Détermination en milieu naturel du dioxide de chlore, des ions chlorite et chlorate basée sur l'utilisation du carmin indigo: étude des interférences

Différentes méthodes fondées sur l'exploitation d'un même réactif à savoir le carmin indigo ont été mises en œuvre pour réaliser le suivi du dioxyde de chlore et des sous-produits de dégradation que sont les ions chlorite et chlorate.L'étude de la stabilité du carmin indigo a permis de montrer que la détermination du dioxyde de chlore doit être effectuée dans les premières heures qui suivent l'ajout de carmin indigo, une légère diminution de l'absorbance étant observée au delà de vingt heures. L'absorbance du carmin indigo en présence d'ions chlorite et chlorate reste en revanche stable plusieurs jours.La recherche d'éventuelles interférences (substances humiques, ozone, hypochlorite) a également été effectuée. Les ions chlorite et chlorate réagissent avec les substances humiques en milieu acide selon une cinétique réactionnelle beaucoup plus lente que celle des ions chlorite et chlorate sur le carmin indigo. De ce fait, les pourcentages d'erreur sur les concentrations restent faibles. L'hypochlorite ou plus précisément l'acide hypochloreux réagit avec le carmin indigo ce qui conduit à des erreurs dans la détermination du dioxyde de chlore, des ions chlorite et chlorate. Dans le cas du dosage du dioxyde de chlore, les sources d'erreur peuvent être éliminées en ajoutant de l'ammoniaque avant l'introduction du carmin indigo dans l'échantillon.Après avoir été validés dans des milieux synthétiques, les protocoles ont été appliqués à un milieu naturel : l'eau de distribution de la ville de Brest. Une analyse statistique a été effectuée dans le but de comparer les résultats avec ceux déduits d'autres méthodes basées sur des principes différents.Over the last decade, chlorine dioxide has been increasingly used for disinfecting drinking water in many countries. A guarantee for the protection of the consumer is the presence of a sufficient residual concentration of the bactericidal reagent in drinking water. Thus it is important to determine exactly and accurately the levels of chlorine dioxide at the tap. During water treatment and subsequent distribution, chlorine dioxide can undergo a variety of reduction and disproportionation reactions producing primarily chloride but also chlorite and chlorate, which have been shown to cause haemolytic anemia. Reliable analytical methods are needed to identify and determine levels of chlorine dioxide, chlorite and chlorate in drinking water. A procedure based on the use of indigo carmine for the determination of each species in natural waters is suggested in this paper.In phosphate buffer (pH 6.8), two moles of chlorine dioxide oxidize one mole of indigo carmine. The concentration of the bactericidal reagent can be determined by measuring the difference in absorbance of the dye at 610 nm before and after reaction with chlorine dioxide. This method is selective as chlorite and chlorate do not react with indigo carmine in phosphate buffer at pH 6.8. Although the spectrophotometric method can be used successfully used at levels of chlorine dioxide down to 30 µg/l, the determination of lower levels in tap water requires a more sensitive method such as an electrochemical stripping procedure. This analysis is based on the measurement of the decrease in the indigo carmine signal after addition of chlorine dioxide. The detection limit is around 1 µg/l.At pH=2, one mole of indigo carmine reduces one mole of chlorite. Thus the chlorite concentration can be determined by measuring the indigo carmine absorbance at pH=2. At pH=0, indigo carmine reacts with both chlorite and chlorate. A measurement at pH=0 allows chlorate concentrations to be determined since the decrease in absorbance due to the presence of chlorite can be calculated.The stability of indigo carmine absorbance has been studied. An indigo carmine solution prepared in phosphate buffer is stable over several days if kept in light-proof bottles. It is not surprising that the presence of chlorite and chlorate does not lead to a change in absorbance as they do not react with the dye at pH=6.8. A slight decrease in absorbance of an indigo carmine solution containing chlorine dioxide is observed after about twenty hours. This means that the chlorine dioxide concentration has to be determined in the first hours, which follow the addition of the dye to the sample in order to avoid errors.Interferences can arise from other residual oxidants, which may also be used in water treatment, or from substances present in the sample, which may react with indigo carmine, chlorite and chlorate. Accordingly, we have considered the influence of humic substances, ozone and hypochlorite. The absorbance of indigo carmine at pH=2 and at pH=0 does not change in presence of natural organic matter (1 mg/l). Chlorite and chlorate react with humic substances but the kinetics are much slower than those of the reactions with indigo carmine. Errors arising from humic substances in chlorite and chlorate measurements are thus very weak. Ozone may interfere in analyses as it reacts with indigo carmine. However its existence in the distribution network is unlikely as it also reacts with chlorine dioxide, which is in excess, and chlorite to give chlorate. Hypochlorite causes errors in chlorine dioxide, chlorite and chlorate determinations as a result of a reaction with indigo carmine. In the case of chlorine dioxide determinations, errors can be eliminated by adding ammonia to the sample before indigo carmine.Once the validity of the procedures had been proven in synthetic media, the methods were applied to a natural water, that of the water distribution network of the city of Brest, France. The results have been compared with those of other analytical techniques

