Mercury distribution in plants and soils from the former mining area of Abbadia San Salvatore (Tuscany, Central Italy).

The distribution of heavy metals in plants (Castanea sativa, Sambucus nigra, Verbascum thapsus, Popolus spp., Salix spp., Acer pseudoplatanus, Robinia pseudoacacia) growing in soils from active and abandoned mining areas is of scientific significance as it allows to recognize their ability to survive in a hostile environment and provide useful indications for phytoremediation operations. In this work, soils from the former Hg-mining area of Abbadia San Salvatore (Tuscany, Central Italy) were analyzed for total, leached Hg, % of organic and inorganic-related Hg. The dehydrogenase enzyme activity (DHA) was also measured with the aim to evaluate the status of the soil, being characterized by high Hg contents (up to 1068 mg kg-1). Eventually, the concentration of Hg in the different parts of the plants growing on these soils was also determined. Most studied soils were dominated by inorganic Hg (up to 92%) while the DHA concentrations were < 151 µg TPF g-1 day-1, suggesting that the presence of Hg is not significantly affecting the enzymatic soil activity. This is also supported by the bioaccumulation factor (BF), being predominantly characterized by values < 1. Sambucus nigra and Verbascum thapsus had the highest Hg contents (39.42 and 54.54 mg kg-1, respectively). The plant leaves appear to be the main pathways of Hg uptake, as also observed in other mining areas, e.g., Almadèn (Spain), indicating that particulate-Hg and Hg0 are the main forms entering the plant system, the latter derived by the GEM emitted by both the edifices hosting the roasting furnaces and the soils themselves.

Mercury distribution in plants and soils from the former mining area of Abbadia San Salvatore (Tuscany, central Italy).

The distribution of heavy metals in plants growing in soils from active and abandoned mining areas is of scientific significance as it allows one to recognize their ability to survive in a hostile environment and to provide useful indications for phytoremediation operations. In this work, soils developed in the former Hg-mining area of Abbadia San Salvatore (Tuscany, Central Italy) were analyzed for total, leached Hg, % of organic- and inorganic-related Hg. The dehydrogenase enzyme activity (DHA) was also measured with the aim to evaluate the status of the soil, being characterized by high Hg content. Eventually, the concentration of Hg in the different parts of the plants growing on these soils was analyzed. The soils showed Hg content up to 1068 mg kg - 1 and in most of them is dominated by inorganic Hg (up to 92%). The DHA concentrations were < 151 µg TPF g - 1 day - 1 , suggesting that the presence of Hg is not significantly affecting the enzymatic soil activity. This is also supported by the bioaccumulation factor (BF) that is < 1 in most of the studied plants. Generally speaking, the plant leaves appear to be one of the main pathways of Hg uptake, as also observed in other mining areas, e.g. Almaden (Spain), suggesting that particulate-Hg and Hg 0 are the main forms entering the plant system, the latter derived by the GEM emitted by both the edifices hosting the roasting furnaces and the soils themselves.

Biogeochemical assessment of the impact of Zn mining activity in the area of the Jebal Trozza mine, Central Tunisia.

Soil pollution associated with potentially toxic elements (PTEs) from mining residues is a significant problem worldwide. The decommissioned Jebal Trozza mine, located in central Tunisia, may pose a serious problem because of the possible high concentrations of PTEs present in its wastes. This mine is a potential source of contamination for agriculture in this area due to both direct causes (pollution of agricultural soils) and indirect causes (pollution of sediments that accumulate in a dam used for irrigation). The aim of the study reported here was to assess the effects of local mining activity in two respects: (1) in terms of soil quality, as determined by soil edaphological parameters and PTEs contents in the mining wastes and local soils; and (2) in terms of biological quality, as evaluated by quantification of enzymatic activity as an indicator of bacterial activity in soils and wastes. The mine tailings contained high levels of Pb (1.83-5.95%), Zn (7.59-12.48%) and Cd (85.95-123.25 mg kg-1). The adjacent soils were also highly contaminated with these elements, with average concentrations of Pb, Zn and Cd that exceeded the European standard values for agricultural soils (3, 300 and 300 mg kg-1 for Cd, Pb and Zn, respectively). Enzymatic dehydrogenase showed zero activity in waste piles and very low activity in PTE-contaminated soils, but this activity returned to normal values as the pollution decreased, thus demonstrating the effect that the contamination load had on the health of the studied soils. A Statistical Factor Analysis clearly distinguished three groups of samples, and these are related to the influence that mining on the soils and sediments had on the PTE concentrations and their effects on the biological quality of the soil. An environmental assessment based on the enrichment factor criteria indicated risk levels that varied from strongly to severely polluted. The risk appears to be greater close to the mine, where the highest PTE levels were determined.

