Iberian Pyrite Belt Research Articles

Unveiling High-Tech Metals in Roasted Pyrite Wastes from the Iberian Pyrite Belt, SW Spain

The Iberian Pyrite Belt (IPB), in the southwestern Iberian Peninsula, is a large metallogenic province exploited since ancient times. As a result of historical and current mining activity, a vast volume of metallic mineral waste, mainly derived from the processing of pyrite, is still in situ and polluting the environment. A specific mine waste residuum locally known in the area as “morrongos”, which was produced during pyrite roasting mainly in the 19th century, is evaluated here in order to unravel untapped resources of high-tech metals commonly used in high-tech devices. Applying a combination of whole-rock geochemical (ICP-AES, ICPMS, FA-AAS) and single-grain mineralogical techniques (EPMA, LA-ICP-MS, FESEM, and FIB-HRTEM) on the “morrongos”, we unhide the still-present remarkable concentrations of Au, Ag, Pb, Zn, and Cu in them. The mineralogical expressions for these economic metals include oxides (hematite, magnetite, and hercynite), arsenates, sulfates of the jarosite group, native metals, and, to a lesser extent, relictic sulfides. This first-ever estimation of these economic metals in this type of residue allows their revalorization, highlighting them as suitable sources for the exploitation and recovery of metals necessary for the clean energy transition.

Biostratigraphic and structural research in the Guedelhinha–Lançadoiras–Algaré sector in the context of the geology of the Neves–Corvo mine region, Iberian Pyrite Belt

Based on drill hole sampling and sedimentary rock dating by palynology, the present research focuses on the palynostratigraphic events established in the key geological section of Guedelhinha–Lançadoiras–Algaré located in the Portuguese Neves–Corvo mine region, Iberian Pyrite Belt. The age data allow detailing the lithostratigraphic sequence and further understanding the complex structural setting, representing an important contribution to the geological knowledge of this sector located to the immediate WNW of the Neves–Corvo VMS deposit. The combination of the studied events allows the reconstruction of the Devonian-Carboniferous sedimentation and paleoenvironments along the Iberian Pyrite Belt. Several stratigraphic hiatuses identified in the Neves–Corvo region by the palynological record are confirmed, mainly occurring from the mid Frasnian to mid Famennian, from the early and mid Strunian, and from the early to late Tournaisian, which were mainly coincident with the worldwide extinction events, in particular during Frasnian–Famennian and Late Devonian times. Extensional tectonics and related gravitational faults, local uplift mechanisms and intense volcanic activity could also explain the lack of palynological data and sedimentary hiatus. In this research, the importance of the late Strunian times in the Iberian Pyrite Belt (Miospore Biozone LN of the Neves Formation) is highlighted, confirming the contemporaneity of felsic volcanism, hydrothermalism, sulphide mineralization precipitation and black shale anoxic sedimentation.

Vitamin B12 Auxotrophy in Isolates from the Deep Subsurface of the Iberian Pyrite Belt.

Vitamin B12 is an enzymatic cofactor that is essential for both eukaryotes and prokaryotes. The development of life in extreme environments depends on cofactors such as vitamin B12 as well. The genomes of twelve microorganisms isolated from the deep subsurface of the Iberian Pyrite Belt have been analyzed in search of enzymatic activities that require vitamin B12 or are involved in its synthesis and import. Results have revealed that vitamin B12 is needed by these microorganisms for several essential enzymes such as ribonucleotide reductase, methionine synthase and epoxyqueosine reductase. Isolate Desulfosporosinus sp. DEEP is the only analyzed genome that holds a set core of proteins that could lead to the production of vitamin B12. The rest are dependent on obtaining it from the subsurface oligotrophic environment in which they grow. Sought proteins involved in the import of vitamin B12 are not widespread in the sample. The dependence found in the genomes of these microorganisms is supported by the production of vitamin B12 by microorganisms such as Desulfosporosinus sp. DEEP, showing that the operation of deep subsurface biogeochemical cycles is dependent on cofactors such as vitamin B12.