Kinetic studies on Sb(III) oxidation by hydrogen peroxide in aqueous solution

cited By 39International audienceKnowledge of antimony redox kinetics is crucial in understanding the impact and fate of Sb in the environment and optimizing Sb removal from drinking water. The rate of oxidation of Sb(III) with H2O 2 was measured in 0.5 mol L-1 NaCl solutions as a function of [Sb(III)], [H2O2], pH, temperature, and ionic strength. The rate of oxidation of Sb(III) with H2O2 can be described by the general expression: -d[Sb(III)]/dt = k[Sb(III)][H 2O2][H+]-1 with log k= -6.88 (±0.17) [k: min-1]. The undissociated Sb(OH)3 does not react with H2O2: the formation of Sb(OH) 4 - is needed for the reaction to take place. In a mildly acidic hydrochloric acid medium, the rate of oxidation of Sb(III) is zeroth order with respect to Sb(III) and can be described by the expression -d[Sb(III)]/dt = k[H2O2][H+][Cl-] with log k = 4.44 (±0.05) [k: L2 mol-2 min -1]. The application of the calculated rate laws to environmental conditions suggests that Sb(III) oxidation by H2O2 may be relevant either in surface waters with elevated H2O2 concentrations and alkaline pH values or in treatment systems for contaminated solutions with millimolar H2O2 concentrations

The effect of the presence of trace metals on the oxidation of Sb(III) by hydrogen peroxide in aqueous solution

cited By 5International audienceDespite its importance for understanding the behaviour of antimony in the environment, the oxidation kinetics of Sb(III) with natural oxidants is still not well understood. We have studied the oxidation of Sb(III) by hydrogen peroxide on a time scale of hours in the presence of some trace metals, Cu(II), Mn(II), Zn(II) and Pb(II), under pH and concentration conditions close to natural ones. The effects that these trace metals have on Sb(III) oxidation by hydrogen peroxide vary. Zn(II) had no catalytic effect at all, but Cu(II), Mn(II) and Pb(II) did, though their effects were not uniform. Cu(II) significantly accelerated the reaction, which remained first-order with respect to Sb(III) at any Cu(II) concentration tested. Pb(II) and Mn(II) also enhanced the reaction rates, but the apparent order of the reaction with respect to Sb(III) changed to two. The trace metal effect observed was concentration dependent for Pb(II). The addition of the hydroxyl radical scavenger 2-propanol suggests that the trace metal catalytic effect observed involves the action of hydroxyl radicals, but that they are not responsible for the oxidation of Sb(III) by H2O2 in the absence of trace metals. The fact that Sb(III) can be oxidized by hydroxyl radicals present in water, even if it is not capable of producing them, has important environmental implications because hydroxyl radicals are known to be abundant in many natural waters such as seawater, humic-rich surface waters or rainwater. © The Royal Society of Chemistry 2005