Experimental assessment of the daily exchange of atmospheric mercury in Epipremnum aureum.

Mercury (Hg) exchange at the plant leaf-atmosphere interface is an important issue when considering vegetation as a sink or source of this global pollutant. The aim of the study described here was to clarify this process by studying Hg exchange under laboratory conditions with a plant model, namely Epipremnum aureum. The desorption and absorption processes were studied under similar conditions in natural daylight. Hg exchange was measured at the foliar surface, and micrometeorological parameters and stomatal conductance were assessed. The results of the Hg exchange study showed different rhythms for the two processes, i.e. desorption (14-196 ng m-2 day-1) was slower than absorption (170-1341 ng m-2 day-1). The daily cycle was more complex in the desorption process, with a maximum when stomatal conductance was high but also with high values during nocturnal hours and a trend to absorption in the mornings. The daily absorption cycles were relatively simple, with values that coincided with positive stomatal conductance values and null values during nocturnal hours. The main factors involved in desorption were stomatal conductance and temperature, but other factors may need to be considered. The absorption process only involved total gaseous Hg, stomatal conductance and relative humidity. A net balance of the two experiments provided data on the amount of Hg transferred per unit leaf area (167 ng m-2 for desorption and 9213 ng m-2 for absorption), which implies total amounts of 23 ng of Hg desorbed and 1280 ng absorbed during the whole experiment. Finally, the reversible/non-reversible nature of the Hg exchange process must be reconsidered bearing in mind that Hg within the leaf can be emitted if changes in ambient conditions are appropriate to favour this process.

Particulate matter and particulate-bound mercury in a heavily polluted site related to ancient mining and metallurgy: a proposal for dry deposition modeling based on micrometeorological conditions.

This manuscript reported data for total suspended particulate matter (TSPM), particle-bound mercury (PBM), and total gaseous mercury (TGM) in Almadenejos, a rural zone of ancient Hg mining and metallurgical works. Concentrations of TSPM characterize the study site as being a rural area, with levels below 40 µg m-3 during most of the year and sporadic events involving dust intrusions from Africa. Mercury speciation of PM and nearby soils, which contain both cinnabar and organic Hg, confirms that the PM comes from local soil emissions involving the soils polluted by ancient metallurgical works. Conversely, PBM and TGM levels (average 1.8 ng m-3 and 88 ng m-3, respectively) define Almadenejos as a contaminated site similar to urban areas. A multiple linear regression analysis showed that evapotranspiration is the micrometeorological parameter that best explains the TSPM and PBM data, with the creation of a diurnal mixing layer being the main process involved in Hg emissions in the solid and gaseous states. Based on these findings, a micrometeorological-based model has been developed to acquire a complete set of daily PBM data and these were used to obtain dry deposition rates (317 µg m-2 year-1), which were seasonally distributed as 40% in summer, 33% in autumn, 16% in spring, and 11% in winter. In addition, an estimation of PBM emissions showed that 335 g year-1 can be suspended in the Almadenejos environment. A large proportion of this PBM should be removed from the atmosphere through dry deposition in a continuous Hg exchange at the soil-atmosphere interface. Mercury fractionation (cinnabar and organic Hg) can increase the risk to the human population and nearby ecosystems of Almadenejos.

The role of native lichens in the biomonitoring of gaseous mercury at contaminated sites.

Contamination by atmospheric mercury has been assessed in two different areas from Spain (Las Cuevas, Ciudad Real and Flix, Tarragona) using lichens as biomonitors. The relationship established between mercury contents in the soils and the gaseous mercury (GM) was also observed. It was found that the GM is highest in the vicinity of the source and it is dispersed depending on of the distance to the source and the wind directions. The mercury concentration in the gas phase in Flix was higher than that found in Las Cuevas and also higher than the value that the US EPA recommended. The mercury bioaccumulation in the native lichens from genders Ramalina and Xanthoria were used as biomonitors for absorbing mercury in Las Cuevas and Flix, respectively. The mercury uptake by Ramalina was higher than the amount accumulated by Xanthoria, a difference that was mainly due to the lichen characteristics. The content of mercury in lichens in relation to the mercury in gas was fitted by a Freundlich type equation, indicating that the equilibrium between both phases was established. Besides, transplanted Ramalina lichen in Las Cuevas allowed to obtain the kinetic of mercury uptake. A kinetic model of first order based on the equilibrium was proposed and the mass transfer constants for each sampling station were estimated. As it was expected, these values increased with the predominant wind flow direction.

