Assessment of commercially available polymeric materials for sorptive microextraction of priority and emerging nonpolar organic pollutants in environmental water samples

Among the different organic pollutants, persistent organic pollutants and emerging organic contaminants (EOCs) are of particular concern due to their potentially dangerous effects on the ecosystems and on human health. In the framework of the analysis of some of these organic pollutants in water samples, sorptive extraction devices have proven to be adequate for their monitoring. The efficiency of four commercially available and low-cost polymeric materials [polypropylene, poly(ethylene terephthalate), Raffia, and polyethersulfone (PES)] for the simultaneous extraction of 16 organic compounds from five different families from environmental water samples was evaluated in this work. Firstly, the homogeneity of the sorbent materials was confirmed by means of Raman spectroscopy. After the optimization of the parameters affecting the extraction and the liquid desorption steps, it was found that PES showed the largest efficiencies for slightly polar analytes and, to a lesser extent, for nonpolar analytes. Additionally, Raffia rendered good extraction efficiencies for nonpolar compounds. Thus sorptive extraction methods followed by large volume injection-programmable temperature vaporizer-gas chromatography-mass spectrometry were validated using PES and Raffia as sorbent materials. The validation of the method provided good linearity (0.978?r ²?r ²?-1 level). Finally, these materials were applied to the analysis of contaminants in environmental water samples.     

Assessing demineralization treatments for PVC effluent reuse in the resin polymerization step

To reduce fresh water consumption in a polyvinyl chloride (PVC) plant, the effluent from a biological treatment must be demineralized to be re-used in the resin polymerization process. Demineralization is a critical process, since the quality and the stability of the PVC resins are highly influenced by the water quality used in the process. The main target values for water parameters are the following: conductivity <10 μScm^?1, TOC < 10 mg L^?1, and Al < 0.1 mg L^?1. To achieve this quality, several reverse osmosis membranes from different materials and suppliers were tested and compared in the demineralization treatment. Polyamide membranes showed higher salt rejection compared to cellulose acetate membranes yielding both types similar flux and permeability. Two-pass reverse osmosis treatment was necessary to reach conductivities lower than 10 μS cm^?1. On the other hand, a good quality effluent for reuse was obtained by combining RO and ionic exchange resins. Results showed that good quality PVC resins in terms of color, granulometry, porosity, and bulk density were obtained when demineralized water from two-pass reverse osmosis was used as fresh water, proving the feasibility of the effluent reuse in the PVC industry.     

Molecular insight into the population structure of common and spotted dolphins inhabiting the pelagic waters of the Northeast Atlantic

Several cetacean species exhibit fine-scale population structure despite their high dispersal capacities and the apparent continuity of the marine environment. In dolphins, most studies have focused on coastal areas and continental margins, and they revealed differentiated populations within relatively small geographic areas, sometimes in conjunction with a specialisation for different habitats (ecotypes). We analysed the population genetic structure of short-beaked common dolphins (Delphinus delphis) and Atlantic spotted dolphins (Stenella frontalis) in the Azores and Madeira, the two most isolated archipelagos of the North Atlantic. The archipelago of the Azores is divided into three groups of islands and stands 900 km away from Madeira. It is not known whether individuals migrate between groups of islands and archipelagos, nor whether distinct ecotypes are present. These questions were investigated by genetic analyses of 343 biopsy samples collected on free-ranging dolphins. The analyses consisted in sequencing part of the mitochondrial hyper-variable region, screening up to 14 microsatellite loci, and molecular sexing. Results did not unravel any population structure at the scale of the study area. Lack of differentiation matches expectations for spotted dolphins, which are transient in both archipelagos, but not for common dolphins, which are present year-round in the Azores and potentially resident. Absence of genetic structure over hundreds and even thousands of kilometres implies the existence of gene flow over much larger distances than usually documented in small delphinids, which could be achieved through individual movements. This finding indicates that population structure in oceanic habitat differs from that observed in coastal habitat.     

