Stir bar sorptive extraction-thermal desorption-gas chromatography-mass spectrometry: An effective tool for determining persistent organic pollutants and nonylphenol in coastal waters in compliance with existing Directives

A multi-residual method based on stir bar sorptive extraction coupled with thermal desorption-gas chromatography-mass spectrometry (SBSE-TD-GC-MS) has been developed to measure 49 organic pollutants (organochlorine pesticides, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, polybrominated diphenyl ethers and nonylphenol) in seawater. Using 100 ml of water, the method exhibited good linearity, with recoveries between 86% and 118% and relative standard deviation between 2% and 24% for almost all compounds. The method was applied to determine target contaminants in Catalonian seawater, including coastal areas, ports and desalination plant feed water. Overall individual compound levels oscillated between 0.16 and 597 ng l⁻¹; PAHs and nonylpenol were the compounds found at the highest concentrations. The method provided LODs between 0.011 and 2.5 ng l⁻¹, lower than the Environmental Quality Standards (EQS) fixed by Directive 2008/105/EC. In compliance with the directive, this method can be used as a tool to survey target compounds and is aimed at protecting coastal ecosystems from chemical pollution.     

Hydrological and geomorphological criteria to evaluate the dispersion risk of waste sludge generated by the Aznalcollar mine spill (SW Spain)

Following the Aznalcóllar pyrite mine disaster (Seville, Spain) which caused the spilling of some 4.5?hm³ of acid water, the floodplains of the rivers Agrio and Guadiamar were rapidly cleaned of waste sludge. However, despite the efficiency of cleaning activities, there is still evidence of a fine superficial layer of sludge and some soil contamination, with the consequent risk of remobilisation of the pollutants by water erosion. There is much concern that these contaminated sediments may affect the precious ecosystems of the Doñana National Park and the Guadalquivir marshlands. This report describes the evaluation of the risk of mobilisation of the waste sludge through (1) detailed geomorphological analysis, indicating potential areas of erosion-sedimentation on the floodplains of the rivers Agrio and Guadiamar, and predicted dynamics of the waste sludge, and (2) evaluation of the potential dispersion of the waste sludge provoked by future flood events, including hydraulic calculations to model channel flow and the analysis of the texture of the sludge to obtain critical transport and sedimentation values. Findings suggest that the waste sludge is likely to be transported and deposited within the Doñana National Park during future flood events.     

Investigating young water fractions in a small Mediterranean mountain catchment: Both precipitation forcing and sampling frequency matter

The proportion of water younger than 2–3 months (young water fraction, F_yw) has become increasingly investigated in catchment hydrology. F_yw is typically estimated by comparing seasonal tracer cycles in precipitation and streamflow, through water sampling. However, some open research questions remain, such as: (i) whether part of the summer precipitation should be discarded because the high evapotranspiration demand, (ii) how well F_yw serves as a metric to compare catchments, and (iii) how sampling frequency affects F_yw estimates. To address these questions, we investigated F_yw in soil-, ground- and stream waters for the small Mediterranean Can Vila catchment. Rainfall was sampled at 5-mm intervals. Mobile soil water and groundwater were sampled fortnightly. Stream water was sampled depending on flow at variable time intervals (30 min to 1 week). Over 58 months, this sampling provided 1,529 δ¹⁸O determinations. Isotopic analyses results led us to include summer precipitation in the input signal. We found the highest F_yw in mobile soil waters (34%), while this was almost zero for groundwater except during wet periods. For stream waters, F_yw depended on the discharge variations, so that the flow-weighted young water fraction () was 22.6%, whereas the time-weighted F_yw was just 6.2%. Both and its discharge sensitivity (S_d) varied when different 12-month sampling periods were investigated. The young water fraction that would be obtained from a virtual thorough sampling () was estimated from the S_d and the observed stream flow. This showed an underestimation of by 25% for the frequent dynamic sampling and 66% for weekly sampling, due to missing high flows. Our results confirm that F_yw and its discharge sensitivity are metrics very sensitive to meteorological forcing during the analysed period. Thus, comparisons between catchments need long-term mean annual values and their variability. Our findings also support the dependence of F_yw estimates on the sampling rate and show the advantages of flow-weighted analysis. Finally, catchment water turnover investigations should be accompanied by the analysis of flow duration curves.     

Local earthquakes seismic tomography in the Betic Cordillera (southern Spain)

A crustal tomographic image, from the surface down to 35 km depth beneath the Betic Cordillera (southern Spain), is obtained using data on local earthquakes recorded at stations from the National and Andalusian Seismic Networks. The velocity structure and the hypocentre locations are derived from the inversion of P first arrival times, using an iterative simultaneous inversion method. The reliability of the results is assessed using different control parameters. The inverted velocity field in the uppermost layers shows a significant lateral variability which reflects most of the large-scale geological features of the Betic Cordillera. Well determined local surface anomalies allow to constrain the location and geometry of the most prominent Neogene sedimentary basins. The upper crust is well resolved throughout the whole region, and is characterized by relatively high velocities in the Internal Betics and in the South Iberian Massif and lower velocities within the External Betics. A relatively well constrained event cluster displays a NNE–SSW trend, and outlines the contact zone between the Internal and the External domains. The middle and lower crustal levels show reliable results beneath the central part of the Betic Cordillera. High averaged velocities are obtained within the South Iberian and the Alboran domains, in contrast to a relatively low velocity anomaly which characterizes the boundary between them. These findings support the hypothesis of the lack of well differentiated crustal levels below the contact zone, while crustal layering is better defined beneath the Alboran and the Iberian domains.     