Mercury transfer from soil to olive trees. A comparison of three different contaminated sites.

Mercury contents in soil and olive tree leaves have been studied in 69 plots around three different source areas of this element in Spain: Almadén (Ciudad Real), Flix (Tarragona) and Jódar (Jaén). Almadén was the world's largest cinnabar (HgS) mining district and was active until 2003, Flix is the oldest Spanish chlor-alkali plant (CAP) and has been active from 1898 to the present day and Jódar is a decommissioned CAP that was active for 14 years (1977-1991). Total mercury contents have been measured by high-frequency modulation atomic absorption spectrometry with Zeeman effect (ZAAS-HFM) in the soils and olive tree leaves from the three studied areas. The average soil contents range from 182 µg kg(-1) in Flix to 23,488 µg kg(-1) in Almadén, while the average leaf content ranges from 161 µg kg(-1) in Jódar to 1213 µg kg(-1) in Almadén. Despite the wide range of data, a relationship between soil-leaf contents has been identified: in Almadén and Jódar, multiplicative (bilogarithmic) models show significant correlations (R = 0.769 and R = 0.484, respectively). Significant correlations were not identified between soil and leaf contents in Flix. The continuous activity of the Flix CAP, which remains open today, can explain the different uptake patterns for mercury, which is mainly atmospheric in origin, in comparison to the other two sites, where activity ceased more than 10 years ago and only soil uptake patterns based on the Michaelis-Menten enzymatic model curve are observed.

Heavy metal contamination in sediments of an artificial reservoir impacted by long-term mining activity in the Almadén mercury district (Spain).

Sediments from the Castilseras reservoir, located downstream on the Valdeazogues River in the Almadén mercury district, were collected to assess the potential contamination status related to metals(oids) associated with river sediment inputs from several decommissioned mines. Metals(oids) concentrations in the reservoir sediments were investigated using different physical and chemical techniques. The results were analyzed by principal component analysis (PCA) to explain the correlations between the sets of variables. The degree of contamination was evaluated using the enrichment factor (EF) and the geoaccumulation index (Igeo). PCA revealed that the silty fraction is the main metals(oids) carrier in the sediments. Among the potentially harmful elements, there is a group (Al, Cr, Cu, Fe, Mn, Ni, and Zn) that cannot be strictly correlated to the mining activity since their concentrations depend on the lithological and edaphological characteristics of the materials. In contrast, As, Co, Hg, Pb, and S showed significant enrichment and contamination, thus suggesting relevant contributions from the decommissioned mines through fluvial sediment inputs. As far as Hg and S are concerned, the high enrichment levels pose a question concerning the potential environmental risk of transfer of the organic forms of Hg (mainly methylmercury) from the bottom sediments to the aquatic food chain.

An estimation of mercury concentrations in the local atmosphere of Almadén (Ciudad Real Province, South Central Spain) during the twentieth century.

We show the first estimations of long-term (100 years, 1900 to 2000) total gaseous mercury concentrations (TGM) in the urban area of Almadén. The estimation was carried out by comparing data on known metallic mercury production with measured TGM concentrations. The estimated diurnal background level ranges from 60 to 120 ng m(-3) and corresponds to periods when the metallurgical complex (cinnabar roasting plant) was shut down. The average TGM concentration during the period from 1900 to 2000 was about 600 ng m(-3) (with peaks above 1,200 ng m(-3)). Additionally, a 24-h-based TGM monitoring program has highlighted significant differences between the diurnal and nocturnal concentrations, particularly during the warmer months. In this regard, given that the average nocturnal to diurnal ratio is 2.12, we suggest that the average nocturnal concentrations must have exceeded 1,200 ng m(-3), and peak nocturnal concentrations could have reached levels up to 2,400 ng m(-3). Our estimations indicate that most parts of the town of Almadén were generally exposed to TGM concentrations in air that exceed the World Health Organization air quality guideline for Hg (1,000 ng m(-3)) for countryside and urban areas.

