Influence de la préoxydation sur la coagulation par le chlorure ferrique de la matière organique

La coagulation par le Fe(III) de substances humiques aquatiques est optimale à pH = 5,5 pour un rapport massique Fe/COT de l'ordre de 2, quant à l'élimination du COT. Le but de cet article est d'étudier l'influence d'une préoxydation sur l'élimination de la matière organique par coagulation dans ces conditions.La préoxydation (ozone, bioxyde de chlore ou chlore) à faibles doses induit une légère dégradation des rendements de coagulation des acides fulviques. Un taux de préoxydant fort (≈ 0,5 mg oxydant par mg de carbone organique initial), pratiqué avant la coagulation, implique de mettre en oeuvre une dose de coagulant plus élevée [≈ 3 mg Fe(III) par mg de COT]. Cette augmentation est moins marquée dans le cas d'une préchloration.Les substances humiques ne représentant qu'une partie de la matière organique des eaux naturelles, des manipulations sur des eaux brutes ont donc été entreprises. L'effet de faibles doses d'ozone conduit à une légère amélioration de la coagulation. Cependant de fortes doses d'oxydant (0,5 mg d'ozone ou de bioxyde de chlore par mg COT) nécessitent l'emploi de plus fortes doses de coagulant. De plus, le rendement d'élimination est aussi affecté.We present here some works which take place in the particular frame of the study of the drinking water treatment of reservoir waters containing organics at high concentration, mainly humic substances. Previous studies (LEFEBVRE and LEGUBE, 1990) on coagulation of fulvic acid solutions have proven that the optimal removal of organic matter was reached at pH = 5.5 with 2 mg of ferric iron per mg of organic carbon. The main question in this study is to know the impact of preoxidation (ozone, chlorine dioxide, chlorine) on the removal of organics by iron(III) coagulation.The reconstituted waters obtained by dissolving fulvic acids (table 1) in a solution of salts in high-purity water (table 2), are defined by both a low inorganic content (as calcium, sulfate and bicarbonate ions) and a high organics concentration, main characteristics of real impounded waters (table 3). The experimental procedures of coagulation-flocculation-clarification followed the treatment lines shown in figure 1. Ozonation was carried out in a semi-continuous system (batch solution), by bubbling ozone (fig. 2). Chlorination and preoxidation with chlorine dioxide were performed in a batch reactor. The preoxidation steps were carried out at pH of reconstituted waters or of raw waters. A Dohrmann DC 80 was used for the determination of TOC. The accuracy of TOC measurement was found to be ± 0.05 mg/l C (for the range of studied concentration). Residual iron was analysed by atomic absorption on a Perkin Elmer 2380 apparatus (oxy-acetylene flame).As shown in table 4, preozonation induced a slight decrease of Cebron fulvic acid removal by iron(III) coagulation at high ozone dose applied (= 0.5 mg O3 per mg TOCi). In order to try to understand why ozone partially inhibits the efficiency of iron coagulation to remove fulvic acid at acidic pH, we determined the optimum dosage of coagulant required to obtain the best percent of removal on preozonated fulvic acid solutions. Figure 4 shows that preozonation at about 0.5 mg O3 per mg TOCi appears to have shifted the region of the optimal TOC removal towards the higher Fe/TOCi mass ratios (≈ 3 mg Fe(III) per mg TOCi, for two fulvic acids).Prechlorination (> 1 mg Cl2/mg TOCi) induced a decrease of Cebron fulvic acid removal by iron(III) coagulation (table 5). Hence, we examined the optimum dosage of coagulant required to obtain the best percent of removal on prechlorinated fulvic acid solutions (fig. 6). The region of the optimal TOC removal was still obtained for a Fe/TOCi mass ratio of 2. However, the difference between the percent TOC remaining for inital fulvic acid of 10 and 15 mg/l was not significant (respectively 61.4 % and 61.9 %). A greater prechlorinatlon dosage (> 0.5 mg Cl2/mg TOCi) would probably give a shift of the optimal mass ratio.Preoxidation with chlorine dioxide (even without ClO2 residual) before a coagulation induced a decrease at TOC (table 4). So, we studied the shift of optimum dosage of coagulant required to remove the organic matter. Figure 5 shows that preoxidation (≈ 0.5 mg ClO2/mg TOCi) shifted the region of optimal TOC removal towards higher Fe/TOCi mass ratio (≈ 3 mg per mg for Cebron fulvic acid, in figure 5).The fulvic acids represent only an amount of TOC of a raw waters. So we carried out experiments on real impounded waters. For the study of the influence of the preozonation on the coagulation efficiency, we chose to work at the optimal coagulant dose determined from previous experiments. Several runs were conducted with different dosages of ozone between 0 and 2 mg/l O3. Results reported in tables 6 and 7 indicate that for these two raw waters (Moulin Papon and Cebron), the preozonation slightly improved the efficiency of iron coagulation at acidic pH. These results can only be compared with Cebron fulvic acid when applied ozone dose was 0.2 mg O3/mg TOCi.Consequently, other experiments were carried out at a high ozone dose (- 0.5 mg O3/mg TOCi). They showed a shift in the region of the optimal TOC removal towards the higher coagulant dose (fig. 7), as already observed with the fulvic acid solutions.Only one experiment was made with chlorine dioxide in the case of Moulin Papou raw water. This preoxidation (≈ 0.5 mg ClO2/mg TOCi) induced a shift to higher coagulant dosage but also a decrease of the efficiency of iron coagulation whatever the applied coagulant dosage (fig. 8).As compared to humic chlorination literature, little information exists concerning ozonation of humics. Furthermore, in spite of small amounts of identified by-products in the literature, ozonation was usually found to increase smaller size materials in humic substances (GLOOR et al., 1981; VEENSTRA et al., 1983; FLOGSTAD and ODEGAARD, 1985; ANDERSON et al., 1986; AMY et al., 1987; LEGUBE et al., 1989). Moreover, analyses of carboxyl-group on the Cebron fuivic acid allowed us to show that the carboxyl content increased as ozone dosage increased (fig. 9).Some works (VAN BREEMEN et al., 1979) have proven the rate of carboxyl groups in the stoichiometry of coagulation reaction of humics with iron(III) at slightly acidic pH. Consequently, it is not surprising that preozonation of fulvic acids appears to have shifted the region of TOC removal up into the higher iron dose range, according to the enhancement of the carboxyl content in the fulvic acids by ozone. This effect of preozonation was already reported by others (JEKEL, 1983; RECKHOW and SINGER, 1983).Chlorination (GLAZE and PEYTON, 1978) or oxidation with chlorine dioxide (NORWOOD et al., 1983; COLCLOUGH Of al., 1983) led also to a decrease of the molecular weight of aquatic organic matter. The oxidative action of chlorine and chlorine dioxide gave many products like aromatic and aliphatic acids (chlorinated or not chlorinated) and probably increased the carboxyl content of humic substances. Hence, those oxidants inhibit the coagulation-flocculation of organic matter

