Methods,fluxes and sources of gas phase alkyl nitrates in the coastal air

The daily and seasonal atmospheric concentrations, deposition fluxes and emission sources of a few C3–C9 gaseous alkyl nitrates (ANs) at the Belgian coast (De Haan) on the Southern North Sea were determined. An adapted sampler design for low- and high-volume air-sampling, optimized sample extraction and clean-up, as well as identification and quantification of ANs in air samples by means of gas chromatography mass spectrometry, are reported. The total concentrations of ANs ranged from 0.03 to 85 pptv and consisted primarily of the nitro-butane and nitro-pentane isomers. Air mass backward trajectories were calculated by the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model to determine the influence of main air masses on AN levels in the air. The shorter chain ANs have been the most abundant in the Atlantic/Channel/UK air masses, while longer chain ANs prevailed in continental air. The overall mean N fluxes of the ANs were slightly higher for summer than those for winter-spring, although their contributions to the total nitrogen flux were low. High correlations between AN and HNO₂ levels were observed during winter/spring. During summer, the shorter chain ANs correlated well with precipitation. Source apportionment by means of principal component analysis indicated that most of the gas phase ANs could be attributed to traffic/combustion, secondary photochemical formation and biomass burning, although marine sources may also have been present and a contributing factor.     

Evidence for two genetically and chemically defined host races of Tyria jacobaeae (Arctiidae, Lepidoptera)

Summary. A widely distributed host race of Tyria jacobaeae lives on Senecio jacobaea and related species and accumulates pyrrolizidine alkaloids (“PA race”), another race, which is restricted to the Alps and found on Petasites paradoxus, sequesters sesquiterpenes, such as petasol and isopetasol. Nucleotide sequences of the mitochondrial 16S rDNA gene show 1% sequence divergence, indicating that genetical differences exist between the PA exploiting and the terpene-sequestering host races of T. jacobaeae. This finding suggests that both host races of T. jacobaeae must have been separated for some time already, possibly since the Pleistocene. Received 2 May 2001; accepted 1 June 2001.     

Analysis of the Structure-Properties Relationships of Different Multiphase Systems Based on Plasticized Poly(Lactic Acid)

Poly(lactic acid) is one of the most promising biobased and biodegradable polymers for food packaging, an application which requires good mechanical and barrier properties. In order to improve the mechanical properties, in particular the flexibility, PLA plasticization is required. However, plasticization induces generally a decrease in the barrier properties. Acetyl tributyl citrate (ATBC) and poly(ethylene glycol) 300 (PEG), highly recommended as plasticizers for PLA, were added up to 17 wt% in P(D,L)LA. In the case of PEG, a phase separation was observed for plasticizer contents higher than 5 wt%. Contrary to PEG, the T_g decrease due to ATBC addition, modelled with Fox’s law, and the absence of phase separation, up to 17 wt% of plasticizer, confirm the miscibility of PLA and ATBC. Contents equal or higher than 13 wt% of ATBC yielded a substantial improvement of the elongation at break, becoming higher than 300%. The effect of PLA plasticization on the barrier properties was assessed by different molecules, with increasing interaction with the formulated material, such as helium, an inert gas, and oxygen and water vapour. In comparison to the neat sample, barrier properties against helium were maintained when PLA was plasticized with up to 17 wt% of ATBC. The oxygen permeability coefficient and the water vapour transmission rate doubled for mixtures with 17 wt% ATBC in PLA, but increased five-fold in the PEG plasticized samples. This result is most likely caused by increased solubility of oxygen and water in the PEG phase due to their mutual miscibility. To conclude, ATBC increases efficiently the elongation at break of PLA while maintaining the permeability coefficient of helium and keeping the barrier properties against oxygen and water vapour in the same order of magnitude.     

Photolytic and photocatalytic degradation of quinclorac in ultrapure and paddy field water: identification of transformation products and pathways

Quinclorac (QNC) is an effective but rather persistent herbicide commonly used in rice production. This herbicide presents a mean persistence in the environment so its residues are considered of environmental relevance. However, few studies have been conducted to investigate its environmental behavior and degradation. In the present work, direct photolysis and TiO₂ photocatalysis of the target compound in ultrapure and paddy field water were investigated. After 10 h photolysis in ultrapure water, the concentration of QNC declined 26% and 54% at 250 and 700 W m⁻², respectively. However, the amount of quinclorac in paddy field water remained almost constant under the same irradiation conditions. QNC dissipated completely after 40 min of TiO₂ photocatalysis in ultrapure water, whereas 130 min were necessary to degrade 98% of the initial concentration in paddy field water.Possible QNC photolytic and photocatalytic degradation pathways are proposed after structure elucidation of the main transformation products, through liquid chromatography-electrospray ionization-quadrupole time-of-flight mass spectrometry and exact mass measurements. Pyridine ring hydroxylation at C-9 followed by ring opening and/or oxidative dechlorination were the key steps of QNC degradation.     

Optimization of methyl parathion biodegradation and detoxification by cells in suspension or immobilized on tezontle expressing the opd gene

The goal of this study was to optimize methyl parathion (O,O-dimethyl-O-4-p-nitrophenyl phosphorothioate) degradation using a strain of Escherichia coli DH5α expressing the opd gene. Our results indicate that this strain had lower enzymatic activity compared to the Flavobacterium sp. ATCC 27551 strain from which the opd gene was derived. Both strains were assessed for their ability to degrade methyl parathion (MP) in a mineral salt medium with or without the addition of glucose either as suspended cells or immobilized on tezontle, a volcanic rock. MP was degraded by both strains with similar efficiencies, but immobilized cells degraded MP more efficiently than cells in suspension. However, the viability of E. coli cells was much higher than that of the Flavobacterium sp. We confirmed the decrease in toxicity from the treated effluents through acetylcholinesterase activity tests, indicating the potential of this method for the treatment of solutions containing MP.     

