Biodegradation of petroleum hydrocarbon vapors: laboratory studies on rates and kinetics in unsaturated alluvial sand

Predictions of natural attenuation of volatile organic compounds (VOCs) in the unsaturated zone rely critically on information about microbial biodegradation kinetics. This study aims at determining kinetic rate laws for the aerobic biodegradation of a mixture of 12 volatile petroleum hydrocarbons and methyl tert-butyl ether (MTBE) in unsaturated alluvial sand. Laboratory column and batch experiments were performed at room temperature under aerobic conditions, and a reactive transport model for VOC vapors in soil gas coupled to Monod-type degradation kinetics was used for data interpretation. In the column experiment, an acclimatization of 23 days took place before steady-state diffusive vapor transport through the horizontal column was achieved. Monod kinetic parameters Ks and vmax could be derived from the concentration profiles of toluene, m-xylene, n-octane, and n-hexane, because substrate saturation was approached with these compounds under the experimental conditions. The removal of cyclic alkanes, isooctane, and 1,2,4-trimethylbenzene followed first-order kinetics over the whole concentration range applied. MTBE, n-pentane, and chlorofluorocarbons (CFCs) were not visibly degraded. Batch experiments suggested first-order disappearance rate laws for all VOCs except n-octane, which decreased following zero-order kinetics in live batch experiments. For many compounds including MTBE, disappearance rates in abiotic batch experiments were as high as in live batches indicating sorption. It was concluded that the column approach is preferable for determining biodegradation rate parameters to be used in risk assessment models.     

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.     

How to foster agroecological innovations? A comparison of participatory design methods

Facing contemporary environmental crisis implies fostering agroecological innovations that take into account local ecological regulations and rely on multiple stakeholders' innovation capacities. This paper draws on two fields of literature that remain unconnected so far: participatory approaches and design sciences. It proposes an analysis grid to support a reflexive analysis of cases of implementation of three participatory design methods: ComMod (Companion Modelling for concerted management of natural resources), Forage Rummy (simulation-based board game for designing farming systems) and KCP (collective design workshops to foster innovation). This analysis highlights key features of the methods in view of agroecological innovation challenges, focusing on knowledge management and organisation for exploration.     

Long-Term Maintenance of Rapid Atrazine Degradation in Soils Inoculated with Atrazine Degraders

Two different microbial communities able to degrade atrazine (atz) were inoculated in four different soils. The most critical factor affecting the success of inoculation was the soil pH and its organic matter (OM) content. In two alkaline soils (pH > 7), some inoculations led immediately to a strong increase of the biodegradation rate. In a third slightly acidic soil (pH = 6.1), only one inoculum could enhance atz degradation. In a soil amended with organic matter and straw (pH = 5.7, OM = 16.5%), inoculation had only little effect on atz dissipation on the short as well as on the long-term. Nine months after the microflora inoculations, atz was added again and rapid biodegradation in all alkaline inoculated soils was recorded, indicating the long-term efficiency of inoculation. In these soils, the number of atz degraders was estimated at between 6.5 × 10³ and 1.5 × 10⁶ (g of soil)^-1, using the most probable number (MPN) method. Furthermore, the presence of the atz degraders was confirmed by the detection of the gene atzA in these soils. Denaturing gradient gel electrophoresis (DGGE) analysis of the 16S rDNA genes indicated that the inoculated bacterial communities had little effect on the patterns of the indigenous soil microflora.