A detailed study has been carried out to demonstrate the importance of external and internal mass transfer on the nitrification rates in three distinct treatment processes: flocculent and granular activated sludge, and suspended carrier reactor (SCR) systems. The major emphasis was on external mass transfer, and the impact of system hydrodynamics on this mechanism. Laboratory-scale flocculent and granular sequencing batch reactors were operated for the nitrification of a synthetic wastewater. A two-stage, continuous, nitrifying SCR was operated using the same wastewater feed. Within each stage, biofilm was grown on two types of commercial carriers- the Natrix C10/10 from ANOX AB (Sweden); and the K1 carrier from Kaldnes Miljøteknologi (Norway). Biofilm carriers obtained from each of these reactors was utilised for the mass transfer investigations. The major findings, and contributions of the work to the field of biological wastewater treatment, are described in the following paragraphs. In order to complete the work, a novel experimental tool, the TOGA (Titrimetric and Off-Gas Analysis) sensor was created, which utilises off-gas mass balancing, coupled with pH titration to provide detailed measurement of biological reaction rates. An original method for off-gas mass balancing was developed, within a reactor that allowed modification of the hydrodynamic conditions using gas phase mixing independent of dissolved oxygen control within the liquid phase. This sensor has already proven to be a highly effective tool not only for the measurement of oxygen but also for carbon dioxide and various nitrogen species, and has application for numerous other compounds present in the gas phase of biological reactors (e.g. hydrogen, methane). The application of the TOGA sensor signals to the nitrification process was demonstrated, which enabled the online measurement of oxygen, ammonia, and nitrite reaction rates. The TOGA sensor development underpinned the majority of the subsequent experimental work within this thesis. Dissolved oxygen microelectrodes were also used, enabling microscale measurements to be made in conjunction with the macroscale TOGA sensor analyses. Combined with size and microbiological analyses a detailed study of mass transfer and reaction was able to be carried out on the various systems. For suspended aggregate systems (flocs and granules): A spherical particle model was developed and used to predict the potential for external mass transfer limitation in flocs and granules. The significance of this limitation was confirmed experimentally, by observing changes in reaction rate or concentration boundary layer (in the TOGA sensor or microelectrode study, respectively) upon modification of the system’s flow conditions. Despite this flow effect being small, and only observable under low bulk liquid substrate concentrations, the external mass transfer limitation was concluded to be significant for biological flocs and granules even at higher substrate concentrations. As particle size and the maximum volumetric reaction rate of the biomass increases, external mass transfer effects become increasingly significant. The work highlights the impact of mass transfer limitation on the measurement of Monod half saturation coefficients (KS) in flocs and granules. Without accounting for external or internal mass transfer limitation, KS is seriously overestimated and becomes a lumped parameter, reflecting not only the microbial response but also the mass transfer limitations observed within the system under study. To avoid confusion or generation of erroneous results, care should be taken in defining, measuring and utilising the half saturation coefficient in biological systems where the biomass is not present as individual cells or extremely small flocs. For Suspended Carrier Reactor systems: External and internal mass transfer are both concluded to be important rate limiting steps within suspended carrier reactors. The demonstration of a significant impact of fluid flow conditions on the nitrification rates highlights the impact of external mass transfer limitation within these systems. Application of a one-dimensional biofilm model to the experimental results led to the conclusion that there is little difference between the external mass transfer limitation of the two different carrier types, for carriers grown under the same environmental conditions. However, there was a significantly higher areal nitrification rate observed on the Natrix carriers compared to the Kaldnes carriers. It is the biofilm structure that is critically important in characterising the mass transfer steps. Systems operated under high nitrogen loads, producing filamentous biofilms on the carrier surface, were found to have larger external mass transfer coefficients and responses to changes in fluid flow than those carriers which were operated under nitrogen-limited conditions (producing a flatter, more gel-like biofilm). The structure of the biofilm colonising the carrier surface was far more important in defining the mass transfer coefficient than the actual carrier type used. In a remarkably similar trend to that of the external mass transfer coefficient, the biofilm morphology was again significantly more important than carrier type in determining both the magnitude and response to fluid flow of the gas-liquid mass transfer coefficient for oxygen (kLa) calculated within the laboratory TOGA sensor. These findings led to the postulation that direct gas-biofilm interfacial mass transfer mechanism is occurring within the SCR systems. This hypothesis is an alternative to the standard mechanism of gas transfer from the bubble into the liquid phase, and then into the biofilm. Understanding of interfacial transfer is likely to be important for developing the knowledge of SCR processes. Overall, both external and internal mass transfer phenomena have been demonstrated to create important rate limitations to suspended aggregate systems (flocs and granules) and biofilms grown in suspended carrier reactors. This significantly advances the conceptual understanding of these biological treatment processes.