Tartessos and Atlantic Mediterranean Euro-Africa: Metals, Dolmens and Basque-Iberian origins

Tartessos culture is placed in a wide area in southern Portugal and Spain after archeological and documental studies. Its placement is concordant with that of West Euromediterranean ancient Megaliths, which were constructed at the Bronze Age (5000 year BC or before at Alcalar Dolmen (Portimao, Portugal), where Palelolithic arrows are found. These Megaliths construction and the people that built them up may be related to the metal richness of the core Tartessian Area: The Iberian Pyrite Belt which is rich in gold, silver, copper, iron, and others within this territory. Prehistoric documents place this area around Huelva, Cadiz (Spain) and South Portugal. Age of Tartessos may be older than established (centuries BC): Strabo said that Tartessians wrote 6000 years before. Indeed, we have found Megalithic Linear Scripts in a Megalith context (or not) in Tartessian area, Canary Islands and South Algerian Sahara, Mt Ahaggar area. These may represent a Megalithic Age writing which gave rise to IberianTartessian and other lineal signaries. Humboldt and all previous studies had established since 1st century AD that Basque language was old Iberian-Tartessian language. This has been hotly dismissed in the last 75 years by some Spanish scholars. However, the appearance (2023) of Irulegui Hand written in both Basque and Iberian has brought back the Basque-Iberism. Finally, relatedness with West and East Iberia is evident, because they use the same type of Ibrerian Tartessian writing and Levant Iberian statues (Lady of Cabeza-Lucero, Alicante, Spain) have almost the same Tartessian sculptured face schematic structure which has been recently found in Tartessos West Spain (Casas de Turuñuelo, Badajoz, Spain).

Choosing the site, getting the stones, building the dolmens: local sourcing of andesites at the El Pozuelo megalithic complex (Huelva, Spain)

The geoarchaeological study focuses on the lithological characterization and provenance determination of the rocks of the El Pozuelo dolmens. The difficulty of identifying volcanic rocks in the intensely altered and deformed environment of the Iberian Pyrite Belt has required the implementation of a research methodology combining the archaeological and geological analysis of the megaliths and the area surrounding the Los Llanetes group. A total of 29 thin sections and 14 geochemical analyses (ICP-AES, ICP-MS and REE) have been carried out on samples from the dolmens and potential source areas, focusing on the chemical elements considered immobile during alteration processes. The petrological analyses confirm the identification of different andesite lithotypes and enable us to correlate the rocks used in the construction of the megaliths with source areas and quarries located within a 50–350 m radius. Several patterns are observed in the selection of the rocks, based on the material, visual and symbolic properties of the different lithologies. Foliated andesite is the most common stone used in the monuments, due to its excellent physical properties and technological suitability for extraction and transformation into megalithic supports. Other types of andesite (sheared, massive and amphibole-phyric), white quartz, ferruginous agglomerate and gabbro were also used for different architectural purposes. The results confirm the importance of locally available suitable rocks in determining site location, raw material procurement and monument construction during the Late Neolithic.

Research of an Abandoned Tailings Deposit in the Iberian Pyritic Belt: Characterization and Gross Reserves Estimation

Global situations such as economic recovery after a pandemic, geopolitical instability, and future digital and energy transition are some of the drivers for the European Union (EU) to explore new and existing sources of raw materials. The Iberian Pyrite Belt in the southwest of the Iberian Peninsula (Spain and Portugal) hosts a great number of tailing deposits from centuries of mining operations. A unique tailings deposit has been studied and characterized. The similarities with other tailing deposits deeply studied suggested the presence of critical raw materials. Furthermore, a very gross reserves estimation was made. The characterization and reserves estimations were compared with the bibliography from mining companies who operated in the area decades ago and from the bibliography available at Fundación Riotinto. The presence of critical raw materials was confirmed, some of them in high concentrations. Moreover, a singular difference was found compared with other similar tailings stored within the Iberian Pyrite Belt. The main valuable metals identified were Au (2.25 ppm), Ag (215 ppm), Co (131 ppm) and Cu (0.29%). The reserves estimation showed that this deposit potentially hosts 1.86 t of Au, 177 t of Ag, 108 t of Co or 2358 t of Cu; in other words, with a copper average price of 8366 US$/t in December 2022, the tailings deposit contains a potential value of more than 19 million USD.

