Río Tinto (Huelva, Spain) is located in one of the most important mining regions in the world. Its soils are characterized by their extreme acidity and elevated concentrations of heavy metals. Due to these characteristics, the Tinto ecosystem is considered unique and an ideal location to study biological adaptations to this type of habitat. Plant species that present these adaptations might be useful to mining and other metal pollution restoration programs. This study reports the results for the screening of Ca, Mg, Na, Mn, Fe, Ni, Cu, Zn, As, and Pb in aerial tissues of 97 plant species from the Tinto basin flora. In addition, plant-soil relationships were analyzed using the biological absorption coefficient (BAC) to detect the main plant adaptations in the Tinto flora. The species selected are representative of the biomass of the main dominant edaphophile and climatophile vegetation communities of the three river sections, forest, and subseral stages. Plant and soil elemental analyses were performed using inductively coupled plasma-mass spectrometry technique (ICP-MS). The results indicate that in general, Tinto flora shows a pattern of accumulation of the analyzed elements in aerial tissues which agrees with the nutritional requirements of vascular plants (macronutrients > micronutrients > indifferent or toxic elements). Among macronutrients, Ca seems to be an essential element in this habitat. This element accumulates in the aerial plant tissues. Basically, the Río Tinto flora is made of Fe, Cu, Zn, Ni, As, and Pb excluders, although some analyzed species of Erica, Quercus, Lavandula, Cistus, Genista, and Cytisus genera can be considered Mn accumulators. The results of this study make up a body of fundamental knowledge of the strategies used by plants to thrive in habitats with high concentrations of toxic heavy metals. This information is vital when it comes to planning a restoration program. Plants must be selected and used according to the requirements, always respecting the characteristics of the territory and facilitating the development of suitable vegetation.

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A semiquantitative ICP-MS method suitable for evaluating metal content in plants exposed to high metal concentrations is described. The methodology which has been tested using different plant reference material is able, in only a few minutes, to obtain qualitative and quantitative information from the sample. Recoveries close to 100% were obtained for more than half of the referenced elements with an RSD <10%, thus avoiding the generation of a calibration line for each of the elements to be analyzed. The use of multi-standards improves the results obtained with conventional standards by a factor of two. In these conditions the semiquantitative multi-elemental analysis is a valid alternative for most of the analyzed elements with the exception of Si, Al, and P which requires the use of a quantitative ICP-MS analysis for its determination. Two different digestion protocols were tested, with and without the addition of HF to the HNO(3) + H(2)O(2) extraction mixture. Similar results were obtained for poplar and bush reference materials using the HNO(3) + H(2)O(2) mixture. The addition of HF did not improve the recovery of different elements, in general, but is critical for the quantitative measurements of Al and Si as its presence allows results to be obtained with an RDS <5%.

Although biomineralization in plants is an important area of research, there is very limited information. In this work, we report the location of Na, K, Ca, Mg and Fe biominerals in Sarcocornia pruinosa (Chenopodiacaeae), a halophyte species growing in the estuarine area of Río Tinto, an extreme acidic environment. The estuarine soils of the Tinto basin are characterized by slightly acidic pH and high concentrations of ions. They are exposed to Atlantic Ocean tides that contribute to the increase in pH, Na and Mg concentrations. The aim of this work was to characterize the elemental composition and to identify the biominerals detected in cell tissues of S. pruinosa. Analytical techniques, such as ICP-MS (Inductively coupled plasma mass spectrometry), XRD and microscopy such as OM (optical microscopy) with histochemical staining, SEM and TEM (scanning and transmission electronic microscopy) coupled with EDX (energy dispersive X-ray) were carried out to analyze the plant tissues of S. pruinosa and characterize the detected biominerals. The elemental composition in succulent stems and seeds of S. pruinosa showed high values of Na and K followed by Ca, Mg and Fe. The presence of halite, sylvite, weddellite, glushinskite and Fe oxides biominerals in this halophyte species is reported. Our data suggest the importance of vegetation in the biogeochemical cycles in estuarine areas.