River Restoration in Spain: Theoretical and Practical Approach in the Context of the European Water Framework Directive

River restoration is becoming a priority in many countries because of increasing the awareness of environmental degradation. In Europe, the EU Water Framework Directive (WFD) has significantly reinforced river restoration, encouraging the improvement of ecological status for water bodies. To fulfill the WFD requirements, the Spanish Ministry of the Environment developed in 2006 a National Strategy for River Restoration whose design and implementation are described in this paper. At the same time many restoration projects have been conducted, and sixty of them have been evaluated in terms of stated objectives and pressures and implemented restoration measures. Riparian vegetation enhancement, weir removal and fish passes were the most frequently implemented restoration measures, although the greatest pressures came from hydrologic alteration caused by flow regulation for irrigation purposes. Water deficits in quantity and quality associated with uncontrolled water demands seriously affect Mediterranean rivers and represent the main constraint to achieving good ecological status of Spanish rivers, most of them intensively regulated. Proper environmental allocation of in-stream flows would need deep restrictions in agricultural water use which seem to be of very difficult social acceptance. This situation highlights the need to integrate land-use and rural development policies with water resources and river management, and identifies additional difficulties in achieving the WFD objectives and good ecological status of rivers in Mediterranean countries.     

Removal of phthalates from aqueous solution by different adsorbents: a short review

This work presents a short review of adsorptive materials proposed and tested for removing phthalates from an aqueous environment. The objective is not to present an exhaustive review of all the types of adsorbents used, but to focus on selected types of "innovative" materials. Examples include modified activated carbon, chitosan and its modifications, β-cyclodextrin, and specific types of biomass, such as activated sludge from a wastewater treatment plant, seaweed and microbial cultures. Data from the literature do not confirm the existence of a broad-spectral adsorbent with high sorption efficiency, low production costs and environmentally friendly manufacture. According to the coefficients of Freundlich's isotherm, the most promising adsorbent of those mentioned in this work appears to be the biomass of activated sludge, or extracellular polysaccharides extracted from it. This material benefits from steady production, is cheap and readily available. Nevertheless, before putting it in practice, the treatment and adaptation of this raw material has to be taken into consideration.     

Alternative approaches to dealing with respondent uncertainty in contingent valuation: a comparative analysis

Several strategies have been proposed to deal with response uncertainty in contingent valuation. One approach, often applied to address issues of hypothetical bias, recodes and/or reweights responses according to stated levels of certainty but so far few analyses compare alternative recoding and reweighting strategies. We explore the choice among alternative strategies that exploit a numerical certainty scale obtained from a follow-up to the payment question in a valuation survey about a whale conservation program. Two novel variations of previously followed approaches perform best on our dataset in terms of the efficiency of estimates. The first one uses an exponential transformation of the numerical certainty scale as a weight in the willingness to pay regression. The other one is based on constructing a continuous willingness to pay variable with the highly certain "yes" and "no" original responses to the payment question as extreme values and with mid-point values that correspond to the original "don't know" responses. We find, though, that the effect of using different treatment strategies on mean willingness to pay is rarely statistically significant and we fail to detect a consistent effect on the efficiency of the estimation regardless of the strategy applied.     

Contrasting Patterns of Urban Expansion in Colombia, Ecuador, Peru, and Bolivia Between 1992 and 2009

The global urban population is increasing rapidly, but patterns of urban expansion differ greatly among countries. Urban transition theory predicts that the shift from low to high urbanization depends on a country’s history and level of economic development. This study describes urban expansion in Colombia, Ecuador, Peru, and Bolivia between 1992 and 2009. Urban dynamics were analyzed by combining nighttime lights and census data from 4032 municipalities. High-lit areas (>52–63 pixel values) were correlated with urban populations across municipalities and years (R ² > 0.90). Analyses showed that between 1992 and 2009 Bolivia and Ecuador had rapid population growth and rapidly increasing high-lit areas, while Peru and Colombia had lower rates of population growth and urbanization (i.e., expansion of high-lit areas). We demonstrate how nighttime lights can be a useful tool, providing a homogeneous platform for multi-scale analyses of urban growth.     