Time-space evolution of Iberian Pyrite Belt igneous activity: Volcanic and plutonic lineaments, geochronology, ore horizons and stratigraphic constraints

The volcanism in the Iberian Pyrite Belt migrated from the present day west/southwest to the east/northeast during Devonian/Carboniferous times. Evidence is here discussed based in U-Pb zircon ages of felsic volcanic and plutonic rocks, bounded by enclosed sediments and their biostratigraphic ages, together with hosted massive sulphides deposits and associated plutonic counterparts.Volcano-Sedimentary Complex rocks define several volcanic axes, or lineaments, with the general NW-SE to WNW-ESE belt trending orientation. The usage of all the available data from high-resolution stratigraphy, geology and geophysics lead to establishment of eleven main volcanic axes, nine with zircon U-Pb radiometric ages (166 samples).In this research, we reinforce a previous inter-axes volcanic evolutionary trend, but we also suggest an intra-axis evolutionary trend of the IPB igneous activity with time. This means the basin igneous activity also evolved along most of the volcanic and plutonic lineaments, from west/northwest to east/southeast.Successive weighted average ages for each axis (SW to NE) and opposite end-point sample ages for each axis (NW/W to SE/E) are presented. Similar trends are found with felsic volcanic rocks, subvolcanic and plutonic rocks and even massive sulphide ages correspond to the regional trend corroborating the proposed geological framework.Siliciclastic sediments and lower VSC sequences (sediments, felsic volcanic rocks and massive sulphides) show a comparable age trending evolution although upper VSC sediments seem to be contemporaneous across the province. Older ages, from zircon U-Pb and from associated reworked palynomorph in the sediments, show a long-lasting age distribution along most Devonian times, suggesting the IPB evolved since Lochkovian times (Lower Devonian). Therefore, we propose the IPB inter-axes evolution could be related with a NE-direction plate motion (present-day location) over a heat source, while intra-axes are probably due to the collisional/compressive tectonic interaction of South Portuguese – Ossa-Morena zones tectonic setting.

Biocorrosion of Carbon Steel under Controlled Laboratory Conditions

In the Iberian Pyritic Belt (SW Europe), Acid Mine Drainage (AMD) is the consequence of the interaction of physical-chemical and biological factors, where aerobic Fe and/or S oxidizing chemolithotrophic and anaerobic sulfate reducing bacteria play an essential role. As a result, the polluted waters are highly acidic (pH 2–3) and contain numerous dissolved or suspended metals, which gives them a powerful corrosive action on constructions related to mining activities with high economic losses. To verify the role of bacteria in the corrosion of carbon steel, a common material in buildings exposed to corrosion in acidic waters, several experiments have been carried out under controlled conditions using carbon steel bars and acidic water containing bacteria consortia from an AMD river of the Iberian Pyritic Belt. In all the experiments carried out, a remarkable oxidation of supplemented iron was observed in the presence of bacteria. Using carbon steel as the sole iron source, we observed a slight corrosion of the bars, but when culture media was supplemented with elemental sulfur, steel bars was severely damaged. Since the bacteria inoculum come from the surface water, well oxygenated, nutrient-poor river, the obtained results are discussed based on facultative metabolism of acidophilic chemolithotrophic bacteria.

