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.

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.