Controls on atrazine leaching through a soil-unsaturated fractured limestone sequence at Brévilles, France

The objective of this study was to identify the main controls on atrazine leaching through luvisols and calcisols overlying fissured limestone using the dual-permeability model MACRO. The model parameterisation was based on a combination of direct measurements (e.g. hydraulic properties, adsorption and degradation), literature data and calibration against bromide leaching experiments in field plots. A Monte Carlo sensitivity analysis was carried out for a typical application pattern, considering two different depths of unsaturated limestone (15 and 30 m). MACRO calibrations to the field experiments demonstrated the occurrence of strong macropore flow in the luvisol, while transport in the calcisol could be described by the advection-dispersion equation. MACRO simulations of tritium and atrazine leaching qualitatively matched tritium concentration profiles measured in the limestone and atrazine concentrations measured in piezometers and in aquifer discharge via a spring. The sensitivity analysis suggested that the thickness of the limestone, as well as the transport properties and processes occurring in the unsaturated rock (e.g. matrix vs. fissure flow) will have little significant long-term effect on atrazine leaching, mainly because degradation is very slow in the limestone. No mineralization of atrazine was detected in one-year incubations and a mean half-life of 10 years was assumed in the simulations. Instead, processes occurring in the soil exerted the main control on predicted atrazine leaching, especially variations in the degradation rate and the strength of sorption and macropore flow. However, fissure flow in unsaturated rock is expected to exert a much more significant control on groundwater contamination for compounds that degrade more readily in the deep vadose zone.     

Photocatalytic oxidation of volatile organic compounds using fluorescent visible light

Photocatalytic oxidation (PCO) of volatile organic compounds (VOCs) is a highly attractive alternative technology for purification and deodorization of indoor air. The main objectives of this study were to demonstrate that a common fluorescent visible light (FVL) lamp can be used to effectively remove by PCO low concentrations of VOCs from slightly contaminated air and to provide some fundamental and technical details on the process. The target VOC was n-butanol, which is a standard reference odorant. Its PCO was studied under a long residence time in a 3.7-L cylindrical reactor with commercial titanium dioxide (TiO2) as the reference photocatalyst and using mostly FVL for illumination. For comparison only, a UV (black) light lamp was used. The gas-phase products were detected and quantified online by gas chromatography (GC). The effects of reactor residence time, of inlet concentration, and of the relative light intensity on the efficiency of the process were also evaluated. At a high n-butanol concentration (0.1 vol %), butanal and propanal were identified as the intermediate products of the process; ethanal appeared when the initial concentration was < or = 850 ppm(v). This indicates that PCO leading to CO2 and H2O is relatively slow and proceeds in a stepwise manner. Although the efficiency of the process with an FVL lamp was significantly lower than when using a UV black light, complete PCO of low concentrations was achieved for 100 ppm(v). In a search for a material with photoactivation extended to higher wavelengths or increased photoactivity, several samples of transition metal- or silver ion-doped (2 atomic %) TiO2 as well as SrTi(1-x-)Fe(x)O3 (x = 0.1 and 0.15) perovskites were included in the study. None of these materials was more active than pure TiO2. The results of this study open new horizons in the area of in door air quality (IAQ) control.     

Isolation and characterization of <Emphasis Type="Italic">Bradyrhizobium</Emphasis> sp. SR1 degrading two β-triketone herbicides

In this study, a bacterial strain able to use sulcotrione, a β-triketone herbicide, as sole source of carbon and energy was isolated from soil samples previously treated with this herbicide. Phylogenetic study based on16S rRNA gene sequence showed that the isolate has 100 % of similarity with several Bradyrhizobium and was accordingly designated as Bradyrhizobium sp. SR1. Plasmid profiling revealed the presence of a large plasmid (>50 kb) in SR1 not cured under nonselective conditions. Its transfer to Escherichia coli by electroporation failed to induce β-triketone degrading capacity, suggesting that degrading genes possibly located on this plasmid cannot be expressed in E. coli or that they are not plasmid borne. The evaluation of the SR1 ability to degrade various synthetic (mesotrione and tembotrione) and natural (leptospermone) triketones showed that this strain was also able to degrade mesotrione. Although SR1 was able to entirely dissipate both herbicides, degradation rate of sulcotrione was ten times higher than that of mesotrione, showing a greater affinity of degrading-enzyme system to sulcotrione. Degradation pathway of sulcotrione involved the formation of 2-chloro-4-mesylbenzoic acid (CMBA), previously identified in sulcotrione degradation, and of a new metabolite identified as hydroxy-sulcotrione. Mesotrione degradation pathway leads to the accumulation of 4-methylsulfonyl-2-nitrobenzoic acid (MNBA) and 2-amino-4 methylsulfonylbenzoic acid (AMBA), two well-known metabolites of this herbicide. Along with the dissipation of β-triketones, one could observe the decrease in 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibition, indicating that toxicity was due to parent molecules, and not to the formed metabolites. This is the first report of the isolation of bacterial strain able to transform two β-triketones.     

