Although the application of UK non-agricultural pesticides (mainly herbicides) comprises only 3% of the total amount used, similar concentrations of agriculturally and non-agriculturallyderived pesticides are routinely detected in surface waters. This has led to concern regarding the contamination of drinking water resources at concentrations above the statutory limits of the EC Drinking Water Directive (ECDWD), and the consequent risk to human health. Before the risks to drinking water resources can be fully assessed, it is important to understand and subsequently predict the chronic and transient levels of herbicide occurrence in receiving surface waters as a result of their normal application. The factors which influence herbicide transport to the aquatic environment from sites of application, particularly from the wide variety of application substrates, are not fully understood. This project addresses this lack of knowledge through an eighteen-month programme (January 1992-March 1993) of storm event herbicide monitoring on a mixed land use catchment at North Weald (Essex) which periodically received applications of common agricultural and non-agricultural herbicides including chlorotoluron, isoproturon, diuron, simazine and atrazine. To support the field monitoring programme a robust multi-residue pesticide method was developed for the simultaneous determination of the previously mentioned compounds from storm water. This was based on liquid-liquid extraction into dichloromethane and high performance liquid chromatography using photo diode array detection. The pesticide runoff data from agricultural land agreed with similar experiments carried out in the UK. The ECDWD was frequently exceeded in baseflow conditions and more frequently during storm event periods. The extent of the exceedance was found to be related to the period which had elapsed between the herbicide application and the timing of the surface water sampling. The range of application losses for the agricultural data-set was 4.0xlO-4-O.204% (median; 4.6x10-2%). The range of peak storm event concentrations was 0.03-10.0jJg/1 (median; 0.34pg/I). Similar exceedances of the ECDWD were observed during storm and non-storm conditions for discharged waters from the urban land area of the catchment. For the urban runoff data-set, the range of application losses was 0.01-45.1% (median; 0.28%) and the range of peak storm event concentrations was 0.2-238.4pg/1 (median; 0.7pg/l). The results of the monitoring programme show that the underlying factor that differentiated between the fates of herbicides applied to the North Weald catchment was the difference in the application substrate properties. Specifically, the hard surfaces, where low infiltration capacity promotes the generation of relatively high volumes of surface runoff and where poor retention behaviour exists, allow applied herbicides to be readily transported in storm event runoff to receiving surface waters. The simazine, isoproturon, chlorotoluron and diuron runoff data produced during the monitoring programme were successfully modelled using the fugacity-based Soilfug model. In the case of chlorotoluron, this model s performance was compared with a statistical model produced using multiple linear regression analysis, which showed the former approach to be superior since it required less input data and was not site specific.