Improved interpretation of in-diffusion measurements with confined swelling clays

Diffusion is considered the principal transport mechanism of radio-nuclides and other low-molecular-weight pollutants in compacted clays used as barriers at various disposal and storage sites, for example, at projected deep repositories for radioactive waste. Porous filters are routinely used to confine swelling clays in diffusion studies of radio-tracers. The presence of the filter gives rise to considerable mass-transfer limitations at the clay boundary that result in erroneous diffusion parameters. We have solved the problem of in-diffusion with due account for this phenomenon by means of Fourier transforms. By using literature data on the in-diffusion of traces of radioactive cesium in an argillaceous rock (Opalinus clay) and a compacted bentonite (FEBEX bentonite), we have demonstrated that taking into account the mass-transfer limitations considerably improves the quality of the theoretical fit of the time evolution of radio-tracer concentration in the reservoir. Besides that, we have shown that ignoring the mass-transfer limitations leads to a noticeable underestimation of both the effective diffusion coefficient and the specific sorption capacity of the clay.     

Introducing and Measuring Sustainable Development Initiatives by Local Authorities in Canada and Flanders (Belgium) A Comparative Study

In this paper we examine how Canadian and Flemish municipalities manage and measure sustainable development initiatives. First, we present information on how Canada, Belgium and its Flemish region introduce sustainable development initiatives at the federal and regional levels of government. The introduction at municipal level of impact assessment systems, indicator and monitoring systems, and sustainability reporting systems is discussed in general, followed by a comparison of specific case studies. In Canada, we selected the municipalities of Ottawa, Hamilton-Wentworth and Vancouver and in Flanders, the municipalities of Hasselt, Gent and Leuven. For each case study, we considered the following evaluation criteria: introduction of a long-term vision for a sustainable future; development of goals, targets and indicators; measurement of indicators; involvement and information of the local population; introduction of impact assessment and reporting systems. The discussion section deals with differences in the approach to managing and measuring sustainable development initiatives in Canada and Flanders. This study shows that sustainable development is not yet widely practised at the local level in Canada and Flanders, but Canadian municipalities have more experience with planning processes and vision development, measurement systems and public involvement. The Flemish municipalities were more inclined to go along with international campaigns dealing with local sustainability and take strong sustainable development actions which were not integrated in broader sustainable development policies.     

Sustainability indicators for clean development mechanism projects in Vietnam

The Clean Development Mechanism (CDM) is one of the flexible instruments of the Kyoto Protocol designed to combat climate change so as to bring advantages to developing countries and developed countries alike. Indeed, CDM projects have a two-fold objective: to offset greenhouse gas emissions and to contribute to sustainable development in the host country. However in many cases, the latter objective appears to be marginalized. This is at least partly due to the difficulties surrounding the definition and the measurement of sustainability, in particular in a developing country context. To assess CDM projects’ contribution to sustainable development in the host country, scholars and practitioners need adapted indicator sets. A set of indicators were developed by way of an iterative Delphi approach amongst selected Vietnamese experts. The Delphi approach allowed a systematic collection of the experts’ judgements on the sustainability indicators through a set of sequentially applied questionnaires, interspersed with feedback from earlier responses. This exercise resulted in the selection of a set of 36 indicators, which emphasise economic efficiency, public health and pollution issues. The exercise yielded a locally supported and context-specific set of sustainability indicators that will allow Vietnamese decision-makers to enhance the sustainability of the approved CDM projects. In the future this set should be continually improved through real-life application and further participation from local stakeholders. This study is a first step in a long-term process towards developing an adapted toolkit for sustainability assessment of CDM projects in Vietnam.     

Characterisation of perfluorooctane sulfonate (PFOS) in a terrestrial ecosystem near a fluorochemical plant in Flanders,Belgium

Bioaccumulation of perfluorooctane sulfonate (PFOS) in a restricted terrestrial food chain was investigated with the omnivorous wood mouse (Apodemus sylvaticus) on top of the studied food chain. The levels detected are very high compared with literature as a result of the presence of fluorochemical plant in the immediate vicinity of the study area. Soil, surface water, fruits of European elder and common blackberry, invertebrates, bank vole and wood mouse were collected at two sites, e.g. Blokkersdijk, adjacent to the fluorochemical plant, and Galgenweel, a reference site 2 km further away. In wood mouse, the highest PFOS concentrations were found in the liver followed by the pancreas, lungs and kidneys, with the spleen having the lowest levels. In the liver, the concentrations ranged from 787 to 22,355 ng/g ww at Blokkersdijk and these were significantly correlated with those detected in the kidneys (13.7–4,226 ng/g ww). If current results are compared to the findings of a previous study conducted in 2002 at the same sites, a significant decrease of PFOS in livers of wood mouse is observed. To the best of our knowledge, so far no studies reported levels of PFOS in terrestrial invertebrates under field conditions. At Blokkersdijk, PFOS was detected in all invertebrate species ranging from 28 to 9,000 ng/g. Soil and water were also contaminated with levels of respectively 68 ng/g and 22 ng/L. Biota-to-soil accumulation factors ranged from 0.11 to 68 for earthworms. Biomagnification factors (BMFs) of liver wood mouse/berries were as high as 302. BMFs for invertebrates were remarkably lower (up to 2).