Le Traitement des Eaux de Consommation : La Nécessité d'une Recherche en Chimie de l'Eau

L'objectif principal de cet article est de montrer que les travaux de recherche en chimie de l'eau sont absolument nécessaires à la compréhension des phénomènes régissant la qualité des eaux de consommation produites et distribuées, ainsi qu'au développement de technologies innovantes dans le domaine du traitement de ces eaux. Pour l'atteindre, il a été choisi de présenter trois exemples des recherches menées à l'Université de Poitiers et à l'École Polytechnique de Montréal : deux exemples de recherche fondamentale, sur les matières organiques naturelles et sur les mécanismes d'oxydation par les radicaux hydroxyle et un exemple de la recherche d'application, sur l'évolution de la qualité de l'eau lors de son traitement biologique par ozonation couplée à la filtration sur charbon actif en grains.The main purpose of this paper is to demonstrate that a better understanding of chemical reactions and a better technologies development for the drinking water treatment absolutly needs research in water chemistry. In order to reach this objective, two examples of recent fundamental research works in water chemistry and one example of research applied to drinking water treatment have been selected.The first one concerns a fundamental research on characterization and analysis of natural organic matter. Nowadays, the main analytical tools used for quantification of NOM are DOC (BDOC for the biodegradable fraction) and UV-absorbance. However, a better knowledge of NOM would be useful to predict water quality and determination of doses of some treatment chemicals, such as coagulants and oxidants. This paper presents some data about (i) NOM fractionning by XAD macroporous resins and relationship between UV-absorbance and 13C-NMR, and (ii) study of chlorination of the isolated fractions. Based on these results, one can suppose that aquatic NOM could be soon easily fractionnated and characterized by simples analytical tools. However, many research works are still necessary, particularly on the field of relationships between data of "heavy" analytical tools (13C-NMR, pyrolysis/GC/MS, etc.) and more simple others (UVA/DOC, BDOC, fluorescence etc.).The second paragraph of the paper relates oxidation mechanisms by hydroxyl radicals. In ozonation of drinking water, currently applied in the drinking water treatment, OH radicals production is a necessary consequence, considered as the main action of ozone by some authors. So, disinfection quality, bromate production, BDOC formation, pesticides removal will never be entirely understood as long as hydroxyl radicals participation in ozonation processes will not be really cleared up. To illustrate this purpose, the example of ozonation of a free aminoacid (glycine) by molecular ozone and by OH radicals is shown. Oxidation by "pure" OH radicals, produced by radiolysis, as compared to oxidation by molecular ozone, (at acidic pH in the presence of radical scavengers) shows that two mechanisms are really different. So, some works published some years ago, mixed up the two pathways. Such mechanisms on aminoacids oxidation should allow to understand some more descriptive data on water disinfection and pesticides oxidation.The third example concerns the changes of water quality during ozone/GAC treatment. It is well known that ozonation of naturel waters leads to an enhancement of water biodegradability, in terms of BDOC increase. So, if this BDOC is not removed in the plant, it can be the origin of bacteria regrowth in distribution system. The solutions are either to include, after ozonation step, a biological treatment step on activated carbon (BAC), or to increase chlorination doses applied in final disinfection. The effects of BAC treatment on BDOC and ozonation by-products removals, in the case of the drinking water treatment plant of Sainte-Rose (City of Laval, Quebec, Canada), are described. Finally, taking into account the cost of such a process, the last paragraph of this paper gives some recommandations for conception on BAC treatment.As for general conclusion, some new research topics in water chemistry for the drinking water treatment are enumerated and some ideas about organization and development of applied and fundamental researches in water chermistry for the drinking water treatment, are given

Évolution des acides aminés et de la matière organique dissoute dans une filière de production d'eau potable: Corrélations avec le carbone organique dissous biodégradable et le potentiel de demande en chlore à long terme