The effect of the presence of trace metals on the oxidation of Sb(III) by hydrogen peroxide in aqueous solution

cited By 5International audienceDespite its importance for understanding the behaviour of antimony in the environment, the oxidation kinetics of Sb(III) with natural oxidants is still not well understood. We have studied the oxidation of Sb(III) by hydrogen peroxide on a time scale of hours in the presence of some trace metals, Cu(II), Mn(II), Zn(II) and Pb(II), under pH and concentration conditions close to natural ones. The effects that these trace metals have on Sb(III) oxidation by hydrogen peroxide vary. Zn(II) had no catalytic effect at all, but Cu(II), Mn(II) and Pb(II) did, though their effects were not uniform. Cu(II) significantly accelerated the reaction, which remained first-order with respect to Sb(III) at any Cu(II) concentration tested. Pb(II) and Mn(II) also enhanced the reaction rates, but the apparent order of the reaction with respect to Sb(III) changed to two. The trace metal effect observed was concentration dependent for Pb(II). The addition of the hydroxyl radical scavenger 2-propanol suggests that the trace metal catalytic effect observed involves the action of hydroxyl radicals, but that they are not responsible for the oxidation of Sb(III) by H2O2 in the absence of trace metals. The fact that Sb(III) can be oxidized by hydroxyl radicals present in water, even if it is not capable of producing them, has important environmental implications because hydroxyl radicals are known to be abundant in many natural waters such as seawater, humic-rich surface waters or rainwater. © The Royal Society of Chemistry 2005

Kinetic studies on Sb(III) oxidation by hydrogen peroxide in aqueous solution

cited By 39International audienceKnowledge of antimony redox kinetics is crucial in understanding the impact and fate of Sb in the environment and optimizing Sb removal from drinking water. The rate of oxidation of Sb(III) with H2O 2 was measured in 0.5 mol L-1 NaCl solutions as a function of [Sb(III)], [H2O2], pH, temperature, and ionic strength. The rate of oxidation of Sb(III) with H2O2 can be described by the general expression: -d[Sb(III)]/dt = k[Sb(III)][H 2O2][H+]-1 with log k= -6.88 (±0.17) [k: min-1]. The undissociated Sb(OH)3 does not react with H2O2: the formation of Sb(OH) 4 - is needed for the reaction to take place. In a mildly acidic hydrochloric acid medium, the rate of oxidation of Sb(III) is zeroth order with respect to Sb(III) and can be described by the expression -d[Sb(III)]/dt = k[H2O2][H+][Cl-] with log k = 4.44 (±0.05) [k: L2 mol-2 min -1]. The application of the calculated rate laws to environmental conditions suggests that Sb(III) oxidation by H2O2 may be relevant either in surface waters with elevated H2O2 concentrations and alkaline pH values or in treatment systems for contaminated solutions with millimolar H2O2 concentrations

Antimony in aquatic systems

Antimony is a naturally occurring element. It belongs to group 15 of the periodic table of the elements. Antimony can exist in a variety of oxidation states (–III, 0, III, V) but it is mainly found in two oxidation states (III and V) in environmental, biological, and geochemical samples. Although antimony was already known to the ancients, it is still often overlooked, both as an element of environmental concern and as a subject for study, probably because of its lower abundance and the relative insolubility of most of its compounds. This is reflected in the poor standard of existing data on the behavior of antimony in natural waters. However, interest in the study of this element seems to be growing and an increasing number of papers on the subject are being published. A useful series of comprehensive reviews on antimony in the environment has recently been published (1, 2)

Antimony in aquatic systems

Antimony is ubiquitous in the environment. In spite of its proven toxicity, it has received scant attention so far. This communication presents an overview of current knowledge as well as the early results of a concerted, multidisciplinary effort to unveil antimony behaviour and fate in natural aquatic systems