M.J. Sierra

Mercury uptake and distribution in Lavandula stoechas plants grown in soil from Almadén mining district (Spain)

This work studies mercury root uptake by Lavandula stoechas var. Kew Red (lavender) and the distribution of this metal through the plant under greenhouse conditions along three consecutive seasons. Mercury concentration in plant tissues and in the different products obtained from lavender plants (essential oil, toilet water and in lavender tea) was assessed in order to evaluate the possible cultivation of lavender as a profitable alternative land use to mercury mining in the Almadén area once the mine had been closed down. Mercury concentration in useful parts of the plant was low (0.03-0.55 mg kg(-1)). Likewise, the essential oil, toilet water and tea obtained from these plants presented very low mercury levels, below the detection limit of the used equipment (<0.5 microg kg(-1)). In the case of the obtained tea, according to the recommendations given by the World Health Organization, the maximum daily intake of it without intoxication risk would be 85.2l. So, although other sources of mercury intake should also be considered in order to elaborate a complete toxicological risk assessment. Lavender data, obtained under this greenhouse working conditions, shows that lavender cultivation could be an alternative crop in the Almadén area.

Potential use of Solanum melongena in agricultural areas with high mercury background concentrations.

Solanum melongena L. (eggplant) is a native culture from India, found throughout the world, and is one of the most popular vegetables in the Mediterranean area. This work evaluates the potential use of eggplant as an economic alternative in an area with high mercury background concentrations. This implies the study of several factors such as the mercury absorption capacity of eggplant and the capacity of the soil for agricultural use. The research work has been carried out using soil from the mercury mining district of Almadén (Spain), where total mercury concentration was on average 14.16+/-0.65mgkg(-1). In this area, eggplant is a typical crop that is widely used for human consumption. The experimental work was performed in pots under greenhouse conditions. Three samplings were performed during the entire cultivation cycle. Mercury concentration was determined in the different plant organs, where the highest concentration was located in the root system. The results obtained show that the consumption of eggplant, growing under these controlled conditions, does not suppose a risk for human health according to the recommendations of the World Health Organization.

Oxidative stress in earthworms short- and long-term exposed to highly Hg-contaminated soils.

Exposure to mercury is often assessed by the measurement of molecular and biochemical antioxidant defences against an excessive production of reactive oxygen species. Here we examined some selected biomarkers of oxidative stress in the earthworm Lumbricus terrestris short- (2d) and long-term (44 d) exposed to Hg-contaminated soils (up to 1287 mg/kg dry wt). This level of Hg exposure did not cause earthworm mortality, however it yielded organisms to a situation of oxidative stress which was evidenced by the time-dependent responses of biomarkers. The reduced to oxidized glutathione ratio was a sensitive and early biomarker of Hg exposure, although the glutathione reductase activity back returned their normal physiological concentrations. Metallothioneins and total glutathione seemed to have a significant role in reducing Hg-induced oxidative stress when exposure to Hg prolonged up to 44 d. We combined biomarker responses into an integrate biomarker index which positively correlated with the Hg concentrations measured in the postmitochondrial fraction of the earthworm muscle, and with the available Hg fraction in soil. Current results suggest that glutathione redox cycle can be a complementary tool in the exposure and effect assessment of Hg-polluted soils.

Accumulation of mercury in Typha domingensis under field conditions

Typha species is a common wetland plant used in the treatment of urban and industrial effluents. But, despite their widespread implementation, there are not many studies based on the behaviour of this plant growing in an areas affected by mercury. The present work investigates the ability of Typha domingensis to accumulate mercury under field conditions. The study area was along the Valdeazogues river which flows through the Almadén mining district (Ciudad Real, Spain) that is considered the largest mercury reservoir in the world. The mercury concentration in different plant fractions was measured as well as the available and total concentration in the bottom sediments. The results showed that the highest mercury concentrations were found in the belowground organs. T. domingensis had a high efficiency to accumulate mercury in their organs although available metal concentrations in the environment did not exceed 0.16 mg kg(-1). Bioaccumulation factors (BAF) ranged between 121 and 3168 in roots. Furthermore, significant correlations were found between mercury concentration in all plant organs and Hg in sediments (both total and available). These results demonstrated that T. domingensis could be used as a biomonitor as well as in phytoextraction technology in areas affected by mercury.

Mercury leaching from hazardous industrial wastes stabilized by sulfur polymer encapsulation

European Directive 2013/39/EU records mercury as a priority hazardous substance. Regulation n° 2008/1102/EC banned the exportation of mercury and required the safe storage of any remaining mercury compounds. The present work describes the encapsulation of three wastes containing combinations of HgS, HgSe, HgCl2, HgO2, Hg3Se2Cl2, HgO and Hg(0), according to patent of Spanish National Research Council WO2011/029970A2. The materials obtained were subjected to leaching tests according to standards UNE-EN-12457 and CEN/TS 14405:2004. The results are compared with the criteria established in the Council Decision 2003/33/EC for the acceptance of waste at landfills. The Hg concentrations of all leachates were <0.01mgHg/kg for a liquid/solid ratio of 10l/kg. All three encapsulated materials therefore meet the requirements for storage in inert waste landfills.