Le traitement des sédiments de dragage pollués aux métaux lourds est une alternative à leur stockage sur sites homologués et pourrait permettre la réutilisation des sédiments en technique routière ou en butte paysagère. Le procédé de dépollution envisagé dans ce projet consiste à déposer les sédiments contaminés sur des géotextiles, matériaux présentant une structure poreuse idéale pour la filtration. La lixiviation permet ensuite de rendre mobile une partie des polluants métalliques afin qu’ils puissent être adsorbés par les géotextiles. Cependant, ces matériaux, généralement synthétiques, n’ont pas de capacité intrinsèque à retenir les métaux et doivent donc être fonctionnalisés avec des molécules capables de fixer les métaux lourds. Cette thèse est orientée vers le développement de procédés de fonctionnalisation par plasma et laser, l’objectif final étant d’immobiliser des biomolécules chélatantes à la surface des géotextiles. Ces biomolécules sont fixées par couplage chimique sur des fonctions –COOH obtenues préalablement par greffage d’un agent intermédiaire, l’acide acrylique. La surface des fibres a été analysée à chaque étape de traitement par microscopie électronique à balayage, spectrométrie infrarouge, et par spectrométrie photoélectronique à rayons X, prouvant le greffage covalent de l’acide acrylique puis des biomolécules. Enfin, des tests avec des solutions métalliques ont été effectués afin de pouvoir sélectionner le textile fonctionnalisé le plus efficace pour réaliser des essais à l’échelle pilote. Parallèlement, une étude de modélisation a été amorcée afin d’étudier plus précisément la structure des complexes métal/biomolécule obtenus. / The treatment of dredged sediments contaminated with trace metals is an alternative to the current storage in accredited sites and could allow the reusability of sediments in civil engineering. The remediation process considered in this project consists in the deposition of polluted sediments onto geotextiles, structures possessing filtration properties. The leaching then favors the release of metals that can be sequestered by the geotextiles. However, these textile structures are mainly composed of synthetic polymers and thus cannot retain heavy metals. Therefore, they have to be functionalized with molecules able to adsorb metal ions present in aqueous media. The main objective of this PhD thesis was to develop functionalization processes using plasma and laser techniques, in order to immobilize biomolecules with chelating properties at the surface of the fabrics. These biomolecules were immobilized by chemical coupling onto –COOH groups obtained at the fabric surface by the grafting of a spacer, namely acrylic acid. The surface of the fibers was characterized at the different grafting steps by scanning electron microscopy, infrared spectrometry and X-ray photoelectron spectrometry: evidence of the covalent grafting of acrylic acid and then of biomolecules was given. Some remediation tests were then carried out in order to select the most interesting functionalized materials for further studies at pilot scale. In parallel, a computational study was initiated in order to determine the structure of the metal/biomolecule complexes.

Pentachlorophenol (PCP) is a chlorophenol with a pronounced biocidal activity that has led to its use in a number of applications. It was introduced in the 1930s as a preservative for timber and lumber and since then has found wide use as a biocide in agricultural and industrial applications. Many different physical, chemical and biological methods have been tried for the removal of PCP from wastewater. However, using microalgae for the removal of PCP and other organochlorine compounds from water may prove to be a cheaper alternative and give complete degradation of the compounds. The aim of this project was to study the efficiency of microalgae to degrade PCP. An algal strain named VT -1 and a bacterial strain named AT -14 were isolated from PCP containing conditions in the laboratory. The growth of VT -1 in the presence of PCP was compared with Chlorella emersonii and Chlorella vulgaris in two different autotrophic media. It was observed that VT-1 had the highest IC50 value of 25-26mg }-l PCP and EC50 value of 11.3mg }-1 PCP in S&K medium. With glucose as an additional carbon source the IC50 value for VT-1 in S&K medium was 29-30mg t 1 PCP. Bacterium AT-14 could grow in the presence of PCP, only with glucose as a carbon source. Mineralization of PCP by VT -1 and the two Chlorella strains was compared by using 14C_PCp. With all the three algae exposed to 14C_PCp, only VT-1 showed release of 14C02, which was evidence of mineralization of PCP by VT-1 which occurred only in the presence of light. Bacterium AT-14 did not produce 14C02. However, the consortium of VT-1 and AT-14 showed enhanced 14C02 evolution in the presence of glucose. The release of chloride ions from PCP can also indicate PCP dehalogenation and degradation. The evolution of 14C02 lagged behind chloride release (90 %) indicating that dechlorination of PCP could be the first step in its biodegradation. Breakdown of PCP was also followed by its extraction from the cells and medium. Normally dichloromethane (DCM) was used to extract PCP. The changes in the label extracted in DCM and iso-butanol were studied under different light condjtions, which showed that the 14C counts in DCM reduced and those in iso-butanol extract increased with time. The 14C counts in the iso-butanol extract could be a metabolite of PCP which is more hydrophilic. VT-1 appeared not to degrade PCP completely, since only 15% of 14C was recovered as 14C02. It appears that intermediates are formed which are distributed in the growth medium and in the biomass. It can thus be concluded that VT -1 is tolerant of PCP, appears to dechlorinate PCP and then releases some part of it as CO2.

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