Estimation bias under model selection for distance sampling detection functions

Many simulation studies have examined the properties of distance sampling estimators of wildlife population size. When assumptions hold, if distances are generated from a detection model and fitted using the same model, they are known to perform well. However, in practice, the true model is unknown. Therefore, standard practice includes model selection, typically using model comparison tools like Akaike Information Criterion. Here we examine the performance of standard distance sampling estimators under model selection. We compare line and point transect estimators with distances simulated from two detection functions, hazard-rate and exponential power series (EPS), over a range of sample sizes. To mimic the real-world context where the true model may not be part of the candidate set, EPS models were not included as candidates, except for the half-normal parameterization. We found median bias depended on sample size (being asymptotically unbiased) and on the form of the true detection function: negative bias (up to 15% for line transects and 30% for point transects) when the shoulder of maximum detectability was narrow, and positive bias (up to 10% for line transects and 15% for point transects) when it was wide. Generating unbiased simulations requires careful choice of detection function or very large datasets. Practitioners should collect data that result in detection functions with a shoulder similar to a half-normal and use the monotonicity constraint. Narrow-shouldered detection functions can be avoided through good field procedures and those with wide shoulder are unlikely to occur, due to heterogeneity in detectability.     

Transparent exopolymer particles in a deep-sea hydrothermal system: Guaymas Basin,Gulf of California

This is the first report of transparent exopolymer particle (TEP) concentrations within deep-sea hydrothermal vent systems using colorimetric methods, measuring TEP in supernatants of sediments surrounding the vents, in fluids emanating directly from hydrothermal vents and in neutrally buoyant hydrothermal plumes. Samples were collected at Guaymas Basin (Gulf of California), a sedimented hydrothermal system. TEP concentrations within the hydrothermal fluids were significantly greater than the only other report of TEP in deep water. The range of values for TEP abundance were 8–6,451 μg/L of gum xanthan equivalents, the highest values being associated with supernatants of microbial mat-covered sediments. The potential sources and significance of the high concentrations of TEP observed in this deep-sea hydrothermal environment are discussed.     

Ranging patterns of bottlenose dolphins living in oceanic waters: implications for population structure

Very little is known about the ecology of common bottlenose dolphins (Tursiops truncatus) living in oceanic waters. This study investigated the ranging and residence patterns of bottlenose dolphins occurring in the Azores (Portugal), the most isolated archipelago in the North Atlantic. Data were collected during standardized boat-based surveys conducted over a 6-year period in an area of approximately 5,400 km² (main study area). To investigate the extent of movements of individual animals, non-systematic surveys were also conducted outside this area. Only 44 individuals out of 966 identified were frequently sighted within and between years. The remaining individuals were either temporary migrants from within or outside the archipelago, or transients. Resident dolphins showed strong geographic fidelity to the area. Long-distance movements (of almost 300 km), consistent with foraging or exploratory trips, were observed among non-resident dolphins. Home range size was estimated for 31 individuals sighted ≥10 times. Range areas of these dolphins varied in size and location, but considerable overlap was observed in the areas used, suggesting the absence of habitat partitioning between resident and non-resident dolphins. Estimates of home range size of bottlenose dolphins in the Azores were found to be considerably larger than those previously reported for this species. It is hypothesized that dolphins living in the Azores carry out extensive movements and have large home ranges in response to the lower density and patchy distribution of prey compared to other areas. The extensive ranging behaviour and the lack of territoriality provide an opportunity for interbreeding between dolphins associated with different islands, thus preventing genetic differentiation within the population of the Azores.     

Cadmium and lead in bovine milk in the mining area of the Caudal River (Spain)

The levels of cadmium and lead in 36 raw bovine milk samples were analysed. These samples come from seven farms with a semi-extensive grazing system and were collected between the autumn of 2007 and the winter of 2008. All the farms were located in Asturias (Spain), a zone of great industrial and mining activity in the proximities of the Caudal River. The samples were collected in sterile precleaned polypropylene tubes and frozen until the analysis. After a lyophilization process, the samples were treated with nitric acid and microwave treatment. Cadmium and lead determinations were carried out using inductively coupled plasma mass spectrometry with sensibility under 0.2 ppb for liquid matrix. The lead content was found to vary from 0.71 to 16.06 μg/kg wet weight (w.w.), and the cadmium was lower than 2 μg/kg w.w. The levels of lead in milk are higher in those farms near zones of storage of mining waste depots, thermal power and areas with high levels of traffic. All the values found are in concordance with research carried out at non-polluted areas, and those for the lead are well below the European Union limitations.     

