Abstracts
Résumé
L'utilisation de l'ozone, aujourd'hui très répandue dans les filières de potabilisation, n'est pas sans effet secondaire. De nombreux sous-produits peuvent se former comme notamment les ions bromates, sous produits finaux d'oxydation des bromures contenus dans les eaux. Malheureusement, le mécanisme de production de cette espèce est complexe et dépend de nombreux paramètres difficiles à appréhender.
Sur une installation pilote de type colonne à bulles fonctionnant à contre-courant, nous avons étudié l'influence de différents paramètres, comme le pH, le temps de contact, la dose d'ozone et la dose de peroxyde d'hydrogène, sur la formation des bromates et la dégradation des pesticides, représentée par l'atrazine.
Les résultats de la littérature ont été confirmés lors de l'emploi unique de l'ozone. La formation des ions bromate est influencée par la présence du peroxyde d'hydrogène. Cet oxydant intervient de manière non négligeable sur la consommation des entités intermédiaires. Le couple HOBr/OBr- peut être oxydé par l'ozone moléculaire et le radical OH° mais peut également être réduit par l'ozone et par le peroxyde sous sa forme acide ou sa base conjuguée. En ce qui concerne la dégradation des pesticides, l'utilisation de peroxyde d'hydrogène couplé à l'ozone favorise l'oxydation de la molécule d'atrazine grâce à la présence plus importante de radicaux hydroxyles.
Une pollution accidentelle en pesticides pourra être traitée par l'ajout ponctuel de peroxyde d'hydrogène avec une augmentation de pH, la formation des bromates sera, dans ce cas, faible. La désinfection sera alors assurée par l'étape de chloration.
Mots-clés:
- Bromates,
- ozonation,
- colonne à bulles,
- peroxyde d'hydrogène,
- ozone,
- radicaux hydroxyle,
- oxydation,
- réduction
Abstract
In drinking water treatment plants, ozonation is often used to disinfect, to remove micropollutants and to improve water taste and odour. Ozonation increases organic matter biodegradability before filtration through granular active carbon and reduces the concentration of haloform precursors that react in the final chlorination step. However, by-products that could be detrimental to human health could be formed. For example, bromates, which are classified as carcinogenic compounds by the I.A.R.C, are produced during the ozonation of bromide-containing water. The mechanism of bromate formation is complex, due to the participation of molecular ozone and radical (hydroxyl and carbonate) reactions. The optimisation of the process should allow for a good disinfection and a reduction in the levels of micropollutants, together with low by-product formation.
Using a pilot-scale counter-current bubble column, we have measured the bromate concentration in relation to pesticide removal. Water spiked with bromide and atrazine was stored in a completely stirred-tank (2 m3) before being pumped to the top of the column. The inlet gaseous ozone was measured by an analyser using UV detection, the outlet gaseous ozone was monitored by the potassium iodide method, and the dissolved ozone concentration was determined by the indigo trisulfonate method. Bromides and bromates were quantified by ion chromatography with a conductimetric detector, with a sodium carbonate solution as the eluant. Samples for bromate analysis were pretreated by OnGuard-Ag and OnGuard-H cartridges in series before injection. Atrazine degradation was measured by high performance liquid chromatography with a diode array detector, with a CH3CN/H2O mixture as the eluant. The linearisation of atrazine removal allowed us to calculate the hydroxyl radical concentration in a series of a completely-stirred tank reactors and in a plug-flow reactor.
We have studied the influence of several parameters on bromate formation, including pH, bromide concentration and hydrogen peroxide concentration. As bromate production is a function of bromide concentration, we have chosen to calculate the ratio between the real bromate concentration and the theoretical bromate concentration if all bromide were oxidised to bromate. The pH affects bromate formation: an increase in pH in the absence of hydrogen peroxide increases bromate production, but when this oxidant is applied bromate production decreases when the pH increases. If reaction progress is represented as a function of [O3]*TC, we note that the presence of hydrogen peroxide increases bromate formation because of the increase in hydroxyl radical concentration, which favours radical formation. Nevertheless, if we represent reaction progress as a function of [OH∘]*TC, hydrogen peroxide seems to be an initiator and a scavenger in the mechanism of bromate formation. If we calculate the rates of all the oxidation and reduction reactions for HOBr/OBr- species, the contribution to the reduction of HOBr/OBr- species by peroxide is very important in comparison to the oxidation reactions, which inhibits bromate production. Without the hydrogen peroxide, the contribution of oxidation is equal to that of the reduction reaction, and in this case bromate formation is effective. When, under the same initial operational conditions, we apply hydrogen peroxide with an increase in pH, we observe a decrease in bromate formation with a decrease of the dissolved ozone concentration, which hinders the desired disinfection. The main contribution to atrazine oxidation is from the free-radical reactions, which explains why removal is better when we apply hydrogen peroxide than when we use ozone alone. However, if we want to respect a low bromate level in drinking water, atrazine degradation should not be greater than 90% for the operational conditions on our pilot-scale.
If an accidental high pesticide concentration is observed, an addition of hydrogen peroxide with a concurrent increase of pH, could treat the pollution. In this case, a subsequent chlorination step would then have to be used to assure the disinfection alone.
Keywords:
- River,
- wastewater treatment plant,
- polluted water outlet,
- water pollution,
- systems analysis,
- Mauldre (France)