Potentially Toxic Elements’ Contamination of Soils Affected by Mining Activities in the Portuguese Sector of the Iberian Pyrite Belt and Optional Remediation Actions: A Review

Both sectors of the Iberian Pyrite Belt, Portuguese and Spanish, have been exploited since ancient times, but more intensively during and after the second half of the 19th century. Large volumes of polymetallic sulfide ore were extracted in open pits or in underground works, processed without environmental concerns, and the generated waste rocks and tailings were simply deposited in the area. Many of these mining sites were abandoned for years under the action of erosive agents, leading to the spread of trace elements and the contamination of soils, waters and sediments. Some of these mine sites have been submitted to rehabilitation actions, mostly using constructive techniques to dig and contain the contaminated tailings and other waste materials, but the remaining soil still needs to be treated with the best available techniques to recover its ecosystem functions. Besides the degraded physical structure and poor nutritional status of these soils, they have common characteristics, as a consequence of the pyrite oxidation and acid drainage produced, such as a high concentration of trace elements and low pH, which must be considered in the remediation plans. This manuscript aims to review the results from studies which have already covered these topics in the Iberian Pyrite Belt, especially in its Portuguese sector, considering: (i) soils’ physicochemical characteristics; (ii) potentially toxic trace elements’ concentration; and (iii) sustainable remediation technologies to cope with this type of soil contamination. Phytostabilization, after the amelioration of the soil’s properties with organic and inorganic amendments, was investigated at the lab and field scale by several authors, and their results were also considered.

Unmanned Aerial System-Based Multispectral Water Quality Monitoring in the Iberian Pyrite Belt (SW Spain)

Few studies have assessed mining-associated water pollution using spectral characteristics. We used high-resolution multispectral data acquired by unmanned aerial drones combined with in situ chemical data to assess water quality parameters in 12 relatively small water bodies located in the Tharsis complex, an abandoned mining area in the Iberian pyrite belt (SW Spain). The spectral bands of Micasense RedEdge-MX Dual and spectral band combinations were used jointly with physicochemical data to estimate water quality parameters and develop reliable empirical models using regression analysis. Physicochemical parameters including pH, ORP, EC, Al, Cu, Fe, Mn, S, Si, and Zn were estimated with high accuracy levels (0.81 < R2 < 0.99, 4 < RMSE% < 75, 0.01 < MAPE < 0.97). In contrast, the observed and modelled values for Ba, Ca, and Mg did not agree well (0.42 < R2 < 0.70). The best-fitted models were used to generate spatial distribution maps, providing information on water quality patterns. This study demonstrated that using empirical models to generate spatial distribution maps can be an effective and easy way to monitor acid mine drainage.

The Dual Paradigm of Mining Waste: “From Ecotoxicological Sources to Potential Polymetallic Resources”—An Example from Iberian Pyrite Belt (Portugal)

The main goal of this study was to identify potential chemical elements present in three types of polymetallic mine waste, stored in the old mine site of São Domingos, located in the Iberian Pyrite Belt, Alentejo, Southern Region of Portugal. This study involves the characterization of potential resources in those mine residues, bearing in mind that its reprocessing can facilitate the environmental remediation and rehabilitation activities which are underway at the site. X-ray Fluorescence (XRF) and micro (μ)-XRF 2D mapping surveys were performed. Univariate and multivariate data analysis reveal that differences in compositions are mainly related with element concentration per type of waste. Image processing and clustering analysis allowed the recognition of distinct elemental spatial distribution patterns. Some of these residues, although classified as archeological-industrial heritage materials may present toxicity to the ecological environment and to human health. This fact enhances, therefore, geoethical doubts regarding its remining and exploitability. In this context, a multi-criteria decision analysis considering two geoethical alternatives was performed.

Orange Pickeringite from the Algares 30-Level Adit, Aljustrel Mine, Iberian Pyrite Belt, Portugal

The sheltered environment of the Algares +30 level adit (underground mine gallery) contributes to the preservation of secondary water-soluble minerals formed on the tunnel walls. The massive sulphide and related stockwork zone are hosted by the Mine Tuff volcanic unit and are exposed in the walls of the gallery, showing intense oxidation and hydrothermal alteration. Minerals from the halotrichite group were identified on the efflorescent salts, typically white fine-acicular crystals but also on aggregates with dark orange/brownish colour. Mineral characterization was performed using several methods and analytical techniques (XRD, XRF-WDS, SEM-EDS, DTA-TG), and the chemical formulas were calculated maintaining the ratio A:B ≅ 1:2 in accordance with the general formula of the halotrichite group, AB2(SO4)4·22H2O. This methodology allowed the assignment of the orange colour to the presence of trivalent iron on iron-rich pickeringite in partial substitution of aluminium.

