Numerous wastewater treatment processes are currently available for nitrogen removal or ammonia conversion to nitrate. Those that are economically feasible rely mostly on microbiological processes, which are only effective when the microorganisms remain in a healthy state. If a biological process upset was to occur, due to a toxic shock load or cold weather, it may result in a discharge of ammonia or total nitrogen into the receiving water body. The impact of such a discharge could have deleterious effects on aquatic life or human health. The main objective of the breakpoint pilot study was to define optimum breakpoint pilot plant operating conditions which could then be applied to the design of a full scale breakpoint facility and serve as an emergency backup to biological nitrification. A pilot study was built on site at the Upper Occoquan Sewage Authority's Regional Water Reclamation Facility in Centreville Virginia. Testing was conducted in two phases (I and II) over a two year period in order to determine the operating conditions at which the breakpoint reaction performed best. Tests were performed during Phase I to determine the optimum operating pH, Cl₂:NH₃-N dose ratio, S0₂:Cl₂ dose ratio, and the minimum detention time for completion of the breakpoint reaction. Other testing done during Phase I included several special studies; including examination of appropriate analytical methods for monitoring breakpoint reactions, and investigation of the breakpoint reaction by-product nitrogen trichloride. Phase II testing examined how varying breakpoint operating temperatures, varying influent ammonia concentrations, higher influent organic nitrogen concentrations, and higher influent nitrite concentrations influenced the performance of the breakpoint pilot operation. Averages of data from operation at three different rapid mix pHs (7.0, 7.5, and 8.0) showed that pilot performance (i.e., ammonia oxidation) improved and the reaction was more stable at the higher operating pHs 7.5 and 8.0. Examination of dose ratios used during the study showed that the ideal operating ratios for this particular water was around 8:1 Cl₂:NH₃-N for the breakpoint reaction and 1.3:1 S0₂:Cl₂ for the dechlorination reaction. Although detention times for completion of the breakpoint reaction varied with pilot influent temperature, it generally required around 30-35 minutes to reach ammonia concentrations of < 0.2 mg/L NH₃-N at 8-12°C. Completion of the breakpoint reaction was found to be quickest at 20°C (the highest water temperature tested at the pilot). The tests of varying influent ammonia concentrations showed that although higher influent ammonia concentrations (11.0 mg/L) resulted in faster ammonia oxidation rates initially, the pilot operated better and had the same final performance results when the influent ammonia was lowered. Increasing the organic nitrogen concentrations (~ 1.0 mg/L) in the pilot influent resulted in a slightly higher Cl₂:NH₃-N dose ratio needed to reach breakpoint, a higher S0₂:Cl₂ dose needed to dechlorinate, and resulted in the formation of numerous disinfection byproducts. Increasing the nitrite concentration in the pilot influent increased the chlorination dose requirement. / Master of Science

Le chlore est largement utilisé pour ses propriétés bactéricides dans les piscines. Dans les eaux de piscine, le chlore réagit avec les matières azotées et carbonées générées par l’activité humaine (sueur, salive, urine, peau) pour former divers composés toxiques tels que la monochloramine (NH2Cl), la dichloramine (NHCl2), le trichlorure d'azote (NCl3), le chloroforme (CHCl3), etc… qui se retrouvent dans l’atmosphère. La détection et la quantification de ces composés volatils à des teneurs ppb (partie par milliard) est un réel besoin afin de contrôler la qualité de l’air des piscines. Cependant il n’existe pas à ce jour des appareils à la fois sensibles et peu coûteux.L’objectif de ce travail de thèse est d’élaborer des capteurs chimiques colorimétriques, sensibles, sélectifs et peu coûteux de la monochloramine, du trichlorure d’azote et du chloroforme. Dans ce but, nous avons mis au point des capteurs chimiques réalisés à partir de matrices nanoporeuses de silicate dopée des réactifs. Ainsi le capteur de NCl3 dopé de NaI et d’amylose permet de mesurer de faibles teneurs de NCl3 (5 ppb à 180 ppb) dans les atmosphères humides (50-80% HR) des piscines. Grâce au changement rapide de couleur, de transparent à rose-violet, visible à l’œil nu, le capteur de NCl3 permet de surveiller la qualité de l’air dans les piscines. Le capteur sélectif de NH2Cl est basé sur la réaction de Berthelot. La matrice de silicate nanoporeuse dopée de nitroprussiate de sodium et de phénol en milieu alcalin, initialement transparente, devient bleue lors d’une exposition à NH2Cl gazeux. Ce capteur permet de détecter NH2Cl dans la gamme de 60 à 250 ppb dans une atmosphère très humide (≈ 80%). Utilisé pour la sonder la qualité des eaux de piscine, il permet de mesurer NH2Cl dans l’eau avec une limite de détection de 0,1 µmol•L-1. Une étude préliminaire de la détection de CHCl3 a également été entreprise pour déterminer les molécules-sonde aptes à réagir avec le chloroforme en formant des produits colorés. Les réactifs de la réaction de Fujiwara ont été sélectionnés. L’étude de la réactivité de la 2,2’-bipyridine en solution en présence d’une base forte a permis de mettre en évidence la formation simultanée de deux composés colorés, dont la formation dépend de la nature de l’environnement réactionnel. / In swimming-pools, chlorine is used as a disinfectant to minimize the risk to users from microbial contaminants. In water, chlorine reacts with nitrogen compounds generated by human activity like saliva, sweat, urine and skin, leading to the formation of toxic compounds, such as monochloramine (NH2Cl), dichloramine (NHCl2), nitrogen trichloride (NCl3), chloroform (CHCl3), etc… The detection and the quantification of these volatile compounds at ppb level (part per billion) is an important and significant challenge to be able to monitor the air quality in swimming pool. Or, there is currently no commercially available and low-cost system which can instantaneously measure at ppb concentrations.The aim of this research is to develop a cheap, sensitive and selective chemical and colorimetric sensors of monochloramine, nitrogen trichloride and chloroform. For this purpose, we developed chemical sensors based on the use of nanoporous silicate matrices doped with probe-molecules. The NCl3 sensor doped with NaI and amylose can detect NCl3 at ppb level (5 ppb – 180 ppb) in humid atmospheres (from 50% to 80% relative humidity) at ambient pool temperatures. Due to the fast change of color, visible with naked eyes, these sensors can be used to detect peaks of pollution and to monitor the air quality of indoor pools. The NH2Cl selective sensor is based on the Berthelot reaction. The nanoporous silicate matrices doped with sodium nitroprusside and phenol in an alkaline medium, turn from transparent to blue upon exposure to gaseous NH2Cl. This sensor can detect NH2Cl in the range from 60 to 250 ppb in a very humid atmosphere (≈ 80%). Used to probe the quality of pool water, this sensor can detect NH2Cl in water with a detection limit of 0,1 µmol•L-1. A preliminary study of the CHCl3 detection was also conducted to identify probe-molecules capable of reacting with chloroform to form colored products. The reagents of the Fujiwara reaction were selected. The study of the 2,2’-bipyridine reactivity in solution in the presence of a strong base allowed highlighting the simultaneous formation of two colored compounds, whose formation depends on the nature of the reaction environment.