Veronique Chaplain

Influence of adsorption-desorption phenomena on pesticide run-off from soil using simulated rainfall

The surface run-off of a number of pesticides (diuron, isoproturon, atrazine, alachlor, aclonifen, trifluralin, lindane and simazine), chosen for their range of adsorption behaviours, was studied using simulated rainfall applied to small plots over a short time (one hour). Pesticides were applied together onto bare soil using two different sandy loam soils from Jailliere and Coet Dan sites. The surface run-off samples were collected throughout the running of the event and concentrations of pesticides were measured in both liquid and solid phases. Sorption isotherms for isoproturon and diuron on Jailliere soil as well as eroded particles were measured under equilibrium conditions and compared to their partitioning during surface run-off. At the rainfall intensity used, both soils generated a large load of eroded particles. The average run-off flow rate increased with time for the Jailliere soil, while it remained relatively constant at a higher level for the Coet Dan soil. The concentrations of each pesticide in the run-off samples decreased as the experiments proceeded. The pesticides were classified into two types by their partitioning between the solid and liquid phases. Atrazine, simazine, diuron, isoproturon and alachlor were mainly transported in surface run-off water. By contrast, 90% of trifluralin and aclonifen was adsorbed onto eroded particles. Lindane was intermediate, with a 37% adsorption level. When the contribution of eroded particles was minor, the agrochemical concentrations were inversely proportional to the water flow rate. We have proposed a model that describes the mass of chemicals extracted from soil into surface water during a surface run-off event of a given average duration and flow rate. This model takes into account the dilution of the soil solution and the desorption of chemicals through two parameters called, respectively, the dilution factor and the extraction retardation factor. The desorption kinetic was the limiting step in the surface run-off of weakly sorbed chemicals, such as isoproturon.

Biotransformation of s-Triazine Herbicides and Related Degradation Products in Liquid Cultures by the White Rot Fungus Phanerochaete chrysosporium

The ability of the white rot basidiomycete Phanerochaete chrysosporium to transform s-triazine herbicides has been investigated in laboratory experiments. The chlorinated metabolites formed during atrazine N-dealkylations were not further transformed by the fungus, whereas hydroxyatrazine was converted to an unknown product. P. chrysosporium was also able to carry out the N-dealkylation of the herbicides simazine, propazine and terbuthylazine. Herbicide metabolism was not supported by purified peroxidases. The highest rates of herbicide N-dealkylation were obtained in liquid cultures maintained under moderate temperature allowing a long mycelium growing phase. Atrazine transformation was found to be supported by the mycelium, which contained significant amounts of microsomal cytochrome P450. Herbicide N-dealkylation was decreased in the presence of 1-aminobenzotriazole, in agreement with the involvement of P450 monooxygenases in atrazine metabolism.

Inoculation of Filamentous Fungi in Manufactured Gas Plant Site Soils and PAH Transformation

Abstract Solid carriers have been developed to inoculate Trametes versicolor and Cunninghamella elegans into manufactured gas plant site soils. Pelleted wheat bran carriers were very efficient in stimulating the growth of fungi in an industrial soil containing about 2800 mg kg−1 PAHs. Fungal biomass and activity of extracellular laccases, enzymes produced by T. versicolor as markers of metabolic activity in the contaminated soil, both decreased after 2 weeks of incubation. Supplementing the soil with a mixture of carbon, nitrogen and phosphorus enhanced the fungal activity period. A 38% decrease of solvent extractable PAHs was observed in manufactured gas plant site soils when supplemented with T. versicolor, Glucidex 19TM, ammonium nitrate, lime phosphate and Montanox 80TM, after 20 weeks. Then, the degradation proceeded more slowly during the following 30 weeks, and reached 43% of initial extractable PAHs. Some factors governing a limited PAH biotransformation in the soil are discussed.

Influence of adsorption-desorption phenomena on pesticide runoff measured under controlled conditions*

Abstract The surface runoff of isoproturon and diuron is studied using simulated rainfall applied to small 1 m 2 plots of soil. Isoproturon was less adsorbed by soil than diuron and eroded particles did not contribute to the pesticide transfer. A model is then proposed to describe such transfer of pesticide. This model introduces ( i ) a dilution factor a , which seems proportional to the concentration of the soil solution before applying the artificial rain and ( ii ) an extraction retardation factor b , which is inversely proportional to the partition coefficient between the solid and liquid phase of soil.

