Mobility of antimony in contrasting surface environments of a mine site: influence of redox conditions and microbial communities.

Microbial processes can influence the complex geochemical behaviour of the toxic metalloid antimony (Sb) in mining environments. The present study is aimed to evaluate the influence of microbial communities on the mobility of Sb from solid phases to water in different compartments and redox conditions of a mining site in southwest (SW) Spain. Samples of surface materials presenting high Sb concentrations, from two weathered mining waste dumps, and an aquatic sediment were incubated in slurries comparing oxic and anoxic conditions. The initial microbial communities of the three materials strongly differed. Incubations induced an increase of microbial biomass and an evolution of the microbial communities' structures and compositions, which diverged in different redox conditions. The presence of active bacteria always influenced the mobility of Sb, except in the neutral pH waste incubated in oxic conditions. The effect of active microbial activities in oxic conditions was dependent on the material: Sb oxic release was biologically amplified with the acidic waste, but attenuated with the sediment. Different bacterial genera involved in Sb, Fe and S oxidation or reduction were present and/or grew during incubation of each material. The results highlighted the wide diversity of microbial communities and metabolisms at the small geographic scale of a mining site and their strong implication in Sb mobility.

An approach for evaluating the bioavailability and risk assessment of potentially toxic elements using edible and inedible plants-the Remance (Panama) mining area as a model.

Mining affects the environment, particularly through the persistence of accumulation of tailings materials; this is aggravated under tropical climatic conditions, which favours the release of potentially toxic elements (PTEs) bioavailable to the local flora and fauna and supposing a risk to human health. The Remance gold mine (Panamá), exploited intermittently for more than 100 years, and has remained derelict for over 20 years. Within the area live farmers who carry out subsistence agriculture and livestock activities. The objective of this study has been to study the transference of PTEs in the local agricultural soil-plants system, with the goal of identifying their bioavailability to perform a human risk assessment. The results obtained of the Bioaccumulation coefficient in local plants show very weak to strong absorption of As (< 0.001-1.50), Hg (< 0.001-2.38), Sb (0.01-7.83), Cu (0.02-2.89), and Zn (0.06-5.32). In the case of Cu in grass (18.3 mg kg-1) and plants (16.9 mg kg-1) the concentrations exceed the maximum authorised value in animal nutrition for ruminants (10 mg kg-1). The risk to human health for edible plants exceeds the non-carcinogenic risk for rice, corn, cassava, and tea leaves for Sb (HQ 19.450, 18.304, 6.075, 1.830, respectively), the carcinogenic risk for Cu (CR = 2.3 × 10-3, 7.7 × 10 -4, 1.1 × 10-3, 1.0 × 10-3, respectively), and the carcinogenic risk for As in rice, corn and tea leaves (CR = 8 × 10-5, 3 × 10-5, 3 × 10-5, respectively). Urgent measures are needed to alleviate these effects.

Evaluation of antimony availability in a mining context: Impact for the environment, and for mineral exploration and exploitation.

This work aims to establish Sb mobility, its transfer to biota and its effect on soil health in a semi-arid climate. The results show the presence of stibnite (Sb2S3) as the main primary Sb compound, bindhemite (Pb2Sb2O6(O,OH)), and minor proportions of stibiconite (Sb3+(Sb5+)2O6(OH)) as oxidised Sb species. This research also observes very high total Sb contents in mining materials (max: 20,000 mg kg-1) and soils (400-3000 mg kg-1), with physical dispersion around mining materials restricted to 450 m. The soil-to-plant transfer is very low, (bioaccumulation factor: 0.0002-0.1520). Most Sb remains in a residual fraction (99.9%), a very low fraction is bound to Fe and Mn oxy-hydroxides or organic matter, and a negligible proportion of Sb is leachable. The higher Sb mobility rates has been found under oxidising conditions with a long contact time between solids and water. The main factors that explain the poor Sb mobility and dispersion in the mining area are the low annual rainfall rates that slow down the Sb mobilisation process and the scarce formation of oxidised Sb compounds. All these data suggest poor Sb (III) formation and a low toxicological risk in the area associated with past mining activities. The low mobility of Sb suggests advantages for future sustainable mining of such ore deposits in a semi-arid climate and is also indicative of the limitations of geochemical exploration in the search for new Sb deposits.

Ecological and Health Risk Assessments of an Abandoned Gold Mine (Remance, Panama): Complex Scenarios Need a Combination of Indices.

