Maria João Batista

Inter-population variation on the accumulation and translocation of potentially harmful chemical elements in Cistus ladanifer L. from Brancanes, Caveira, Chança, Lousal, Neves Corvo and São Domingos mines in the Portuguese Iberian Pyrite Belt

PurposeThis study aimed to compare the variation on the accumulation and translocation of potentially harmful chemical elements and nutrients (As, Ca, Cu, Fe, K, Mg, Mn, Ni, Pb and Zn) in Cistus ladanifer L. belonging to populations growing in different mine areas from the Portuguese Iberian Pyrite Belt (Brancanes, Caveira, Chança, Lousal, Neves Corvo, São Domingos). These mines are abandoned (except Neves Corvo that is still operating) and have different contamination levels.Materials and methodsComposite samples of soils (n = 31), developed on different mine wastes and/or host rock, and C. ladanifer plants (roots and shoots) were collected in the mine areas. Soils were characterized for pH, NPK and organic C, by classical methodologies. Soils (total fraction—four acid digestion, and available fraction—extracted with aqueous solution of diluted organic acids, simulating rizosphere conditions) and plants (ashing followed by acid digestion) elemental concentrations were determined by ICP. Soil–plant transfer and translocation coefficients were calculated. Principal components analysis in both ways, the classical method and a second approach with adaptations used mostly in multivariate statistical processes control data, were done in order to compare the plants populations.Results and discussionSoils had large heterogeneity in their characteristics. Caveira, Lousal, Neves Corvo and São Domingos soils showed the highest total concentrations of As, Cu, Pb and Zn. Independently of the mine, available fractions of elements were low. Intra- and inter-population variations in accumulation and translocation of elements were evaluated. Plants were not accumulators of the majority of the analysed elements. Nutrients were mainly translocated from roots to shoots, while trace elements were stored in roots (except in Neves Corvo for As and Pb, and São Domingos for As). Elements concentrations in plant populations from Lousal, Chança and São Domingos did not present much variation. Brancanes soils and plants presented strong differences compared to other areas.ConclusionsCistus ladanifer plants are able to survive in mining areas with polymetallic contamination at different elements concentrations in total and available fraction. This species presented variations inter- and intra-populations in accumulation and translocation of chemical elements; however, all studied populations, except Brancanes, can belong to the same population cluster.

Introduction and Geological Setting of the Iberian Pyrite Belt

The 250 × 20–70 km Iberian Pyrite Belt (IPB) is a Variscan metallogenic province in SW Portugal and Spain hosting the largest concentration of massive sulphide deposits worldwide. The lowermost stratigraphic unit is the early Givetian to late Famennian-Strunian (base unknown) Phyllite-Quartzite Group (PQG), with shales, quartz-sandstones, quartzwacke siltstones, minor conglomerate and limestones at the top. The PQG is overlain by the Volcanic Sedimentary Complex (VSC), of late Famennian to mid-late Visean age, with a lower part of mafic volcanic rocks, rhyolites, dacites and dark shales, hosting VHMS deposits on top (many times capped by a jasper/chert layer), and an upper part, with dark, purple and other shales and volcanogenic/volcaniclastic rocks, carrying Mn oxide deposits. The VSC is covered by the thousands of meters thick Baixo Alentejo Flysch Group of late Visean to Moscovian age. The VSC comprises a bimodal submarine volcanic succession, with VHMS deposits spatially associated to dacites and rhyolites corresponding to effusive/explosive lava-cryptodome-pumice cone volcanoes. The lava/domes consist of coherent lithofacies surrounded by clast-rotated hyaloclastite breccia and minor autobreccia, with massive VHMS ore at the top of the felsic effusive units and stockworks in the autoclastic and pyroclastic breccias. The eastern IPB rocks are intruded by the voluminous Sierra Norte Batholith (tonalite-trondhjemite-granodiorite, TTG series). Felsic volcanic rocks (dacite to high-silica rhyolite) predominating over basalts and dolerites, belong to the calc-alkaline series and plot mostly in the within-plate field in tectonic discriminative diagrams. Several periods of volcanism, from 384 to 359 Ma are recognized. Dacites and rhyolites exhibit Nd and Sr enrichment, typical of a crustal signature, and their overall geochemistry suggests generation by fractionation/partial melting of amphibolites at low pressure. Trace elemental modelling of the basic rocks, involving tholeiitic lavas and alkaline basaltic lavas and dolerites, points to mixing between E- and N-MORB and assimilation of crustal material. Variscan NW-SE/W-E-trending and SW- or S-verging folds (with NE- or N-dipping planar cleavage) and thrusts, occur in west-central and eastern IPB, respectively. In late to post-Variscan time strike-slip oblique faults formed, either N-S to NNW-SSE or NE-SW to ENE-WSW, dextral or sinistral (both extensional), respectively. The first set hosts late Variscan Cu-Pb-Ba veins and Mesozoic(?) dolerite dykes. IPB contains over 90 VHMS deposits, estimated before erosion at >1700 Million tonnes (Mt), with 14.6 Mt Cu, 34.9 Mt Zn, 13.0 Mt Pb, 46,100 t Ag, 880 t Au and many other metals, particularly Sn. Eight of these are giant (≥100 Mt) VHMS deposits, namely Rio Tinto, Tharsis, Aznalcollar-Los Frailes, Masa Valverde, Sotiel-Migollas and La Zarza (Spain) and Neves Corvo and Aljustrel (Portugal). The VHMS deposits are of the felsic-siliclastic type and mostly of the Zn–Pb–Cu and Zn–Cu–Pb metal content types. The deposits range in thickness from 1 m to tens of meters (plus increase from tectonic stacking) and up to a few kilometers in extension, and many are underlain by large stockwork zones. Their age is either Strunian (palynological age) in the southern IPB or mostly Tournaisian in the northern IPB. The major massive ore minerals are pyrite, sphalerite, chalcopyrite, galena (and cassiterite at Neves Corvo), also present with dominant quartz-chlorite-sericite-carbonate in the stockwork ore. Sericite and chlorite were also formed from additional alteration in the hanging wall rocks. Metal zonation in most VHMS deposits consists of a Cu-rich stockwork and base of the massive ore, with Zn–Pb massive ore above and extending laterally. S-, O-, H- and C-isotope data indicate that ore-forming fluids contain predominant or exclusive modified seawater. A magmatic fluid contribution to the dominant seawater has been proposed for some deposits. The deposits are exhalative or formed by shallow subsurface replacement of either muds/shales or coherent felsic volcanic rocks.