Le suivi de la matière organique totale (COD) et spécifique (substances humiques et principalement acides aminés dissous totaux) dans les eaux d'une filière de production d'eau potable a mis en évidence des abattements moyens dans l'eau traitée représentant 40 % du COD et 0 à 75 % des acides aminés. Parallèlement, le potentiel de demande en chlore à long terme est diminué de près de 70 %, alors que la fraction biodégradable connait une élimination de l'ordre de 50 %.Aucune corrélation directe n'a pu être mise en évidence entre les teneurs en acides aminés et la valeur du carbone organique dissous biodégradable (CODB) et de la demande en chlore des eaux brutes ou en cours de traitement. Cependant, compte tenu des teneurs en acides aminés dissous totaux quantifiées dans les eaux traitées de l'usine, leur participation peut être estimée entre 5 et 23 % du potentiel de demande en chlore et entre 5 et 25 % du CODB.La matière organique analysée spécifiquement dans le cadre de cette étude (substances humiques et acides aminés dissous totaux), représente 20 à 35 % du COD des eaux en fin de filière, et la présence de ces composés organiques serait responsable d'une part notable de la demande en chlore à long terme des eaux (40 à 60 %).Dissolved organic compounds (dissolved organic carbon (DOC), biodegradable dissolved organic carbon (BDOC), total amino acids and humic substances) and their chlorine demand were analyzed monthly at different steps of the water treatment plant of Méry-sur-Oise (Paris, France, 270 000 m3/d, Fig. 1).Total dissolved amino acids were determined by HPLC analysis with fluorimetric detection after hydrolysis of combined amino acids (proteins, polypeptides) by hydrochloric acid (DOSSIER BERNE et al., 1994 a); the separation of 17 amino acids was performed after orthophthaldialdehyde (OPA) pre-column derivatization. Humic substances were determined according to the method developed by THURMAN and MALCOLM (1981), by gravity feeding XAD-8 resins with acidified samples. The humic fraction was expressed as the difference between DOC before and after passage through the column. The method developped by JORET and LÉVI (1986) using a biologically active sand inoculum was used for the determination of BDOC.For the determination of chlorine consumption, the kinetic model described by JADAS- HÉCART et al. (1992) was used; it takes into account the long-term chlorine demand in terms of potential demand. This method was automated (DOSSIER BERNE et al., 1994 b) and computer-assisted. The chlorine dose was chosen depending on the DOC value and on the N-NH4+ content of the water; the applied dose was: 3 mg Cl2/mg DOC + 10 mg Cl2/mg N-NH4+. Chlorine determination was performed automatically by the spectrophotometric N, N-diethylphenylene-1,4-diamine (DPD) method.In raw water, DOC values may reach 5.6 to 6.5 mg C l-¹ during the cold season, but the average yield of elimination was generally close to 40 % (Fig. 2). The biodegradable fraction of the organic carbon (BDOC), which represents 25 to 50 % of the DOC in the raw water, was partially removed in the plant and the residual concentration in treated water varied between 0.4 to 1.8 mg C l-¹ (Fig. 2). A transitory increase in the BDOC values was generally observed during the ozonation step; it reached 0.2 to 0.5 mg C l-¹ (Figs. 6 and 7).Whatever the period of the year, extracted humic substances constituted about 50 % of the DOC found in raw water (Fig. 3). This hydrophobic fraction was significantly removed in the treatment plant reducing the proportion of humic substances in the DOC of treated water to 16 - 23 % (Figs. 3, 6 and 7). The concentrations of total dissolved amino acids ranged from 100 to 260 µg l-¹ C in raw water and from 50 to 150 µg l-¹ C in produced water (Fig. 4); the main part of this elimination occurred during the clarification step (Figs. 6 and 7). No important seasonal variations could be observed for chlorine demand (Fig. 5); its removal occurred at each step of treatment and the average global elimination by the plant was of the order of 70 % (Figs. 6 and 7).On account of the low concentrations of amino acids, no direct relation could be shown between amino acid concentrations and the respective values of BDOC or of chlorine demand potential (Figs. 9 and 10). With regards to BDOC and chlorine demand potential, no correlation could be shown between these two parameters either (Fig. 8). However, it was possible to calculate the contribution of specific classes of dissolved organic compounds to chlorine demand and to BDOC. This calculation is based: i) on the concentrations of humic substances and amino acids measured during the monthly experiments at each point of the treatment plant, ii) on bibliographic data concerning the contribution to BDOC (biodegradability) and chlorine consumption