Development of a catalytic dehalogenation (Cl,Br) process for municipal waste plastic-derived oil

Dehalogenation is a key technology in the feedstock recycling of mixed halogenated waste plastics. In this study, two different methods were used to clarify the effectiveness of our proposed catalytic dehalogenation process using various carbon composites of iron oxides and calcium carbonate as the catalyst/sorbent. The first approach (a two-step process) was to develop a process for the thermal degradation of mixed halogenated waste plastics, and also develop dehalogenation catalysts for the catalytic dehydrochlorination of organic chlorine compounds from mixed plastic-derived oil containing polyvinyl chloride (PVC) using a fixed-bed flow-type reactor. The second approach (a single-step process) was the simultaneous degradation and dehalogenation of chlorinated (PVC) and brominated (plastic containing brominated flame retardant, HIPS–Br) mixed plastics into halogen-free liquid products. We report on a catalytic dehalogenation process for the chlorinated and brominated organic compounds formed by the pyrolysis of PVC and brominated flame retardant (HIPS–Br) mixed waste plastics [(polyethylene (PE), polypropylene (PP), and polystyrene (PS)], and also other plastics. During dehydrohalogenation, the iron- and calcium-based catalysts were transformed into their corresponding halides, which are also very active in the dehydrohalogenation of organic halogenated compounds. The halogen-free plastic-derived oil (PDO) can be used as a fuel oil or feedstock in refineries.     

Nuclear magnetic resonance studies of interactions between organic pollutants and soil components,a review

This article presents a short overview of selected recent papers using nuclear magnetic resonance (NMR) to investigate interactions between organic pollutants and soil components such as organic matter, clays, whole soils, and sediments. First, we describe solid state cross polarisation magic angle spinning (CP-MAS) experiments as the main tools to investigate covalent bonds. Second, we report NMR approaches allowing us to assess molecule mobility and to characterise non-covalent interactions. Those approaches include correlations between K _oc values and soil organic matter functions determined by CP-MAS, ²H NMR fingerprints, relaxation time measurements, ¹⁹F and ¹H high resolution (HR)-MAS experiments.     

Conifer needles as passive biomonitors of the spatial and temporal distribution of DDT from a point source

Needles of two conifer species, Picea abies and Pinus nigra, were used as passive samplers for monitoring air contamination by sampling at increasing distances from a suspected point source of DDT. Needle concentrations declined with increasing distance downwind of the point source allowing to identify spatial and temporal trends of accumulation. This suggested that conifer needles are effective biomonitors of contamination levels in areas characterized by the presence of semi-volatile substances. Differences in uptake were apparent between the species. Needle morphology and structure were studied with scanning electron microscope (SEM) as were dimensional parameters (surface area, volume). The results suggest that the concentrations depend on a mechanism involving the inner structure of the needles, specifically the number and accessibility of resin channels rather than their surface area. Pine needles have more channels with greater accessibility than spruce. The results suggest that spruce is more suitable for short term measurement while pine for determining long term cumulative exposure.     

Disruption of biofilms from sewage pipes under physical and chemical conditioning

Biofilms grown inside two sewage collecting pipes located in industrial and residential areas are studied. Bacterial biomass inside three layers of biofilms was evaluated. Biofilm cohesion under different mixing rate and ionic strength was also investigated. Effects of physical and chemical parameters in the biofilms were evaluated by monitoring turbidity, chemical and biochemical oxygen demands. Extracted organic matter from biofilms was partitioned to polar, aromatic and saturated fractions using activated silica column chromatography. Results revealed that bacterial biomass growth depending on biofilm thickness and stratification. The most loaded stratum in bacterial biomass was the sewage-biofilm interface stratum that represented 51% of the total bacterial biomass. Stirring rate and ionic strength of mono and bivalent salts showed a major influence in biofilm disruption. The stirring time enhanced the exchange dynamic and matter capture between biofilm fragments at the critical stirring rate 90 r/min. Sodium chloride showed the dispersing effect on biofilms in suspension, and decreased the BOD5 (biochemical oxygen demand) beyond the physiological salt concentration.     

Determination of persistent organic pollutants by gas chromatography/laser multiphoton ionization/time-of-flight mass spectrometry

An authentic mixture of polychlorinated biphenyls was measured using a short wide-bore capillary column for the group separation of major components present in an actual sample of Kanechlor. The limits of detection were improved by ca. 2 fold in comparison with those obtained using a conventional capillary column, since the retention time was reduced and the amount of analytes introduced into the mass spectrometer per unit time could be increased. On the other hand, surface-water and sediment samples containing polycyclic aromatic hydrocarbons (PAHs) were collected from the river located in the vicinity of a waste water treatment plant. Even acenaphthylene, a minor component of the mixture could be measured for the sediment sample, and the concentrations were determined for several heavy PAHs. As demonstrated, a technique involving laser multiphoton ionization/time-of-flight mass spectrometry was useful as a sensitive and selective analytical tool for the trace analysis of persistent organic pollutants in an environmental sample.     

