Study of Potentially Toxic Elements Uptake into Organs of Quercus spp. from Copper Deposits in Slovakia, Italy and Portugal.

The article is focused on the application of Energy dispersive micro X-ray fluorescence spectroscopy as a specific method to determine the contents of potentially toxic elements and its spread in plant tissues. As a model species, Quercus spp. were selected. In order to compare the obtained results with previous research, four well-described abandoned Cu-deposits were selected for sampling: Lubietová (Slovakia), Libiola and Caporciano (Italy), and São Domingos (Portugal). The results of micro X-ray fluorescence spectrometry confirm the irregular contamination of Quercus spp. by potentially toxic elements. The level of contamination is the highest predominantly in the root cortex, where is also the highest Ca contents (with exception of São Domingos). At Lubietová and Caporciano, high Ni content was described in branches cortex, in branches mesoderm also Fe, Cu and Zn. At the same time, the inhibition influence of Ca was also confirmed regarding the input of these elements into plants.

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.

Field study on the accumulation of trace elements by vegetables produced in the vicinity of abandoned pyrite mines.

To evaluate the accumulation of trace elements (TE) by vegetables produced in the vicinity of abandoned pyrite mines, eighteen different small farms were selected near three mines from the Portuguese sector of the Iberian Pyrite Belt (São Domingos, Aljustrel and Lousal). Total and bioavailable As, Cu, Pb, and Zn concentrations were analyzed in the soils, and the same TE were analyzed in three different vegetables, lettuce (Lactuca sativa), coriander (Coriandrum sativum), and cabbage (Brassica oleracea), collected at the same locations. The soils were contaminated with As, Cu, Pb, and Zn, since their total concentrations exceeded the considered soil quality guideline values for plant production in the majority of the sampling sites. The maximum total concentrations for those TE were extremely high in some of the sampling sites (e.g. 1,851 mg As kg(-1) in São Domingos, 1,126 mg Cu kg(-1) in Aljustrel, 4,946 mg Pb kg(-1) in São Domingos, and 1,224 mg Zn kg(-1) in Aljustrel). However, the soils were mainly circumneutral, a factor that contributes to their low bioavailable fractions. As a result, generally, the plants contained levels of these elements characteristic of uncontaminated plants, and accumulation factors for all elements <1, typical of excluder plants. Furthermore, the estimated daily intake (EDI) for Cu and Zn, through the consumption of these vegetables, falls below the recommended upper limit for daily intake of these elements. The sampling site that stood out from the others was located at São João de Negrilhos (Aljustrel), where bioavailable Zn levels were higher, a consequence of the slight acidity of the soil. Therefore, the Zn content in vegetables was also higher, characteristic of contaminated plants, emphasizing the risk of Zn entering the human food chain via the consumption of crops produced on those soils.

Environmental impact of mining activities in the Lousal area (Portugal): chemical and diatom characterization of metal-contaminated stream sediments and surface water of Corona stream.

Lousal mine is a typical "abandoned mine" with all sorts of problems as consequence of the cessation of the mining activity and lack of infrastructure maintenance. The mine is closed at present, but the heavy metal enriched tailings remain at the surface in oxidizing conditions. Surface water and stream sediments revealed much higher concentrations than the local geochemical background values, which the "Contaminated Sediment Standing Team" classifies as very toxic. High concentrations of Cu, Pb, Zn, As, Cd and Hg occurred within the stream sediments downstream of the tailings sites (up to: 817 mg kg(-1) As, 6.7 mg kg(-1) Cd, 1568 mg kg(-1) Cu, 1059 mg kg(-1) Pb, 82.4 mg kg(-1) Sb, 4373 mg kg(-1) Zn). The AMD waters showed values of pH ranging from 1.9 to 2.9 and concentrations of 9249 to 20,700 mg L(-1) SO(4)(-2), 959 to 4830 mg L(-1) Fe and 136 to 624 mg L(-1) Al. Meanwhile, the acid effluents and mixed stream waters also carried high contents of SO(4)(2-,) Fe, Al, Cu, Pb, Zn, Cd, and As, generally exceeding the Fresh Water Aquatic Life Acute Criteria. Negative impacts in the diatom communities growing at different sites along a strong metal pollution gradient were shown through Canonical Correspondence Analysis: in the sites influenced by Acid Mine Drainage (AMD), the dominant taxon was Achnanthidium minutissimum. However, Pinnularia acoricola was the dominant species when the environmental conditions were extremely adverse: very low pH and high metal concentrations (sites 2 and 3). Teratological forms of Achnanthidium minutissimum (Kützing) Czarnecki, Brachysira vitrea (Grunow) Ross in Hartley, Fragilaria rumpens (Kützing) G. W. F. Carlson and Nitzschia hantzschiana Rabenhorst were found. A morphometric study of B. vitrea showed that a decrease in size was evident at the most contaminated sites. These results are evidence of metal and acidic pollution.