Biogeochemical prospecting of metallic critical raw materials: soil to plant transfer in SW Ciudad Real Province, Spain.

The soil-plant transfer of trace elements is a complex system in which many factors are involved such as the availability and bioavailability of elements in the soil, climate, pedological parameters, and the essential or toxic character of the elements. The present study proposes the evaluation of the use of multielement contents in vascular plants for prospecting ore deposits of trace elements of strategic interest for Europe. To accomplish this general goal, a study of the soil-plant transfer of major and trace elements using Quercus ilex as a study plant has been developed in the context of two geological domains with very different characteristics in geological terms and in the presence of ore deposits: the Almadén syncline for Hg and the Guadalmez syncline for Sb. The results have made it possible to differentiate geological domains not only in terms of individual elements, but also as a combination of major and trace elements using Factor Analysis. The bioconcentration factors have demonstrated the uptake of macronutrients and micronutrients in very high concentrations but these were barely dependent, or even independent of the concentrations in the soil, in addition to high values of this factor for Sb. The Factor Analysis allowed for the differentiation of geogenic elements from other linked to stibnite ore deposits (Sb, S, and Cu). This element (Sb) can be uptake by Quercus ilex via the root and from there translocating it to the leaves, showing a direct relation between concentrations in soil and plants. This finding opens the possibility of using Quercus ilex leaves for biogeochemical prospecting of geological domains or lithological types of interest to prospect for Sb deposits.

PAH levels in sediments from a coastal area heavily subjected to anthropogenic pressure (Asturias, north of Spain).

Ninety-two sediment samples collected along the Asturias coastline (north of Spain), were studied based on their concentrations of 16PAHs. Concentrations of Σ16PAH showed an average of 12.650 mg kg-1 d.w., which is higher than most other studies conducted around the world. The origins of PAHs present in the sediments are mainly from fuel combustion in industrial processes. The main source of PAH to the coastal system seems to be the Nalón River, which played a significant past role related to different industrial activities, highlighting thermal power stations located in the basin. On the other hand, the Avilés Estuary, hotspot of the regional heavy metallurgical industry was the area with the highest concentrations of Σ16PAH, with an average of 5 to 6 times higher than the rest studied. The risk assessment of Σ16PAH concentrations in the study area showed a high potential risk of contamination transfer to other environmental compartments.

Trace metals from different anthropic sources on the mid-west coast of Asturias: Concentrations, dispersion and environmental considerations.

The central coast of Asturias (Spain), which has suffered significant anthropogenic impacts during the last 150 years, has been studied using 71 sediment samples to establish a preliminary scenario of the geochemical and environmental state of sediments, relating them to their potential sources. In general, As (max 28.5 µg g-1), Cd (max 1.1 µg g-1), Pb (max 123.5 µg g-1) and Zn (max 572 µg g-1) were the elements that presented the greatest concern due to 97.2 % of the sediment samples presented Cd concentrations higher than the regional baseline, 91.5 % of the samples for Zn, 90.1 % for Pb and 78.9 % for As. Additionally, Hg presents a particular case due to the existence of a natural geological anomaly which favours the presence of high concentrations. Nevertheless, anthropic activity contributes with a significant effect on the concentration of this element in the coastal environment.

Surface Microanalysis and Sequential Chemical Extraction as Tools for Reliable Environmental Mobility Assessment of Sb and Other Metals.

