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.     

Biological and ecophysiological reactions of white wall rocket (Diplotaxis erucoides L.) grown on sewage sludge compost

We studied the effects of sewage sludge compost on white wall rocket (Diplotaxis erucoides L.) compared with mineral fertilization and control (without any fertilizer) in a greenhouse experiment. The plants grown on the compost-amended soil showed a different growth dynamic: a significant delay in flowering and a bigger root system. Both the compost and the fertilization treatments increased biomass and seed yield. Heavy metal (Cu, Cd, Zn, Ni) distribution within the plant was in the following order: roots > leaves > stems, except for zinc which was homogeneously distributed. The balance of mineral nutrition was not affected by treatments. Zinc was the trace element which was most taken up. Unlike many species of Brassicaceae, white wall rocket is not a hyperaccumulator. Although sewage sludge compost improved plant growth, delay in flowering shows that it is necessary to take precautions when spreading sewage sludge in natural areas.     

Comparison of the method of diffusive gels in thin films with conventional extraction techniques for evaluating zinc accumulation in plants and isopods

The measurement of diffusive gels in thin films (DGT) has recently been developed to assess metal bioavailability in soils. The DGT-method is based on diffusion in a porous matrix. To test the predictive capabilities of the method with regard to metal bioavailability, a study was set up with 28 soils having a variety of textures and amounts of zinc salts added. Correlation and regression analyses were performed to compare DGT-extracted zinc levels to zinc concentrations obtained by extraction with 0.01 M CaCl(2) and 0.43 M HNO(3), digestion with aqua regia and the zinc concentration in pore water. The amount of zinc extracted with CaCl(2) correlated well with DGT-extracted zinc levels in all soils spiked with different amounts of ZnCl(2). A similar correlation was not found for zinc concentrations in soil samples collected in the field. Experiments were performed to compare zinc content in organisms and in soils. The organisms tested were plants (grass, lettuce and lupine) and the hard bodied soil dwelling isopod Oniscus asellus. Good correlations were found between zinc accumulation in grass and lettuce and the C(E) (effective concentration) measured by a DGT-device, CaCl(2) extracted zinc and the zinc content in the pore water of all soils. The correlation with C(E) was not significant for lupine, neither for spiked soils, nor for field soils (p< or =0.001). Zinc levels in the isopods were not significantly related to any set of zinc measurements. From a synthesis of all results obtained it is concluded that the DGT-methodology does not have an additional value in predicting bioavailability of zinc in terrestrial ecosystems as compared to conventional extraction methods.     

Diuron mobility through vineyard soils contaminated with copper

The herbicide diuron is frequently applied to vineyard soils in Burgundy, along with repeated treatments with Bordeaux mixture (a blend of copper sulfate and calcium hydroxide) that result in elevated copper concentrations. Cu could in principle affect the fate and transport of diuron or its metabolites in the soil either directly by complexation or indirectly by altering the populations or activity of microbes involved in their degradation. To assess the effect of high Cu concentrations on diuron transport, an experiment was designed with ten undisturbed columns of calcareous and acidic soils contaminated with 17--509 mg kg(-1) total Cu (field-applied). Grass was planted on three columns. Diuron was applied to the soils in early May and in-ground lysimeters were exposed to outdoor conditions until November. Less than 1.2% of the diuron applied was found in the leachates as diuron or its metabolites. Higher concentrations were found in the effluents from the grass-covered columns (0.1--0.45%) than from the bare-soil columns (0.02--0.14%), and they were correlated with increases in dissolved organic carbon. The highest amounts of herbicide were measured in acidic-soil column leachates (0.98--1.14%) due to the low clay and organic matter contents of these soils. Cu also leached more readily through the acidic soils (32.8--1042 microg) than in the calcareous soils (9.5--63.4 microg). Unlike in the leachates, the amount of diuron remaining in the soils at the end of the experiment was weakly related to the Cu concentrations in the soils.     

Effects of long exposure to low temperatures on nitrifying biofilm and biomass in wastewater treatment

Attached growth biological treatment systems are a promising solution to ammonia removal in cold-temperature climates. Environmental scanning electron microscopy (ESEM) and confocal laser scanning microscopy in combination with fluorescent in situ hybridization (FISH) was used to investigate the effects of 4 months of exposure to 4 degrees C on nitrifying biofilm and biomass. These molecular and microscopic methods were modified to minimize loss of mass and distortion of in situ perspectives. Environmental scanning electron microscopy revealed that nitrifying biofilm did not exhibit significant changes in volume with exposure to 4 degrees C. Confocal laser scanning microscopy in combination with FISH showed that the number of ammonia-oxidizing bacteria (AOB) cells present in the biofilm was statistically consistent during exposure to 4 degrees C. The RNA content of AOB cells remained sufficient for FISH enumeration. The number of nitrite-oxidizing bacteria cells remained steady during exposure to 4 degrees C; however, the RNA content of the cells appeared to decrease with exposure to 4 degrees C, thereby preventing their enumeration using FISH.     

