Unmanned aerial vehicles (UAVs) as a tool for hazard assessment: The 2021 eruption of Cumbre Vieja volcano, La Palma Island (Spain).

Monitoring for assessment of natural disasters, such as volcanic eruptions, presents a methodological challenge for the scientific community. Here, we present Unmanned Aerial Vehicles (UAVs) as a feasible, precise, rapid and safe tool for real time monitoring of the impacts of a volcanic event during the Cumbre Vieja eruption on La Palma Island, Spain (2021). UAV surveys with optical RGB (Red-Green-Blue), thermal and multispectral sensors, and a water sampling device, were carried out in different areas affected by the lava flow, including the upper volcanic edifice and the lava delta formed on the coastal fringe of the island. Our results have provided useful information for the monitoring of the advance of the lava flow and its environmental consequences during the volcanic emergency. Our data shows how La Palma island's growth, with the formation of a new lava delta of 28 ha and a total volume of lava injected into the sea of 5,138,852 m3. Moreover, our Digital Elevation Model (DEM) simulated, with a 70 % accuracy, the probabilistic simulation of the possible path followed by the lava flow in the vicinity of the fissure from which the magma emanates. In addition, significant changes of seawater physical-chemical parameters were registered in coastal surface waters by the in situ seawater samples collected with the automatic water sampling device of our UAV. The first meters of the water column, due to the instant evaporation of the seawater in contact with the hot lava, produce an increase of temperature and salinity of up to 4-5 °C and up to 5 units, respectively.

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).

Sources and coastal distribution of dissolved organic matter in the Gulf of Cadiz.

Dissolved organic matter (DOM) is a major component of the organic matter pool, playing a key role in the global ocean functioning. However, studies on DOM in waters of many ocean regions, such as the Gulf of Cadiz (GoC), are poorly known. Advanced aquatic sensors enable autonomous for long-term deployments in situ collection of high frequency DOM data using fluorescent dissolved organic matter (FDOM) as a proxy. The present study evaluates the relevance of FDOM, the estuarine influence and the environmental factors that determine its spatial distribution in the GoC. Our results suggest that the GoC water mass, under the estuarine influence of three main rivers, is receiving large amounts of DOM transported mainly by Guadalquivir and Guadiana rivers and much less from Tinto-Odiel. Salinity is the main factor explaining the FDOM variability within the Guadalquivir and Guadiana rivers and in the inner shelf of the GoC. In the outer shelf of the GoC, plankton-produced DOM could explain the persistent spatial pattern of FDOM, playing an important role in the dynamics of FDOM from the North area of the GoC through the persistent low-salinity Eastern North Atlantic Central Water. The oceanographic dynamics and the spatial pattern of FDOM concentration in the continental shelf of the GoC suggest a net transport of FDOM through the GCC (Gulf of Cadiz Current) to the Mediterranean Sea.

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.

Tolerance of polar phytoplankton communities to metals.

Large amounts of pollutants reach polar regions, particularly the Arctic, impacting their communities. In this study we analyzed the toxic levels of Hg, Cd and Pb to natural phytoplankton communities of the Arctic and Southern Oceans, and compared their sensitivities with those observed on phytoplankton natural communities from temperate areas. Mercury was the most toxic metal for both Arctic and Antarctic communities, while both Cd and Pb were toxic only for the Antarctic phytoplankton. Total cell abundance of the populations forming the Arctic community increased under high Cd and Pb concentrations, probably due to a decrease of the grazing pressure or the increase of the most resistant species, although analysis of individual cells indicated that cell death was already induced at the highest levels. These results suggest that phytoplankton may have acquired adapting mechanisms to face high levels of Pb and Cd in the Arctic Ocean.

Geographical gradients of dissolved Vitamin B12 in the Mediterranean Sea.

Most eukaryotic phytoplankton require vitamin B12 to grow. However, the cycling of this organic growth factor has received substantially less attention than other bioactive substances such as trace metals in the marine environment. This is especially true in the Mediterranean Sea, where direct measurements of dissolved vitamins have never been reported. We report here the first direct measurements of dissolved vitamin B12 across longitudinal gradients in Mediterranean waters. The range of vitamin B12 concentrations measured over the whole transect was 0.5-6.2 pM, which is slightly higher than the range (undetectable-4 pM) of ambient concentrations measured in other open ocean basins in the Pacific and Atlantic oceans. The concentrations measured in the western basin were significantly higher (p < 0.05) than those of the eastern basin. They were positively correlated with chlorophyll concentrations in the most western part of the basin, and did not show any significant correlation with any other biological variables in other regions of the sampling transect.

Toxic thresholds of cadmium and lead to oceanic phytoplankton: cell size and ocean basin-dependent effects.

Thresholds of cadmium (Cd) and lead (Pb) toxic to oceanic phytoplankton were examined in natural communities from the Mediterranean and Black Seas and the North East Atlantic Ocean. At concentrations of added Cd and Pb greater than 0.11 µg L(-1) , cell abundances and growth rates decreased with increasing addition of Cd and Pb, for all phytoplankton populations. The lethal concentrations at which populations decreased by half (LC50s), ranged from 0.23 to 498.7 µg L(-1) Cd for Atlantic Prochlorococcus and Black Sea picoeukaryotes, respectively, and from 20 to 465.2 µg L(-1) Pb for Mediterranean Synechococcus and Black Sea nanoplankton, respectively. These lethal concentrations were significantly lower than those previously reported for phytoplankton cultures. The LC50s were strongly related to population cell size, increasing as cell size increased, indicating that oceanic picocyanobacteria Prochlorococcus and Synechococcus populations were the most sensitive, and the largest phytoplankton cells the most resistant. Based on this relationship, differences in sensitivity to Cd across systems were detected, with Black Sea phytoplankton communities being more resistant (up to 100 times) than similar sized phytoplankton of the Mediterranean Sea and Atlantic Ocean.

Ultra-trace determination of Persistent Organic Pollutants in Arctic ice using stir bar sorptive extraction and gas chromatography coupled to mass spectrometry.

This study presents the optimization and application of an analytical method based on the use of stir bar sorptive extraction (SBSE) gas chromatography coupled to mass spectrometry (GC-MS) for the ultra-trace analysis of POPs (Persistent Organic Pollutants) in Arctic ice. In a first step, the mass-spectrometry conditions were optimized to quantify 48 compounds (polycyclic aromatic hydrocarbons, brominated diphenyl ethers, chlorinated biphenyls, and organochlorinated pesticides) at the low pg/L level. In a second step, the performance of this analytical method was evaluated to determine POPs in Arctic cores collected during an oceanographic campaign. Using a calibration range from 1 to 1800 pg/L and by adjusting acquisition parameters, limits of detection at the 0.1-99 and 102-891 pg/L for organohalogenated compounds and polycyclic aromatic hydrocarbons, respectively, were obtained by extracting 200 mL of unfiltered ice water. alpha-hexachlorocyclohexane, DDTs, chlorinated biphenyl congeners 28, 101 and 118 and brominated diphenyl ethers congeners 47 and 99 were detected in ice cores at levels between 0.5 to 258 pg/L. We emphasise the advantages and disadvantages of in situ SBSE in comparison with traditional extraction techniques used to analyze POPs in ice.