Sequential extraction procedures (SEPs) are widely used in environmental studies to infer the chemical and/or mineralogical forms of pollutants of concern in soils and sediments. Although there is no general agreement among the scientific community, these methods have shown some limitations, especially those with a lack of objectivity in their interpretation. In this work, a soil sampling campaign was carried out in an area affected by an abandoned Sb mine. Samples (0-15 cm) were carefully prepared and analyzed by an SEP. They were also studied by conventional mineralogical methods (optical and electronic microscopy, both scanning and transmission, with a coupled energy dispersive X-ray (EDX) spectrometer). When comparing the results obtained from both techniques, some discrepancies are highlighted, with As, Cu, Pb, Sb and Zn as elements of concern. For Sb, Cu, Pb and As the predominant fraction (excluding the residual one) is that associated with organic matter (from 8.54 for Sb to 18.90% for Cu). The fractions of pollutants linked to Fe and/or Mn oxides are quantitatively important for As, Pb and Zn (6.46%, 12.05% and 7.43%, respectively) and almost negligible for Cu and Sb. On the contrary, analyses carried out by EDX at a grain scale pointed out that no detectable quantities of the elements of concern were present on the surface of the organic particles. Sb and Pb were always detectable in Fe oxides (up to 1.84 and 5.76%, respectively). Regarding the role of the clayey fraction, the only disagreement between the employed SEP and the microanalysis is in relation to As. Arsenic bound to clay minerals was found to be an order of magnitude lower than As associated with Fe oxides (0.56% and 6.46%, respectively); in contrast, EDX microanalyses showed similar As contents in both groups. Given the objectiveness of EDX microanalysis, these differences should be considered inaccuracies in the interpretation of the sequential extraction results.

Environmental challenges related to cyanidation in Central American gold mining; the Remance mine (Panama).

Mine tailings are a potential source of environmental pollution because they typically contain potentially toxic elements (PTEs) and the residue of chemical compounds used during extraction processes. The Remance gold mine (NW Panama) is a decommissioned mine with mining activity records dating from the 1800s and several periods of abandonment. Very little remediation work has been performed, and waste is exposed to climatic conditions. This study aimed to evaluate the PTEs and cyanide contents in mine waste after mining operations ceased some 20 years ago, and to evaluate the degree of pollution and the environmental risks they pose with the use of the Pollution Load Index (PLI) and the Ecological Risk Index (RI). Although the total cyanide (T-CN) concentration (1.4-1.9 mg kg-1) found in most of the study area falls within the limits of gold mining tailing values for American sites (1.5-23 mg kg-1), it is worth noting that the values of the tailings of the last used mining operation exceed it (25.2-518 mg kg-1) and persist at the site. The PLI and RI suggest that the tailings from the mine and mine gallery sediments represent a source of pollution for soils and surrounding areas given their high content of PTEs (As, Cu, Sb, Hg) and T-CN, which pose serious ecological risks for biota. Therefore, it is necessary to draw up a remediation plan for this area.

Determination of heavy metal baseline levels and threshold values on marine sediments in the Bay of Biscay.

Several international institutions have defined background or baseline levels to assess heavy metal concentrations on marine sediments in order to use these values as a reference for sediment quality indices. This criterion for marine sediment quality is applied to evaluate the potential risk of pollutants in aquatic ecosystems. However, those values were established using samples collected in large areas which present specific geochemical conditions. Then there may be a lack of accuracy in the results when using these parameters in other areas. In this context, 15 sediment cores (8 cm diameter; 2 m length) were recovered along the 400 km Asturian coastline, which is an area with representative lithological conditions for the Bay of Biscay, to determine more precise baseline levels for marine sediments from the Bay of Biscay. An evaluation of statistical and empirical methods was done to determine which method delivers the best results. Statistical methods such as mean±2SD and median±2* Median Absolut Deviation (MAD) are strongly influenced by outliers and data distributions which make these approaches less robust. Graphic techniques such as Cumulative Distribution Function (CDF) avoid the problems that asymmetrical data distributions may cause but introduce a certain level of subjectivity in the results due to the baseline values obtained depending on the researcher's experience. Finally, the Probability Curve (CP) method solves issues which may occur when using other techniques and allows one to establish baseline levels based on different percentiles. Regarding the features of the data analysed in this study, the baselines obtained via the CP method with the 95th percentile appear to be the most accurate for the Bay of Biscay. A wide variation has been found between the new baseline values and other international and national levels. Disparity between those levels and the baselines obtained in this study can be generated by granulometric and geological factors. The notable increase in Hg baseline values with respect to OSPAR Background Concentration values (BCs) (0.05 µg g-1 and 0.6 µg g-1 respectively) and the huge different with CEDEX levels and new threshold levels (0.35 µg g-1 and 1.2 µg g-1 respectively) emphasised the relevance of defining specific baselines and threshold levels, as the ones obtained in this study, not only to obtain more precise criteria for marine sediment quality to be used in environmental assessments, but also to propose new threshold levels for the evaluation of dredged material before dumping into ocean sites.