Fast method for the simultaneous determination of monomethylmercury and inorganic mercury in rice and aquatic plants

Recent investigations revealed that monomethylmercury (MMHg) can be absorbed and accumulated by plants, i.e. rice crops, thus becoming an important route of human exposure to MMHg through diet. The increasing concern about this fact makes that appropriate analytical methods for Hg speciation in these samples are urgently required. Therefore, the aim of this work has been the development of a fast and sensitive method which enables the simultaneous determination of MMHg and inorganic Hg in rice and aquatic plants. The proposed methodology is based on the extraction of Hg species by closed-vessel microwave heating, subsequent derivatization by ethylation and analysis by gas chromatography coupled to atomic fluorescence detection via pyrolysis (GC-pyro-AFS). A careful optimization of the extraction, using both acid (6N HNO3) and alkaline (tetramethylammonium hydroxide, TMAH) extractants, and derivatization conditions has been carried out. Spiked and unspiked aquatic plants (Typha domingensis) and CRMs certified for Total-Hg (BCR-60, BCR-482 and NCS ZC73027, corresponding to aquatic plant, lichen and rice, respectively) have been used. Under the final optimized conditions the simultaneous determination of MMHg and inorganic Hg can be carried out in less than 40min with no tedious clean-up steps. Quantitative recoveries (from 92% to 101%) were obtained in aquatic plants (Typha domingensis) and CRMs spiked with known concentrations of MMHg. For unspiked BCR-60 and BCR-482, no statistically significant differences (p=0.05) were found in Total-Hg concentrations between those obtained by the sum of species and the certified values for both acid and alkaline extraction. For the analysis of low Hg polluted samples, an additional preconcentration step by evaporation under nitrogen stream was required but adequate blanks were only obtained for acid extraction. Detection limits in the low ng/g range (0.7-1.0ng/g) were consequently achieved for both Hg species in the case of acid extraction and the analysis of NCS ZC73027 gave satisfactory results without statistically significant differences between the found and certified values (p = 0.05).

Estudio cinético, en condiciones no-isotérmicas, de la desorción térmica del mercurio en suelos contaminados

The Almadén mining district (Ciudad Real, Spain) was the largest cinnabar (mercury sulphide) mine in the world. Its soils have high levels of mercury a consequence of its natural lithology, but often made much worse by its mining history. The present work examines the thermal desorption of two contaminated soils from the Almadén area under non-isothermal conditions in a N2 atmosphere, using differential scanning calorimetry (DSC). DSC was performed at different heating rates between room temperature and 600 °C. Desorption temperatures for different mercury species were determined. The Friedman, Flynn-Wall-Ozawa and Coasts–Redfern methods were employed to determine the reaction kinetics from the DSC data. The activation energy and pre-exponential factor for mercury desorption were calculated.

Cultivation OF Solanum tuberosum in a former mining district for a safe human consumption integrating simulated digestion

BACKGROUND Potato (Solanum tuberosum) is a global crop and by far the most important non-cereal crop in the world. Therefore, it is necessary to assure its safe consumption. This is especially relevant in the case of its cultivation in abandoned mining areas, where the population tends to return to agriculture. In the present work, the objective is to evaluate the contribution to the diet of nutrients and contaminants of potato grown in soils from the Almadén area (mining district) by studying the intestinal absorption (in vitro) of the tuber, taking into account the preparation methods for its consumption. RESULTS The results of contaminant and nutrient contents show that the potato peel retains significantly more elements (mainly in the case of toxic elements) than the flesh. Furthermore, potato (peel and flesh) is a good source of iron. CONCLUSION It is recommended to boil potatoes with the peel in order to minimize nutrient loss and, before consumption, peeling them to eliminate possible risks due to contaminants. In addition, to minimize the risk due of mercury and to improve the levels of calcium, magnesium, potassium and sodium, it is recommended to add salt during the boiling process.

Mercury species accumulation and distribution in Typha domingensis under real field conditions (Almadén, Spain)

Monomethylmercury (MeHg) is one of the most toxic and the most commonly occurring organomercury compound and the wetlands are one of the main areas of generation of this Hg form. Concretely, it is in the macrophyte root system where better conditions are given for its generation. However, the knowledge of absorption and subsequent distribution of mercury (Hg) and monomethylmercury in aquatic plants is still limited. Mercury mining district such as Almadén (Ciudad Real, Spain) is a natural laboratory where different rivers flow and the species Typha domingensis Pers. is a common macrophyte which grows in their riverbanks. The aim of the present work is to apply a recently developed method specially designed to analyze Hg species in plant tissues to the different fractions of T. domingensis under real field conditions and to study the accumulation and distribution of Hg species (inorganic Hg and MeHg) within the plant. The results proved that whatever Hg species has preference to be accumulated in the belowground fractions and demonstrated a high efficiency in the accumulation of MeHg.

Application of Multi-Sensor Optical Data for Monitoring Land Uses within the Mercury Mining Area of Almadén, Spain

The largest mercury concentration is situated in Almaden, Spain. Mining activities have dominated in the region till the closure of the mines in 2002 and alternative land use has gained importance after the mining activities ceased. The rehabilitation of areas affected by the mining are the main priority within the region. The objective is to identify and monitor abiotic and biotic characteristics of the region affected by mining activities as well as alternative human-induced activities. Multi-senor data are implemented to carry out a regional characterization. Advanced image processing procedures obtain detailed information from hyperspectral data and this information is implemented in the multispectral data to monitor the different land uses. Monitoring results show that the distribution of areas affected by mining activities is rapidly diminishing in the most recent years.