of a large variety of model molecules (free or combined amino acids, aquatic humic substances). The results obtained in this way are reported in Table 3 for the treated water of the M?ry sur Oise plant. These results indicate that the small amounts of total dissolved amino acids present in treated water may account for 5 to 25 % of the BDOC value and for 5 to 23 % of the total chlorine demand potential. With regard to humic substances, their biodegradability was assumed to be very low but their contribution to the chlorine demand of the treated water was estimated between 10 to 40 %, whereas their DOC contribution ranges from 16 to 35 %. As a consequence, both amino acids and humic substances could account for 40 to 60 % to the chlorine demand of treated water. A special point should be noticed for total amino acids: their contribution to the DOC values of treated water was only 2 to 7 %, but they may account for a larger proportion of BDOC or chlorine demand potential (5 to 25 %)

Formation des ions bromate lors de l'ozonation des ions bromures en présence de la matière organique

Cet article rassemble les résultats de l'étude en laboratoire des conditions de formation des ions bromate (BrO3-) lors de l'ozonation des ions bromure. Les expériences ont été réalisées en réacteur fermé, en milieu tamponné à la température ambiante, (ª23 °C) et en présence de matière organique. La concentration initiale en ions bromure a été fixée à 200 mg/L et le taux d'ozone appliqué à 5 mg/L. La matrice étudiée a été préparée à partir de différentes fractions de la matière organique extraites d'eaux naturelles (acides fulviques et acides hydrophiles) et d'une fraction synthétique (tripeptide). Les fractions ont été étudiées individuellement ou en mélange dans des proportions compatibles avec la matière organique naturelle. L'étude a porté sur l'impact de la matière organique, du pH, de l'azote ammoniacal, de l'alcalinité et du peroxyde d'hydrogène sur la formation des ions bromate. L'analyse de BrO3- a été effectuée par chromatographie ionique après 24 heures de temps de réaction (ozone résiduel négligeable) ; la limite de détection de la mesure est de 2 mg/L.The objective of our work was to evaluate the importance of various parameters (natural organic matter, pH, ammonia, bicarbonate, hydrogen peroxide) affecting the formation of bromate during the ozonation of natural waters containing bromide. Bench scale experiments were carried out on synthetic solutions prepared in phosphate buffer (10-2 - 10-3 M). Bromate concentrations were determined by ion chromatography after the complete consumption of the added ozone (24 h contact time); the ion chromatograph was equipped with a suppressed conductivity detection system (DIONEX) with a detection limit of ca. 2 µg BrO3-/L.The impact of organic matter was evaluated with model organic compounds: fulvic acid and hydrophilic acids (FA and HyA) isolated from a river water with XAD8 and XAD4 resins, and a tripeptide (Tyr-Gly-Gly). These different organic compounds were studied individually or as a mixture (60% FA, 30% HyA, 10% tripeptide). All solutions were spiked with 200 mg/L of bromide and the applied ozone dose was 5 mg O3/L; the DOC content varied from 0 to 5 mg C/L.For given experimental conditions, bromate formation varies depending on the origin and nature of the organic matrix (natural organic matter or tripeptide), probably due to their respective ozone consumption. For a particular ozone dose, an increase in DOC results in decreasing bromate production. In fact, ozone consumption by the natural organic matter reduces the available ozone and somewhat inhibits the efficiency of bromate formation reactions.More bromate is formed with increasing pH, for the relative proportion of hypobromite increases in relation to hypobromous acid. In the presence of ammonia and natural organic matter, bromate formation is lowered because ammonia diverts part of the HOBr to form organobrominated compounds, and thus participates indirectly in ozone consumption.Bicarbonate addition favors molecular ozone type reactions by scavenging free radicals. Ozone is stabilized in the medium and thus more bromate is formed than in the absence of any scavenger. The reaction of OH radicals leading to bromate formation needs the presence of BrO-. Thus the use of hydrogen peroxide with an excess of ozone, or ozonation prior to hydrogen peroxide addition, may lead to the production of high bromate concentrations. This experiments shows that the higher the available ozone, the higher the bromate production. The use of ozone for disinfection purposes involves maintaining a residual ozone concentration during a due time in order to achieve the required C. t for bacterias and viruses inactivation. This increasing C. t may result in high bromate formation