A detailed study has been carried out to demonstrate the importance of external and internal mass transfer on the nitrification rates in three distinct treatment processes: flocculent and granular activated sludge, and suspended carrier reactor (SCR) systems. The major emphasis was on external mass transfer, and the impact of system hydrodynamics on this mechanism. Laboratory-scale flocculent and granular sequencing batch reactors were operated for the nitrification of a synthetic wastewater. A two-stage, continuous, nitrifying SCR was operated using the same wastewater feed. Within each stage, biofilm was grown on two types of commercial carriers- the Natrix C10/10 from ANOX AB (Sweden); and the K1 carrier from Kaldnes Miljøteknologi (Norway). Biofilm carriers obtained from each of these reactors was utilised for the mass transfer investigations. The major findings, and contributions of the work to the field of biological wastewater treatment, are described in the following paragraphs. In order to complete the work, a novel experimental tool, the TOGA (Titrimetric and Off-Gas Analysis) sensor was created, which utilises off-gas mass balancing, coupled with pH titration to provide detailed measurement of biological reaction rates. An original method for off-gas mass balancing was developed, within a reactor that allowed modification of the hydrodynamic conditions using gas phase mixing independent of dissolved oxygen control within the liquid phase. This sensor has already proven to be a highly effective tool not only for the measurement of oxygen but also for carbon dioxide and various nitrogen species, and has application for numerous other compounds present in the gas phase of biological reactors (e.g. hydrogen, methane). The application of the TOGA sensor signals to the nitrification process was demonstrated, which enabled the online measurement of oxygen, ammonia, and nitrite reaction rates. The TOGA sensor development underpinned the majority of the subsequent experimental work within this thesis. Dissolved oxygen microelectrodes were also used, enabling microscale measurements to be made in conjunction with the macroscale TOGA sensor analyses. Combined with size and microbiological analyses a detailed study of mass transfer and reaction was able to be carried out on the various systems. For suspended aggregate systems (flocs and granules): A spherical particle model was developed and used to predict the potential for external mass transfer limitation in flocs and granules. The significance of this limitation was confirmed experimentally, by observing changes in reaction rate or concentration boundary layer (in the TOGA sensor or microelectrode study, respectively) upon modification of the system’s flow conditions. Despite this flow effect being small, and only observable under low bulk liquid substrate concentrations, the external mass transfer limitation was concluded to be significant for biological flocs and granules even at higher substrate concentrations. As particle size and the maximum volumetric reaction rate of the biomass increases, external mass transfer effects become increasingly significant. The work highlights the impact of mass transfer limitation on the measurement of Monod half saturation coefficients (KS) in flocs and granules. Without accounting for external or internal mass transfer limitation, KS is seriously overestimated and becomes a lumped parameter, reflecting not only the microbial response but also the mass transfer limitations observed within the system under study. To avoid confusion or generation of erroneous results, care should be taken in defining, measuring and utilising the half saturation coefficient in biological systems where the biomass is not present as individual cells or extremely small flocs. For Suspended Carrier Reactor systems: External and internal mass transfer are both concluded to be important rate limiting steps within suspended carrier reactors. The demonstration of a significant impact of fluid flow conditions on the nitrification rates highlights the impact of external mass transfer limitation within these systems. Application of a one-dimensional biofilm model to the experimental results led to the conclusion that there is little difference between the external mass transfer limitation of the two different carrier types, for carriers grown under the same environmental conditions. However, there was a significantly higher areal nitrification rate observed on the Natrix carriers compared to the Kaldnes carriers. It is the biofilm structure that is critically important in characterising the mass transfer steps. Systems operated under high nitrogen loads, producing filamentous biofilms on the carrier surface, were found to have larger external mass transfer coefficients and responses to changes in fluid flow than those carriers which were operated under nitrogen-limited conditions (producing a flatter, more gel-like biofilm). The structure of the biofilm colonising the carrier surface was far more important in defining the mass transfer coefficient than the actual carrier type used. In a remarkably similar trend to that of the external mass transfer coefficient, the biofilm morphology was again significantly more important than carrier type in determining both the magnitude and response to fluid flow of the gas-liquid mass transfer coefficient for oxygen (kLa) calculated within the laboratory TOGA sensor. These findings led to the postulation that direct gas-biofilm interfacial mass transfer mechanism is occurring within the SCR systems. This hypothesis is an alternative to the standard mechanism of gas transfer from the bubble into the liquid phase, and then into the biofilm. Understanding of interfacial transfer is likely to be important for developing the knowledge of SCR processes. Overall, both external and internal mass transfer phenomena have been demonstrated to create important rate limitations to suspended aggregate systems (flocs and granules) and biofilms grown in suspended carrier reactors. This significantly advances the conceptual understanding of these biological treatment processes.