Degradation mechanism of t-butyl methyl ether (MTBE) in atmospheric droplets

The aim of this study was to obtain information about the degradation of t-butyl methyl ether (MTBE; (CH(3))(3)C-O-CH(3)) in atmospheric water droplets (rain, clouds, fog). These water droplets contain hydrogen peroxide and iron ions, which are a source of the powerful oxidising radical OH degrees, particularly under solar irradiation (photo-Fenton reaction). MTBE was chosen for this work because of its current use as an oxygenated additive in gasoline.In this study we found that MTBE is not stable in the atmosphere. More than 15 intermediate products were identified, five of which were quantified (t-butyl formate (TBF), methyl acetate (MA), t-butyl alcohol (TBA), acetone (AC), formaldehyde). The evaluation of the disappearance kinetic of the main intermediate compounds shows the following activity pattern k((TBA))>k((MTBE))>k((TBF)),k>((AC)). Acetone was found to be about 15 times more stable than MTBE in atmospheric conditions. The degradation pathways are discussed on the basis of these identifications and on the degradation of the main intermediate products in similar conditions to MTBE.     

The evaluation of dioxin and dioxin-like contaminants in selected food samples obtained from the Belgian market: comparison of TEQ measurements obtained through the CALUX bioassay with congener specific chemical analyses

A limited number of different foods were analysed for dioxin-like compounds by the CALUX bioassay which is an in vitro luciferase reporter gene assay measuring chemical activation of the aryl hydrocarbon receptor. Sixty-two milk samples were obtained from a surveillance campaign, 34 meat samples and 34 fishery products were purchased from the Belgian market. Bio-analytical and chemo-analytical dioxin toxicity equivalents (TEQ) values of the same milk samples were compared. Spearman's Rank correlation coefficients of 0.72, 0.67, 0.73 were obtained respectively between CALUX-TEQ and PCDD/F-TEQ, DL-PCB-TEQ and PCDD/F+DL-PCB-TEQ. The bioassay limit of detection was 0.1 pg TEQ from 1 g animal lipid, the limit of quantification was 0.4 pg TEQ. The repeatability of the CALUX bioassay (variability of butter fat samples analysed in the same run) showed a coefficient of variation (CV) of 10%, intra laboratory reproducibility based on independent runs of the same butter fat samples showed more variation (CV of 26% for samples above 2 pg TEQ/g lipid). All milk samples with a chemical TEQ value above the current limit value in Belgium showed an elevated CALUX-TEQ concentration, above 6 pg TEQ/g lipid. No false negative results were obtained. Based on the good correlation between CALUX-TEQ and chemically measured TEQ levels, the CALUX bioassay can be recommended as a screening tool for routine measurement of potentially toxic PHAHs in milk samples. Chemical analyses could then largely be restricted to positive samples, in order to identify the nature and to quantify the concentration of the chemicals that give the positive signal. Meat samples showed lower CALUX-TEQ values per gram lipid compared to fish samples. The fish samples showed a wider range of CALUX-TEQ values than the meat samples.     

Diversity pattern and spatial scale: a study of a tropical rain forest of Malaysia

Scale is emerging as one of the critical problems in ecology because our perception of most ecological variables and processes depends upon the scale at which the variables are measured. A conclusion obtained at one scale may not be valid at another scale without sufficient knowledge of the scaling effect, which is also a source of misinterpretation for many ecological problems, such as the design of reserves in conservation biology.This paper attempts to study empirically how scaling may affect the spatial patterns of diversity (tree density, richness and Shannon diversity) that we may perceive in tropical forests, using as a test-case a 50 ha forest plot in Malaysia. The effect of scale on measurements of diversity patterns, the occurrence of rare species, the fractal dimension of diversity patterns, the spatial structure and the nearest-neighbour autocorrelation of diversity are addressed. The response of a variable to scale depends on the way it is measured and the way it is distributed in space.We conclude that, in general, the effect of scaling on measures of biological diversity is non-linear; heterogeneity increases with the size of the sampling units, and fine-scale information is lost at a broad scale. Our results should lead to a better understanding of how ecological variables and processes change over scale.     

Mechanistic Virtual Modeling: Coupling a Plant Simulation Model with a Three-dimensional Plant Architecture Component

The aim of this research is to integrate plant architectural modeling or “visualization modeling” and “mechanistic” or physiologically based modeling to describe how a real plant functions using a virtual crop. Virtual crops are life-like computer representations of crops based on individual plants and including the representation of the substrate on which the plants grow. The integration of a three-dimensional expression and the mechanistic model of plant development and growth requires the knowledge of the position of the organs along the different plant axes (the topology), their sizes, their forms, and their spatial orientation. The plant simulation model simulates the topology and organ weight or length. The superposition of spatial position and the topology produces the architecture of the plant. The association between sizes and organs creates what we refer to as the plant morphological model. Both components, the architectural model and the morphology model, are detailed in this paper. Once the integration is complete, the system produces a movie-like animation that shows the plant growing. The integrated model may simulate one or several plants growing simultaneously (in parallel). Visual capabilities make the proposed system very unique as it allows users to judge the results of the simulation the same way a farmer judges the situation of the crops in real life, by visually observing the field.     