Vectors to ore in replacive volcanogenic massive sulfide (VMS) deposits of the northern Iberian Pyrite Belt: mineral zoning, whole rock geochemistry, and application of portable X-ray fluorescence

In this work we have performed a detailed study of vectors to ore to a representative volcanic-rock-hosted replacive volcanogenic massive sulfide (VMS) deposit located in the northern Iberian Pyrite Belt (Spain), the Aguas Teñidas deposit. The investigated vectors include the following: (1) mineralogical zoning, (2) host sequence characterization and mineralized unit identification based on whole rock geochemistry discrimination diagrams, (3) study of the characteristics and behaviour of whole rock geochemical anomalies around the ore (e.g. alteration-related compositional changes, characteristics and extent of geochemical halos of indicative elements such as Cu, Zn, Pb, Sb, Tl, and Ba around the deposit), and (4) application of portable X-ray fluorescence (p-XRF) analysis to the detection of the previous vectors. In the footwall, a concentric cone-shaped hydrothermal alteration zone bearing the stockwork passes laterally, from core to edge, from quartz (only local) to chlorite–quartz, sericite–chlorite–quartz, and sericite–quartz alteration zones. The hydrothermal alteration is also found in the hanging wall despite being tectonically allochthonous to the orebody: a proximal sericite alteration zone is followed by a more distal albite-rich one. Whole rock major elements show an increase in alteration indexes (e.g. AI, CCPI) towards the mineralization, a general SiO2 enrichment, and FeO enrichment as well as K2O and Na2O depletion towards the centre of the hydrothermal system, with MgO showing a less systematic behaviour. K2O and Na2O leached from the centre of the system are transported and deposited in more external areas. Copper, Pb, and Zn produce proximal anomalies around mineralized areas, with the more mobile Sb, Tl, and Ba generating wider halos. Whereas Sb and Tl halos form around all mineralized areas, Ba anomalies are restricted to areas around the massive sulfide body. Our results show that proposed vectors, or adaptations designed to overcome p-XRF limitations, can be confidently used by analysing unprepared hand specimens, including the external rough curved surface of drill cores. The data presented in this work are not only applicable to VMS exploration in the Iberian Pyrite Belt, but on a broader scale they will also contribute to improving our general understanding of vectors to ore in replacive-type VMS deposits.

Geochemical and Volcanological Criteria in Assessing the Links between Volcanism and VMS Deposits: A Case on the Iberian Pyrite Belt, Spain

VMS deposits in the Iberian Pyrite Belt (IPB), Spain and Portugal, constitute the largest accumulation of these deposits on Earth. Although several factors account for their genetic interpretation, a link between volcanism and mineralization is generally accepted. In many VMS districts, research is focused on the geochemical discrimination between barren and fertile volcanic rocks, these latter being a proxy of VMS mineralization. Additionally, the volcanological study of igneous successions sheds light on the environment at which volcanic rocks were emplaced, showing an emplacement depth consistent with that required for VMS formation. We describe a case on the El Almendro–Villanueva de los Castillejos (EAVC) succession, Spanish IPB, where abundant felsic volcanic rocks occur. According to the available evidence, their geochemical features, εNd signature and U–Pb dates suggest a possible link to VMS deposits. However, (paleo)volcanological evidence here indicates pyroclastic emplacement in a shallow water environment. We infer that such a shallow environment precluded VMS generation, a conclusion that is consistent with the absence of massive deposits all along this area. We also show that this interpretation lends additional support to previous models of the whole IPB, suggesting that compartmentalization of the belt had a major role in determining the sites of VMS deposition.

Pb-Nd-Sr Isotope Geochemistry of Metapelites from the Iberian Pyrite Belt and Its Relevance to Provenance Analysis and Mineral Exploration Surveys

The boundary in the Iberian Pyrite Belt is a world-class metallogenic district developed at the Devonian-Carboniferous boundary the Iberian Variscides that currently has seven active mines: Neves Corvo (Cu-Zn-Sn) and Aljustrel (Cu-Zn) in Portugal, and Riotinto (Cu), Las Cruces (Cu), Aguas Teñidas (Cu-Zn-Pb), Sotiel-Coronada (Cu-Zn-Pb), and La Magdalena (Cu-Zn-Pb) in Spain. The Iberian Pyrite Belt massive sulfide ores are usually hosted in the lower sections of the volcano-sedimentary complex (late Famennian to late Visean), but they also occur in the uppermost levels of the phyllite-quartzite group at the Neves Corvo deposit, stratigraphically below the volcano-sedimentary complex. A Pb-Nd-Sr isotope dataset was obtained for 98 Iberian Pyrite Belt metapelite samples (from Givetian to upper Visean), representing several phyllite-quartzite group and volcano-sedimentary complex sections that include the footwall and hanging-wall domains of ore horizons at the Neves Corvo, Aljustrel, and Lousal mines. The combination of whole-rock Nd and Sr isotopes with Th/Sc ratios shows that the siliciclastic components of Iberian Pyrite Belt metapelites are derived from older quartz-feldspathic basement rocks (–11 ≤ εNdinitial(i) ≤ –8 and (87Sr/86Sr)i up to 0.727). The younger volcano-sedimentary complex metapelites (upper Tournaisian) often comprise volcanic-derived constituents with a juvenile isotopic signature, shifting the εNdi up to +0.2. The Pb isotope data confirm that the phyllite-quartzite group and volcano-sedimentary complex successions are crustal reservoirs for metals found in the deposits. In Neves Corvo, where there is more significant Sn- and Cu-rich mineralization, the higher (206Pb/204Pb)i and (207Pb/204Pb)i values displayed by phyllite-quartzite group and lower volcano-sedimentary complex metapelites (up to 15.66 and 18.33, respectively) suggest additional contributions to the metal budget from a deeper and more radiogenic source. The proximity to Iberian Pyrite Belt massive sulfide ore systems hosted in metapelite successions is observed when (207Pb/204Pb)i &gt;15.60 and Fe2O3/TiO2 or (Cu+Zn+Pb)/Sc &gt;10. These are important criteria that should be considered in geochemical exploration surveys designed for the Iberian Pyrite Belt.