LC-MS-MS analysis and occurrence of octyl- and nonylphenol, their ethoxylates and their carboxylates in Belgian and Italian textile industry, waste water treatment plant effluents and surface waters

Alkylphenols (APs), alkylphenol ethoxylates (APEOs), ethoxycarboxylate metabolites (APECs) and bisphenol A were determined in surface water using solid-phase extraction (SPE) followed by triple-quadrupole LC-MS-MS. APs were separated by LC from APECs using an acetonitrile-water-gradient without the addition of any buffer. Nonylphenol ethoxycarboxylates (NPECs) interfere in the detection of nonylphenols (NPs) when using an acidic mobile phase, because they produce the same MS-MS fragment ions (219>133 and 147). 4n-NP shows the characteristic transition 219>106; it is well suited as internal standard. Nonylphenol ethoxylates NPE(n)Os (n=1-17) were analysed separately in a second run by positive ionization using an ammonium acetate mobile phase. Textile industry discharges, the corresponding wastewater treatment plant (WWTP) effluents and the receiving rivers in Belgium and Italy were analysed. Among the substances investigated, NPE1C and NPE2O exhibited the highest concentrations in the water samples, up to 4.5 microg l(-1) NPE1C in a WWTP effluent and 3.6 microg l(-1) NPE2O in a river. The highest NP levels were found in the receiving rivers (max. 2.5 microg l(-1)). The predicted no-effect concentration (PNEC) for NP of 0.33 microg l(-1) for water species was frequently exceeded in the surface waters investigated, suggesting potential adverse effects to the aquatic environment.     

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.     

An Evaluation of Restoration Efforts in Fishless Lakes Stocked with Exotic Trout

Abstract: Detrimental effects of introduced fishes on native amphibian populations have prompted removal of introduced cutthroat ( Oncorhynchus clarki ), rainbow ( Oncorhynchus mykiss ), and brook trout (  Salvelinus fontinalis ) from naturally fishless lakes at Mt. Rainier National Park, Washington ( U.S.A.). Using paleolimnological indicators (diatoms, invertebrates, and sediment characteristics) in eight 480-year-old sediment cores from eight lakes, we (1) derived estimates of baseline environmental conditions and natural variation, (2) assessed the effects of stocking naturally fishless lakes, and (3) determined whether lakes returned to predisturbance conditions after fish removal (restoration). Diatom floras were relatively stable between 315 and 90 years before present in all lakes; we used this time period to define lake-specific "baseline" conditions. Dissimilarity analyses of diatoms revealed sustained, dramatic changes in diatom floras that occurred approximately 80 years ago (when fish were introduced) in four of five stocked lakes, whereas the diatom floras in two unstocked lakes had not changed significantly in the last 315 years. Diatoms were not preserved in an eighth lake. State changes also occurred in two lakes over 200 years before European settlement of the Pacific Northwest. Preserved invertebrate densities fluctuated dramatically over time in all cores, providing a poor reference for assessing the effects of fishes. Nevertheless, fish-invertebrate interactions have been demonstrated in other paleolimnological studies and may be useful for lower-elevation or more productive lakes. Because diatom communities have not returned to predisturbance assemblages in restored lakes, even 20–30 years after fish removal, we conclude that Mt. Rainier lakes were not successfully restored by the removal of fishes.     

Utility of North Atlantic Right Whale Museum Specimens for Assessing Changes in Genetic Diversity

Abstract: We examined six historical specimens of the endangered North Atlantic right whale ( Eubalaena glacialis ) using DNA isolated from documented baleen plates from the late nineteenth and early twentieth centuries. Sequences from the mitochondrial DNA (mtDNA) control region from these samples were compared with those from a near-exhaustive survey (269 of approximately 320 individuals) of the remaining right whales in the western North Atlantic Ocean. Our results suggest that there has been only relatively modest change in maternal lineage diversity over the past century in the North Atlantic right whale population. Any significant reduction in genetic variation in the species most likely occurred prior to the late nineteenth century. One historical specimen was from the last documented female capable of propagating one of the maternal lineages in the population today; no females in the existing population have been found to carry this mtDNA haplotype. Analysis of the only specimens from the eastern North Atlantic right whale population ever to be examined revealed that eastern and western North Atlantic right whales may not have been genetically differentiated populations. Loss of gene diversity experienced by North Atlantic right whales over the last century has been modest, and the six decades of protection have been successful in maintaining much of the maternal lineage diversity that was present in the late nineteenth century.     

