Volume 7, Number 2, 1994

FR:

Les échanges de phosphore à l'interface eau-sédiment ont été étudiés dans la retenue Al Massira. La campagne de prélèvements a été menée pendant la faible oxygénation des eaux profondes au mois d'octobre 1991. Les mesures des échanges de phosphore ont été réalisées in situ en chambre benthique.

Les valeurs de pH sont élevées et reflètent clairement l'influence de la nature géologique du bassin versant sur la composition chimique des eaux. Ce bassin versant, formé essentiellement de roches sédimentaires calcaires, est vraisemblablement à l'origine des concentrations élevées en calcium mesurées dans les chambres benthiques.

En période de faible oxygénation, on note une augmentation des teneurs en phosphore particulaire dans les eaux surnageantes en raison de la présence de complexes calcium-phosphore, fer-phosphore et manganèse-phosphore.

En période d'anoxie, la réduction de ces complexes est accompagnée d'une aug- mentation des teneurs en phosphore.

La densité bactérienne et la concentration en phosphore total et notamment en orthophosphates suivent une évolution temporelle comparable. Une fraction non négligeable du phosphore particulaire serait liée aux bactéries.

Des mesures drastiques de déphosphatation du tributaire Oum Errbia doivent être prises pour éviter la dissociation des complexes Ca, Fe, Mn-Phosphore et le relargage de phosphore biodisponible.

EN:

Phosphorus exchange at the sediment-water interface was studied in the Al Massira reservoir. This reservoir, located on the Oum Errbia river, is the most important freshwater resource in Morocco. It provides drinking water to the whole population of Casablanca and contributes to farming and to the functioning of several industrial plants. Our investigations were made in October 1991 and coincided with low oxygen concentrations in the deep layers. The measurements of phosphorus exchange have been made in sitn with a benthic chamber device.

The results showed that these exchanges were regulated by a combination ofthe physical chemical variability of the environment and the geological composition of the catchment basin.

The pH, which permanently exceeded 7 in Massira, suggests that calcium-bound phosphorus was primarily CaHFO₄. Moreover, given the high phosphonrs inputs into the reservoir (570 tonnes. year^-1), and despite the fact that, as soon as it reached the reservoir, a large fraction of this element was associated with to calcium, it's likely that the Massira reservoir is subject to eutrophication.

In low oxygenated deep layers, we observed an increase in particulate phosphorus concentrations of the overlying water, due to the simultaneous presence of calcium-phosphorus, iron-phosphorus and manganese-phosphorus forms. Under anoxic conditions, the reduction ofthese complexes resulted in an increase of phosphorus concentrations.

Bacterial cell numbers and total phosphorus concentratioru showed a comparable temporal behaviour. This would suggest that attached bacteria contributed at least partially to the total particulate phosphoms concentrations.

We suggest that a drastic control of phosphorus inputs into the waters must be done through a program of dephosphorylation of tributaries to avoid the dissocation of calcium-, iron-, manganese-bound phosphorus with release upwards of bioavailable phosphorus.

FR:

L'isolement sporadique de coliformes sur certains réseaux de distribution en période chaude et en absnce de tout épisode décelable de contamination (défaut de traitement, post-contamination) laisse supposer que la présence de ces germes dans l'eau pourrait être associée à la présence d'un biofilm important à la surface des canalisations.

Cette hypothèse a pu être vérifiée lors de cette étude, réalisée sur différents réseaux de la banlieue parisienne.

Ce travail a mis en évidence une relation entre la fréquence d'observation des coliformes sur les sites du réseau et le dépassement de seuils critiques pour quatre paramètres:

- le niveau de salissure bactériologique de l'eau évalué par le dénombrement de la flore bactérienne planctonique totale par microscopie en épifluorescence

- la température

- la consommation de matière organique biodégradable (CODB)

- la concentration en chlore libre résiduel.

Le degré d'exposition des sites d'un réseau de distribution a pu être estimé par comptabilisation des dépassements des seuils critiques pour ces quatre paramètres. Trois niveaux de risques croissants (sans risque, faiblement exposé et exposé) ont été établis correspondant à des fréquences de plus en plus importantes d'apparition des coliformes sur les sites du réseau de distribution.

Pour une semaine donnée, le calcul de la moyenne des dépassements simultanés des seuils critiques enregistrés sur l'ensemble des sites a permis de définir quatre niveaux de risques moyens d'apparition des coliformes sur l'ensemble des sites (minimum, non négligeable, critique et maximum) en relation avec des observations de coliformes de plus en plus fréquentes sur le réseau.