Bayesian estimation of species relative abundances and habitat preferences using opportunistic data

We develop a new statistical procedure to monitor relative species abundances and their respective preferences for different habitat types, using opportunistic data. Following Giraud et al. (Biometrics 72(2):649–658, 2015), we combine the opportunistic data with some standardized data in order to correct the bias inherent to the opportunistic data collection. Species observations are modeled by Poisson distributions whose parameters quantify species abundances and habitat preferences, and are estimated using Bayesian computations. Our main contributions are (i) to tackle the bias induced by habitat selection behaviors, (ii) to handle data where the habitat type associated to each observation is unknown, (iii) to estimate probabilities of selection of habitat for the species. As an illustration, we estimate common bird species habitat preferences and abundances in the region of Aquitaine (France).     

Polymer biodegradation: mechanisms and estimation techniques

Within the frame of the sustainable development, new materials are being conceived in order to increase their biodegradability properties. Biodegradation is considered to take place throughout three stages: biodeterioration, biofragmentation and assimilation, without neglect the participation of abiotic factors. However, most of the techniques used by researchers in this area are inadequate to provide evidence of the final stage: assimilation. In this review, we describe the different stages of biodegradation and we state several techniques used by some authors working in this domain. Validate assimilation (including mineralisation) is an important aspect to guarantee the real biodegradability of items of consumption (in particular friendly environmental new materials). The aim of this review is to emphasise the importance of measure as well as possible, the last stage of the biodegradation, in order to certify the integration of new materials into the biogeochemical cycles. Finally, we give a perspective to use the natural labelling of stable isotopes in the environment, by means of a new methodology based on the isotopic fractionation to validate assimilation by microorganisms.     

Bages-Sigean and Canet-St Nazaire lagoons (France): physico-chemical characteristics and contaminant concentrations (Cu,Cd, PCBs and PBDEs) as environmental quality of water and sediment

Environmental characteristics in water and sediments of two contrasted coastal Mediterranean lagoons, Bages-Sigean and Canet-St Nazaire, were measured over a three season survey. The urban pollution (treatment plant discharges) is very important in Canet-St Nazaire lagoon reflecting untreated sewages, while in Bages-Sigean, the northern part appears more impacted due to larger anthropogenic inputs. Dissolved Cd concentrations are on the whole similar in both lagoons, whereas Cu concentrations are by far higher in lagoon Canet-St Nazaire. Cu concentrations appear to be highly dependent on dissolved organic carbon whereas salinity seems to control Cd variations. Concerning the sediments, the confined northern part of lagoon Bages-Sigean shows organic carbon and total nitrogen enrichment whereas lipid concentrations are much higher in the Canet-St Nazaire lagoon. Cu complexation seems to be strongly related to organic matter as evidenced by the two significant positive relationships, on one hand between Cu and organic carbon, and on the other hand, between Cu and lipids. On the contrary, Cd concentrations appear to be mainly controlled by carbonates. PCBs and PBDEs were detected only in sediments and show relatively low concentrations compared to similar lagoon environments. Regarding the sediment quality guidelines, Cd, Cu and PCBs in both lagoons did not exceed any Probable Effect Concentration (PEC).     

Bioaccessibility of trace elements as affected by soil parameters in smelter-contaminated agricultural soils: a statistical modeling approach

An investigation was undertaken to identify the most significant soil parameters that can be used to predict Cd, Pb, and Zn bioaccessibility in smelter-contaminated agricultural soils. A robust model was established from an extended database of soils by using: (i) a training set of 280 samples to select the main soil parameters, to define the best population to be taken into account for the model elaboration, and to construct multivariate regression models, and (ii) a test set of 110 samples to validate the ability of the regression models. Total carbonate, organic matter, sand, P(2)O(5), free Fe-Mn oxide, and pseudototal Al and trace element (TE) contents appeared as the main variables governing TE bioaccessibility. The statistical modeling approach was reasonably successful, indicating that the main soil factors influencing the bioaccessibility of TEs were taken into account and the predictions could be applicable for further risk evaluation in the studied area.     

A DFT study of the reactions of O3 with Hg° or Br

In the mid 1980s the study of ozone reactivity gained a significant interest with the discoveries of the stratospheric ozone hole (Farman et al., 1985) and of the ozone depletion events in the polar boundary layer (Oltmans et al., 1989). In the stratosphere, the mechanism involves heterogeneous reactions on polar stratospheric clouds that lead to chlorine activation (Solomon et al., 1986). In contrast, tropospheric ozone depletion occurring during polar springtime rather involves reactive bromine species. They are released during a series of photochemical and heterogeneous reactions often called the bromine explosion (see the review of Simpson et al., 2007). In this reaction sequence, an essential step is the generation of photolyzable Br₂, the precursor of two Br atoms, via the multiphasic reaction (1):

(1)

HOBr + Br⁻ + H⁺ → H₂O + Br₂

The production of reactive HOBr could occur with the oxidation of BrO by HO₂.