possibilities therefore are promising in foot- and hanging-wall environments within an orebody, as well as in disseminated and stringer ores in its footwall.     

The Filon Norte orebody (Tharsis, Iberian Pyrite Belt): a proximal low-temperature shale-hosted massive sulphide in a thin-skinned tectonic belt

The Filón Norte orebody (Tharsis, Iberian Pyrite Belt) is one of the largest pyrite-rich massive sulphide deposits of the world. The present structure of the mineralization consists of an internally complex low-angle north-dipping thrust system of Variscan age. There are three major tectonic units separated by thick fault zones, each unit with its own lithologic and hydrothermal features. They are internally organized in a hinterland dipping duplex sequence with high-angle horses of competent rocks (igneous and detritic rocks and massive sulphides) bounded by phyllonites. The mineralization is within the Lower Unit and is composed of several stacked sheets of massive sulphides and shales hosting a stockwork zone with no obvious zonation. The Intermediate Unit is made up of pervasively ankeritized shales and basalts (spilites). Here, hydrothermal breccias are abundant. The Upper Unit is the less hydrothermally altered one and consists of silicified dacites and a diabase sill. The tectonic reconstruction suggests that the sequence is inverted and the altered igneous rocks were originally below the orebody. Carbon, oxygen and sulphur isotopes in the massive sulphides and hydrothermal rocks as well as the mineral assemblage and the paragenetic succession suggest that the sulphide precipitation in the sea floor took place at a low temperature (<≈150?°C) without indication, at least in the exposed section, of a high-temperature copper-rich event. Sporadic deep subsea-floor boiling is probably responsible for the formation of hydrothermal breccias and the wide extension of the stockwork. Its Co-Au enrichment is interpreted as being related with the superposition of some critical factors, such as the relationship with black shales, the low temperature of formation and the boiling of hydrothermal fluids. The present configuration and thickness of the orebody is due to the tectonic stacking of a thin and extensive blanket (2–4?km²) of massive sulphides with low aspect ratio. They were formed by poorly focused venting of hot modified seawater equilibrated with underlying rocks into the seafloor. Massive sulphide precipitation took place by hydrothermal fluid quenching, bacteriogenic activity and particle settling in an unusual, restricted, euxinic and shallow basin (brine pool?) with a low detritic input but with important hydrothermal activity related to synsedimentary extensional faulting. Resedimentation of sulphides seems to be of major importance and responsible for the observed well-mixed proximal and distal facies. The tectonic deformation is largely heterogeneous and has been mostly channelled along the phyllonitic (tectonized shales) deformation bands. Thus, sedimentary and diagenetic textures are relatively well-preserved outside the deformation bands. In the massive sulphides, superimposed Variscan recrystallization is not very important and only some early textures are replaced by metamorphic/tectonic ones. The stockwork is much more deformed than the massive sulphides. The deformation has a critical effect on the present morphology of the orebody and the distribution of the ore minerals. This deposit is a typical example of the sheet-like, shale-hosted, anoxic, low temperature and Zn-rich massive sulphides developed in a ensialic extensional basin.