Étude comparative de la vitesse de décomposition de H2O2 et de l'atrazine par les systèmes Fe(III)/H2O2, Cu(II)/H2O2 et Fe(III)/Cu(II)/H2O2

Cette étude a eu pour objectif de comparer les vitesses de décomposition du peroxyde d'hydrogène et d'oxydation de l'atrazine par les systèmes catalytiques Fe(III)/H2O2, Cu(II)/H2O2, et Fe(III)/Cu(II)/H2O2. Les expériences ont été réalisées à pH 3,0, à une température de 25,0 (± 0,2) °C, en milieu perchlorate, en présence et en absence d'oxygène dissous. L'étude comparative a confirmé que les vitesses de décomposition de H2O2 et d'oxydation de l'atrazine sont beaucoup plus lentes en présence de Cu(II) qu'en présence de Fe(III) et l'addition de Cu(II) augmente l'efficacité du système Fe(III)/H2O2. Pour nos conditions expérimentales ([composé organique]o < 1 µM) les expériences de cinétique compétitive, réalisées avec des solutions aqueuses contenant trois composés organiques (atrazine, 1,2,4-trichlorobenzène, 2,5-dichloronitrobenzène), ont montré que le radical hydroxyle représente la principale espèce responsable de l'oxydation des composés organiques. Les résultats ont également mis en évidence la formation très rapide d'un composé entre Cu(II) et H2O2 (étude spectrophotométrique) et ont montré l'importance de la concentration en oxygène dissous sur les vitesses globales de décomposition de H2O2 et de l'atrazine par les systèmes Cu(II)/H2O2 et Fe(III)/Cu(II)/H2O2.Toxic and refractory organic pollutants in industrial wastewater can be degraded by advanced oxidation processes (AOPs) alone, or in combination with physico-chemical and biological processes. Of these oxidation methods, Fenton's reagent (Fe(II)/H2O2) and Fenton-like reagents (Fe(III)/H2O2, Mn+ or Mn+1 /H2O2) are effective oxidants of large variety of organic pollutants.The mechanism of decomposition of H2O2 and of oxidation of organic solutes by Fenton's and Fenton-like reactions has been the subject of numerous studies. However, there are still many uncertainties as to the nature of the oxidant species formed and the rate constants of elementary reactions (Table 1).Our recent studies carried out in HClO4 /NaClO4 solutions and in the presence of very low concentrations of organic solutes (atrazine, 1,2,4-trichlorobenzene; concentration < 3 µM) have shown that the reaction of Fe(II) with H2O2 leads to the formation of two intermediates and that the overall initiation step (reaction 1, Table 1) at pH < 3.5 leads to the formation of OH radical (Gallard et al., 1998a). Other work with different organic compounds and higher concentrations of organic solutes indicates that the intermediates (Fe(II)-hydroperoxy complexes, ferrous ion) might also oxidize organic compounds. Ferric ion can also catalyze the decomposition of H2O2. The mechanism is initiated by the formation of two Fe(III)-peroxy complexes at pH < 3.5 (reaction 2a, Table 1) followed by their slow decomposition into Fe(II) and HO2·/O2·- (reaction 2b, Table 1) (Gallard et al., 1999; De Laat and Gallard, 1999; Gallard and De Laat, 1999).The formation of intermediates (complexes, cupryl ion) has also been postulated for the catalytic decomposition of H2O2 by Cu(II). Depending on the experimental conditions (nature and concentrations of organic solutes, pH,…), the degradation of organic compounds might be attributed to the hydroxyl radical (reaction 1, Table 1) or to other species like the cupryl ion (Cu(III)). Production of Cu(III) by reaction of OH· with Cu(II) has also been demonstrated by pulse radiolysis experiments. Kinetic data indicate that the rate of decomposition of H2O2 and the rate of oxidation of organic compounds are faster with Fe(III)/H2O2 than with Cu(II)/H2O2 and that Cu(II) can improve the efficiency of the Fe(III)/H2O2 process.The present study has been undertaken in order to compare the rates of decomposition of H2O2 and the rates of oxidation of atrazine by Fe(III)/H2O2, Cu(II)/H2O2 and Fe(III)/Cu(II)/H2O2 under identical conditions. These conditions (pH 3.0, I=0.1 M, [Atrazine]o < 1 µM) were the same as those used in previous studies of the Fe(II)/H2O2 and Fe(III)/H2O2 systems.Experiments were carried out in MilliQ water, in the dark, at 25.0 (± 0.2) °C, pH 3.0, ionic strength (I) of 0.1 M, in the presence and in the absence of dissolved oxygen. pH and I were adjusted with perchloric acid and sodium perchlorate. The concentrations of hydrogen peroxide ([H2O2]o ≤ 10 mM) and of atrazine ([atrazine]o ≤ 1 µM) were determined iodometrically and by HPLC, respectively.In the absence of organic solutes, experimental results have shown that the rate of decomposition of H2O2 is faster with Fe(III) than with Cu(II) (Figure 2). In agreement with previous data (De Laat and Gallard, 1999), the initial rate of decomposition of H2O2 by Fe(III) can be described by a pseudo first-order kinetic law with respect to H2O2, and dissolved oxygen (0-1 mM) has no effect on the rate of decomposition. For the Cu(II)/H2O2 system, our spectrophotometric data (Figure 1) gave evidence that the decomposition of H2O2 by Cu(II) goes through the formation of an intermediate which might be a Cu(II)-hydroperoxy complex and which absorbs in the region 350-600 nm. Furthermore, the rate of decomposition of H2O2 by Cu(II) does not follow a first-order kinetic law and is affected by the concentration of dissolved oxygen (Figures 2 et 3).As far as the oxidation of atrazine is concerned, a preliminary study of the oxidation of solutions containing atrazine, 1,2,4 trichlorobenzene and 2,5 dichloronitrobenzene in very dilute aqueous solutions ([organic solutes]o < 3 µM) has been conducted at pH 3.0. Experimental results showed that the relative rates of decomposition of organic solutes by Fe(III)/H2O2, Fe(II)/H2O2 and Cu(II)/H2O2 were identical and could be described by the competitive kinetic expression (Figure 4). These data suggest that the oxidation of the organic solutes by the three systems of oxidation tested can be attributed to a unique oxidant species, the hydroxyl radical, under our experimental conditions.The rate of oxidation of atrazine by Cu(II)/H2O2 was found to be much slower than by Fe(III)/H2O2 (Figure 5), to be dependent on the concentrations of reactants ([Cu(II)]o, [H2O2]o Figure 6) and to decrease in the presence of dissolved oxygen (Figure 7). These data confirm that the rate of decomposition of H2O2 by Cu(II), and as a consequence, the rate of production of OH radicals by Cu(II)/H2O2, are much slower than by Fe(III)/H2O2. In addition, a fraction of Cu(I) may be oxidized by dissolved oxygen and this reaction, which competes with the reaction of Cu(I) with H2O2, may also decrease the rate of formation of OH radical.For the Fe(III)/Cu(II)/H2O2 system, experimental data have demonstrated that the addition of Cu(II) increases the rate of decomposition of H2O2 (Figure 8a) and atrazine (Figure 8b) by Fe(III)/H2O2 and that these increases in reaction rates depend on the concentration of dissolved oxygen. This catalytic effect of Cu(II) has been attributed to a fast regeneration of Fe(II) (which is the major source of OH radical) by the reaction of Cu(I) with Fe(III). Since this reaction competes with oxidation of Cu(I) by O2 and H2O2, the catalytic properties of Fe(III) and Cu(II) mixtures will depend on the experimental conditions, such as the relative concentrations of reactants. In conclusion, this comparative study has confirmed that the rates of decomposition of H2O2 and atrazine, in dilute aqueous solution, by Fe(III)/Cu(II)/H2O2 are faster than by Fe(III)/H2O2 and Cu(II)/H2O2. This study has also demonstrated that dissolved oxygen has a significant effect on the reaction rates in the Cu(II)/H2O2 and Fe(III)/Cu(II)/H2O2.oxidation systems. The effects of dissolved oxygen and of the addition of Cu(II) on the efficiency of the Fe(III)/H2O2 system could be explained by assuming that the OH radical is the major oxidant species under our experimental conditions. However, additional research is needed in order to better understand the mechanism of decomposition of H2O2 by Cu(II) and Cu(I) and to determine the rate constants of individual reactions involved in the Cu(II)/H2O2 and Cu(I)/H2O2 systems

