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.

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.

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.

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).

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.

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.

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.

A risk assessment tool applied to the study of shale gas resources.

The implementation of a risk assessment tool with the capacity to evaluate the risks for health, safety and the environment (HSE) from extraction of non-conventional fossil fuel resources by the hydraulic fracturing (fracking) technique can be a useful tool to boost development and progress of the technology and winning public trust and acceptance of this. At the early project stages, the lack of data related the selection of non-conventional gas deposits makes it difficult the use of existing approaches to risk assessment of fluids injected into geologic formations. The qualitative risk assessment tool developed in this work is based on the approach that shale gas exploitation risk is dependent on both the geologic site and the technological aspects. It follows from the Oldenburg's 'Screening and Ranking Framework (SRF)' developed to evaluate potential geologic carbon dioxide (CO2) storage sites. These two global characteristics: (1) characteristics centered on the natural aspects of the site and (2) characteristics centered on the technological aspects of the Project, have been evaluated through user input of Property values, which define Attributes, which define the Characteristics. In order to carry out an individual evaluation of each of the characteristics and the elements of the model, the tool has been implemented in a spreadsheet. The proposed model has been applied to a site with potential for the exploitation of shale gas in Asturias (northwestern Spain) with tree different technological options to test the approach.

An ANN-based smart tomographic reconstructor in a dynamic environment.

In astronomy, the light emitted by an object travels through the vacuum of space and then the turbulent atmosphere before arriving at a ground based telescope. By passing through the atmosphere a series of turbulent layers modify the light's wave-front in such a way that Adaptive Optics reconstruction techniques are needed to improve the image quality. A novel reconstruction technique based in Artificial Neural Networks (ANN) is proposed. The network is designed to use the local tilts of the wave-front measured by a Shack Hartmann Wave-front Sensor (SHWFS) as inputs and estimate the turbulence in terms of Zernike coefficients. The ANN used is a Multi-Layer Perceptron (MLP) trained with simulated data with one turbulent layer changing in altitude. The reconstructor was tested using three different atmospheric profiles and compared with two existing reconstruction techniques: Least Squares type Matrix Vector Multiplication (LS) and Learn and Apply (L + A).