Electrochemical reactions driving Mn-enrichment in Fe[sbnd]Mn supergene ores: A mineralogical perspective

Iron and manganese oxides embody a geochemical system of great environmental, biological, and economical relevance. Chemical equilibria and the stability of FeMn phases under surface or near-surface conditions can influence the fate of contaminants in the environment, impact biological metabolic processes, or Fe and Mn phase distribution in weathered ores. In the present work, we focus on the textural, mineralogical, and chemical study of FeMn ores from the weathered zone of a vein-hosted deposit outcropping in the Iberian Pyrite Belt, SW Portugal, by means of micro-Raman spectroscopy coupled with electron microprobe microanalysis. The aims of our investigation are i) identifying the several Fe and Mn phases occurring in differently enriched ores samples, ii) relating their chemical composition with possible mineralization mechanisms, and iii) defining the mineral paragenetic pathway related to the observed textural features. Our approach enabled both the identification of the coexisting Fe and Mn phases, and unravelling paragenetic pathways leading to supergene enrichment mineralizations. Collected evidence demonstrates that changes in Eh/pH can lead to goethite dissolution under reductive conditions, promoting the release of Fe2+ into solution, whose electrochemical interaction with Mn4+ results in the formation of several types of Mn oxides, and secondary goethite. Our data shows a clear relationship between the type of Mn oxide crystallized and the ratio of aqueous Mn3+/Mn4+, alongside other prevalent cations, incorporated into tunnel or interlayer structural sites, which may be also desorbed/solubilized from primary goethite.

Critical Raw Materials recovery potential from Spanish mine wastes: A national-scale preliminary assessment

In Spain, due to its important mining past, there are many abandoned mine waste facilities. This study evaluates the potential of Spanish mine wastes for the recovery of critical and strategic raw materials and other elements of economic relevance. For this purpose, 20 mine waste facilities have been selected in different parts of Spain based on criteria such as tonnage, element content or metal market price. Surface samples were taken at the facilities, considered representative of these, for subsequent granulometric, mineralogical and chemical analysis. The grain size data were obtained by standard sieving (ASTM 5000), while the mineralogy was obtained by X-ray Diffraction (XRD). For chemical characterization, Wavelength Dispersion X-ray Fluorescence Spectrometry (WDXRF) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) were used to analyze 38 chemical elements (Be, Sc, V, Cr, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, Sn, Sb, I, Cs, Ba, La, Ce, Nd, Sm, Hf, Ta, W, Tl, Pb, Bi, Th and U), many of them included in the European Union’s list of Critical Raw Materials (CRMs). In addition, leachate data from mine wastes in the Iberian Pyritic Belt were analyzed to assess their bioleaching potential. The calculated enrichment factors (EF) indicate that some critical elements, as well as others with strategic and economic interest, are highly enriched in the wastes, including Sb, Bi, As, Pb, Cu, Ag, Zn, Cd, Sn, Se and Th. The most promising facilities with the highest recovery potential are located in the historic Riotinto and Tharsis mines (both in Huelva, Iberian Pyrite Belt) and the Rubiais mine in Lugo, whose tailings could contribute up to 3.2 billion dollars gross, according to the current market metal prices. This paper aims to provide a first step to promote mine waste recycling and circular mining in Spain, an initiative that would also help to mitigate the environmental damage derived from abandoned mine wastes.

Geochemical distribution in residual soils of Iberian Pyrite Belt (Spain)

The Iberian Pyrite Belt (IPB) is a volcanic- and shale-hosted massive sulfides world-class province of the Upper Paleozoic age that includes some supergiant ore deposits with a unique mining operations history. An extensive soil (multi-element) geochemical survey in the IPB has been performed to create a geochemical database to increase the knowledge of the studied area. Both univariate and multivariate treatments have been done to manage a large amount of new data. The studied area shows higher background concentrations of several elements (e.b. Cu, Pb, Zn, Cd, Sn, In, Bi, As, or Sb) than in other terrains in Spain due to the IPB volcano-sedimentary ore deposits and their associated mining wastes. Mapping chemical elements help understand their behavior, controls and associations in natural environments. According to this, the mono-elemental contour maps show single-element distributions with geological control (e.g., Na), ore deposit control (e.g., Cu) or a mixture of both. On the other hand, multivariate analysis has been applied to reduce the large geochemical database maintaining the same information. We have chosen Factorial Analysis (FA) and obtained six factors that explain approximately 70% of the variability. Four of these factors (F1, F2, F4 and F5) show an intense geological control that improves the geological information of the IPB, while the other two (F3 and F5) show an ore deposit control. These factors allow distinguishing between different types of deposits in the IPB and help discover new possible exploration targets for future studies.