Analytical and statistical study of a lake system under various processes of eutrophication

L'étude des phénomènes d'eutrophisation se heurte essentiellement à deux difficultés qui sont inhérentes d'une part, à la diversité spatio-temporelle des eaux superficielles, et d'autre part, à l'action qu'exercent en retour les phénomènes d'eutrophisation sur ces eaux.- La diversité spatio-temporelle des systèmes aquatiques s'accompagne d'une diversité des phénomènes d'eutrophisation qui en sont le siège et a pour conséquence de rendre difficile sinon impossible l'établissement de critères de comparaisons entre les différents systèmes aquatiques. Dans ces conditions il est peu aisé de faire le choix objectif d'un état de référence universel qui seul permettrait de déterminer de manière absolue le niveau trophique d'une eau.- La deuxième difficulté, et sans doute la plus grande, est liée à l'action qu'exercent les phénomènes d'eutrophisation sur les variables analytiques du système. Cette action a pour conséquence de rendre les valeurs intrinsèques de ces variables impropres à l'étude de ces phénomènes et de leur évolution. Ces variables étant liées simultanément aux causes et aux conséquences des diverses manifestations des phénomènes d'eutrophisation.Les 10 lacs que nous avons étudié ici, présentent l'avantage peu courant d'être alimentés par les mêmes eaux traversant une zone géographique restreinte et par conséquent géologique et climatique identique. Ils sont soumis à l'influence d'activités agricoles ou urbaines différentes mais bien identifiées, entraînant pour ces eaux des caractéristiques trophiques différentes. Dans un tel cas, il aurait pu sembler a priori possible d'établir une classification des différents états trophiques des lacs. Cependant, même dans une situation aussi idéale, et essentiellement à cause des deux difficultés mentionnées précédemment, nous tentons de montrer ici qu'il n'en est rien. Cela amène les commentaires d'ordre général suivants:- Si pour le système lacustre étudié ici, probablement parmi les plus idéaux, il est difficile à partir des critères généralement retenus dans la plupart des études, (nutriments azotés, phosphorés , chlorophylle, oxygène dissous, etc.) d'établir un classement trophique, il semble a fortiori peu probable que cela puisse être réalisé sur des systèmes moins idéaux.- La littérature actuelle fait clairement apparaître ce problème majeur. Cependant pour y remédier, elle propose généralement de faire le choix d'autres indicateurs physico-chimiques ou même biologiques qui, pour les mêmes raisons, semblent également voués à l'échec.En conclusion de cette étude, nous proposons donc d'abandonner de tels indicateurs liés au milieu et de choisir de nouveaux critères qui prendraient en compte les perturbations apportées par le phénomène aux interactions liant les variables analytiques: les différents états trophiques d'une eau étant probablement mieux caractérisés par les différents états des relations liants les variables analytiques que par les valeurs intrinsèques de ces variables.One of the problems water managers and researchers have had to deal with for a long time is that of identifying the symptoms of eutrophication, with all its multiple facets. The search for a simplified model of this complex process does not seem, so far, to have attained this objective. In order to identify and classify the various trophic states of waters (lakes or rivers), two main types of trophic indicators have been and are still being used, those belonging to the biocenosis (biological factors) and those belonging to the biotope (physical-chemical factors).- The aim of the biological approach to eutrophication is to measure its impact on the environment's biodiversity. Thus, several classification indices have been drawn up, for example: the Biotic Index, which is one of the oldest; the General Quality Biological Index, which has been improved to become the Normalised Global Biological Index (NGBI) method; and more recently the Trophic Diatom Index. Working with such indices requires quite complex analyses since it is necessary to identify the local fauna and flora. Furthermore, these indices only apply to rivers, not to lentic environments.- For the physical-chemical approach, the aim is to quantify the trophic state of an aquatic environment by measuring a number of physical-chemical parameters. This approach is easier to implement and the results provided are those currently used by water managers.It is obvious that the two approaches are linked, since the biodiversity of an aquatic environment is conditioned by the physical-chemical quality of its water. However, the study of the eutrophication process in surface waters faces two main difficulties, which are inherent in the very nature of the system and the phenomena under study:1. Since aquatic systems naturally differ one from the other, it is obviously difficult if not impossible to establish a reference state to determine the trophic level of a water with absolute accuracy.2. The second difficulty lies in the choice that must be made among the analytical parameters, to select those that are the most appropriate to describe the phenomenon. Although it is currently admitted that the nitrogen, phosphorus and phytoplankton parameters, among others, cannot be ignored, their intrinsic values are not sufficient to completely describe the process of eutrophication. Indeed, the values of most of these parameters are linked both to the causes and the effects of eutrophication, and as a consequence they cannot be interpreted unambiguously. The same restriction applies to correlations that are established between these parameters and the plant biomass. Because of the originality of the lake system with which we are dealing, the present study offers the opportunity to better understand the reasons for both these problems.The ten lakes we have studied (number 1 to 10) present the rare advantage of being supplied by the same streams, running across a restricted geographical zone that is geologically and climatically similar. However, the trophic characteristics of these waters have been altered by their passage through different agricultural and urban zones. Thus, lakes 1 to 4 are located in an area of low urban density and are colonised by phytoplankton, the density of which decreases from Lake 1 to Lake 4; macrophytes are not present in these lakes.Lake 5, located in the centre of the town, receives domestic waste water. This lake was, over a long period of time, entirely covered with water hyacinths (Eichhornia crassipes), very invasive floating macrophytes, and with lotuses (Nelumbo nucifera) and rooted macrophytes. During the study period, following the manual removal of the macrophytes in July 1995, the water was strongly colonised by algae, as can be seen from the high concentration of chlorophyll-a, close to 200 µg/l.Lake 6 presents a similar situation; it was almost entirely covered by Eichhornia crassipes until July 1997, and was then manually cleared. As the elimination of the water hyacinths profoundly modified the characteristics of this lake, we will show the two periods of time separately.Lake 7 receives the waste water from a densely populated area. After being cleared in July 1997 of a thick layer of various plants that had covered it for several years, the lake was invaded by water lettuce (Pistia stratiotes), a floating macrophyte, which has dominated the lake since December 1997.Finally lakes 9 and 10 are almost completely covered by lotuses (Nelubo nucifera), which are rooted macrophytes, along with a few Pistia stratiotes, while Lake 8 is periodically colonised by water lilies (Nymphea lotus) and algae.To follow changes in the water quality of the 10 lakes studied, 21 sampling stations were chosen, usually at the entrance and exit of each lake. The mean values for the physical-chemical parameters for any lake gave a reasonable representation of the lake water under study. Sample collection in the ten lakes lasted two hours (between 8 and 10 a.m.). The sample collection, and the analysis of the 19 physical-chemical parameters taken into account, was carried out between April 1996 and April 1998 (twice a month in the rainy season and once a month otherwise), which represented about 15 000 measurements. At each location, a litre of water was taken, 50 cm below the surface, with a polyethylene bottle fixed on a 5 m bamboo pole. Portions of 250 ml were then transferred into a brown glass bottle, for later analysis of chlorophyll. After the in-situ analyses, the bottles were kept in the dark in a cooler.Because of the unique sampling situation, it might have been anticipated that the comparison of the different trophic states on the basis of the physical-chemical variables would be possible, but this was not the case. On the contrary, this study tended to show that the physical-chemical characteristics of these waters are as much influenced by the feedback effect of eutrophication as by the external factors, so that the contribution of each of the variables to the various types of eutrophication cannot be clearly determined. This is particularly true in the case of parameters characteristic of nutrients or those reflecting the water response.Although it may appear trivial, this "feedback action" can naturally be generalised to all lake systems, in temperate or tropical climates, whatever the kind of biomass that colonises them. The trophic level of these waters must therefore be evaluated on the basis of new criteria, which will take into account all the relations that link the various parameters

Performance de la nanofiltration pour l'élimination de la matière organique naturelle: essais sur l'usine de Méry/Oise

