The role of the Gulf of Cadiz circulation in the redistribution of trace metals between the Atlantic Ocean and the Mediterranean Sea.

The GoC shelf waters present much higher concentrations of dissolved Cu, Cd, and Zn than other coastal areas, constituting an important source of these elements onto its neighbouring basins, i.e., the Atlantic Ocean and the Mediterranean Sea. In this study we assessed the role of the GoC surface currents in the trace metals transport. For this purpose, ten dissolved (<0.22 µm) trace metals were sampled (Ag, Cd, Co, Cu, Fe, Mo, Ni, Pb, Zn, V) along the GoC continental shelf, and their spatial and temporal distribution was interpreted according to the surface circulation. Results show that the complex surface circulation over the shelf confines the metals concentration mainly along the inner shelf and determines their transport patterns: under southeastward currents, Cd, Co, Cu, Ni, and Pb are transported toward the Mediterranean Sea; under northwestward countercurrents, Cd, Co, Cu, Fe, Ni, and Zn are transported toward the southern and, occasionally, the western Portuguese shelf; under variable currents, Ag, Cd, Co, Cu, Fe, Pb, and Zn tend to accumulate near their source. Considering that some of these metals have not been analysed before in this region (Ag, Mo, V), or that the spatial distribution of certain metals (Ag, Fe, Mo, Pb, V) has not been interpreted in terms of the ocean circulation, this work could be considered as a baseline study for future comparisons.

Trace metal characterization and fluxes from the Guadiana, Tinto-Odiel and Guadalquivir estuaries to the Gulf of Cadiz.

Metals transported into the coastal zone by the South Iberian rivers are key to understand the biogeochemical cycles and distribution of trace elements in the Gulf of Cadiz (GoC hereinafter) and the exchange with the Mediterranean Sea. Previous studies carried out in the 80s have suggested that metal enrichment in the Alboran Sea (Western Mediterranean) is related with fluvial inputs from acid mine drainage from the Tinto and Odiel rivers. The present study evaluates the contribution of dissolved trace metal concentrations (i.e. Cd, Co, Cu, Fe, Mo, Ni, Pb, V, Zn) from the three main rivers discharging into the GoC (i.e. Guadiana, Tinto-Odiel and Guadalquivir rivers). Our results show that the metal composition of water discharged from each river is impacted by the activities developed in the course of the rivers, which clearly influence the GoC coastal surface waters composition. Metal fluxes from the Guadalquivir river are quantitatively higher than those from the Tinto-Odiel (e.g. up to 73% and 19% higher for Ni and Cu, respectively). Although the metal concentrations spatial distributions in the GoC are dominated by the circulation pattern between the Atlantic and the Mediterranean Sea, the concentrations within the GoC continental shelf could be explained by a greater contribution from the Guadalquivir estuary (e.g. 80.5%, 54.6%, 56.5% and 56.6% for Ni, Cu, Mo, and V respectively).

Effects of TiO2 nanoparticles and sunscreens on coastal marine microalgae: Ultraviolet radiation is key variable for toxicity assessment.

Given the large numbers of sunbathers on beaches, sunscreen compounds are being released into the coastal aquatic environment in significant amounts. Until now the effect of these potential pollutants on microbiota has been not well-known. Phytoplankton is a key component of the microbiota community. It forms the basis of the aquatic trophic networks, and any change in the natural population of phytoplankton can affect the structure of aquatic biota. This paper describes an experiment performed outdoors (in natural sunlight conditions including ultraviolet radiation (UVR) and with UVR blocked) on mixed microalgae populations (four species from different key marine taxonomic groups, Nannochloropsis gaditana, Chaetoceros gracilis, Pleurochrysis roscoffensis and Amphidinium carterae), for three days, exposed to a range of concentrations of three commercial sunscreens (with variable TiO2 concentrations: highest concentration for sunscreen C, followed by sunscreen A; and sunscreen B did not contain TiO2 in its composition). With regard to UVR effect, in the absence of sunscreens, the most sensitive species is the centric diatom, Chaetoceros gracilis, and the least is Nannochloropsis gaditana; this last species presented the same behavior in the absence of UVR and with high sunscreen concentrations. The toxicity gradient obtained for sunscreens and nanoparticles under UVR is: TiO2 NPs>Sunscreen C>Sunscreen A>Sunscreen B. The differential sensitivity of microalgae to sunscreens and TiO2 NPs can produce a change in the dynamics of phytoplankton populations and provoke undesirable ecological effects (such as giving dinoflagellates more prominence). The effects of UVR, commonly neglected in bioassays, could alter the results in important ways and should be considered when performing environmentally-relevant bioassays. The toxicity mediated by hydrogen peroxide production associated with the concentration of TiO2 NPs cannot be considered the only factor responsible for the toxicity: the organic compounds in the sunscreens must also be taken into account.

Determination of UV filters in both soluble and particulate fractions of seawaters by dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry.

An analytical method to determine the total content (i.e., not only in the soluble fraction but also in the particulate one) of eight commonly used UV filters in seawater samples is presented for the first time. Dispersive liquid-liquid microextraction (DLLME) is used as microextraction technique to pre-concentrate the target analytes before their determination by gas chromatography-mass spectrometry (GC-MS). In order to release the UV filters from the suspended particles an ultrasound treatment is performed before DLLME. The ultrasound treatment time was studied in order to achieve a quantitative lixiviation of the target analytes. The type and volume of both disperser and extraction solvent, the sample volume, the pH and the ionic strength involved in the DLLME have been optimized to provide the best enrichment factors. Under the optimized conditions, the method was successfully validated showing good linearity, enrichment factors between 112 and 263 depending on the analyte, limits of detection and quantification in the low ng L(-1) range (10-30 ng L(-1) and 33-99 ng L(-1), respectively) and good intra- and inter-day repeatability (RSD <15%). No significant matrix effects were found. Finally, the method was satisfactorily applied to the analysis of three seawater samples from different origin. Results showed significant amounts of UV filters in the particulate fraction that would have been ignored if only the soluble fraction had been considered. This fact shows that the UV filters are also accumulated in the suspended particles contained in water, what should be taken into account from an environmental standpoint.