Increase in mercury and methylmercury levels with depth in a fish assemblage.

Despite their remoteness, deep-sea species bioaccumulate mercury, mostly in the form of the neurotoxin methylmercury (MeHg). Although the concentration of MeHg in the water column is known to increase with depth down to a maximum found at the base of the permanent thermocline, the knowledge of the relationship between MeHg content in marine species and their depth of occurrence is limited. We analyzed total mercury (THg) and MeHg concentrations in 25 species of fish inhabiting the Avilés Submarine Canyon and its adjacent shelf (Cantabrian Sea, North-East Atlantic) between 50 and 1868 m depth. THg concentrations ranged from 0.03 µg g-1 in wet weight (ww) in Chauliodus sloani and 4.0 µg g-1 ww in Coryphaenoides guentheri. 65% of the species analyzed exceeded 0.5 µg g-1 ww of MeHg, the maximum level for safe consumption recommended by FAO/WHO. THg and MeHg contents in muscle tissue increased with the depth of occurrence of fish and was influenced by their habitat so that demersal species had higher THg content than pelagic species inhabiting the same depth. MeHg accounted for an average 76 ± 3.9% of THg (mean ± SD), which is lower than that reported for other fish communities and can be explained by the high concentration of Hg present in sediments of the Nalón estuary, which discharges right off the Avilés Canyon head. The % of THg as MeHg was also strongly correlated with δ15N values, confirming that MeHg can be an indicator of the trophic identity of a species within the food web.

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.

Mercury and arsenic mobility in resuspended contaminated estuarine sediments (Asturias, Spain): A laboratory-based study.

Estuarine sediments must be dredged to allow for navigation, and where these sediments are placed after dredging depends upon guidelines based only on the total concentration of contaminants. However, resuspension events could seriously affect the mobility and speciation of contaminants, including potentially toxic trace elements stored in sediments. The effects of resuspension on the cycling of mercury (Hg) and arsenic (As) between the sediment and water column was investigated in a mesocosm study. Four experiments were conducted in three estuaries in northern Spain based on samples collected from sites which have been impacted by decommissioned Hg and As mines and periodically subjected to dredging activities. Designed to mimic the resuspension of particles, each of the experiments revealed that the release of Hg and As species does not only depend on the total concentration in the sediments (16.3-50.9 mg kg-1, for As and 0.52-5.01 mg kg-1 for Hg). The contribution from porewaters and the subsequent reductive dissolution and/or desorption appear to be the main processes responsible for the abrupt increase in dissolved Hg and As species (maximum release of 427% and 125%, respectively). In some cases, As and Hg continued to remain at high concentrations in the water column even after the experiments were completed, thus testifying to their critical persistence in the dissolved form. Conversely, at the other sites, the restoration of pre-resuspension conditions was observed only a few hours after resuspension, mainly due to the role of Fe oxy-hydroxides which provides suitable surfaces for adsorption and/or co-precipitation involving dissolved Hg (maximum removal of -58%) and As (maximum removal of -25%) species. The results of this research could be helpful to take appropriate decisions regarding dredging especially at the Nalòn estuary, where the release of dissolved As(V) and MeHg appeared to be favoured by sediment resuspension.

Geochemical distribution of selected heavy metals in the Asturian coastline sediments (North of Spain).

Sediments from 35 beaches along the Asturian coastline in the north of Spain were studied. Geochemical analyses were conducted to assess the distribution of metal(oid) concentrations on the coast. Samples were correlated by a cluster analysis based on their geochemical concentrations, showing three different groups. Group 1 and Group 2 were composed of the samples of the occidental and oriental beaches, respectively, while Group 3 was formed by the beaches that are in the area of influence of one of the main harbours in the north of Spain where there is an established metal and chemical industry. These associations may explain the origin of the metal concentrations in the coastline. Both geological and anthropic sources generated geochemical anomalies in the sediment concentrations that sometimes surpassed quality OSPAR criterion.

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.

Assessment of the toxicity toward Vibrio fischeri in sediments of a mining impacted estuary in the north of Spain.