L'intérêt croissant que les traiteurs d'eaux portent à l'élimination de la matière organique naturelle (MON) a abouti au développement de nouvelles technologies de traitement. Dans ce but, un prototype de nanofiltration à l'échelle industrielle (2 x 1400 m 3 j-¹) est installé à l'usine de Méry sur Oise depuis juillet 1992. Utilisé en traitement de finition après clarification et filtration sur sable, il alimente depuis février 1993 un réseau test de la commune d'Auvers sur Oise (6 000 hbts) en région parisienne.L'objectif de cette publication est de présenter quelques uns des résultats de caractérisation de la MON obtenus pendant 9 mois d'expérimentation (octobre 1992 à juillet 1993), et en particulier ceux concernant les rendements d'élimination de la matière organique naturelle et par voie de conséquence de la demande en chlore.Ces rendements sont généralement supérieurs à 90 % en termes de COD,CODB et d'absorbance UV à 254 et 270 nm éliminés. L'analyse des potentiels de réactivité avec le chlore (taux de chloration: 2,5 mg Cl2/mg C, temps de réaction: 72 heures, pH = 7,5, 20 °C) montre que le perméat est peu consommateur de chlore (demande en chlore < 0,2 mg l-¹ Cl2) et peu précurseur de chloroforme et de trihalométhanes (PFCHC13 < 3 µg l-¹, PFTHM < 11 µg l-¹). Les rendements d'élimination des PFTHM et PFTOX sont généralement supérieurs à 90 %.L'analyse spécifique des constituants majoritaires du perméat montre que les acides aminés totaux (hydrolyse acide puis dérivation à l'OPA/HPLC) constituent une proportion importante du COD (25 à 60 % selon les saisons). Ces composés représentent la quasi totalité de la demande en chlore du perméat si l'on se réfère aux données bibliographiques.Compte tenu de ces résultats, la nanofiltration apparaît comme un excellent procédé de traitement de finition des eaux à potabiliser. En effet, bien qu'elle constitue une barrière de sécurité contre les germes pathogènes, la très faible charge organique du perméat obtenu par nanofiltration (COD~0,15 à 0,3 mg l-¹ C, CODB<0,1 mg l-¹ C) rend plus aisée la maîtrise du résiduel de chlore (lorsqu'une chloration est nécessaire pour maintenir la qualité de l'eau dans les réseaux) et constitue une limitation importante de la formation des sous-produits de chloration.Increasing interest in removing natural organic matter (NOM) has lead to the development of new drinking water treatment technologies. Since July 1992, a nanofiltration demonstration plant (2 x 1400 m3 d-1) has been used to treat sandfiltered water from the Oise river. The permeate has been distributed since February 1993 to the 6000 inhabitants of Auvers/Oise in the Paris suburb. The purpose of this paper is to present and discuss some ofthe results obtained over nine months of operation of this full scale plant, particularly yields of NOM removal and consequently the decreasing of chlorine reactivity (chlorine demand, TTIM and TOX formation potentials).Dissolved organic carbon (DOC) and UV-absorbance were determined using DOC analyser and a spectrophotometer. Biodegradable dissolved organic carbon (BDOC), which represents the biologically assimilable portion of DOC, was determined using the method of JORET et LEVI (1986). Chlorine demand, trihalomethane and total organohalide formation potentials (THMFP and TOXFP) were carried out under the following experimental conditions: applied chlorine dose of 2.5 mg Cl2/mg DOC, pH = 7,5 72 h-contact time and 20°C. Ultrafiltration experiments involved the use ofa laboratory ultrafiltration cell, Total amino-acids were analysed by HPLC after hydrolysis and orthophtaldialdehyde (OPA) derivatization. Aldehyde and ketone determination was based on the method developedby GLAZE et al. (1989) involving pentafluorobenzyl hydroxyl amine (PFBHA) derivatization.Characterization of sand-filtered water (SFW): The sand-frltered water (SFW) upstream of the nanofiItraton membranes has a DOC between 2.4 and 4.l mg l-1, depending on the season (table 1). Its BDOC ranges from 0.7 to l.l mg l-1 C. In fact, a BDOC value higher than 0.3 mg l-1 C has been mentioned by several authors as the limit above which possible bacterial regrowth can take place in the distribution network.The chlorine consumption curves, shown in figure 2 for five sampling campaigns, indicate that the chlorine demand of the SFW can reach 3.4 to 5.2 mg l-1 depending on the season (table 2). The THMFP and the TOXFP are 108-149 ug l-1 and 344-446 ug l-1 Cl- respectively. Note that the ratio of chlorine demand over DOC varies from 1.0 to 1.7 mg Cl2/mg DOC while the THMFP/DOC and TOXFP/DOC ratios present average values of 47.5 ug/mg DOC and 160 ugCl-/mg DOC respectively.The distribution of the SFW (table 3) indicates that the fraction with apparent mo lecular weight Iess than 3 kilodatons contains the major compounds at this stage of the water treatment. This fraction presents the highest chlorine consumption. Specific total amino acids (TAA) analyses demonstrate that TAA represent 3 to 8% of the DOC of the sand-filtered water. The most abundant arnino acids are glycine, aspartic acid, glutamic acid, serine and alanine. The chlorine consumption attributed to these amino acids is evaluated as 1 mg l-1 Cl2, that is to say 1/5 to 1/3 of the SFW chlorine demand. Formaldehyde and acetaldehyde seem to be the major aldehydes present in the SFW with a level of 7 ug l-1 and 20 ug l-1 of formaldehyde and acetaldehyde respectively. They represent only about 0.5 to 0.6 % of the SFW DOC.Characterization of the permeate: The nanofiltration permeate presents a very low NOM level in terms of DOC, BDOC and UV absorbance at 270 nm, that is to say 0.14 to 0.34 mg l-1 C, < 0.1 mg l-1 C and < 0.006 cm-1-l respectively (table 6).The chlorine consumption curves, showt in figure 4 for five sampling campaigns, demonstrate the low permeate reactivity with chlorine. The chlorine demands (table 7) after 72 hours are between 0.12 and 0.32 mg l-1. Moreover chlorine demand/DOC ratios have a value from 0.46 to 0.93 mg Cl2/mg DOC, i.e. half the values measured for SFW. The THMFP and TOXFP (72hours) range from 7 to 11 ug l-1 and 26 to 31 ug l-1 Cl- respectively.Total amino acid (TAA) analyses showed that TAA represent 35 to 60% of the permeate DOC and can account almost entirely for the chlorine consumption. Formaldehyde and acetaldehyde (the major aldehydes analysed) represent 7 to 8% of the permeate DOC.According to the results presented in this paper, nanofiltration appears to be an excellent technolory as a polishing step in surface water treatment. Whereas the level of sand-fïltered water (SFW) DOC varies from 2.4 to 4.1 mg l-1 C (depending on the season), the permeate DOC is consistently lower than 0.3 mg l-1 C. The efficiency of nanofiltration is about 90% for DOC, BDOC and consequently for chlorine demand, THMFP and TOXFP. The high retention of NOM is probably in relation with the percentage (75%) of compounds with apparent molecular weight above 500 daltons in the SFW. In fact the low values of BDOC and chlorine demand justify the use of nanofiltration for the production of a water which represents a very low risk of bacterial regrowth and a low risk of formation of disinfection by product in the network when distributed with a low concentration of residual chlorine

Etude sur les acides fulviques extraits d'eaux superficielles françaises - Extraction, caractérisation et réactivité avec le chlore

