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Au cours des dernières années, divers travaux visant à identifier et à quantifier les sous-produits organohalogénés (SPOX) issus du traitement des eaux brutes de rivières à la monochloramine ont été menés. Un effort particulier a été porté sur le suivi des sous-produits organohalogénés réglementés et/ou connus et au paramètre analytique AOX (composés organohalogénés adsorbables sur charbon actif). Ce paramètre permet d’estimer la quantité totale de sous-produits organohalogénés générés.Un état des lieux récent montre qu’en dépit du nombre important de ces composés sur des échantillons d’eau « réels », le pourcentage de ces sous-produits identifiés imputables au traitement à la monochloramine reste très faible.Le travail réalisé dans la thèse s’inscrit dans la continuité des travaux menés par EDF R&D sur la spéciation des SPOX constitutifs d’AOX, selon une démarche analytique interconnectée. Cette dernière a permis la réduction d’incertitudes liées à la manière d’établissement du bilan de matière par (1) la mise en place de protocoles efficaces d’extraction et d’enrichissement des SPOX sur phase solide, (2) le développement de méthodes d’analyse sensibles permettant de doser simultanément plusieurs SPOX ou familles de SPOX connus, (3) la fiabilisation de la méthode de mesure des AOX en améliorant son étape de préparation d’échantillon et le développement d’une méthode d’analyse permettant d’établir le taux d’incorporation des différents halogénures (Cl, Br, I) dans les AOX, et (4) la réalisation d’essais de « screening » non ciblé par GC-MS et LC-MS ainsi que l’analyse en haute résolution par le FT-ICR/MS, pour l’identification des SPOX de haut poids moléculaire.Cette démarche a été appliquée sur des échantillons d’eau réels et a permis un gain de sensibilité par rapport aux méthodes actuelles, ainsi que l’identification de nouveaux SPOX, non répertoriés dans les études antérieures d’EDF R&D. / Over the last years, various studies have been carried out to identify and quantify the organohalogen by-products (OXBPs) resulting from the treatment of river waters with monochloramine. A particular effort was made to monitor the regulated and/or known organohalogen by-products with the analytical parameter AOX (Adsorbable Organic Halides). This parameter estimate the quantity of organohalogen by-products generated.A recent inventory shows that despite the large number of these compounds on "real" water samples, the percentage of these identified by-products attributable to monochloramine treatment remains very low.The thesis project is a continuation of previous studies carried out by EDF R&D on the speciation of OXBPs constituents of AOX, according to an interconnected analytical approach. This latter allowed the reduction of uncertainties related to how the material balance was established : (1) setting up efficient extraction and enrichment protocols for OXBPs on solid phase, (2) the development of sensitive analytical methods for monitoring simultaneously several known OXBPs, (3) improving the reliability of the AOX measurement method by improving its sample preparation step and developing a method of analyzing Analysis in order to establish the rate of incorporation of the various halides (Cl, Br, I) in AOX, and (4) non-targeted screening tests by GC-MS and LC-MS, as well as analysis in high resolution by FT-ICR/MS for the identification of OXBPs with high molecular weight.This approach was applied to real water samples and increased sensitivity to current methods, as well as the identification of new OXBPs not listed in previous EDF R&D studies.

