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.

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.

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.