Après avoir présenté quelques données bibliographiques sur les substances humiques aquatiques, l'extraction de plusieurs substances humiques issues de onze eaux de surface françaises, est discutée en terme de rendements d'extraction. Quelques paramètres de caractérisation des acides fulviques sont présentés et en particulier, l'analyse élémentaire, l'absorption UV, les fonctions carboxyles et les potentiels de réactivité avec le chlore. Concernant la chloration, une attention particulière a été portée d'une part sur la nature produits organo-chlorés formés et d'autre part sur les corrélations qui existent entre la nature des acides fulviques et leur potentiel de réactivité avec le chlore.Numerous procedure for the isolation of aquatic humic substances are described in literature. The first part of this study presents the extraction of fulvic and humic acids from eleven French surface waters, using XAD 8 macroreticular resin as developed by TRURMAN and MALCOLM (1981). The results are discussed in terms of extraction yield and fulvic acid/humic acid mass ratio.The second part of the paper presents some structural parameters of the extracted fulvic acids such as elemental analysis, UV-absorbance, carboxyle-function content and in some cases of fulvic acids, infrared spectrum and apparent molecular weight investigated by ultra filtration.The third part of the work concerns the study of fulvic acids chlorination. Firstly, the gas chromatography - mass spectrometry analysis of one chlorinated fulvic acid allowed us to identify some chlorination by-products and especially chloroform, dichloro-acetic and trichloroacetic acids and some other chlorinated aliphatic acids. Secondly, the chlorine reactivity potentials of each fulvic acids were determined and results are discussed in terms of chlorine consumption, chloroform and total organohalides formation potentials. Some relationships are established between the chlorine reactivity potentials and UV-absorbance of the extracted fulvic acids

Analyse par HPLC et CG/SM des constituants du carbone organique dissous (COD), du COD biodégradable (CODB) et des composés organohalogénés (TOX) d'un perméat de nanofiltration

Pour limiter la formation de composés organohalogénés des eaux traitées et la reviviscence bactérienne des réseaux, il est important d'éliminer la majeure partie du carbone organique dissous (COD) et du carbone organique dissous biodégradable (CODB) contenus dans les eaux naturelles. Des travaux récents nous ont permis de montrer que la nanofiltration est une technologie de choix pour répondre à ces contraintes.L'objectif de cet article est de présenter à partir de travaux de laboratoire un inventaire détaillé du carbone organique résiduel d'un perméat prélevé le 21/04/93 sur le prototype industriel de nanofiltration de Méry/Oise en banlieue parisienne. Pour atteindre cet objectif il a été nécessaire de mettre en œuvre des 'techniques analytiques impliquant l'utilisation de la chromatographie liquide haute performance (CLHP) et de la chromatographie en phase gazeuse (CG) soit équipée d'un détecteur à ionisation de flamme (FID) ou d'un détecteur à capture d'électrons (ECD), soit couplée à la spectrométrie de masse (SM).Les résultats obtenus ont montré que le COD du perméat étudié est constitué d'environ 60% d'acides aminés libres et combinés, de 7% d'aldéhydes et de 10 à 20% de composés divers identifiables en CG/SM. Ces derniers composés comprennent majoritairement des acides gras aliphatiques et des acides aromatiques de faibles masses. La concentration de chacun de ces composés a été estimée à 0,3 µg l-¹ C. On peut raisonnablement penser, d'après la bibliographie que les hydrates de carbone (non analysés dans cette étude) représenteraient une part importante de COD du perméat. En outre, cette étude a montré que la part prise par les acides aminés totaux dans le CODB du perméat est importante.Seul le tiers des potentiels de formation d'organohalogénés totaux (PFTOX) a été identifié comme étant des trihaloméhanes (THM) et des acides haloascétiques. Toutefois, étant donné que les acides aminés totaux représentent à eux seuls la quasi totalité de la demande en chlore du perméat, les autres sous-produits de chloration non identifiés seraient probablement des nitriles chlorés, des chloramines et des chloroaldéhydes qui sont parmi les principaux intermédiaires réactionnels de la coloration des acides aminés.Removal of dissolved organic carbon (DOC) and biodegradable dissolved organic carbon (BDOC) is one of the most important means to prevent disinfection by-products (DBPs) formation during water treatment and bacterial regrowth in distribution systems. In previous investigations, the authors have shown that nanofiltration, over nine months of operation at industrial scale in Paris suburbs, was an effective technology to meet the new guidelines concerning chlorine DBPs.This paper reports laboratory investigations aimed to identify and quantify the main organic components included in the low DOC, BDOC and TOXFP (Total - Organohalides Formation Potential) residuals of a nanofiltration permeate sampled on April 21, 1993.Details on DOC, BDOC, organohalides, amino acids and aldehydes analysis procedures were described elsewhere (AGBEKODO et al., 1994). Chlorination was undertaken in potential conditions k: 2.5 mg Cl2/mg DOC, pH=7.5 (phosphate buffer), 72 hours contact time, in dark at 20°C. Haloacetic acids determination consisted (after chlorination in potential conditions) in liquid-liquid extraction, methylation with diazomethane and gas chromatography analysis. Extraction procedure based on XAD8/XAD4 adsorption prior to gas chromatography/Mass Spectrometry (GC/MS) analysis (Fig. 3), allowed a 19000 fold concentration of the permeate. To prevent possible contamination of the permeate, the extraction system consisted of four glass columns and teflon materials. The flow through the columns was performed under high purity nitrogen gas pressure.Analysis involving high performance liquid chromatography (HPLC) and gas chromatography (GC) in combination with Mass Spectrometry (MS), showed that the studied permeate DOC (- 0.15 mg l-¹ c) consisted of amino acids at an average of 60% of DOC, aldehydes (7%) and 10 to 20% of several other compounds (analyzed in GC/MS) including primarily fatty and aromatic acids of low molecular weight (Table 4a and Table 4b). The maximum concentration of each compound (identified hy GC/MS) has been roughly assessed to 0.3 µg l-¹ C. According to literature, sugars represent probably an important portion of the remaining DOC of the permeate. Moreover, the authors have shown that amino acids represented a large portion of permeate BDOC.Only 34% of the total organohalide potentials were identified as trihalomethanes and haloacetic acids. However, since amino acids represent almost the entire chlorine demand of the permeate, the non- identified chlorination DBPs are likely chlorinated nitriles, chloramines and chloraldehydes which are known as the main reactionnal intermediates of aminoacid chlorination