The Chlorine-Ammonia Process was developed recently as a preoxidation process to minimize the formation of bromate during ozonation of the waters containing a significant bromide concentration. Chlorine is added first, followed by ammonia 5-10 minutes later, with the goal of sequestering bromide in monobromamine before the subsequent ozonation step. The goal of this research was to improve the Chlorine-Ammonia Process by introducing a very short prechlorination step (i.e., 30 seconds before addition of ammonia) to minimize overall disinfection by-product formation. Also, in this strategy, formation of a powerful halogenating agent, HOBr, is minimized and bromochloramine (NHBrCl) is used predominantly instead of monobromamine to sequester bromide during ozonation. To support this improved approach to bromide sequestration, this study examined the formation and decay of bromochloramine as a function of operating conditions, such as pH and Cl2/N ratio, and refined a chemical kinetic model to predict haloamine concentrations over time. Two natural organic matter (NOM) sources were used in this study (Lake Austin, Texas and Claremore Lake, Oklahoma) to study the effect of NOM on monochloramine and total chlorine decay after 30 seconds of prechlorination. The rate of the reaction between haloamines and fast and slow sites on the NOM was estimated. A kinetics model was developed to model total chlorine decay after a short prechlorination time. The model is based on the Unified Haloamine Kinetic Model developed by Pope (2006). Pope`s model failed to model the initial monochloramine concentration after 30 seconds prechlorination time as well as the monochloramine and total chlorine decay over time. The modified model shows an excellent prediction of monochloramine and total chlorine decay after 30 seconds prechlorination time at pH range of 6.5-8.0 and over a carbonate buffer concentration range of 2-10 mM. The model includes a new bromochloramine decay scheme via the reaction with monochloramine and with itself. In addition, new rate constants for the reaction of HOCl with bromide ion and reaction of HOBr with monochloramine were added. The hypobromous acid formation rate was found to be an acid-catalyzed reaction, which confirms the finding of Kumar et al. (1987). A new value of the acid catalysis effect of hydrogen ion was estimated. New terms were introduced to the hyprobromous acid formation rate including the acid catalysis effect of bicarbonate, carbonic acid, and ammonium ion. In addition, the reaction of HOBr with monochloramine to form bromochloramine was found to be an acid-catalyzed reaction, and a new value of the rate constant was estimated. / text

abstract: The deterioration of drinking-water quality within distribution systems is a serious cause for concern. Extensive water-quality deterioration often results in violations against regulatory standards and has been linked to water-borne disease outbreaks. The causes for the deterioration of drinking water quality inside distribution systems are not yet fully understood. Mathematical models are often used to analyze how different biological, chemical, and physical phenomena interact and cause water quality deterioration inside distribution systems. In this dissertation research I developed a mathematical model, the Expanded Comprehensive Disinfection and Water Quality (CDWQ-E) model, to track water quality changes in chloraminated water. I then applied CDWQ-E to forecast water quality deterioration trends and the ability of Naegleria fowleri (N.fowleri), a protozoan pathogen, to thrive within drinking-water distribution systems. When used to assess the efficacy of substrate limitation versus disinfection in controlling bacterial growth, CDWQ-E demonstrated that bacterial growth is more effectively controlled by lowering substrate loading into distribution systems than by adding residual disinfectants. High substrate concentrations supported extensive bacterial growth even in the presence of high levels of chloramine. Model results also showed that chloramine decay and oxidation of organic matter increase the pool of available ammonia, and thus have potential to advance nitrification within distribution systems. Without exception, trends predicted by CDWQ-E matched trends observed from experimental studies. When CDWQ-E was used to evaluate the ability N. fowleri to survive in finished drinking water, the model predicted that N. fowleri can survive for extended periods of time in distribution systems. Model results also showed that N. fowleri growth depends on the availability of high bacterial densities in the 105 CFU/mL range. Since HPC levels this high are rarely reported in bulk water, it is clear that in distribution systems biofilms are the prime reservoirs N. fowleri because of their high bacterial densities. Controlled laboratory experiments also showed that drinking water can be a source of N. fowleri, and the main reservoir appeared to be biofilms dominated by bacteria. When introduced to pipe-loops N. fowleri successfully attached to biofilms and survived for 5 months. / Dissertation/Thesis / Ph.D. Civil and Environmental Engineering 2010