Demographic Forecasting in Koala Conservation

Abstract: The koala currently needs conservation intervention. There is clear evidence of decline in many populations, but the existence of other stable or expanding populations offers the possibility of a variety of creative solutions to their conservation problems. The 1998 National Koala Conservation Strategy emphasizes the need to obtain demographic information and to use this information to assess management options for koalas. We need accurate diagnoses of the status of koala populations and forecasts of their demographic future with and without particular management actions. In a qualitative fashion, this process has been undertaken many times on a local and national scale. Quantitative demographic forecasting tools are increasingly available, and koala management could benefit from their application both at the scale of individual populations and more broadly. There is already a considerable body of suitable data on the dispersal, effects of normal and catastrophic environmental variation on reproduction and survival, and on the effects of habitat change. Demographic forecasting, however, is hampered because the full suite of information is rarely available from a single population. In two Queensland populations, retrospective population viability analyses provided forecasts that were in agreement with observed population trends. Work is needed to determine whether data from one population can be applied to other populations. Models can then be developed to make projections at a multipopulation level on the basis of local population dynamics and dispersal. Certain koala populations, because of their long history of study, offer the opportunity to test demographic models retrospectively. These tests will not only aid in fine-tuning the models for koala biology and data but will also assist with the more general process of validating the models.     

Conservation Genetics at the Species Boundary

Abstract: Conservation genetics has expanded its purview such that molecular techniques are now used routinely to prioritize populations for listing and protection and infer their historical relationships in addition to addressing more traditional questions of heterozygosity and inbreeding depression. Failure to specify whether molecular data are being used for diagnosis-related questions or for population viability questions, however, can lead either to misinterpretation of character data as adaptive information or to misinterpretation of frequency or distance data as diagnostic or historical information. Each of these misinterpretations will confound conservation programs. The character-based approach to delimiting phylogenetic species is both operationally and logically superior to "diagnostic" methods that involve distance- or frequency-based routines, which are unstable over time. Tree-based criteria for the diagnosis of conservation "units" are also inappropriate because they can depend on patterns inferred without reference to diagnostic characters. Intraspecific studies, conservation-related or otherwise, that adopt terminology and methods designed to infer nested hierarchic relationships confuse diagnosis with historical inferences by treating diagnoses as outcomes rather than as precursors to phylogeny reconstruction. A character-based diagnostic approach recognizes the analytical dichotomy between species hierarchies and population statistics and provides a framework for the understanding of each. No species concept, however, should be viewed as an absolute criterion for protecting populations, but as part of a framework from within which identification of protection and management goals can be achieved effectively and defensibly.     

Heat wave vulnerability and exposure mapping for Osaka City,Japan

Heat waves and heat-related stresses are increasing environmental concerns in urban areas. The impact of heat waves is dependent on the intensity and duration of each event and on underlying environmental and socio-demographic factors which influence population vulnerability. In order to develop effective adaptation strategies, it is important to develop a method to clearly identify the most vulnerable areas based on these factors. The purpose of this study is to develop and map a heat wave vulnerability index combined with heat exposure analysis to identify areas where interventions can be targeted. The vulnerability index was derived from a principle component analysis of eight key variables that influence heat wave vulnerability. Eight proxy measures of vulnerability were obtained from 2010 census and land-use data for the 1904 census districts of Osaka City. Three principle components explained >77 % of the variance (age, employment and education; social isolation; density and lack of green space). The components were combined and weighted to produce a vulnerability score for each census district. The vulnerability scores ranged from 0 to 106, were categorised into eight vulnerability levels and were overlaid with fine-scale air temperature observations. The resulting output identified the distribution of population vulnerability and exposure. This assessment of vulnerability, combining exposure and sensitivity components, can provide precedent for efficient, targeted action to be taken to reduce the impact of heat waves at present and under climate change.     