The derelict Remance gold mine is a possible source of pollution with potentially toxic elements (PTEs). In the study area, diverse mine waste has been left behind and exposed to weather conditions, and poses risks for soil, plants and water bodies, and also for the health of local inhabitants. This study sought to perform an ecological and health risk assessment of derelict gold mining areas with incomplete remediation, including: (i) characterizing the geochemical distribution of PTEs; (ii) assessing ecological risk by estimating the pollution load index (PLI) and potential ecological risk index (RI); (iii) assessing soil health by dehydrogenase activity; and iv) establishing non-carcinogenic (HI) and carcinogenic risks (CR) for local inhabitants. Soil health seems to depend on not only PTE concentrations, but also on organic matter (OM). Both indexes (PLI and RI) ranged from high to extreme near mining and waste accumulation sites. As indicated by both the HI and CR results, the mining area poses a health risk for local inhabitants and particularly for children. For this reason, it will be necessary to set up environmental management programs in the areas that are most affected (tailings and surrounding areas) and accordingly establish the best remediation strategies to minimize risks for the local population.

Occurrence and environmental constraints of gray monazite in red soils from the Campo de Montiel area (SW Ciudad Real province, south central Spain).

Monazite ((Ce, La, Nd, Th) PO4) is a rare and strategic mineral that occurs naturally as an accessory and minor mineral in diverse igneous and metamorphic rocks. This mineral does not frequently form mineable ore deposits and it has different typologies, including those formed by endogenous processes (generally "yellow monazite" mineralizations) and those formed by exogenous processes ("gray monazite" mineralizations). The mineral is an important ore of Rare Earth Elements (REEs), which have been identified by the European Union as critical raw materials. Monazite can be considered a weathering-resistant mineral, and the mobility of the REE and associated elements is low. The study reported here concerns a mineralogical and geochemical assessment of the occurrence and risks associated with the presence of concentrations of monazite in a typical, well-developed, and representative red Mediterranean soil, in order to establish the associated risk with their future mining. The results confirmed that monazite ore is particularly poor in radioactive elements, and it is concentrated in the most surficial soil horizons. The chemical mobility of REEs present in the soil, as assessed by selective extraction with ammonium acetate in acidic media, follows the order Y > Dy > U > Tb > Gd > Eu > Sm > La > Th > Ce. The mobility of REEs contained in monazite proved to be higher than that of the REE compounds in the upper horizons of the soil profile suggesting the immobilization in other REE-containing minerals, while light REEs show lower mobility rates than heavy REEs, due to an immobilization of LREE by sorption with iron oxy-hydroxides. Further studies are required in order to obtain better speciation data for REEs in soils aimed to identify soluble and insoluble compounds.

Evolution of the Speciation and Mobility of Pb, Zn and Cd in Relation to Transport Processes in a Mining Environment.

Elements in mining extracts can be potentially toxic if they are incorporated into soils, sediments or biota. Numerous approaches have been used to assess this problem, and these include sequential extractions and selective extractions. These two methods have limitations and advantages, and their combined use usually provides a rough estimate of the availability or (bio)availability of potentially toxic elements and, therefore, of their real potential as toxicants in food chains. These indirect speciation data are interesting in absolute terms, but in the work described here, this aspect was developed further by assessing the evolution of availability-related speciation in relation to the transport processes from the emission source, which are mainly fluvial- and wind-driven. This objective was achieved by characterizing tailings samples as the source of elements in soils and sediments at increasing distances to investigate the evolution of certain elements. The standard procedures employed included a sequential five-step extraction and a selective extraction with ammonium acetate. The results show that the highest percentages of Zn and Pb in tailings, soils and sediment samples are associated with oxyhydroxides, along with a significant presence of resistant mineralogical forms. In the case of Cd, its association with organic matter is the second-most important trapping mechanism in the area. The physicochemical mechanisms of transport did not transform the main mineralogical associations (oxyhydroxides and resistant mineralogical forms) along the transects, but they produced a chaotic evolution pattern for the other minor matrix associations for Zn and a decrease in exchangeable and carbonate-bound forms for Pb in soils. Interestingly, in sediments, these mobile forms showed a decrease in Zn and a chaotic evolution for Pb. The most probable reason for these observations is that Zn2+ can form smithsonite (ZnCO3) or hydrozincite (Zn5(CO3)2(OH)6), which explains the retention of a carbonate-bound form for Zn in the soil transect. In contrast, Pb and Cd can appear as different mineral phases. The order of (bio)availability was Pb > Zn > Cd in tailings but Cd > Pb > Zn in soils. The physicochemical processes involved in transport from tailings to soils produce an increase in Cd (bio)availability. The trend is a decrease in bioavailability on moving away from the source (tailings), with maximum values obtained for Cd near to the source area (200-400 m).