Converging hazard assessment of gold nanoparticles to aquatic organisms

The gold nanoparticles (Au-NPs) are being increasingly used because of their huge diversity of applications, and consequently, elevated levels in the environment are expected. However, due to their physico-chemical properties and functionalization a high variety of Au-NPs can be found, and complete toxicological information for each type of Au-NPs still lacks, and even, the toxicological information for the same species is sometimes contradictory. Therefore, hazard assessment should be done case by case. Hence, the objective of this study was to obtain ecotoxicological information of the same Au-NPs in aquatic organisms and to find a rationale for Au-NPs toxicity. For such a purpose, bare and hyaluronic acid capped Au-NPs (12.5 nm) along with Au-NPs bulk material were tested on freshwater algae, Daphnia and zebrafish. Results showed that while gold nanoparticles were found to be harmless to the tested organisms, the soluble gold showed to be toxic to algae and Daphnia, with an LC₅₀ between 1 and 2 mg L⁻¹. Comparing our results with those gathered in the literature, it appears that a common hazard assessment of Au-NPs on the studied organisms can be elucidated.     

Photodegradation of sulfonamides and their N 4-acetylated metabolites in water by simulated sunlight irradiation: kinetics and identification of photoproducts

Once released into the aquatic environment, pharmaceuticals may undergo different degradation processes. Photodegradation, for example, might be an important elimination process for light-sensitive pharmaceuticals, such as antibiotics. In this study, the fate of sulfonamides (sulfamethazine, sulfadiazine, and sulfamethoxazole) and their N ⁴-acetylated metabolites (N ⁴-acetylsulfadiazine, N ⁴-acetylsulfamethazine, and N ⁴-acetylsulfamethoxazole) under simulated sunlight irradiation was investigated. The irradiation resulted in total or almost total degradation (88 to 98 %) of the pharmaceuticals tested, except for sulfamethazine (52 %), during 24 h of irradiation. The photoproducts of all investigated pharmaceuticals have been analyzed using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Structure elucidation performed from photodegradation products of both, sulfonamides and their N ⁴-acetylated metabolites, clearly showed two major formation pathways. These were cleavage of the sulfonamide bond as well as SO₂ extrusion. In total, nine photoproducts were elucidated. Among these photoproducts, the tautomers of sulfamethoxazole and desulfonated products of sulfadiazine and sulfamethazine were also present. Tautomers of sulfadiazine and sulfamethazine have been characterized here for the first time as well as some photoproducts of sulfadiazine, sulfametoxazole, and their metabolites N ⁴-acetylsulfadiazine and N ⁴-acetylsulfametoxazole. The obtained results are an important piece in the complex puzzle for assessing the environmental fate of sulfonamides and their metabolites in the environment.     

Antibacterial behavior of silver-modified clinoptilolite-heulandite rich tuff on coliform microorganisms from wastewater in a column system

The water disinfecting behavior of silver-modified clinoptilolite–heulandite rich tuff (ZSAg) as an antibacterial agent against coliform microorganisms from water in a continuous mode was investigated. Silver recovery from the disinfected effluents by the sodium-modified clinoptilolite–heulandite rich tuff (ZSNa) was also considered. Escherichia coli (ATCC 8739) and total coliform microorganisms, as indicators of microbiological contamination of water, were chosen to achieve the disinfection of synthetic wastewater or municipal wastewater. Ammonium (NH₄⁺) and chloride (Cl⁻) ions were added to the synthetic wastewater as an interfering chemical species on the disinfection processes. The antibacterial activity of the ZSAg as a bactericide was measured by the coliform concentration as evaluated by the APHA method. The amount of silver in the disinfected effluents was determined using atomic absorption spectroscopy. The inactivation of the ZSAg was calculated from the breakthrough curves based on the model reported by Gupta et al. It was found that when the silver concentration in the effluent is less than 0.6 μg/mL, the bacterial survival percentage increased and the volume of disinfected water diminished. The total silver amounts found in the effluent at the end of the disinfection processes varied depending on the water treated (synthetic or municipal wastewater). The presence of NH₄⁺ ions in synthetic wastewater influent notably improved the disinfected water volume (zero NVC/100 mL), in comparison to the disinfection of the same influent without NH₄⁺ ions. A contrary water disinfection behavior was observed in the presence of Cl⁻ ions. The silver recovery does not depend on the mass of the sodium zeolitic bed according with the wastewater to be treated (synthetic or municipal wastewater) and the presence of NH₄⁺ or Cl⁻ ions in the influent also influenced the silver recovery from wastewater. The ZSNa did not have antibacterial activity. Therefore the amount of bactericide agent (silver-modified natural zeolite), coliform microorganisms from water (E. coli or consort of coliform microorganisms) as well as the water quality (synthetic wastewater or municipal wastewater) influenced both the disinfection process and the silver recovery in a column system.     