Assessment of aquatic experimental versus predicted and extrapolated chronic toxicity data of four structural analogues

The present study was developed to assess the chronic toxicity predictions and extrapolations for a set of chlorinated anilines (aniline (AN), 4-chloroaniline (CA), 3,5-dichloroaniline (DCA) and 2,3,4-trichloroaniline (TCA)). Daphnia magna 21 d chronic experimental data was compared to the chronic toxicity predictions made by the US EPA ECOSAR QSAR tools and to acute-to-chronic extrapolations. Additionally, Species Sensitivity Distributions (SSDs) were constructed to assess the chronic toxicity variability among different species and to investigate the acute versus chronic toxicity in a multi-species context.Since chlorinated anilines are structural analogues with a designated polar narcotic mode of action, similar toxicity responses were assumed. However, rather large interchemical and interspecies differences in toxicity were observed. Compared to the other three test compounds, TCA exposure had a significantly larger impact on growth and reproduction of D. magna. Furthermore, this study illustrated that QSARs or a fixed ACR are not able to account for these interchemical and interspecies differences. Consequently, ECOSAR was found to be inadequate to predict the chronic toxicity of the anilines and the use of a fixed ACR (of 10) led to under of certain species. The experimental ACRs determined in D. magna were substantially different among the four aromatic amines (ACR of 32 for AN, 16.9 for CA, 5.7 for DCA and 60.8 for TCA). Furthermore, the SSDs illustrated that Danio rerio was rather insensitive to AN in comparison to another fish species, Phimphales promelas. It was therefore suggested that available toxicity data should be used in an integrative multi-species way, rather than using individual-based toxicity extrapolations. In this way, a relevant overview of the differences in species sensitivity is given, which in turn can serve as the basis for acute to chronic extrapolations.     

Extractability of water-soluble soil organic matter as monitored by spectroscopic and chromatographic analyses

Purpose

Cold and hot water processes have been intensively used to recover soil organic matter, but the effect of extraction conditions on the composition of the extracts were not well investigated. Our objective was to optimize the extraction conditions (time and temperature) to increase the extracted carbon efficiency while minimizing the possible alteration of water extractable organic matter of soil (WEOM).

Method

WEOM were extracted at 20°C, 60°C, or 80°C for 24?h, 10?C60?min, and 20?min, respectively. The different processes were compared in terms of pH of suspensions, yield of organic carbon, spectroscopic properties (ultraviolet?Cvisible absorption and fluorescence), and by chromatographic analyses.

Results

For extraction at 60°C, the time 30?min was optimal in terms of yield of organic carbon extracted and concentration of absorbing and fluorescent species. The comparison of WEOM 20°C, 24?h; 60°C, 30?min; and 80°C, 20?min highlighted significant differences. The content of total organic carbon, the value of specific ultraviolet absorbance (SUVA₂₅₄), the absorbance ratio at 254 and 365?nm (E ₂/E ₃), and the humification index varied in the order: WEOM (20°C, 24?h)?Conclusions For the soil chosen, extraction at 60°C for 30?min is the best procedure for enrichment in organic chemicals and minimal alteration of the organic matter.     

The combined effect of uranium and gamma radiation on biological responses and oxidative stress induced in Arabidopsis thaliana

Uranium never occurs as a single pollutant in the environment, but always in combination with other stressors such as ionizing radiation. As effects induced by multiple contaminants can differ markedly from the effects induced by the individual stressors, this multiple pollution context should not be neglected. In this study, effects on growth, nutrient uptake and oxidative stress induced by the single stressors uranium and gamma radiation are compared with the effects induced by the combination of both stressors. By doing this, we aim to better understand the effects induced by the combined stressors but also to get more insight in stressor-specific response mechanisms. Eighteen-day-old Arabidopsis thaliana seedlings were exposed for 3 days to 10 μM uranium and 3.5 Gy gamma radiation. Gamma radiation interfered with uranium uptake, resulting in decreased uranium concentrations in the roots, but with higher transport to the leaves. This resulted in a better root growth but increased leaf lipid peroxidation. For the other endpoints studied, effects under combined exposure were mostly determined by uranium presence and only limited influenced by gamma presence. Furthermore, an important role is suggested for CAT1/2/3 gene expression under uranium and mixed stressor conditions in the leaves.