The most difficult part of water treatment is to ensure that water will be delivered to consumer in unchanged form and hygienic unexceptionable. To hygienic safety is using doses of chlor, whiches are deadly for organisms and inhibite their proliferation in pipeline. Modern way how to clear water from organism is called chloramination. By the help of ammonium salts chlor is released in sequence. So large single-shot doses of chlor aren´t necessary. Due the big dose was THM and another dangerous compounds formed.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第16387号 / 工博第3468号 / 新制||工||1524(附属図書館) / 29018 / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 田中 宏明, 教授 清水 芳久, 教授 伊藤 禎彦 / 学位規則第4条第1項該当

Thesis (MScEng)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: The increased water demand to be supplied by municipal water distribution systems, and subsequent increased storage period of reserve water, may have implications with regards to water ageing and subsequently may have an impact on health and safety. Current master planning design standards could have a negative effect on water residence time. The decay of the disinfectant potential is a function of the residence time in the distribution system. The objective of this study is to identify and measure existing systems to optimally increase water quality in a distribution system while supplying an increase in demand, dealing with the deterioration of pipe infrastructure and the introduction of alternative water sources. To do this, one must understand the dynamics of water networks and the parameters that affect water quality. The foundation of a water quality model is based on the construction of an accurate hydraulic model. To identify and measure these systems, one must understand the aspects of water purification and the techniques used to achieve water standards in a distribution system. These techniques and standards play a huge role in the prediction of water quality. In this paper the fundamentals and techniques used to determine and measure such a model are discussed. Consequently, additional design parameters to assess water quality must be incorporated into current master planning practice to optimally design water networks. These models are used to determine the appropriate levels of disinfectant at strategic locations in a system. To illustrate these design parameters and systems currently used in practice, a case study involving Umgeni Water (UW) and EThekwini municipality (EWS) was used to determine the most suitable disinfectant strategy for a municipality’s distribution system. Future scenarios and the impact of disinfectant mixing and increased residence time of the water in the system were also determined. The use of this water quality model in a distribution system will ultimately provide a sustainable platform for a risk monitoring procedure. / AFRIKAANSE OPSOMMING: Die verhoogde aanvraag na water in munisipale voorsieningstelsels, en die daaropvolgende verhoogde stoortydperk van reserwe water, kan implikasies inhou met betrekking tot water veroudering waarna dit ‘n impak op gesondheid en veiligheid kan hê. Huidige meesterbeplanning ontwerpstandaarde kan 'n noemenswaardige uitwerking op water retensietyd hê, veral omdat chloor se vervaltyd op sy beurt 'n funksie van water retensietyd is. Die doel van hierdie studie is om 'n prosedure te identifiseer om watergehalte optimaal te verhoog in 'n waterverspreidingstelsel, terwyl die toename in water aanvraag voortduur. Om dit te kan doen moet die dinamika van water netwerke en die parameters wat die gehalte van water beïnvloed, bestudeer word. Die opstel van 'n waterkwaliteit model is gebaseer op die bou van 'n akkurate hidrouliese model. Om uiteindelik die ontwerp van 'n waterkwaliteit oplossing suksevol uit te voer, moet 'n mens al die aspekte van watersuiwering en die tegnieke wat gebruik word om waterstandaarde te handhaaf in 'n verspreidingstelsel verstaan. In hierdie verslag word die beginsels en tegnieke wat gebruik word om so 'n model op te stel, bespreek. Bykomende waterkwaliteit ontwerpparameters moet by huidige meesterbeplanning gevoeg word om waternetwerke optimaal te ontwerp. Hierdie modelle word gebruik om die geskikte vlakke van ontsmettingsmiddel op strategiese plekke in 'n stelsel te bepaal. 'n Gevallestudie van Umgeni Water (UW) en eThekwini-munisipaliteit (EWS) is gebruik om die mees geskikte ontsmettingsmiddel strategie vir 'n munisipaliteit se verspreiding te illustreer. Toekomstige scenario's en die impak van ontsmettingsmiddelvermenging en verhoogde retensietyd van die water in die stelsel sal ook bepaal kan word. Die gebruik van hierdie gehalte-watermodel in 'n verspreidingstelsel sal uiteindelik 'n volhoubare platform vir 'n risiko moniteringstelsel inhou.