Il a aussi été possible de définir un taux de chlore à appliquer sur un site afin de diminuer le niveau de contamination bactérienne de l'eau et par conséquent réduire le risque d'apparition des coliformes sur ce site.

EN:

Coliform occurrences in drinking water in the absence of known breaches of treatment barriers are still a problem inthe drinking water industry. The purpose of this study was to define threshold values for different bacteriological, chemical and physical parameters, beyond which coliforms occurred more frequently along a full scale distribution system in a northern suburb of Paris. A predictive model of coliform occurrence at different sites of a distribution network was produced (AL COL model).

This study consisted of two stages. The first one involved following coliform occurrences, epifluorescent counts, temperature, biodegradable dissolved organic carbon (BDOC), and residual chlorine level in the treatment plant effluent and at five distribution sampling sites. Each site was sampled once a week for one year (n=47 ; February 1991 - February 1992). This first stage of study showed that the occurrence of coliforms in the network could be associated with temperatures greater than a threshold value of 15°C, a BDOC consumption greater than 0.15 mg/l, a logarithm of the epifluorescent counts higher than 5.2 and a residual chlorine lower than 0.10 mg/l. Graduation of coliform occurrences was possible by the combination ofoverstepped thresholds for these four parameters. Three levels of risk associated with an increasing frequency of coliform occurrence were defined : site with no risk when no or only one threshold value was exceeded, slightly exposed site when 2 or 3 threshold values were exceeded and exposed site when 4 threshold values were exceeded.

The second stage of the study concerned the application of this predictive model. It consisted of following weekly the same parameters as in the first stage at 7 and 10 distribution sites situated on two difrerent distribution systems (Nortlrern and Eastern suburbs of Paris) for 21 weeks (April - September 1992). The threshold values determined were similar for the two distribution systems. They were 15°C for temperature ; 0.10 - 0.15 mg/l for BDOC consumption, 5 - 5.2 for the logarithm of epifluorescent counts and 0.10 mg/l for residual chlorine. The frequency of coliform occurrences was about 60 % at sampling points assessed as exposed sites, 5 % at sampling points assessed as slightly exposed sites and 1 % at sites considered with no risk.

Moreover, it was possible to define a model of mean risk of coliform ocurrences over all sites (corresponding to the mean of overstepped thresholds at the different studied sites for a given week). Four levels of mean risk (minimum, non negligible, critical, and maximum) were associatcd with increasing frequencies of coliform observations in the distribution network.

The AL COL model could be an efficient and simple tool to control and limit occunences of coliforms in drinking water. When a site is assessed as exposed, disinfection treatments have to be performed in order to reduce this risk and to prevent coliform occurrences during the weeks following this risk. Moreover, it was also possible to define a chlorine level in the water to reduce the bacterial contamination and subsequently decrease the risk of coliform occurrences at the sites of the network.

FR:

Les qualités de fonctionnement d'un décanteur primaire de station d'épuration d'eaux usées dépendent essentiellement de ses caractéristiques hydrauliques. Le but de ce travail est la caractérisation et la modélisation de l'hydrodynamique d'un décanteur réel d'une station d'épuration d'eaux usées urbaines.

Cette opération s'effectue par la détermination de la Distribution des Temps de Séjour (DTS) de la phase liquide du décanteur par traçage au chlorure de lithium. Simultanément, les évolutions des débits d'effluent à traiter et des rendements d'épuration en Matières En Suspension (MES) ont été suivis.

La courbe de DTS obtenue a permis une modélisation de l'hydrodynamique du décanteur primaire par des associations en série ou en parallèle de Réacteurs Parfaitement Agités (RPA). Le modèle hydrodynamique proposé, dont les résultats sont en très bonne concordanoe avec les résultats expérimentaux, est composé de 2 branches associées en parallèle: l'une traversée par une fraction a = 0,14 d'effluent entrant dans le décanteur est une cascade de 7 RPA d'un volume total de 77 m³. L'autre branche traversée par la fraction de débit restante (l-a) est composée de 2 modules en série: le premier module, caractérisant une zone de recirculation, est un RPA de 645 m³ en échange avec un second RPA de 1935 m³, la fraction de débit ß échangée est de 28. Le deuxième module de cette branche, représentant un écoulement uniforme, est une cascade de 7 RPA d'un volume total de 1 183 m³.