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.

Antigerminative comparison between naturally occurring naphthoquinones and commercial pesticides. Soil dehydrogenase activity used as bioindicator to test soil toxicity.

As important secondary plant metabolites, naphthoquinones exhibit a wide range of biological activities, and one of their roles in the competition among plants is a well-known process called allelopathy. Their potential as a sustainable alternatives to herbicides has been investigated. In this study, we aim to take advantage of these naturally occurring substances to control the germination of spontaneous flora. In this work, the sensitivity of the germination of different plant species (horticultural, grasses and spontaneous flora) was tested. The results indicate that most of the plants are sensitive to juglone. The comparison between naphthoquinones and commercial pesticides did not provide enough evidence to use naphthoquinones to control spontaneous flora. Assessing the toxicity of pesticides is crucial because the sustainability of the ecosystem could be endangered by their use. In this study, the toxicity of certain pesticides (metam Na, oxyfluorfen, glyphosate, metribuzin and diuron) was evaluated based on dehydrogenase activity (DHA). DHA has become a good bioindicator for assessing the toxicity of xenobiotics. A toxicity index was proposed to compare the different degrees of toxicity among the tested substances. Finally, a toxicity threshold was constructed using the slopes of the fitted lines of the data, assuming that the maximum toxicity (10) represented the slope of the biocide HgCl2 and that the minimum toxicity (1) was attributed to the DHA obtained from soil without pesticides.

Geochemical distribution of major and trace elements in agricultural soils of Castilla-La Mancha (central Spain): finding criteria for baselines and delimiting regional anomalies.

Castilla-La Mancha (central Spain) is a region characterized by significant agricultural production aimed at high-quality food products such as wine and olive oil. The quality of agricultural products depends directly on the soil quality. Soil geochemistry, including dispersion maps and the recognition of baselines and anomalies of various origins, is the most important tool to assess soil quality. With this objective, 200 soil samples were taken from agricultural areas distributed among the different geological domains present in the region. Analysis of these samples included evaluation of edaphological parameters (reactivity, electrical conductivity, organic matter content) and the geochemistry of major and trace elements by X-ray fluorescence. The dataset obtained was statistically analyzed for major elements and, in the case of trace elements, was normalized with respect to Al and analyzed using the relative cumulative frequency (RCF) distribution method. Furthermore, the geographic distribution of analytical data was characterized and analyzed using the kriging technique, with a correspondence found between major and trace elements in the different geologic domains of the region as well as with the most important mining areas. The results show an influence of the clay fraction present in the soil, which acts as a repository for trace elements. On the basis of the results, of the possible elements related with clay that could be used for normalization, Al was selected as the most suitable, followed by Fe, Mn, and Ti. Reference values estimated using this methodology were lower than those estimated in previous studies.

Factors influencing mercury uptake by leaves of stone pine (Pinus pinea L.) in Almadén (Central Spain).

The use of trees for biomonitoring of mercury (Hg) and other atmospheric pollutants is of increasing importance today. Leaves from different species have been the most widely used plant organ for this purpose, but only pine bark, and not leaves, was used to monitor Hg pollution. In Almadén (South Central Spain), the largest cinnabar (HgS) deposits in the world have been mined for over 2000 years to obtain metallic Hg and this activity has caused the widespread dispersion of this toxic element in the local environment. A strip of pine trees, 2750 m in length, adjacent and to the South of the mining town has been studied in order to evaluate pine tree needles as monitors for Hg contamination in this heavily polluted area. The study involved the collection of pine tree leaves from several discrete sites along the strip, as well as samples from other nearby locations, together with soil samples and monitoring of atmospheric Hg in the area during both the day and night. Leaves and soils were analyzed for total Hg concentration by means of atomic absorption spectrometry; the leachable fraction of soil Hg was also analyzed by the CV-AFS technique. The results indicate that soils from the investigated area were not directly affected by mining related pollution, with low total Hg levels (3-280 mg kg-1) found in comparison with the nearby Almadén metallurgical precinct and very low leachable Hg contents (0.27-59.65 mg kg-1) were found. Moreover, pine tree needles have a low uptake capacity, with lower THg levels (0.03-6.68 mg kg-1) when compared to those of olive trees in Almadén. However, pine needles do show significant variability with regard to the distance from the source. Gaseous Hg exhibits a similar pattern, with higher levels close to the source, especially during night time (225 ng m-3). A multiple linear regression analysis (MLRA) revealed that gaseous Hg in the nocturnal period is the prime factor that influences the amount of Hg uptake by pine tree needles. This finding makes pine needles a promising candidate to biomonitor gaseous Hg on a local or regional scale worldwide. Almadén pine tree needles have been exposed to a number of different Hg sources, including the primary one, namely the old mine dump, and secondary sources such as polluted roads or illegal urban residual waste. The secondary sources cause some minor discrepancies in the model established by the MRLA. The biomonitoring capacity of pine needles needs to be evaluated in areas far from the source. The process involved in gaseous Hg uptake by pine needles appears more likely to involve sorption in the external part of the needle than uptake through stomas, thus making this process strongly dependent on high atmospheric Hg concentrations.