Integument coloration signals reproductive success,heterozygosity, and antioxidant levels in chick-rearing black-legged kittiwakes

Carotenoid pigments are important for immunity and as antioxidants, and carotenoid-based colors are believed to provide honest signals of individual quality. Other colorless but more efficient antioxidants such as vitamins A and E may protect carotenoids from bleaching. Carotenoid-based colors have thus recently been suggested to reflect the concentration of such colorless antioxidants, but this has rarely been tested. Furthermore, although evidence is accruing for multiple genetic criteria for mate choice, carotenoid-based colors have rarely been shown to reflect both phenotypic and genetic quality. In this study, we investigated whether gape, tongue, eye-ring, and bill coloration of chick-rearing black-legged kittiwakes Rissa tridactyla reflected circulating levels of carotenoids and vitamins A and E. We further investigated whether integument coloration reflected phenotypic (body condition and fledging success) and genetic quality (heterozygosity). We found that the coloration of fleshy integuments was correlated with carotenoid and vitamin A levels and fledging success but only in males. Furthermore, the coloration of tongue and eye-ring was correlated with heterozygosity in both males and females. Integument colors might therefore be reliable signals of individual quality used by birds to adjust their parental care during the chick-rearing period.     

Marine aquaculture and bottlenose dolphins’ (<Emphasis Type="Italic">Tursiops truncatus</Emphasis>) social structure

In this study, we investigate association patterns of 249 bottlenose dolphin feeding groups off Sardinia Island (Italy) from January 2000–May 2007 and describe how their association behaviour is related to their response to food patches created by a marine fin fish farm. We also tested the hypothesis that dolphins have different social structures with different feeding activities: Associations should decrease during opportunistic feeding behaviours as it is easier to capture prey, and cooperation is not as necessary. Sixteen individually identified bottlenose dolphins were observed participating in both opportunistic and not opportunistic feeding activities, with a mean of 30 ± 8 times and 9.6 ± 1 times, respectively. Bottlenose dolphins show non-random social behaviour during feeding and this behaviour differs depending on their specific foraging activity. Dolphin associations during feeding can be divided into three categories: acquaintances, affiliates, and feeding associates. Association behaviour during fish farm feeding is consistent with our hypothesis that during opportunistic behaviours, benefits from cooperation decrease, as it is easier to capture prey. Group size homogeneity in both feeding activities demonstrates that the number of dolphins engaging in foraging is not necessarily related with cooperation levels. Moreover, an adult dolphin may prefer to associate with a specific individual, independent of the sex, who shares the same foraging priorities. This study is the first to show how aquaculture is not only directly affecting marine predators but could also indirectly affect their social structure and behaviour.     

Resource defense polygyny shifts to female defense polygyny over the course of the reproductive season of a Neotropical harvestman

Although studies classify the polygynous mating system of a given species into female defense polygyny (FDP) or resource defense polygyny (RDP), the boundary between these two categories is often slight. Males of some species may even shift between these two types of polygyny in response to temporal variation in social and environmental conditions. Here, we examine the mating system of the Neotropical harvestman Acutisoma proximum and, in order to assess if mate acquisition in males corresponds to FDP or RDP, we tested four contrasting predictions derived from the mating system theory. At the beginning of the reproductive season, males fight with other males for the possession of territories on the vegetation where females will later oviposit, as expected in RDP. Females present a marked preference for specific host plant species, and males establish their territories in areas where these host plants are specially abundant, which is also expected in RDP. Later in the reproductive season, males reduce their patrolling activity and focus on defending individual females that are ovipositing inside their territories, as what occurs in FDP. This is the first described case of an arachnid that exhibits a shift in mating system over the reproductive season, revealing that we should be cautious when defining the mating system of a species based on few observations concentrated in a brief period. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Seasonal water stress tolerance and habitat associations within four neotropical tree genera

We investigated the relationship between habitat association and physiological performance in four congeneric species pairs exhibiting contrasting distributions between seasonally flooded and terra firme habitats in lowland tropical rain forests of French Guiana, including Virola and Iryanthera (Myristicaceae), Symphonia (Clusiaceae), and Eperua (Caesalpiniaceae). We analyzed 10-year data sets of mapped and measured saplings (stems >150 cm in height and <10 cm diameter at breast height [dbh]) and trees (stems > or =10 cm dbh) across 37.5 ha of permanent plots covering a 300-ha zone, within which seasonally flooded areas (where the water table never descends below 1 m) have been mapped. Additionally, we tested the response of growth, survival, and leaf functional traits of these species to drought and flood stress in a controlled experiment. We tested for habitat preference using a modification of the torus translation method. Strong contrasting associations of the species pairs of Iryanthera, Virola, and Symphonia were observed at the sapling stage, and these associations strengthened for the tree stage. Neither species of Eperua was significantly associated with flooded habitats at the sapling stage, but E. falcata was significantly and positively associated with flooded forests at the tree stage, and trees of E. grandiflora were found almost exclusively in nonflooded habitats. Differential performance provided limited explanatory support for the observed habitat associations, with only congeners of Iryanthera exhibiting divergent sapling survival and tree growth. Seedlings of species associated with flooded forest tended to have higher photosynthetic capacity than their congeners at field capacity. In addition, they tended to have the largest reductions in leaf gas exchange and growth rate in response to experimental drought stress and the least reductions in response to experimental inundation. The corroboration of habitat association with differences in functional traits and, to a lesser extent, measures of performance provides an explanation for the regional coexistence of these species pairs. We suggest that specialization to seasonally flooded habitats may explain patterns of adaptive radiation in many tropical tree genera and thereby provide a substantial contribution to regional tree diversity.