Diel cycles of arsenic speciation due to photooxidation in acid mine drainage from the Iberian Pyrite Belt (Sw Spain)

Twenty four hours diel cycles of arsenic speciation in Acid Mine Drainage (AMD) due to photooxidation have been reported for the first time. AMD samples were taken during 48 h (31st March and 1st April, 2005) at 6 h intervals from the effluent of a massive abandoned polymetallic sulphide mine of the Iberian Pyrite Belt (Sw Spain). Samples were preserved in situ using cationic exchange prior to analysis by coupled high performance liquid chromatography, hydride generation and atomic fluorescence spectrometry (HPLC-HG-AFS) for arsenic speciation. The results indicated the presence of inorganic arsenic species with daily means of 262mugl(-1) for As(V) and 107 microg l(-1) for As(III). No marked diel trend was observed for As(V). However, a marked diel trend was observed for As(III) in the two studied days, with maximum concentrations during nighttime (141-143 microg l(-1)) and minimum concentrations at daytime (72-77 microg l(-1)). This difference in concentration during daytime and nighttime is ca. 100%. A similar diel cycle was observed for iron. An explanation for the arsenic diel cycles observed is the light induced photooxidation of As(III) and the elimination of As(V) due to its adsorption onto Fe precipitates during the daytime. Furthermore, the diel changes in arsenic speciation emphasize the importance of designing suitable sampling strategies in AMD systems.     

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.     

The Influence of Artificial Photodegradation on Properties of Poly(3-hydroxybutyrate-<Emphasis Type="Italic">co</Emphasis>-3-hydroxyvalerate)(PHBV)/Graphite Nanosheets (GNS) Nanocomposites

The potential use of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/graphite nanosheets (GNS) as a biodegradable nanocomposite has been explored. PHBV/GNS nanocomposites films were prepared by solution casting at various concentrations of GNS—0.25, 0.50 and 1.00 wt% GNS. The films were exposed to artificial ultraviolet radiation (UV) during 52 h. The effect of GNS on PHBV photodegradation was investigated and compared to neat PHBV film. The artificial photodegradation induced changes in physical (weight loss), chemical carbonyl index by Fourier transform infrared spectroscopy, thermal degree of crystallinity and melting temperature by differential scanning calorimetry and morphological scanning electron microscopy characteristics. Based on the results obtained from aforementioned analyzes it was verified that GNS inhibits the oxidative degradation of PHBV matrix.     

Baked Foams Based on Cassava Starch Coated with Polyvinyl Alcohol with a Higher Degree of Hydrolysis

The aims of this work were to produce trays based on cassava starch, coated with polyvinyl alcohol (PVA) with a higher degree of hydrolysis (98%), and to study the effects of the coating on the mechanical and water sorption properties of the trays. Two types of PVA were tested: SELVOL? 325 (degree of polymerization?=?1000–1500) and SELVOL? 107 (degree of polymerization?=?350–650). A decrease in the water absorption capacity of 50% was observed when the coated samples were compared with the control sample after 30 min of immersion in water. It was observed in both coated samples a reduction of the initial rate of water adsorption sorption and a decrease in hydrophilicity compared with the control sample. Tensile strength and elongation were increased with application of the coatings. The use of the two types of PVA resulted in materials with similar mechanical and water sorption properties.     

One-Component Spray Polyurethane Foam from Liquefied Pinewood Polyols: Pursuing Eco-Friendly Materials

The use of petroleum-derived products should be avoided regarding the principles of green and sustainable chemistry. The work reported herein, is aimed at the liquefaction of pine shavings for the production of an environmentally-friendly polyol suitable to be used in the formulations of sprayable polyurethane foams. The biopolyols were obtained in high yield and were used to replace those derived from fossil sources, to produce more “greener” polyurethane foams and therefore, less dependent on petroleum sources, since the polyol component was substituted by products resulting from biomass liquefaction. The partial and fully exchange of the polyols was accomplished, and the results compared with a reference foam. The foams were afterward, chemical, physical, morphological, and mechanically characterized. The complete replacement of polyether polyol and polyol polyester has presented some similar characteristics as that used as a reference, validating that the path chosen for the development of more sustainable materials is on the right track for the contribution to a cleaner world.     

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.