Orientador: Maria Aparecida Carvalho de Medeiros / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Tecnologia / Made available in DSpace on 2018-08-27T02:18:56Z (GMT). No. of bitstreams: 1 Oliveira_AndreFelipede_M.pdf: 2184303 bytes, checksum: b46c30ed510d7f32eb7aae82b851f80d (MD5) Previous issue date: 2015 / Resumo: Há uma preocupação crescente na área de Saneamento Ambiental com relação a qualidade das águas dos corpos hídricos, tendo em vista que pesquisas têm revelado que os sistemas de tratamentos convencionais de esgotos e de água para abastecimento público não possuem eficiências adequadas para remoção de compostos orgânicos classificados como Desreguladores Endócrinos (DE). Nesta classe de compostos são destacados os estrógenos naturais 17 ß-estradiol (E2), estriol (E3), estrona (E1) e o sintético 17 ?-etinilestradiol (EE2). Os efeitos destes hormônios sexuais, que são compostos extremamente ativos biologicamente, têm sido citados como agentes etiológicos de feminilização em peixes e também de vários tipos de cânceres. Neste sentido, trabalhos aplicando tecnologias avançadas de tratamento destes DE estão sendo desenvolvidos por vários grupos de pesquisas. Apesar de que as Legislações ambientais relacionadas aos parâmetros de lançamento (RESOLUÇÃO CONAMA no. 430 de 2011) e de parâmetros de potabilidade (Portaria no. 2914 de 2011) não contemplarem estes compostos DE, sendo que diversos trabalhos têm sido publicados com quantificação destes compostos em água da ordem de ng L-1. Neste contexto, o presente trabalho teve como objetivos: (1) adaptação e validação de metodologia analítica para confirmar e quantificar simultaneamente os hormônios E1, E2, E3 e EE2, nas águas bruta e tratada do rio Atibaia, manancial que abastece o município de Campinas, utilizando a técnica de extração em fase sólida (EFS), juntamente com a técnica de Cromatografia Líquida acoplada à espectrometria de massas em tandem (CL-EM/EM), (2) aplicação de tecnologias de degradação destes compostos E1, E2, E3 e EE2 em escala piloto, pelos processos de ozonização e cloroamoniação, visando contribuir com as determinação das dosagens, do tempo de contato e da eficiências de remoção. Os resultados obtidos nas análises via EFS-LC-MS/MS mostraram a ocorrência do hormônio sexual natural E1, na água bruta do rio Atibaia com concentração de 17 ng L-1, sendo que para os demais E2 e E3 os valores obtidos foram inferiores ao limite de quantificação 2 ng L-1 e para o EE2 inferior a 5 ng L-1. As técnicas de oxidação ozonização e cloroamoniação utilizadas nos ensaios demonstraram eficiências de degradação em média, maiores do que 95% dos DE estudados, com exceção de E1, cuja eficiência de remoção ficou entre 87% a 93%, dependendo da faixa de fortificação / Abstract: There is growing concern in the field of Environmental Sanitation regarding the water quality of water bodies, given that research has shown that systems of conventional treatments of sewage and public water supply does not have adequate efficiencies to removal of some organic compounds Endocrine Disruptors (DE). In this class of compounds are included the natural estrogens 17 ß-estradiol (E2), estriol (E3), estrone (E1) and the synthetic 17 ?-ethinylestradiol (EE2). The effects of these sex hormones, which are highly biologically active compounds, have been cited as etiological agents of feminization in fish and various types of cancers. In this regard, several works by applying advanced technologies for treating these DE are being developed by many research groups. Although the environmental legislations related to the parameters of launch (CONAMA RESOLUTION. 430 of 2011) and potability parameters (Ordinance no. 2914 2011) does not address these DE compounds, several studies have been published with quantification of these compounds in the order of ng L-1. In this context, the aimsmof this paper were: (1) adaptation and validation of the analytical methodology to confirm and to quantify simultaneously the E1, E2, E3 and EE2 hormones, raw water and treated in the Atibaia River, a source that supplies the municipality Campinas, using the technique of solid phase extraction (EFS) with the technique of Liquid Chromatography coupled to mass spectrometry in tandem (LC-MS/MS), (2) applying degradation technologies of these compounds E1, E2, E3 and EE2 in pilot scale, by using the processes of ozonation and