Photo-Stabilisation and UV Blocking Efficacy of Coated Macro and Nano-Rutile Titanium Dioxide Particles in Paints and Coatings

Surface treated macro and nanoparticle TiO₂ samples have been prepared, characterised and their efficiency as UV blockers evaluated in clear coatings and paints. The particle size of the ‘base’ TiO₂ has been optimised to block UV radiation and the surface treatment developed to deactivate the photocatalytic activity of the surface of the TiO₂ particles. The resultant UV blockers have been evaluated in both solvent and water-based clear coatings. Nanoparticle TiO₂ has been prepared from ‘seed’ and the particle size was controlled by calcination. It was found that the choice of particle size is a compromise between UVA absorption, UVB absorption, visible transmission and photoactivity. It has been demonstrated that TiO₂ with a crystallite size of 25 nm yields a product with the optimum properties. A range of dispersants was successfully used to disperse and mill the TiO₂. Both organic and inorganic dispersants were used; 2-amino-2-methyl-1-propanol and 1-amino-2-propanol (MIPA) and P₂O₅ and Na₂SiO₃ respectively. The surface of the nano-TiO₂ was coated with mixed oxides of silicon, aluminium, zirconium and phosphorous. Addition of the resultant coated nano-rutiles to an Isocyanate Acrylic clear coating prolonged the lifetime of that coating compared to the blank. Generally, a surface treatment based on SiO₂, Al₂O₃ and P₂O₅ was more successful than one based on ZrO₂, Al₂O₃ and P₂O₅. Higher addition levels of the surface treatment were beneficial for protecting the polymeric coating. The UV blocker products were also evaluated in a water-based acrylic, first a water-based dispersion of the UV blocker was prepared before addition to the acrylic. The dispersions and resultant acrylic thin films were evaluated using UV/Vis spectroscopy and durability assessed. The ratio of absorbance at 300:500 nm for the water-based dispersion was shown to be a good predictor of both the transparency of the resultant acrylic thin film and the durability of that film, in terms of weight loss. Macro grade titanium dioxide pigments were also prepared and coated with treatments of silica, alumina and siloxane and their photo-stabilising activity in alkyd paint film assessed and found to be directly related to the electron–hole pair mobility and trapping as determined by micro-wave spectroscopy.     

Biopolymer (Chitin) from Various Marine Seashell Wastes: Isolation and Characterization

Chitin has been produced from different sea waste sources including, molluscs (mussel and oyster shell), crustacean (prawn and crab) and fish scale (pang and silver scales) using deproteinization and demineralization as chemical methods. The conditions of chemical extraction process determine the quality of chitin. The obtained results revealed that, about 1 and 10% HCl and NaOH were adequate concentrations for deproteinization and demineralization process respectively. Chitin from oyster and crab shell waste had the highest yield of 69.65 and 60.00% while prawn, mussel shell, pang and silver scales had the lowest yield of 40.89, 35.03, 35.07 and 31.11% respectively. Chitin solubility is controlled by the quantity of protonated acetyl groups within the polymeric chain of the chitin backbone, thus on the percentage of acetylated and non-acetylated d-glucos-acetamide unit. Good solubility results were obtained in mussel, oyster and crab shells respectively. The chitin molecular weight characteristics and activity are controlled by the degree of acetylation (DA) and the distribution of acetyl group extending in the polymer chain. DA is determined by acid-base titration methods and molecular weight determined by Brookfield viscometry. Both methods are found to be effective.