Analysis of perfluorooctanoate (PFOA) and other perfluorinated compounds (PFCs) in the River Po watershed in N-Italy

C7-C11 perfluorinated carboxylates (PFACs) and perfluorooctansulfonate (PFOS) were analysed in selected stretches of the River Po and its major tributaries. Analyses were performed by solid-phase extraction (SPE) with Oasis HLB cartridges and methanol elution followed by LC-MS-MS detection using 13C-labelled internal standards. High concentration levels ( approximately 1.3 microg l(-1)) of perfluorooctanoate (PFOA) were detected in the Tánaro River close to the city Alessandria. After this tributary, levels between 60 and 337 ng l(-1) were measured in the Po River on several occasions. The PFOA concentration close to the river mouth in Ferrara was between 60 and 174 ng l(-1). Using the river discharge flow data in m3 s(-1) at this point (average approximately 920 m3 s(-1) for the year 2006), a mass load of approximately 0.3 kg PFOA per hour or approximately 2.6 tons per year discharged in the Adriatic Sea has been calculated. PFOS concentration levels in the Po River at Ferrara were approximately 10 ng l(-1).     

Enhancement of the CO(2) retention capacity of X zeolites by Na- and Cs-treatments

Adsorption of carbon dioxide on alkaline modified X zeolites was investigated by temperature programmed desorption (TPD) analysis of these materials previously saturated with CO(2) at 50, 100 and 200 degrees C. Parent X zeolite (in its sodium form) was treated with different sodium and cesium aqueous solutions, using both carbonates and hydroxides as precursors. The resulting materials were characterised by nitrogen physisorption, XRD, and NH(3)-TPD, in order to determine their morphological, crystallographic and chemical properties. Slight desilication phenomena were observed using hydroxides as precursors, whereas the treatment with Cs salts lead to higher crystallinity losses. Several successive adsorption-desorption cycles were carried out in order to check the regenerability of the adsorbents. Cesium-treated zeolites present higher carbon dioxide retention capacities than the sodium treated and than the parent material. When working with these Cs-modified materials, the desorption takes place mainly at temperatures between 250 and 400 degrees C, results of great practical interest, since it allows the use these kinds of materials for adsorption-desorption cycles. The evolution of the retention capacity with temperature is also markedly more positive for Cs-treated zeolite, especially when carbonate is used as the precursor. These materials maintain high retention capacities at 100 degrees C (10mg g(-1)) and even at 200 degrees C (3mg g(-1)), temperatures at which the most of the adsorbents are inactive.     

Multiscale analysis of heavy metal contents in Spanish agricultural topsoils

This study characterized and mapped the spatial variability patterns of seven topsoil heavy metals (Cr, Ni, Pb, Cu, Zn, Hg and Cd) within the Ebro river basin (9.3 million ha) by Multivariate Factorial Kriging. The variograms and cross-variograms of heavy metal concentrations showed the presence of multiscale variation that was modeled using three variogram models with ranges of 20km (short-range), 100km (medium-range) and 225km (long-range). Our results indicate that the heavy metal concentration is influenced by bedrock composition and dynamics at all the spatial scales, while human activities have a notorious effect only at the short- and medium-range scale of variation. Sources of Cu, Pb and Zn (and secondary Cd) are associated with agricultural practices (at the short-range scale of variation), whereas Hg variation at the short- and medium-range scale of variation is related to atmospheric deposition.