Impact des traitement de potabilisation sur le CODB et la distribution des substances humiques et non humiques de la matière organique naturelle

Cette étude a consisté à évaluer et à comparer l'impact des traitements de coagulation-floculation, ozonation et filtration sur charbon actif en grains sur la matière organique dissoute de différentes eaux de rivières et de retenues françaises en s'appuyant sur le suivi de deux paramètres principaux, la fraction biodégradable du carbone organique dissous (CODB) et la distribution des substances humiques et non humiques (établie sur la base d'un protocole de filtration en série sur résines XAD-8 et XAD-4 ).Dans le cas des eaux étudiées, la coagulation-floculation s'est accompagnée d'une diminution importante du COD, soit 38 à 70 %, impact qui se répercute dans des proportions équivalentes au niveau de sa fraction biodégradable soit 38 à 88%. Dans la majorité des cas, la clarification conduit à l'élimination préférentielle des substances humiques (définies comme hydrophobes), qui correspondent aux fractions de plus hautes masses moléculaires. Comparativement, et pour des taux supérieurs à 1 mg O3/mg C, l'ozonation entra"ne une réduction de la fraction des substances humiques qui se traduit par une augmentation de la fraction des substances non humiques et en particulier des substances hydrophiles non adsorbées sur résines XAD-8 et XAD-4. Cette modification, d'autant plus marquée que le taux d'ozone est important, s'accompagne d'une augmentation proportionnelle de la fraction biodégradable du COD. Le suivi en usine a montré que les taux d'ozone appliqués lors d'une interozonation modifient peu la nature du COD. Par contre, la filtration sur charbon actif en aval change de manière importante la distribution de la matière organique dissoute avec une augmentation relative de la fraction hydrophobe et des composés de faibles masses moléculaires apparentes (< 1 000 daltons).The goal of our study was to evaluate the impact of water treatment processes (i.e. coagulation- flocculation, ozonation and GAC filtration) on the natural organic matter (NOM) of various river and reservoir waters based on DOC and BDOC analyses and the determination of the humic/non humic NOM distribution (fractionation of the DOC at acidic pH using two successive XAD-8 and XAD-4 resin columns). Analyses carried out on ten French raw surface waters have shown that the BDOC fraction accounted for 11 to 38 % of the DOC. The humic/non humic distribution of the NOM varied slightly with the origin of the studied water. About 50 to 60 % of the DOC was found to be incorporated into the humic fraction (NOM adsorbed on the XAD-8 resin), the hydrophilic acids (adsorbed on the XAD-4 resin) accounted for 10 to 25 % of the DOC while the non adsorbed hydrophilic solutes (hydrophilic neutrals that constitute the XAD-8/XAD-4 effluent) represented 15 to 30 % of the DOC.Clarified water samples were collected from water treatment plants after coagulation/flocculation/sand filtration when no preoxidation was used. For water utilities which included a preoxidation step in their treatment process, raw water samples were coagulated and flocculated at a laboratory scale with Jar Test equipment using the same conditions (nature of the coagulant, pH, dose) as those used in the corresponding treatment plant. Globally, 38 to 70 % of the DOC and 38 to 88 % of the BDOC were removed during coagulation-flocculation, depending on the water site. In general, the humic/non humic NOM distribution of clarified waters showed a slight increase in the proportion of the non humic organic fraction as compared to raw waters, which indicates that humic substances (higher molecular weight organics) are preferentially removed during coagulation-flocculation. Ozonation experiments were carried out on a raw water and a clarified water sampled from the same water site using a semi batch reactor (ozone was generated from high purity oxygen). For both waters, very little variation of the humic/non humic NOM distribution was observed for applied ozone doses around 0.5 mg O3/mg C or below. For higher ozone doses, the NOM distribution was dramatically changed despite only a small reduction of the DOC. The large reduction of the humic fraction was followed by a proportional increase of the non adsorbed hydrophilic solute fraction (small reduction of the DOC). As the applied ozone dose was increased from 1 to 3 mg O3/mg DOC, the non-adsorbed hydrophilic solute fraction also increased. The shift from high molecular weight organics such as humic materials to more hydrophilic organics (high polarity and low molecular weight organic solutes) during ozonation has often been mentioned in the literature. The increase of the non humic substances was followed by an increase of the BDOC. Results have also shown that higher ozone doses yield higher BDOC. Similar observations could be made with the raw and the clarified water.As a conclusion of this work, samples were collected at the different steps of a water treatment plant (raw water, clarified water, intermediate ozonated water, GAC filtered water). The impact of coagulation/flocculation, and intermediate ozonation on BDOC and the humic/non humic NOM distribution confirmed the previous observations. The GAC filtration had a large impact on the DOC distribution while the BDOC was only slightly reduced. The NOM of the treated water was found to be more hydrophobic in nature with compounds that showed apparent molecular weights below 1 000 daltons (more than 80 % of the DOC)

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Model Predictions of Metal Speciation in Freshwaters Compared to Measurements by In Situ Techniques

Measurements of trace metal species in situ in a softwater river, a hardwater lake, and a hardwater stream were compared to the equilibrium distribution of species calculated using two models, WHAM 6, incorporating humic ion binding model VI and visual MINTEQ incorporating NICA-Donnan. Diffusive gradients in thin films (DGT) and voltammetry at a gel integrated microelectrode (GIME) were used to estimate dynamic species that are both labile and mobile. The Donnan membrane technique (DMT) and hollow fiber permeation liquid membrane (HFPLM) were used to measure free ion activities. Predictions of dominant metal species using the two models agreed reasonably well, even when colloidal oxide components were considered. Concentrations derived using GIME were generally lower than those from DGT, consistent with calculations of the lability criteria that take into account the smaller time window available for the flux to GIME. Model predictions of free ion activities generally did not agree with measurements, highlighting the need for further work and difficulties in obtaining appropriate input data