Preliminary Results of a Risk Assessment Study for Uranium Contamination in Central Portugal

The Central region of Portugal contains a large number of U-mineral occurrences and 60 abandoned uranium mines exploited since 1907. The U mineralisation is mainly hosted in granitic rocks, naturally radioactive. Thus, the objective of this study is to evaluate the risk for population of the mining explorations and unexploited mineralisations. The study consisted of two units approach, one, where specific regional indicators: land use, lithology, natural gamma radiation, geoaccumulation index of uranium in stream sediments, distance from uranium mines to land use categories, and a classification of mines based on: type of exploitation, volume of waste, leaching and acid water presence, are used as hazard potential. Vulnerability was considered as a “number of inhabitants per water system.” Another approach uses municipality as unit (NUTS IV) where the hazard potential is characterised by the number of mines per municipality, water system per municipality, inhabitants per water system, and the classification of mines. The vulnerability was divided in damage potential and coping capacity, damage potential is regional gross domestic product (GDP) per capita and population density and coping capacity is number of doctors per 1,000 inhabitants and national GDP per capita. In the first approach, the areas enriched are bigger than the mining areas, meaning that natural radioactivity can be important in this hazard characterization. In the second approach, the higher risk municipalities have open pit uranium mines with acid mine drainage, high volumes of waste materials and medium population density, GDP per capita and less doctors per 1,000 inhabitants. These municipalities are Gouveia, Guarda, Mangualde. The results are conditioned by the available data to introduce in the study, specially the vulnerability data that may change with time.

The interaction of heavy metals and metalloids in the soil–plant system in the São Domingos mining area (Iberian Pyrite Belt, Portugal)

São Domingos belongs among the most important historic Iberian Pyrite Belt Cu mines. The anthrosoil is contaminated by a very high content of heavy metals and metalloids. The study was focused on evaluating the interaction of some chemical elements (Ca, Mg, Fe, Mn, Cu, Pb, Zn, Ag, Cd, Ni, Co, As, Sb) in the system soil vs. five autochthonous dominant plant species: Pinus pinaster Aiton, Quercus rotundifolia Lam., Agrostis sp., Juncus conglomeratus L. and Juncus effusus L. The plants are heavily contaminated by Cu, Pb, As and Zn. The bioconcentration factor proved that they exhibit features of metal tolerant excluders. The trees are accumulators of Ag, whereas the graminoids are hyper-accumulators of Ag and Juncus effusus of Co. The translocation factor confirmed that the selected elements are immobilised in the roots except for Mn and Zn in Pinus pinaster and Mn in Quercus rotundifolia and Juncus conglomeratus. The bioaccumulation of Mn, Zn and Cu at low pH increases. The increased content of Ca and Mg in the soil inhibits, in the case of some metals and metalloids, their intake to plants. Although the studied plants, despite their fitness and vitality at the contaminated sites, are not suitable for phytoextraction (except Co and Ag), they can be used for phytostabilisation at the mining habitats.