Fe(III) Biomineralization in the Surface Microlayer of Acid Mine Waters Catalyzed by Neustonic Fe(II)-Oxidizing Microorganisms

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.

Metal Pollution and Mining in the Iberian Pyrite Belt: New Remediation Technologies to Improve the Ecosystem Services of the River Basins

The highly metal-contaminated Odiel-Tinto River basin, located in the Iberian Pyrite Belt (IPB), has been the focus of many environmental studies as a natural lab for biodiversity and environmentally catastrophic scenarios and as a reference site for mining places with similar conditions. This study demonstrates the feasibility and effectiveness of two different technologies to recover ecosystems affected by acid mine drainage (AMD) in the area of IPB. The current study compiles results of two newest technologies for AMD remediation: passive remediation (dispersed alkaline substrate—DAS) and a new disruptive technology (Adiabatic Sonic Evaporation and Crystallization—ASE&C) that purifies the contaminated water, obtaining two by-products (high-quality water and metal conglomerates) that improve the general quality of the ecosystem including biodiversity by eliminating more than 90% of the contaminants from AMD and mining waters. The removal of contaminants, enhancement of AMD treatment efficiency, and offset operating costs were compared and analyzed for the different uses of the decontaminated effluents, including an old tailing pond failure, the Aznalcóllar mining spill. The efficiency of the removal of elements from the contaminated water is significant using both technologies, although the passive DAS does not still reach the international benchmark for some compounds (such as Fe, sulfates, and Mn); whereas ASE&C obtains distilled water fulfilling all the international benchmarks with conductivity values lower than 120 µS cm−1 or metal concentrations lower than µg/L. Both technologies are eco-friendly and cost-effective as a result of the generation of valuable by-products such as fresh water and metal conglomerates as potentially commercial products while remediating aquatic ecosystems impacted by mining activities.

Quantification of Pollutants in Mining Ponds Using a Combination of LiDAR and Geochemical Methods—Mining District of Hiendelaencina, Guadalajara (Spain)

More than twenty years after the last mining operations were completed in the Hiendelaencina Mining District, it is necessary to carry out a geochemical characterisation of the tailings stored in two contiguous mine ponds. Both have significant amounts of quartz, siderite, barite and muscovite and show significant contents of As, Ba, Pb, Sb and Zn. The tailings show alkaline pH and low electrical conductivity values, which support the visual observation that rules out acid drainage into the environment. The comparison of the National Topographic Map of 1954 with LiDAR data from 2014 has allowed estimating the volume of abandoned waste. Based on the volume of slurry and its average density, the total tonnage of pollutants has been estimated at 279 ± 9 t stored in Pond North and 466 ± 11 t stored in Pond South. Although these are significant quantities that pose a risk to the environment and nearby populations, they are lower than those present in other Spanish districts, such as the Iberian Pyrite Belt or Cartagena-La Unión. The combined use of LiDAR data, aerial imagery and geochemical methods has proven to be very useful for the estimation of the volume of pollutants stored in mine ponds.

The use of copper isotopes for understanding metal transfer mechanisms within the continuum mine-river-dam (Huelva Region, Spain).