cloroamoniation, to contribute to the determination of dosage, contact time and degradation efficiencies. The results obtained in this study via EFS-LC-MS / MS showed the occurrence of natural sex hormone E1 in the Atibaia River raw water with a concentration of 17 ng L-1, and for the other E2 and E3 the values were lower the quantification limit of 2 ng L-1 and EE2 less than 5 ng L-1. The ozonation and chloroamoniation oxidation techniques used for the degradation tests were with efficiencies on average more than 95% of the studied DE, except E1, the removal efficiency was between 87% to 93% depending on the fortification range, by using ozonation in pre oxidation and cloroamoniation and the disinfection step / Mestrado / Tecnologia e Inovação / Mestre em Tecnologia

La désinfection de l'eau potable par le chlore permet d'inactiver les micro-organismes pathogènes et de contrôler la croissance microbienne au cours du transport de l'eau dans le réseau de distribution municipal. En présence de la matière organique et inorganique dans l'eau brute, ce procédé de traitement conduit à la formation de sous-produits de la désinfection (SPD) incluant les trihalométhanes (THM) et les acides haloacétiques (AHA) qui sont réglementés. Afin de respecter les normes pour ces SPD formés au cours de la chloration, les rayons ultraviolets et d'autres oxydants tels que l'ozone, le dioxyde de chlore ou la chloramine peuvent être utilisés comme désinfectants alternatifs pour la désinfection primaire. L'ozonation est communément appliquée durant la production d'eau potable non seulement pour permettre la diminution de la teneur en SPD réglementés mais aussi en raison de sa puissance comme désinfectant et oxydant. Néanmoins, compte tenu de courte demi-vie de l'ozone dans l'eau (l'ozone n'a pas d'effet rémanent), son utilisation requiert l'application de chlore ou de chloramine suivant l'ozonation afin de s'assurer la sécurité de l'eau distribuée. Toutefois, ce scénario de désinfection de l'eau potable (ozone-chlore/chloramine) favorise la formation des acétaldéhydes halogénés (halogenated acetaldehydes, HAL). Ces derniers attirent de plus en plus d'attention dans les dernières années en raison de leur abondance (troisième plus grande famille de SPD) et de leur cytotoxicité élevée. La présente thèse s'est donc consacrée à améliorer les connaissances sur la présence et la variabilité spatio-temporelle des HAL dans les réseaux d'aqueduc ainsi que sur les niveaux d'exposition de la population à ces contaminants dans les eaux potables désinfectées à l'ozone. Dans un premier temps, différents paramètres (pH, agent de conservation et durée de conservation) ont été optimisés pour la conservation des échantillons afin d'analyser les acétaldéhydes trihalogénés (trihalogenated acetaldehydes, THAL) et acétaldéhydes dihalogénés (dihalogenated acetaldehydes, DHAL) par une méthode analytique consolidée qui a été validée en laboratoire. Par la suite, quatre campagnes d'échantillonnage ont été réalisées sur deux ans (entre 2017 et 2019) au sein de deux systèmes d'eau potable sélectionnés comme cas à l'étude. La première campagne d'échantillonnage s'est échelonnée sur une année et a généré une base de données robuste sur le comportement de HAL dans les usines de traitement d'eau potable (UTEP) et leur variabilité spatio-temporelle dans les réseaux de distribution. À la suite de cette campagne, la relation entre l'ozonation et la variation de HAL dans l'eau traitée a été évaluée pendant un mois via une campagne d'échantillonnage intensive, dans une UTEP où les changements de pratique de l'ozonation avaient lieu. Finalement, deux autres campagnes d'échantillonnage ont été effectuées pour évaluer les effets de manipulations domestiques de l'eau sur la concentration de HAL à laquelle la population est exposée. Les résultats obtenus ont permis d'identifier les facteurs contribuant à la formation de HAL dans l'eau potable et de déterminer les stratégies de manipulation domestique pour réduire l'exposition aux HAL via l'eau potable. En se basant sur les concentrations de THM, la prédiction de la concentration de THAL est devenue possible grâce aux fortes corrélations entre les concentrations de THM et de THAL dans les deux systèmes d'eau potable à l'étude. / Disinfection of drinking water with chlorine results in the inactivation of targeted pathogens and the control of