Industrial and natural sources of gaseous elemental mercury in the Almadén district (Spain): an updated report on this issue after the ceasing of mining and metallurgical activities in 2003 and major land reclamation works.

Two events during the last decade had major environmental repercussions in Almadén town (Spain). First it was the ceasing of activities in the mercury mine and metallurgical facilities in 2003, and then the finalization of the restoration works on the main waste dump in 2008. The combination of both events brought about a dramatic drop in the emissions of gaseous elemental mercury (GEM) to the atmosphere. Although no one would now call the Almadén area as 'mercury-free', the GEM levels have fallen beneath international reference safety levels for the first time in centuries. This has been a major breakthrough because in less than one decade the site went from GEM levels in the order of "tens of thousands" to mere "tens" nanogram per cubic meter. Although these figures are per se a remarkable achievement, they do not mark the end of the environmental concerns in the Almadén district. Two other sites remain as potential environmental hazards. (1) The Las Cuevas mercury storage complex, a partially restored ex-mining site where liquid mercury is being stored. The MERSADE Project (LIFE-European Union) has tested the Las Cuevas complex as a potential site for the installation of a future European prototype safe deposit of surplus mercury from industrial activities. Despite restoration works carried out in 2004, the Las Cuevas complex can still be regarded as hotspot of mercury contamination, with high concentrations above 800µgg(-1) Hgsoil and 300ngm(-3) Hggas. However, as predicted by air contamination modeling using the ISC-AERMOD software, GEM concentrations fade away in a short distance following the formation of a NW-SE oriented narrow plume extending for a few hundred meters from the complex perimeter. (2) Far more dangerous from the human health perspective is the Almadenejos area, hosting the small Almadenejos village, the so-called Cerco de Almadenejos (CDA; an old metallurgical precinct), and the mines of La Nueva Concepción, La Vieja Concepción and El Entredicho. The CDA is an old metallurgical site that operated between 1794 and 1861, leaving behind a legacy of extremely contaminated soils (mean concentration=4220µgg(-1) Hg) and GEM emissions that in summer can reach levels up to 4,000-5,000ngm(-3). Thus the CDA remains the sole 'urban' site in the district surpassing GEM international reference safety levels. In order to prevent these emissions, the CDA requires immediate action regarding restoration works. These could involve the full removal of soils or their permanent capping to create an impermeable barrier.

XANES speciation of mercury in three mining districts - Almadén, Asturias (Spain), Idria (Slovenia).

The mobility, bioavailability and toxicity of mercury in the environment strongly depend on the chemical species in which it is present in soil, sediments, water or air. In mining districts, differences in mobility and bioavailability of mercury mainly arise from the different type of mineralization and ore processing. In this work, synchrotron-based X-ray absorption near-edge spectroscopy (XANES) has been taken advantage of to study the speciation of mercury in geological samples from three of the largest European mercury mining districts: Almadén (Spain), Idria (Slovenia) and Asturias (Spain). XANES has been complemented with a single extraction protocol for the determination of Hg mobility. Ore, calcines, dump material, soil, sediment and suspended particles from the three sites have been considered in the study. In the three sites, rather insoluble sulfide compounds (cinnabar and metacinnabar) were found to predominate. Minor amounts of more soluble mercury compounds (chlorides and sulfates) were also identified in some samples. Single extraction procedures have put forward a strong dependence of the mobility with the concentration of chlorides and sulfates. Differences in efficiency of roasting furnaces from the three sites have been found.