This study has been carried out on the Nalón estuary, a mining impacted estuarine contaminated by metals(oid), to evaluate how the metals(oids) concentrations in the sediments contributes to the toxicity and, therefore, supposes a potential risk for the biota. For this purpose, a total of 14 surface sediment samples were collected and analysed by different techniques. Estuary sediments showed a maximum high concentration of As (68.10 µg g-1), Hg (1.33 µg g-1) and Pb (189.60 µg g-1), exceeding the NOAA Effects Range Low. Likewise, these three elements were one of the most bioavailable in the sediments according to the toxicity characteristic leaching procedure performed, reaching average values of 14.28% for As, 12.81% for Hg and 9.23% for Pb. The bioavailable concentrations of As and Hg significantly correlated with toxicity (R > 0.92), suggesting that both were the main contributors to the toxicity of the sediments. Toxicity values detected (avg. 499 TU g-1) were similar to those showed by other sites considered contaminated in the Cantabrian coastline, confirming its status as a contaminated area. The location of the highest toxicity values in the estuary was restricted to the port areas where the fine sediments that act of sink of metals(oids) are mainly deposited. This result is very important if re-mobilization of sediments take place in these areas related to dredging or other human activities.

Historical accumulation of potentially toxic trace elements resulting from mining activities in estuarine salt marshes sediments of the Asturias coastline (northern Spain).

The extensive extraction activity of mercury ores in Asturias (northwest Spain), also rich in As and Sb, has impacted the Nalón river estuary. The objective of this research was to assess the historical evolution of As-Hg-Sb accumulation in the salt marsh sediments of this area. For this purpose, sediment cores were collected from two different salt marshes (eastern and western river banks) in the estuarine environment to evaluate the degree of anthropogenic enrichment and the geochronology of As-Hg-Sb accumulation. Core subsampling was performed by cutting 2-cm-thick slices of sediments. The subsamples were then analysed for several physical and chemical parameters. Sedimentation rate was assessed by measuring short-lived radionuclides (excess 210Pb and 137Cs). Pre-mining levels of As-Hg-Sb were observed at core depths below 50 cm. In the less extended salt marsh (eastern river bank), maximum As-Hg-Sb concentrations of 87.48, 3.66, and 5.75 µg·g-1, respectively, were found at the core top as a consequence of long-term mining activity in the area. The vertical distribution of As-Hg-Sb was influenced by the single-point contamination sources, whereas grain-size variability and diagenetic remobilisation did not seem affected. Geochronological measurements showed that the depositional fluxes of As-Hg-Sb were influenced by anthropogenic input after 1900, when mining activity in the area was most intense. Hg mining ceased in 1969; however, the corresponding core profiles did not show a drastic decreasing trend in element fluxes, implying that the river drainage basin retains some "memory" of contamination which affects riverine sediments. A preliminary gross estimation of total As-Hg-Sb "trapped" in the Nalón river salt marsh sediments amounted to approximately 18.7, 1.0, and 0.7 t, respectively. These morphological structures suffer erosive processes, thus representing a potential source of these elements associated with sediments; consequently, management conservation and monitoring of salt marshes should be taken into consideration from this environmental point of view.

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.

Occurrence and speciation of arsenic and mercury in estuarine sediments affected by mining activities (Asturias, northern Spain).

Sediments contaminated by Hg and As from two historical mining areas have been deposited in the Nalón estuary (Asturias, northern Spain) since 1850. Total mercury (Hgtotal) concentrations in the sediments range from 0.20 µg g-1 to 1.33 µg g-1, most of it in the form of sulphides. Concentrations of methylmercury (303.20-865.40 pg g-1) are up to two orders of magnitude lower than the concentration of Hgtotal. Total As concentration (Astotal) is enriched compared to the background level for the area. The relative abundance of As(V) on As(III) in the sediments ranges from 97.6% to 100%, whereas inorganic Hg accounts for more than 99% of the total Hg. The occurrence of the most toxic species, inorganic As(III) and organic methylmercury, seem to be related to redox conditions together with the amounts of sulphur which act as natural barriers which inhibit the biological and chemical speciation processes. Despite the high amounts of Hg and As present in the sediments, their transference to the water column appear to be limited thus converting sediments in an effective sink of both elements. Special attention should be paid to potential variations of the environmental conditions which might increase the element mobility and exchange between sediments and the water column.

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.