Distribution of Mercury and Monomethylmercury in Sediments of Vigo Ria, NW Iberian Peninsula

Fifty four samples of surface sediments (1-cm of thickness) and a gravity core of 154-cm long were collected in the Vigo Ria, NW of Iberian Peninsula. In the laboratory the sediments were oven dried at 40°C, desegregated, homogenised and analyzed for total Hg, monomethylmercury (MMHg), Al, and particulate organic carbon (POC). Mercury in sediments varied within a broad range: 0.09 to 8.9 nmol g^?1 the higher concentrations being found in the shipyards and docks areas of Vigo port (southern–middle Ria zone). No correlation was found between Hg and POC. The good exponential correlation between total Hg and Al levels suggests that Hg is closely associated with the fine fraction of sediments. Monomethylmercury concentrations in surface sediments ranged between <1.4 (DL) and 8.5 pmol g^?1 being the spatial distribution similar to that observed for total Hg. The lack of correlations MMHg–Al and MMHg–POC suggests that in situ processes of methylation/demethylation are responsible for MMHg distribution rather than the sediment characteristics. Additionally, these processes appear mercury-dependent only for Hg concentrations above 2.5 nmol g^?1. On the basis of these results it was estimated that 155 kg of Hg (0.1% MMHg) are present in the surface sediments of Vigo Ria, being 61% of anthropogenic origin.     

Lanthanides and yttrium in the sediments of the lower Minho River (NW Iberian Peninsula): imprint of tributaries

Purpose

Rare earth elements have been used as sediment tracers in river, estuarine and coastal environments but rarely applied as fluvial tributary tracers. Lanthanides (Ln) and yttrium (Y) were quantified in fluvial sediments of the Minho River lower course (NW Iberian Peninsula), where the catchment contains heterogeneous lithologies, to define the characteristic imprints of tributaries and their relevance in the riverine system.

Materials and methods

Surface sediments were sampled at 36 points in the lower Minho riverbed and its nine main tributaries.The <?2-mm fraction was sieved and ground, and ≈?100 mg was completely acid-digested with HF and aqua regia in closed Teflon bombs at 100 °C for 1 h. The residue was evaporated, re-dissolved with HNO₃ and Milli-Q water, heated 20 min at 75 °C and diluted to 50 cm³ with Milli-Q water. Lanthanides and yttrium were determined using a quadrupole ICP-MS equipped with a Peltier impact bead spray chamber and a concentric Meinhard nebuliser. Blanks accounted for less than 1% of the element concentrations in the samples. The precision and accuracy of the analytical procedures were controlled through reference materials AGV-1 and MAG-1.

Results and discussion

Contents ranged from 22 to 153 mg Ln kg^?1 and 1.5–22.9 mg Y kg^?1 and ES-normalised light-heavy Ln fractionation, (L_N/H_N), varied between 0.6 and 2.6. These wide ranges, together with Eu and Ce anomalies and element-by-element Ln, varied with changes in parental rocks of the lower Minho basin. Minho sediments showed negative Ce anomalies (0.81?±?0.29) and positive Eu anomalies (1.23?±?0.18). Sediments received traces of granitic pegmatites and gneissic peralkaline rocks from two tributaries: the Gadanha (22.9 mg Y kg^?1; 83 mg Ln kg^?1; 0.60 L_N/H_N; 0.51 Eu/Eu*; 0.88 Ce/Ce*) and the Louro (15.9 mg Y kg^?1; 110 mg Lnkg^?1; 0.97 L_N/H_N; 0.69 Eu/Eu*; 1.49 Ce/Ce*). The Tamuxe tributary, flowing through a slate and quartzite fault, provided the lowest source (1.6 mg Y kg^?1; 28 mg Ln kg^?1; 2.48 L_N/H_N; 1.01 Eu/Eu*; 0.55 Ce/Ce*).

Conclusions

Lanthanide and Y signatures in sediments may be used to trace land-tributary-river influences. The imprints are observed downstream of fluvial confluences but not in all cases, responding to basin lithological changes, particularly for pegmatites and peralkaline rocks. The general REE trend is described using Y contents only. Tributaries, which are responsible for one-fifth of the Minho water load, provide one-half of their sediments. Non-homogeneous sediment patterns may be magnified in dammed rivers such as the Minho.