The distribution and sources of yttrium and rare-earth elements (YREE) in surface sediments were studied on 78 samples collected in the Tagus estuary (SW Portugal, SW Europe). Yttrium and total REE contents ranged from 2.4 to 32mg·kg and 18 to 210mg·kg, respectively, and exhibited significant correlations with sediment grain-size, Al, Fe, Mg and Mn, suggesting a preferential association to fine-grained material (e.g. aluminosilicates but also Al hydroxides and Fe oxyhydroxides). The PAAS (Post-Archean Australian Shale) normalized patterns display three distinct YREE fractionation pattern groups along the Tagus estuary: a first group, characterized by medium to coarse-grained material, a depleted and almost flat PAAS-normalized pattern, with a positive anomaly of Eu, representing one of the lithogenic components; a second group, characterized mainly by fine-grained sediment, with higher shale-normalized ratios and an enrichment of LREE relative to HREE, associated with waste water treatment plant (WWTP) outfalls, located in the northern margin; and, a third group, of fine-grained material, marked by a significant enrichment of Y, a depletion of Ce and an enrichment of HREE over LREE, located near an inactive chemical-industrial complex (e.g. pyrite roast plant, chemical and phosphorous fertilizer industries), in the southern margin. The data allow the quantification of the YREE contents and its spatial distribution in the surface sediments of the Tagus estuary, identifying the main potential sources and confirming the use of rare earth elements as tracers of anthropogenic activities in highly hydrodynamic estuaries.

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The Northern coast of Galicia, NW Iberian Peninsula, exhibits a variety of geological features: Ortegal allochthonous complex, Ollo-de-Sapo autochthonous domain and massifs of Bares, Barqueiro and San-Ciprian. In order to examine the influence of terrestrial lithologies on coastal sediments, 103 samples were collected in the Rias of Ortigueira, Barqueiro and Viveiro, their neighbouring shelf and the estuaries of Mera, Sor and Landro rivers. Aluminium, Fe, Sc, particulate inorganic and organic carbon and rare earth elements (REE) were determined in the <2 mm fraction. In addition, calcite, muscovite, quartz and riebeckite minerals were identified and quantified in 33 selected samples. The distributions of riebeckite and Fe reflect the influence of Ortegal complex on the coastal areas around the Cape Ortegal. The highest concentrations of ΣREE were found in fine sediments from confined inner parts of the Rias (up to 233 mg•kg-1), while most of the sands contained 11-70 mg•kg-1. ΣREE normalized to European Shale (ES) highlights the relative abundance of lanthanides (ΣREE N >6) near Cape Ortegal and the innermost ria zones. The ratio between light and heavy REE (L/H) showed lower values (4-11) around Cape Ortegal and the shelf while higher ratios (15-23) were detected in west of the Cape Estaca-de-Bares and in the inner Viveiro Ria due to elevated contributions of La and Ce. The L/H values normalized to ES reflects the importance of HREE in the adjacent area to Ortegal Complex (L N /H N <0.8) and the LREE (L N /H N >1.4) in the inner estuaries and west Cape Estaca-de-Bares. The highest REE individual ES normalised were measured in fine-grained sediments of the Mera and Sor estuaries. Sediments from the eastern shelf of Cape Ortegal presented enhanced ratios only for HREE. These results indicate that distribution of REE in the northern Galician region is highly depending on the neighbouring lithological pattern, contrasting with the situation found in the western Galician shelf and the Bay of Biscay. Lanthanides can, thus, provide a useful tool to follow the sediment pathway in the land-sea boundary zones, denoting continental geochemical imprint or fluvial outputs accordingly to the existing hydrological and geological conditions.

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