Mining areas and in particular those containing massive sulfides have left a heavy environmental legacy with soils and hydrographic networks highly contaminated with metals and metalloids as for example in the Iberian Pyrite Belt (Huelva, Spain). Here, we present new data on copper (Cu) isotopic composition of waters and solids collected along a continuum Mine (Tharsis)-River (Meca)-Lake (Sancho) in the Iberian Pyrite Belt. Our results show that the isotopic signature of pit lakes is spatially variable, but remains stable over the seasons; this signature seems to be controlled by water-rock interaction processes. The data obtained on the Meca River imply a number of attenuation processes such as decrease in the metal concentration by precipitation of secondary minerals. This is accompanied by preferential retention of the heavy isotope (65Cu) with a possibility of living organisms (e.g., algae) participation. The terminal Sancho lake demonstrated constant isotopic signature over the entire depth of the water column despite sizable variations in Cu concentrations, which can be tentatively explained by a superposition of counter-interacting biotic and abiotic processes of Cu fractionation. Overall, the understanding of the isotopic variations along the hydrological continuum is useful for a better understanding of metal element transfer within mining environments and surrounding surface waters.

Evidence of rare earth elements origin in acid mine drainage from the Iberian Pyrite Belt (SW Spain)

Acid mine drainage (AMD) is a worldwide pollution problem of watersheds. In addition to toxic metal(oid)s and acidity, many elements of economic interest are released into the environment, which make AMD a potential strategic secondary source of these elements such as rare earth elements (REE). Despite the importance of these metals, their origin in AMD is still uncertain. Recent hypotheses suggest preferential leaching of REE-enriched minerals as a possible source. Leaching tests with H2SO4 have been developed to simulate the interaction under AMD formation conditions with sulfide bodies and host rocks from two representative mining areas in the Iberian Pyrite Belt: the Perrrunal and Poderosa mines (SW of Spain). The REE patterns and Ce and Eu anomalies of the rock leachates have confirmed the geochemical relationship between the AMD and certain country rocks (felsic and mafic volcanics, and shales). A detailed chemical and mineralogical study has confirmed the existence of a diversity of minerals with high concentrations of REE. Thus, the minerals with the highest REE contents are also those with the fast dissolution kinetics under acid conditions: REE phosphates (monazite and xenotime type) and carbonates (parisite type). Finally, petrographic evidence of the selective leaching of these minerals clearly supports these minerals as the main source of REE in the AMD.

Rare earth element signature modifications induced by differential acid alteration of rocks in the Iberian Pyrite Belt

The efficient use of REE as tracers of weathering processes requires further data acquisition to establish robust connections between mechanisms, mineral assemblages and REE concentration patterns. Here, results are provided corresponding to rocks from four locations in the Iberian Pyrite Belt that were altered with different intensity by sulfuric fluids. The acidic alteration was mild (pH 5–7) in Calañas and El Villar, while strong (pH below 3 to 5) in Quebrantahuesos and Tharsis. The main REE reservoir before alteration were phyllosilicates (and plagioclase/feldspar in El Villar only). Mild alteration generated mainly kaolinite while illite and some plagioclase/feldspar were preserved. Mildly altered rocks approximately preserved the relative REE concentrations of their precursors, interpreted as indicating a low fluid/rock ratio environment where binding sites in minerals outnumbered those in fluids. Strong acid alteration produced alunite, jarosite, beudantite and goethite, with partial illite preservation. Where illite and/or goethite were major minerals, this alteration generated REE patterns enriched in light REE over heavy REE or did not modify the relative REE concentrations of the original rock. However, samples where REE concentrations were controlled by alunite or jarosite had LREE > > HREE. In alunite the maximum concentration corresponded to Nd and Sm. In jarosite concentrations decreased from La to Lu, except that a positive Eu anomaly was preserved from the precursor. These REE concentration patterns are interpreted as due to crystallographic factors, controlled by the best fit of REE with charge 3+ in the 12-fold coordination site of K in jarosite and alunite. This site is larger in jarosite and fits La best, whereas the smaller site in alunite best fits Nd and Sm. Goethite REE signature is variable, perhaps due to two formation routes, (1) silicates ➔ goethite and (2) silicates ➔ jarosite ➔ goethite. Our interpretations of REE concentration in alunite, jarosite and goethite are novel and provide new routes to further develop REE as tracers of acid alteration processes.