Fate of Pesticides in Soils: Toward an Integrated Approach of Influential Factors

Despite constraining legislation and increasing efficiency of pesticides (with a decrease in the applied amounts), their use still cause a contamination of environment (air, soil and water). To conciliate agricultural and environmental interests, a better understanding of the fate of pesticides is needed, in particular because it will determine the exposure and consequently the impact of pesticides on the target and non-target organisms. This goal requires new efforts of research at different scales (from molecular to field scale). Following application, most of the pesticides reach the soil either after direct application or after foliage wash-off. As a major interface between other environmental compartments, the soil plays a preponderant buffering role in the fate of pesticides. Apart volatilization, the main processes that control the fate of pesticides in soils are retention on soil particles and degradation (biotic and abiotic). These coupled bio-physico-chemical processes can lead to a transitory or permanent accumulation of pesticides in soils or, on the contrary, to their elimination from the environment. They determine the pesticide concentration in the soil solution, and have a large influence on pesticide transfer toward ground or surface waters and on their ecotoxicological impacts on soil organisms as well. The main difficulties in studying and predicting the retention and degradation of pesticides in soils are the diversity of chemical structures and reactivities of pesticides, the high diversity of soils and their heterogeneous composition and structure. In addition, the pedoclimatic conditions, in particular soil temperature and water content, have a strong influence on retention and degradation because of their effect on soil biological, chemical and physical properties. Therefore, the objective of this chapter is to provide an overview of the factors involved in the retention and degradation of pesticides in soils and to discuss and clarify the needs of new integrated approach. In particular, this work will examine (i) the pertinent scales (among elementary constituents, aggregates and mesoscopic scales) for both retention and degradation studies, (ii) the integrative properties that should be considered, such as hydrophobicity of the organo-clay granulometric fraction or soil structure, and (iii) the primordial role of water.

Interference of Soil Contaminants with Laccase Activity During the Transformation of Complex Mixtures of Polycyclic Aromatic Hydrocarbons in Liquid Media

The biotransformation of 16 polycyclic aromatic hydrocarbons (PAHs) in mixture was investigated in reactors in the presence of purified laccases of the fungus Pycnoporus cinnabarinus, ABTS as a redox mediator, 25% acetonitrile, and Tween 20. Several hydrocarbons from a synthetic mixture, such as anthracene and benzo[ a ]pyrene, were converted up to 80% into quinones, whereas others also belonging to three- and five-ring chemicals were less transformed. Chrysene and benzo[ k ]fluoranthene were not oxidized by the laccase mediator system. Moreover, hydrocarbons extracted from an industrial soil were all recalcitrant to enzymatic attack. This lack of reactivity of the laccases toward the hydrocarbons could be due to the presence of interfering compounds coextracted from the soil, such as metals.

Heterogeneous dissolution of benzo(a)pyrene by surfactant solutions

Abstract The dissolution of a solid deposit of benzo(a)pyrene (BaP) has been investigated using three surfactants, a cationic (benzyldimethyl dodecylammonium bromide), an anionic (sodium dodecyl sulfate) and a neutral ( t -octylphenoxypolyethoxyethanol). Dissolution is a heterogeneous process characterized by the fragmentation of the solid deposit into solid particles. Successive filtrations have defined three granulometric classes: the coarse fraction greater than 0.45 μm, the fine fraction ranging between 0.05 and 0.45 μm and the micellar fraction lower than 0.05 μm. The chemical nature of the surfactant influences the repartition into the different classes. The coarse fraction becomes negligible when the concentration of the cationic surfactant is increased. It still represents more than 80% of the deposit with neutral and anionic surfactants, even in a large excess of surfactant concentration compared to the critical micellar concentration value. The cationic surfactant is also the most efficient towards the solubilization in micellar phase. This efficiency is attributed to the contribution of two mechanisms: a partition process into the hydrophobic core of the micelle and a surface solubilization into the palisade layer due to specific interactions, surface solubilization being the major contribution. Electrophoretic mobility measurements have shown (i) the pronounced negative charge carried by the deposit surface and by BaP particles (ii) the strong affinity of the cationic surfactant towards these surfaces. The break up of the deposit into fine fragments and the solubilisation by the cationic surfactant is correlated to this adsorption.

Wet sand cultures to screen filamentous fungi for the biotransformation of polycyclic aromatic hydrocarbons

The biodegradation of phenanthrene and benzo[a]pyrene was assayed in liquid and wet sand cultures in the presence of five filamentous fungi. In the controls, 85% volatilisation of phenanthrene occurred within 28 days in liquid cultures while it was only 50% in wet sand. In the later system, remaining phenanthrene and benzo[a]pyrene amounted to 6–51 and 53–92% of their initial levels, respectively, according to the strains. Then, wet sand used as a screening tool evidenced Trametes versicolor and Cunninghamella elegans as the most efficient polycyclic aromatic hydrocarbons degraders among ten strains.