Oxidation of trichloroethene over metal oxide catalysts: kinetic studies and correlation with adsorption properties

The performance of bulk chromium oxide is compared with that of a Mn commercial catalyst for the deep oxidation of trichloroethene (1000-2500ppmv, 55h(-1) space velocity) in air, in dry and wet (20000ppm of H(2)O) conditions, in terms of activity, selectivity and stability. Chromium oxide was found to be more active (on a catalyst weight basis), however its activity decreases continuously with time on stream. The presence of water increases its stability, the Mn catalyst showing the opposite behaviour. The effect of water on the Cr catalyst can be explained according to the Deacon equilibrium, as the presence of water tends to decrease the Cl(2) concentration, assumed to be responsible of the catalyst deactivation. Regarding to the selectivity, the Mn catalyst yields C(2)Cl(4), CCl(4) and CHCl(3) as organochlorinated by-products, whereas chromium oxide produces only trace amounts of CCl(4). Simple power-law kinetics expressions (first-order for Mn and zero-order for Cr) provide fairly good fits for the evolution of the conversion with the temperature. Furthermore, the kinetic behaviour of chromium oxide can be represented with a Langmuir-Hinshelwood model taking into account the chlorine inhibitory effect.     

Bioaccumulation of lead, mercury, and cadmium in the greater white-toothed shrew, Crocidura russula, from the Ebro Delta (NE Spain): sex- and age-dependent variation

We quantified bioaccumulation of lead, mercury, and cadmium in bones from 105 greater white-toothed shrews (Crocidura russula) collected at the Ebro Delta, a polluted area, and the Medas Islands, a control site. Lead and mercury levels varied with site, age, and sex, although statistical significances depended on each factor. Globally, shrews from the polluted area exhibited significantly higher concentrations of Pb and Hg. Increment of Pb with age was particularly remarkable in wetland animals and was interpreted in relation to human activities, namely hunting. Unlike males, females from the Ebro Delta maintained low Hg levels, which were associated with gestation and lactation. Cadmium levels did not differ between sites, sexes, or ages. This study provides the first data on heavy metals in mammals from this wetland and suggests that C. russula is a good bioindicator of metal pollution. We concluded that sex and age may represent an important source of variation in the bioaccumulation of these metals in wild populations.     

Recent Changes in Stream Flashiness and Flooding,and Effects of Flood Management in North Carolina and Virginia

The southeastern United States has undergone anthropogenic changes in landscape structure, with the potential to increase (e.g., urbanization) and decrease (e.g., reservoir construction) stream flashiness and flooding. Assessment of the outcome of such change can provide insight into the efficacy of current strategies and policies to manage water resources. We (1) examined trends in precipitation, floods, and stream flashiness and (2) assessed the relative influence of land cover and flow‐regulating features (e.g., best management practices and artificial water bodies) on stream flashiness from 1991 to 2013. We found mean annual precipitation decreased, which coincided with decreasing trends in floods. In contrast, stream flashiness, overall, showed an increasing trend during the period of study. However, upon closer examination, 20 watersheds showed stable stream flashiness, whereas 5 increased and 6 decreased in flashiness. Urban watersheds were among those that increased or decreased in flashiness. Watersheds that increased in stream flashiness gained more urban cover, lost more forested cover and had fewer best management practices installed than urban watersheds that decreased in stream flashiness. We found best management practices are more effective than artificial water bodies in regulating flashy floods. Flashiness index is a valuable and straightforward metric to characterize changes in streamflow and help to assess the efficacy of management interventions.     

Bison and cattle grazing management,bare ground coverage,and links to suspended sediment concentrations in grassland streams

This study quantified the impact of bison and cattle grazing management practices on bare ground coverage at the watershed, riparian, and forested riparian scales within the Flint Hills ecoregion in Kansas. We tested for correlations between bare ground coverage and fluvial suspended sediment concentrations during base‐flow and storm‐flow events. We used remotely sensed imagery combined with field surveys to classify ground cover and quantify the presence of bare ground. Base‐flow water samples were collected bi‐monthly during rain‐free periods and 24 h following precipitation events. Storm‐flow water samples were collected on the rising limb of the hydrograph, using single‐stage automatic samplers. Ungrazed treatments contained the lowest coverage of bare ground at the watershed, riparian, and forested riparian scales. Bison treatments contained the highest coverage of bare ground at the watershed scale, while high‐density cattle treatments contained the highest coverage of bare ground at the riparian and forested riparian scales. In bison and cattle‐grazed treatments, a majority of bare ground was located near fence lines, watershed boundaries, and third‐ and fourth‐order stream segments. Inorganic sediment concentrations at base flow were best predicted by riparian bare ground coverage, while storm‐flow sediment concentrations were best predicted by watershed scale bare ground coverage.     