Ce modèle hydrodynamique permet d'analyser les résultats obtenus quant à l'évolution des rendements d'épuration en MES mesurés dans le décanteur.

EN:

The operating performances of wastewater treatment plant primary clarifiers essentially depend on hydraulic conditions. The aim of this paper is to characterize and to simulate the hydraulic flow regime of an existing sedimentaton tank.

This study was carried out on a wastewater treatment plant primary clarifier. It is a circular clarifier of 3900 m³ in volume, 42 m in diameter, 2.1 m in straight useful height, and, 2.1m in height for the conical part. The inlet flow rate is between 1400 and 2700 m³/h, whereas the sequental (3 primary clarifiers) sludge extraction flow rate is about 20 m³/h.

To characterize the liquid phase residence time distribution (RTD) in the clarifier, we did a tracing operation (pulse injection) with lithium chloride as tracer (20 kg of lithium chloride dissolved in 120 litres of tap-water). After the tracer injection, the lithium concentration at the outlet of the clarifier was measured as a function of time. During this experiment we also followed the evolution of inlet flow rates and the suspended solid (SS) retention efliciency ofthe clarifier. For 350 min of experimental time, the recuperation of lithium was 92.7%.

The experimental RTD curve allowed us to develop a model for the primary clarifier hydrodynarnics by association of elementary units (completely stirred reactors, CSTR) in series or in parallel. The transfer function in the LAPLACE domain, G (s), and the mathematical expressions of the first order and second central order moments were determined for this model. The nurnerical simulation of RTD between the inlet and the outlet of the system was performed with the help of a general computer code which numerically calculates the RTD, using Fast Fourier Trandormation techniques, from a given transfer fucnction.

The hydrodynamic model proposed in this study matches very well with the experimental results. It comprises two trranches associated in parallel. The first one, which is drived by an effluent flow rate fraction α (α=0,14), is treated as 7 CSTR's in series of 77 m³ in total volume. The second branch, which is drived by the remaining eflluent flow rate fraction (1-α), is composed of two modules associated in series. The first module, which characterizes a recycling zone, is treated as a CSTR of 645 m³ in volume exchanging with a second CSTR of 1935 m³ in volume, the exchanged flow rate fraction, ß, being equal to 28. The second module of this branch. which characterize a uniform flow zone, is represented by 7 CSTR's in series of 1183 m³ in total volume.

These results are confirmed by the comparison of the first order and the second central order moments. Indeed, between t = 0 and t = 350 min., we find for the experimental curve µ₁=l27 min and µ₂=6957, and, for the proposed hydrodynamic model curve µ₁=129 min and µ₂=7154 which are equivalent values.

Finally, the proposed hydrodynamic model makes possible the analysis of the primary clarifier performance with respect to suspended solid removal.

FR:

A partir des réactions possibles entre l'ozone, les radicaux et les principaux composants d'une eau à potabiliser, des formules théoriques de formations de radicaux et de décomposition de l'ozone sont établies.

La matière organique est schématisée par les composés qui réagissent avec l'ozone (Si), les initiateurs, les promoteurs et les inhibiteurs de la réaction radicalaire (SIi, Sp,i, Ss,i). La décomposition de l'ozone est ensuite mesurée pour 56 eaux naturelles caractérisées par les analyses suivantes (pH, Absorbance à 254 nm, COT, Alcalinité). En se basant sur les connaissances acquises et les valeurs expérimentales du taux spécifique de consommation de l'ozone w, l'équation théorique est simplifiée et on obtient:

-(d[O₃]/dt)=([O₃](∑k_DlS_l,i)(∑k_lDP,i[S_P,i])) / ([HCO₃^-](k₉+k₁₀ 10^pH-10,25))

En prenant le COT comme représentatif des [Sp,i] (attaque radicalaire non sélective) et l'absorbance à 254 nm comme representative de SI,i (attaque directe sur les cycles aromatiques), une analyse multifactorielle permet d'obtenir l'expression:

log₁₀w = -3,93 + 0,24pH + 0,75 log₁₀ Absorbance à 254 mm + 1,08 log₁₀ COT - 0,19 log₁₀ alcalinité

L'équation ainsi obtenue peut être utilisée dans tous les modèles prédictifs faisant appel aux bilans massiques sur l'oxydant.