Coastal Mediterranean plankton stimulation dynamics through a dust storm event: An experimental simulation

An enhancement of aeolian inputs to the ocean due to a future increase in aridity in certain parts of the world is predicted from global change. We conducted an experimental simulation to assess the biological response of NW Mediterranean coastal surface waters to an episodic dust addition. On the assumption that planktonic growth was limited by phosphorus, dust effects were compared to those induced by equivalent enrichments of phosphate. The experiment analyzed the dynamics of several parameters during one week: inorganic nutrients, total and fractioned chlorophyll a, bacterial abundance, phytoplankton species composition, abundance of autotrophic and heterotrophic flagellates, particulate organic carbon and particulate organic nitrogen. The maximum addition of dust (0.5 g dust L⁻¹) initiated an increase in bacterial abundance. After 48 h, bacterial numbers decreased due to a peak in heterotrophic flagellates and a significant growth of autotrophic organisms, mainly nanoflagellates but also diatoms, was observed. Conversely, lower inputs of dust (0.05 g dust L⁻¹) and phosphate enrichments (0.5 μmol PO₄³⁻ L⁻¹) only produced increases in phototrophic nanoflagellates. In our experiment, dust triggered bacterial growth, changed phytoplankton dynamics and affected the ratio of autotrophic to heterotrophic biomass, adding to the variability in the sources that affect system dynamics, energy and carbon budgets and ultimately higher trophic levels of the coastal marine food web.     

Spatial assessment of fishing effort around European marine reserves: implications for successful fisheries management

We examined the spatial dynamic of artisanal fishing fleets around five European marine protected areas (MPAs) to derive general implications for the evaluation of MPAs as fisheries management tools. The coastal MPAs studied were located off France, Malta and Spain and presented a variety of spatial designs and processes of establishment. We developed a standardized methodology to define factors influencing effort allocation and to produce fishing effort maps by merging GIS with geostatistical modelling techniques. Results revealed that in most cases the factors “distance to the no-take”, “water depth”, and “distance to the port” had a significant influence on effort allocation by the fishing fleets. Overall, we found local concentration of fishing effort around the MPA borders. Thus, neglecting the pattern of fishing effort distribution in evaluating MPA benefits, such as spillover of biomass, could hamper sound interpretation of MPAs as fisheries management tools.     

Particle fluxes dynamics in Blanes submarine canyon (Northwestern Mediterranean)

Within the framework of the multidisciplinary RECS project and with the aim of describing the particle flux transfer from the continental shelf to the deep basin, an array of five mooring lines equipped with a total of five pairs of PPS3/3 sequential-sampling sediment traps and RCM-7/8 current meters were deployed 30 m above the bottom from March 2003 to March 2004 inside and outside the Blanes Canyon. One mooring line was located in the upper canyon at 600 m depth, one in the canyon axis at 1700 m depth and other two close to the canyon walls at 900 m depth. A fifth mooring line was deployed in the continental open slope at 1500 m water depth.The highest near-bottom downward particle flux (14.50 g m⁻² d⁻¹) was recorded at the trap located in the upper canyon (M1), where continental inputs associated with the presence of the Tordera River are most relevant. On the other hand, the downward fluxes (4.35 g m⁻² d⁻¹) in the canyon axis (M2) were of the same order as those found in the western flank (M3) of the canyon. Both values were clearly higher than the value (1.95 g m⁻² d⁻¹) recorded at the eastern canyon wall (M4). The open slope (M5) mass flux (5.42 mg m⁻² d⁻¹) recorded by the sediment trap located outside the canyon system was three orders of magnitude lower than the other values registered by the inner canyon stations. The relevance of our data is that it explains how the transport pathway in the canyon occurs through its western flank, where a more active and persistent current toward the open ocean was recorded over the entire year of the experiment.Off-shelf sediment transport along the canyon axis showed clear differences during the period of the study, with some important events leading to strong intensifications of the current coupled with large transport of particle fluxes to the deepest parts of the canyon. Such events are primarily related to increases in river discharge and the occurrence of strong storms and cascading events during the winter.In summary, in this study it is shown that the dynamics of the water masses and the currents in the study area convert the sharp western flank of the Blanes Canyon in a more active region that favors erosion processes than the eastern flank, which has a smoother topography and where the absence of erosional conditions yields to steadier sedimentary processes.