Improving Pro-environmental Behaviours in Spain. The Role of Attitudes and Socio-demographic and Political Factors

Over the last 30 years, Spain has witnessed great economic growth. Nevertheless, in spite of an increasing degree of environmental concern, environmentally friendly attitudes and behaviours are still clearly below the European average. In this context, this paper analyses the impact of personal control and attitudes, and of certain socio-demographic, economic and political variables in the development of two environmentally friendly behaviours in Spain: consumption and purchase. The data were provided by a survey carried out in 2007 by the Centro de Investigaciones Sociológicas (Centre for Sociological Research) in Spain. The results show the importance of personal control, level of environmental information, political ideology, age and educational level variables to explaining the development of pro-environmental-related consumption behaviours. Personal attitudes, work situation, female gender and level of environmental information influence pro-environmental purchase behaviour in a positive way. Taking into account that personal attitudes are more determining of pro-environmental purchase than consumption behaviour, policy measures such as informal education, tax measures, social and individual norms and interpersonal and institutional trust are discussed to increase the development of pro-environmental behaviours in Spain.     

First inter-laboratory comparison exercise for the determination of anticancer drugs in aqueous samples

The results of an inter-laboratory comparison exercise to determine cytostatic anticancer drug residues in surface water, hospital wastewater and wastewater treatment plant effluent are reported. To obtain a critical number of participants, an invitation was sent out to potential laboratories identified to have the necessary knowledge and instrumentation. Nine laboratories worldwide confirmed their participation in the exercise. The compounds selected (based on the extent of use and laboratories capabilities) included cyclophosphamide, ifosfamide, 5-fluorouracil, gemcitabine, etoposide, methotrexate and cisplatinum. Samples of spiked waste (hospital and wastewater treatment plant effluent) and surface water, and additional non-spiked hospital wastewater, were prepared by the organising laboratory (Jo?ef Stefan Institute) and sent out to each participant partner for analysis. All analytical methods included solid phase extraction (SPE) and the use of surrogate/internal standards for quantification. Chemical analysis was performed using either liquid or gas chromatography mass (MS) or tandem mass (MS/MS) spectrometry. Cisplatinum was determined using inductively coupled plasma mass spectrometry (ICP-MS). A required minimum contribution of five laboratories meant that only cyclophosphamide, ifosfamide, methotrexate and etoposide could be included in the statistical evaluation. z-score and Q test revealed 3 and 4 outliers using classical and robust approach, respectively. The smallest absolute differences between the spiked values and the measured values were observed in the surface water matrix. The highest within-laboratory repeatability was observed for methotrexate in all three matrices (CV?≤?12 %). Overall, inter-laboratory reproducibility was poor for all compounds and matrices (CV 27–143 %) with the only exception being methotrexate measured in the spiked hospital wastewater (CV?=?8 %). Random and total errors were identified by means of Youden plots.     

Heavy metal contamination in sediments of an artificial reservoir impacted by long-term mining activity in the Almadén mercury district (Spain)

Sediments from the Castilseras reservoir, located downstream on the Valdeazogues River in the Almadén mercury district, were collected to assess the potential contamination status related to metals(oids) associated with river sediment inputs from several decommissioned mines. Metals(oids) concentrations in the reservoir sediments were investigated using different physical and chemical techniques. The results were analyzed by principal component analysis (PCA) to explain the correlations between the sets of variables. The degree of contamination was evaluated using the enrichment factor (EF) and the geoaccumulation index (Igeo). PCA revealed that the silty fraction is the main metals(oids) carrier in the sediments. Among the potentially harmful elements, there is a group (Al, Cr, Cu, Fe, Mn, Ni, and Zn) that cannot be strictly correlated to the mining activity since their concentrations depend on the lithological and edaphological characteristics of the materials. In contrast, As, Co, Hg, Pb, and S showed significant enrichment and contamination, thus suggesting relevant contributions from the decommissioned mines through fluvial sediment inputs. As far as Hg and S are concerned, the high enrichment levels pose a question concerning the potential environmental risk of transfer of the organic forms of Hg (mainly methylmercury) from the bottom sediments to the aquatic food chain.     

Biodegradability of the anticancer drug etoposide and identification of the transformation products

Etoposide susceptibility to microbiological breakdown was studied in a batch biotransformation system, in the presence or absence of artificial wastewater containing nutrients, salts and activated sludge at two concentration levels. The primary focus of the present study was to study etoposide transformation products by ultra-high performance liquid chromatography coupled to high-resolution hybrid quadrupole-Orbitrap tandem mass spectrometry (MS/MS). Data-dependent experiments combining full-scan MS data with product ion spectra were acquired to identify the molecular ions of etoposide transformation products, to propose the molecular formulae and to elucidate their chemical structures. Due to the complexity of the matrix, visual inspection of the chromatograms showed no clear differences between the controls and the treated samples. Therefore, the software package MZmine was used to facilitate the identification of the transformation products and speed up the data analysis. In total, we propose five transformation products; among them, four are described as etoposide transformation products for the first time. Even though the chemical structures of these new compounds cannot be confirmed due to the lack of standards, their molecular formulae can be used to target them in monitoring studies.