Lupinus albus plants acquire mercury tolerance when inoculated with an Hg-resistant Bradyrhizobium strain.

One strain of Bradyrhizobium canariense (L-7AH) was selected for its metal-resistance and ability to nodulate white lupin (Lupinus albus L.) plants, from a collection of rhizobial strains previously created from soils of the Almadén mining district (Spain) with varying levels of Hg contamination. Plants were inoculated with either strain L-7AH (Hg-tolerant) or L-3 (Hg-sensitive, used as control), and watered with nutrient solutions supplemented with various concentrations (0-200 µM) of HgCl2 in a growth chamber. L. albus inoculated with L-7AH were able to nodulate even at the highest concentration of Hg while those inoculated with L-3 had virtually no nodules at Hg concentrations above 25 µM. Plants inoculated with L-7AH, but not those with the control strain, were able to accumulate large amounts of Hg in their roots and nodules. Nodulation with L-7AH allowed plants to maintain constant levels of both chlorophylls and carotenoids in their leaves and a high photosynthetic efficiency, whereas in those inoculated with L-3 both pigment content and photosynthetic efficiency decreased significantly as Hg concentration increased. Nitrogenase activity of plants nodulated with L-7AH remained fairly constant at all concentrations of Hg used. Results suggest that this symbiotic pair may be used for rhizoremediation of Hg-contaminated soils.

In vitro studies evaluating leaching of mercury from mine waste calcine using simulated human body fluids.

In vitro bioaccessibility (IVBA) studies were carried out on samples of mercury (Hg) mine-waste calcine (roasted Hg ore) by leaching with simulated human body fluids. The objective was to estimate potential human exposure to Hg due to inhalation of airborne calcine particulates and hand-to-mouth ingestion of Hg-bearing calcines. Mine waste calcines collected from Hg mines at Almaden, Spain, and Terlingua, Texas, contain Hg sulfide, elemental Hg, and soluble Hg compounds, which constitute primary ore or compounds formed during Hg retorting. Elevated leachate Hg concentrations were found during calcine leaching using a simulated gastric fluid (as much as 6200 microg of Hg leached/g sample). Elevated Hg concentrations were also found in calcine leachates using a simulated lung fluid (as much as 9200 microg of Hg leached/g), serum-based fluid (as much as 1600 microg of Hg leached/g), and water of pH 5 (as much as 880 microg of Hg leached/g). The leaching capacity of Hg is controlled by calcine mineralogy; thus, calcines containing soluble Hg compounds contain higher leachate Hg concentrations. Results indicate that ingestion or inhalation of Hg mine-waste calcine may lead to increased Hg concentrations in the human body, especially through the ingestion pathway.

Mercury speciation and microbial transformations in mine wastes, stream sediments, and surface waters at the Almadén Mining District, Spain.

Speciation of Hg and conversion to methyl-Hg were evaluated in mine wastes, sediments, and water collected from the Almadén District, Spain, the world's largest Hg producing region. Our data for methyl-Hg, a neurotoxin hazardous to humans, are the first reported for sediment and water from the Almadén area. Concentrations of Hg and methyl-Hg in mine waste, sediment, and water from Almadén are among the highestfound at Hg mines worldwide. Mine wastes from Almadén contain highly elevated Hg concentrations, ranging from 160 to 34,000 microg/g, and methyl-Hg varies from <0.20 to 3100 ng/g. Isotopic tracer methods indicate that mine wastes at one site (Almadenejos) exhibit unusually high rates of Hg-methylation, which correspond with mine wastes containing the highest methyl-Hg concentrations. Streamwater collected near the Almadén mine is also contaminated, containing Hg as high as 13,000 ng/L and methyl-Hg as high as 30 ng/L; corresponding stream sediments contain Hg concentrations as high as 2300 microg/g and methyl-Hg concentrations as high as 82 ng/g. Several streamwaters contain Hg concentrations in excess of the 1000 ng/L World Health Organization (WHO) drinking water standard. Methyl-Hg formation and degradation was rapid in mines wastes and stream sediments demonstrating the dynamic nature of Hg cycling. These data indicate substantial downstream transport of Hg from the Almadén mine and significant conversion to methyl-Hg in the surface environment.