EN:

From the numerous reactions between ozone and other components of raw water in a drinking water plant, we obtain theoretical equations for hydroxy radical concentrations (1) and for the disappearance of ozone (2). Dissolved organic matter is divided in to four components: substances which react with ozone by a direct mechanism (Si), initiators, promotors, and scavengers ofradical reactions (S_I,i, S_P,i, S_S,i). We also take into account the reactions between hydrogen peii*iâô. orThe, and free radicals to simulate advanced oxidation processes.

[OH^∘]= ([O₃]{2k₁∙10^pH-14+2k₂ 10^pH-11,6 [H₂O₂] + ∑k_dl,i [S_l,i]}) / (k_lD[P]+[HCO₃^-] (k₉+k₁₀∙10^pH-10,25)+∑k_lDS,i [S_s,i])   (1)

-(d[O₃])/(dt) = {k_D[P]+∑k_D,i[Si]+∑k_Dl,i[S_l,i]+3k₁10^pH-14+k₂10^pH-11,6H₂O₂]}[O₃]+[OH^∘]{k₈[O₃]+[H₂O₂](k₂10^pH-11,6+K₇)+∑k_lDP,i[S_P,i]   (2)

For 56 natural water samples, we measured the disappearence of ozone directly in a completely stirred batch reactor. Water samples were characterized by pH, TOC, 254 nm UV absorbance and alkalinity. Kinetics were first order with respect to ozone

(d[O₃])/(dt) = -w[O₃]

with w : specific ozone disappearence rate.

Each term of equation 2 is discussed and, based on the experimental values of w, a simplified equation 3 obtained :

-(d[O₃])/(dt) = ([O₃](∑k_DIS_l,i)(∑k_lDP,i[S_P,i))/([HCO₃](k₉+k₁₀ 10^pH-10,25))

The TOC parameter can represent [S_P,i] because radical reactions are non selective, where as the 254 nm UV absorbance can represent [S_i] because organic matter (Fulvic and Humic acid) can react directly with ozone via its constituent aromatic rings.

Using the data set of 56 w values measured in natual water samples, mathematical correlations can be calculated :

log₁₀w = -3,93 + 0,24pH + 0,75 log₁₀ Absorbance à 254 mm + 1,08 log₁₀ COT - 0,19 log₁₀ alcalinity

A strong correlation between experimental measurements and predicted w values is obtained.

FR:

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.

EN:

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.

FR:

Les modèles de simulation de propagation de polluants dans les eaux souterraines sont de plus en plus utilisés comme outils de gestion de cette ressource. La qualité des simulations dépend étroitement des connaissances que l'on a des processus et des paramètres de transport nécessaires à la mise en application des modèles. La fiabilité des résultats repose sur:

- le choix du bon modèle en fonction de l'échelle d'observation

- la mesure des paramètres représentatifs du transport liée à l'échelle de discrétisation du site

- la spatialisation de mesures locales.

Compte tenu des spécificités des hydrosystèmes souterrains (invisibilité, accès coûteux), la connaissance du milieu restera trop fragmentaire pour réaliser des simulations fines. Seules les approches stochastiques permettent alors d'intégrer ces incertitudes dans les simulations.

EN:

Groundwater quality modelling has become a tool for water management. The accuracy of the simulations closely depends on the available knowledge concerning the transport processes and the parameters used in the model. The accuracy of the results depends on the choice ofa suitable model adapted to the observation scale, the measurement of the effective parameters linked to the discretization of the field and the spatialization of the local measurements.

The mathematical model used to describe mass transport in porous media is the dispersion-convection equation. The velocity is calculated by solving the flow equation. For heterogeneous media, numerical schemes which simultaneously solve heads and velocities have to be preferred to classical finite element or finite differences techniques. The dispersion coefficient represents the velocity fluctuations around the average velocity. Therefore, it strongly depends on the dimension and the scale of the discretization.

A predictive simulation of the Twin Lake Tracer Test experiment has been done. After a very fine calibration of the flow (differences between measured and calculated heads less than 1 cm), the transport simulation did not succeed. The headgradients were not calculated with enough accuracy and the simulated plume travelled in a wrong direction.

Due to the nature of groundwater (invisible, expensive rneasurements), knowledge of the structure of the aquifer will always be too incomplete to perform very detailed simulations. Stochastic computations may be the way to take into account uncertainities in groundwater modening.