Estimating parameters of neutral communities: from one single large to several small samples

The neutral theory of S. P. Hubbell postulates a two-scale hierarchical framework consisting of a metacommunity following the speciation-drift equilibrium characterized by the "biodiversity number" theta, and local communities following the migration-drift equilibrium characterized by the "migration rate" m (or the "fundamental dispersal number" I). While Etienne's sampling formula allows simultaneous estimation of theta and m from a single sample of a local community, its applicability to a network of (rather small) samples is questionable. We define here an alternative two-stage approach estimating theta from an adequate subset of the individuals sampled in the field (using Ewens' sampling formula) and m from community samples (using Etienne's sampling formula). We compare its results with the simultaneous estimation of theta and m (one-stage estimation), for simulated neutral samples and for 50 1-ha plots of evergreen forest in South India. The one-stage approach exhibits problems of bias and of poor differentiability between high-theta, low-m and low-theta, high-m solution domains. Conversely, the two-stage approach yielded reasonable estimates and is to be preferred when several small, scattered plots are available instead of a single large one.     

Patch departure rules in Bumblebees: evidence of a decremental motivational mechanism

The patch living rules of a pollinator, the bumblebee Bombus terrestris L., are studied here in the framework of motivational models widely used for parasitoids: The rewarding events found during the foraging process are supposed to increase or decrease suddenly the tendency of the insect to stay in the current patch and therefore to adjust the patch residence time to the patch profitability. The foraging behaviour of these pollinators was observed in two environment types to determine their patch-leaving decisions. The rich environment was composed of male-fertile flowers, offering pollen and nectar, and the poor one of male-sterile flowers, offering little nectar and no pollen. The experimental design consisted of a patch system in which inflorescences were evenly arranged in two rows (1 m distance). Residence times of foragers inside inflorescences and rows were analysed by a Cox proportional hazards model, taking into account recent and past experience acquired during the foraging bout. Most of the results showed a decremental motivational mechanism, that is, a reduction in the residence time on the inflorescence or in the row related to exploitation of flowers within inflorescences and inflorescences within rows These results indicate that bumblebees tend to leave the patch using departure rules similar to those found in parasitoids. The results also provide information on the memory, learning and evaluating capabilities of bumblebees especially when rich and poor environments were compared. The patch-leaving mechanism suggested by this study is consistent with the central place foraging theory.     

Reproductive plasticity in bumblebee workers (<Emphasis Type="Italic">Bombus terrestris</Emphasis>)—reversion from fertility to sterility under queen influence

Worker sterility in the bumblebee Bombus terrestris is conditional and is linked to the social development of the colony. Workers refrain from reproducing or overtly challenging the queen until gyne production has initiated, at the so-called competition point (CP). It is not known whether this behavior is hard-wired or workers show reproductive plasticity. It also remains unclear whether worker reproductive decision is under queen and/or worker control. In this study, we tested worker reproductive plasticity in an attempt to assess whether and under which conditions worker sterility/fertility are reversible. We introduced egg-laying workers into colonies with different social structures for 1 week then monitored their reproductive status. We revealed a remarkable reproductive plasticity in the introduced workers that was social-condition-dependent. In the presence of a pre-CP queen, the introduced workers reverted to sterility, whereas in the presence of a post-CP queen, such workers remained egg-layer. Reversion to sterility does not occur when direct contact with the queen is prevented, as the introduced workers remained egg-layer in the queenright colonies with a confined queen. Egg-laying workers that were introduced into queenless colonies mostly maintained their fertility regardless of colony social phase. This shows that worker transition from cooperative to selfish behavior is reversible depending on the social context.     

Development of a solid phase microextraction (SPME) method for the sampling of VOC traces in indoor air

Solid-phase microextraction (SPME) was studied for the measurement of volatile organic compounds (VOCs) in indoor air. An adsorptive PDMS/Carboxen fibre was used and an analytical methodology was developed in order to overcome competitive adsorption. Kinetics and adsorption isotherms were investigated for different sample volumes and model compounds. In order to evaluate competitive adsorption on the fibre, these compounds were studied alone and in mixture. From the results obtained, the operating conditions allowing co-adsorption of the target compounds were determined: the air sample is enclosed in a 250 mL glass bulb where the SPME fibre is exposed until adsorption equilibrium. This procedure was combined with GC/MS analysis for the identification and quantification of VOCs in indoor air. The performances were determined by using a standard gas containing 10 VOCs representative of indoor environments (acetaldehyde, acetone, BTX, alpha-pinene, trichloroethylene, alkanes). The detection limits were determined in single ion monitoring mode and for a signal to noise ratio of 3. Except acetaldehyde (6 microg m(-3)), they are all below 0.5 microg m(-3). Calibration curves are linear up to 10 micromol m(-3) for all the compounds with good correlation coefficients (above 0.99). The reproducibility ranges from 6 to 12% according to the compound. The methodology was then applied to the comparison of the VOCs content in classrooms of two different schools.     

A hydrological modeling framework for defining achievable performance standards for pesticides

This paper proposes a hydrological modeling framework to define achievable performance standards (APSs) for pesticides that could be attained after implementation of recommended management actions, agricultural practices, and available technologies (i.e., beneficial management practices [BMPs]). An integrated hydrological modeling system, Gestion Intégrée des Bassins versants à l'aide d'un Système Informatisé, was used to quantify APSs for six Canadian watersheds for eight pesticides: atrazine, carbofuran, dicamba, glyphosate, MCPB, MCPA, metolachlor, and 2,4-D. Outputs from simulation runs to predict pesticide concentration under current conditions and in response to implementation of two types of beneficial management practices (reduced pesticide application rate and 1- to 10-m-wide edge-of-field and/or riparian buffer strips, implemented singly or in combination) showed that APS values for scenarios with BMPs were less than those for current conditions. Moreover, APS values at the outlet of watersheds were usually less than ecological thresholds of good condition, when available. Upstream river reaches were at greater risk of having concentrations above a given ecological thresholds because of limited stream flows and overland loads of pesticides. Our integrated approach of "hydrological modeling-APS estimation-ecotoxicological significance" provides the most effective interpretation possible, for management and education purposes, of the potential biological impact of predicted pesticide concentrations in rivers.