Investigating Metals and Metalloids in Soil at Micrometric Scale Using µ-XRF Spectroscopy—A Case Study

Micrometric 2D mapping of distinct elements was performed in distinct soil grain-size fractions of a sample using the micro-X-ray Fluorescence (µ-XRF) technique. The sample was collected in the vicinity of São Domingos, an old mine of massive sulphide minerals located in the Portuguese Iberian Pyrite Belt. As expected, elemental high-grade concentrations of distinct metals and metalloids in the dependence of the existent natural geochemical anomaly were detected. Clustering and k-means statistical analysis were developed considering Red–Green–Blue (RGB) pixel proportions in the produced 2D micrometric image maps, allowing for the identification of elemental spatial distributions at 2D. The results evidence how elemental composition varies significantly at the micrometric scale per grain-size class, and how chemical elements present irregular spatial distributions in the direct dependence of distinct mineral spatial distributions. Due to this fact, elemental composition is more differentiated in coarser grain-size classes, whereas griding-milled fraction does not always represent the average of all partial grain-size fractions. Despite the complexity of the performed analysis, the achieved results evidence the suitability of µ-XRF to characterize natural, heterogeneous, granular soils samples at the micrometric scale, being a very promising investigation technique of high resolution.

Distribution of critical metals in evolving pyrite from massive sulfide ores of the Iberian Pyrite Belt

With >90 known deposits containing original reserves of >2400 Mt of sulfide ore, the Iberian Pyrite Belt (IPB) is the largest volcanogenic massive sulfide (VMS) province on Earth. In these evolving mineral systems, texturally different pyrite exhibits characteristic mineralogy and trace element fingerprints. Pyrite (Py-1), which is well preserved in the polymetallic ores that crystallized at the earliest stage of VMS deposit formation, consists of kernels of pyrite framboids surrounded by concentric colloform bands and ended by faceted outlines. It is rich in some metals like Pb, Zn, Sb and As (mostly hosted as nano-to-micron-sized particles, including galena, tetrahedrite and arsenopyrite) but depleted in Cu, Co and Bi. In contrast, pyrite from the pyritic and Cu-rich ore overprinted by late fluids exhibits spongy-looking (Py-2) or homogenous (Py-3) cores surrounded by external facets with crystallographic continuity across the whole single grains due to re-crystallization. Py-2 is depleted in most trace elements with the exception of Au and Bi, which occur both in solid solutions and as nano-to-micron-sized inclusions. Py-3 has the highest Cu, Ag, Co and Ni (mainly associated to nano-to-micron-sized particles of tennantite, chalcopyrite and gersdorffite) and the lowest Au contents in the form of native gold. The progressive increase in metal contents from inner to outer parts of Py-1 matches with the onset of the economic metal endowment of VMS deposits in the IPB, whereas Py-2 and Py-3 are associated with metal shoot processes that led to both leached and high-grade ores, very likely when mafic rocks were emplaced into the footwall of the deposits.

Effects of estuarine water mixing on the mobility of trace elements in acid mine drainage leachates

This research reports the effects of pH increase on contaminant mobility in acid mine drainage from the Iberian Pyrite Belt by seawater mixing in the laboratory, simulating the processes occurring in the Estuary of Huelva (SW Iberian Peninsula). Concentrations of Al, Fe, As, Cu and REY in mixing solutions significantly decreased with increasing pH. Schwertmannite precipitation at pH 2.5–4.0 led to the total removal of Fe(III) and As. Subsequently, iron-depleted solutions began to be controlled by precipitation of basaluminite at pH 4.5–6.0, which acted as a sink for Al, Cu and REY. Nevertheless, as the pH rises, schwertmannite becomes unstable and releases back to solution the previously retained As. Moreover, other elements (S, Zn, Cd, Ni and Co) behaved conservatively in mixing solutions with no participation in precipitation processes. Some toxic elements finally end up to the Atlantic Ocean contributing to the total pollutant loads and environmentally threatening the coastal areas.