The production of rhamnolipid by a Pseudomonas aeruginosa strain isolated from a southern coastal zone in Brazil

The production and properties of a rhamnolipid-type biosurfactant, synthesized by the Pseudomonas aeruginosa LBM10 strain, isolated from a southern coastal zone in Brazil, were investigated. The assays were conducted in a rotary shaker at 30 degrees C and 180 rpm for a period of 96 h. Soybean oil and sodium nitrate were the best sources of carbon and nitrogen, respectively. A nitrogen-limiting condition (C/N ratio of 100) was favorable to biosurfactant production. The formation of stable emulsions was better in saline concentrations below 0.5%, pH values in the range from 6 to 9 and temperatures in the range from 35 to 40 degrees C, maintaining about 80% of its original activity for salinity up to 3% and 120 min of exposure at 100 degrees C. The biosurfactant may be produced with this microorganism using renewable substrates that are readily available, reaching values of 1.42 g l(-1) measured as rhamnose. This biosurfactant has interesting and useful properties for many industrial applications.     

Ranging patterns of bottlenose dolphins living in oceanic waters: implications for population structure

Very little is known about the ecology of common bottlenose dolphins (Tursiops truncatus) living in oceanic waters. This study investigated the ranging and residence patterns of bottlenose dolphins occurring in the Azores (Portugal), the most isolated archipelago in the North Atlantic. Data were collected during standardized boat-based surveys conducted over a 6-year period in an area of approximately 5,400 km² (main study area). To investigate the extent of movements of individual animals, non-systematic surveys were also conducted outside this area. Only 44 individuals out of 966 identified were frequently sighted within and between years. The remaining individuals were either temporary migrants from within or outside the archipelago, or transients. Resident dolphins showed strong geographic fidelity to the area. Long-distance movements (of almost 300 km), consistent with foraging or exploratory trips, were observed among non-resident dolphins. Home range size was estimated for 31 individuals sighted ≥10 times. Range areas of these dolphins varied in size and location, but considerable overlap was observed in the areas used, suggesting the absence of habitat partitioning between resident and non-resident dolphins. Estimates of home range size of bottlenose dolphins in the Azores were found to be considerably larger than those previously reported for this species. It is hypothesized that dolphins living in the Azores carry out extensive movements and have large home ranges in response to the lower density and patchy distribution of prey compared to other areas. The extensive ranging behaviour and the lack of territoriality provide an opportunity for interbreeding between dolphins associated with different islands, thus preventing genetic differentiation within the population of the Azores.     

Coelomocyte biomarkers in the earthworm Eisenia fetida exposed to 2,4,6-trinitrotoluene (TNT)

Contamination by 2,4,6-trinitrotoluene (TNT) is a global environmental problem at sites of former explosive production, handling, or storage, and could have deleterious consequences for human and ecological health. We investigated its sublethal effects to Eisenia fetida, using two nonspecific biomarkers. In coelomocytes of earthworms exposed 24, 48, or 72 h, we evaluated DNA damage (comet assay) and neutral red retention time (NRRT), using the filter paper contact test. Both percentage of damage (D%) and calculated damage index showed significant DNA damage at almost all concentrations, at all time points assayed. Along exposure time, two different patterns were observed. At the lower TNT concentrations (0.25?C0.5 ??g/cm²) an increased DNA migration at 48 h, with a decrease close to initial levels after 72 h exposure, was observed. This decrease could be attributed to activation of the DNA repair system. At higher concentrations (1.0?C2.0 ??g/cm²), the high DNA damage observed remained constant during the 72 h exposure, suggesting that the rate of DNA repair was not enough to compensate such damage. Analysis of NRRT results showed a significant interaction between time and treatment. After 48 h, a significant decrease was observed at 4.0 ??g/cm². After 72 h, NRRT presented a concentration-dependent decrease, significantly different with respect to control at 0.5, 1.0, 2.0, and 4.0 ??g/cm². The two assayed methods, performed on the same sample, showed clear responses to sublethal TNT exposure in E. fetida, providing sensitive unspecific biomarkers of cell injury and DNA damage.