microbial growth during the transportation through the distribution system, while in the presence of naturally occurring organic and inorganic matter, disinfection by-products (DBPs) are formed. For instance, trihalomethanes (THMs) and haloacetic acids (HAAs) are regulated in many countries. In order to meet the regulations, ultraviolet irradiation and other oxidants such as ozone, chlorine dioxide or chloramines are used as alternative disinfectants for primary disinfection. Ozonation is commonly applied during water treatment not only due to the intended reduction in the levels of regulated THMs and HAAs but also its numerous advantages as oxidant and disinfectant. However, the use of chlorine or chloramines following ozonation is generally required to ensure the safety of drinking water in distribution systems due to the short half-life of ozone. Unfortunately, this disinfection scenario (ozone-chlorine/chloramines) promotes the formation of halogenated acetaldehydes (HALs), which attract more and more attention in the last years due to their abundance in drinking water (third largest group of identified DBPs by weight) and their relatively high cytotoxicity. This thesis is therefore devoted to improving the knowledge about the occurrence and spatio-temporal variability of HALs as well as the levels of human exposure to these contaminants in ozonated drinking water. First, various parameters (pH, quenching agent and sample holding limit) were optimized for sample preservation in order to analyze trihalogenated acetaldehydes (THALs) and dihalogenated acetaldehydes (DHALs) using a consolidated analytical method. Subsequently, four sampling campaigns were conducted over two years (between 2017 and 2019) in two drinking water systems. The first one-year sampling campaign generated a robust database of HALs regarding their behavior in drinking water treatment plants (DWTPs) and the spatio-temporal variability in distribution networks. Then the relationship between ozonation and HAL variation in treated water was assessed during a one-month intensive sampling campaign, in a DWTP where changes regarding ozonation procedures occurred. Finally, two more sampling campaigns were carried out to evaluate the effects of household tap water handling on the exposure of HALs. The results allow to identify the contributing factors to HAL formation in drinking water and to determine strategies of household handling for the control of HAL exposure via drinking water. The prediction of the occurrence of THALs based on THMs was made possible because of the strong correlations between THM levels and THAL levels in both drinking water systems.

Le traitement de l'eau permet à tout un chacun d'avoir de l'eau potable simplement en ouvrant le robinet. Pourtant, un nombre grandissant de consommateurs préfère boire de l'eau embouteillée. Les raisons de ce choix sont essentiellement esthétiques et en lien étroit avec les goûts et les odeurs. Cette préférence se manifeste notamment parmi les citoyens de Sainte-Foy, ville dont le réseau est alimenté par le fleuve Saint-Laurent. La présente étude a pour objectifs de comprendre ce qui peut engendrer ces problèmes organoleptiques. Pour ce faire, un suivi des paramètres physicochimiques et un profil des qualités esthétiques de l'eau ont été effectués, au moyen d'un groupe témoin de dégustation (panel), en plusieurs points du réseau de la ville de Sainte-Foy ainsi qu'à l'usine de traitement. Or, les principaux problèmes qui ont été retenus résident dans les goûts et les odeurs de chlore. Par conséquent, la mise en relation des pôles analyses et perceptions devait permettre de comprendre pourquoi ces problèmes étaient présents et comment ils évoluaient. Ainsi, de cette opération, la seule certitude mise en lumière se retrouve en début de réseau où il est nettement clair que l'acide hypochloreux est responsable des odeurs de chlore, et ce, durant toute l'année. En ce qui concerne les autres points du réseau, des composés autres que ceux étudiés dans cette recherche interviendraient de 40 à 50 % dans la responsabilité de ces odeurs de chlore. Le reste se partage entre l'acide hypochloreux et la trichloramine. En conséquence, les problèmes de goût et d'odeur seraient dus à une contribution partagée entre plusieurs composés présents dans l'eau. Cependant, tous ces composés n'ont pas fait l'objet de cette recherche.