Evaluation of oxygen injection as a means of controlling sulfide production in a sewer system

Oxygen injection is often used to control biogenic production of hydrogen sulfide in sewers. Experiments were carried out on a laboratory system mimicking a rising main to investigate the impact of oxygen injection on anaerobic sewer biofilm activities. Oxygen injection (15-25 mg O₂/L per pump event) to the inlet of the system decreased the overall sulfide discharge levels by 65%. Oxygen was an effective chemical and biological oxidant of sulfide but did not cause a cessation in sulfide production, which continued in the deeper layers of the biofilm irrespective of the oxygen concentration in the bulk. Sulfide accumulation resumed instantaneously on depletion of the oxygen. Oxygen did not exhibit any toxic effect on sulfate reducing bacteria (SRB) in the biofilm. It further stimulated SRB growth and increased SRB activity in downstream biofilms due to increased availability of sulfate at these locations as the result of oxic conditions upstream. The oxygen uptake rate of the system increased with repeated exposure to oxygen, with concomitant consumption of organic carbon in the wastewater. These results suggest that optimization of oxygen injection is necessary for maximum effectiveness in controlling sulfide concentrations in sewers.     

A biofilm model for prediction of pollutant transformation in sewers

This study developed a new sewer biofilm model to simulate the pollutant transformation and biofilm variation in sewers under aerobic, anoxic and anaerobic conditions. The biofilm model can describe the activities of heterotrophic, autotrophic, and sulfate-reducing bacteria (SRB) in the biofilm as well as the variations in biofilm thickness, the spatial profiles of SRB population and biofilm density. The model can describe dynamic biofilm growth, multiple biomass evolution and competitions among organic oxidation, denitrification, nitrification, sulfate reduction and sulfide oxidation in a heterogeneous biofilm growing in a sewer. The model has been extensively verified by three different approaches, including direct verification by measurement of the spatial concentration profiles of dissolved oxygen, nitrate, ammonia, and hydrogen sulfide in sewer biofilm. The spatial distribution profile of SRB in sewer biofilm was determined from the fluorescent in situ hybridization (FISH) images taken by a confocal laser scanning microscope (CLSM) and were predicted well by the model.     

Nitrate stimulation of indigenous nitrate-reducing, sulfide-oxidising bacterial community in wastewater anaerobic biofilms

The role of the nitrate-reducing, sulfide-oxidising bacteria (NR-SOB) in the nitrate-mediated inhibition of sulfide net production by anaerobic wastewater biofilms was analyzed in two experimental bioreactors, continuously fed with the primary effluent of a wastewater treatment plant, one used as control (BRC) and the other one supplemented with nitrate (BRN). This study integrated information from H(2)S and pH microelectrodes, RNA-based molecular techniques, and the time course of biofilm growth and bioreactors water phase. Biofilms were a net source of sulfide for the water phase (2.01 micromol S(2-)(tot)m(-2)s(-1)) in the absence of nitrate dosing. Nitrate addition effectively led to the cessation of sulfide release from biofilms despite which a low rate of net sulfate reduction activity (0.26 micromol S(2-)(tot)m(-2)s(-1)) persisted at a deep layer within the biofilm. Indigenous NR-SOB including Thiomicrospira denitrificans, Arcobacter sp., and Thiobacillus denitrificans were stimulated by nitrate addition resulting in the elimination of most sulfide from the biofilms. Active sulfate reducing bacteria (SRB) represented comparable fractions of total metabolically active bacteria in the libraries obtained from BRN and BRC. However, we detected changes in the taxonomic composition of the SRB community suggesting its adaptation to a higher level of NR-SOB activity in the presence of nitrate.     

Effects of long-term pH elevation on the sulfate-reducing and methanogenic activities of anaerobic sewer biofilms

The dosage of alkali is often applied by the wastewater industry to reduce the transfer of hydrogen sulfide from wastewater to the sewer atmosphere. In this paper the activities of Sulfate Reducing Bacteria (SRB) and Methanogenic Archaea (MA) under elevated pH conditions (8.6 and 9.0) were evaluated in a laboratory scale anaerobic sewer reactor. Compared to those in a control reactor without pH control (pH 7.6 ± 0.1), the SRB activity was reduced by 30% and 50%, respectively, at pH 8.6 and pH 9.0. When normal pH was resumed, it took approximately 1 month for the SRB activity to fully recover. Methanogenic activities developed in the control reactor in 3 months after the reactor start-up, while no significant methanogenic activities were detected in the experimental reactor until normal pH was resumed. The results suggest that elevated pH at 8.6-9.0 suppressed the growth of methanogens. These experimental results clearly showed that, in addition to its well-known effect of reducing H₂S transfer from the liquid to the gas phase, pH elevation considerably reduces sulfide and methane production by anaerobic sewer biofilms. These findings are significant for the optimal use of alkali addition to sewers for the control of H₂S and CH₄ emissions. A model-based study showed that, by adding the alkali at the beginning rather than towards the end of a rising main, substantial savings in chemicals can be achieved while achieving the same level of sulfide emission control, and complete methane emission control.     

Sulfur transformation in rising main sewers receiving nitrate dosage

The anoxic and anaerobic sulfur transformation pathways in a laboratory-scale sewer receiving nitrate were investigated. Four reactors in series were employed to imitate a rising main sewer. The nitrate-dosing strategy was effective in controlling sulfide, as confirmed by the long-term sulfide measurements. Anoxic sulfide oxidation occurred in two sequential steps, namely the oxidation of sulfide to elemental sulfur (S⁰) and the oxidation of S⁰ to sulfate (SO₄²⁻). The second oxidation step, which primarily occurred when the first step was completed, had a rate that is approximately 15% of the first step. When nitrate was depleted, sulfate and elemental sulfur were reduced simultaneously to sulfide. Sulfate reduction had a substantially higher rate (5 times) than S⁰ reduction. The relatively slower S⁰ oxidation and reduction rates implied that S⁰ was an important intermediate during anoxic and anaerobic sulfur transformation. Electron microscopic studies indicated the presence of elemental sulfur, which was at a significant level of 9.9 and 16.7 mg-S/g-biomass in nitrate-free and nitrate-exposed sewer biofilms, respectively. A conceptual sulfur transformation model was established to characterize predominant sulfur transformations in rising main sewers receiving nitrate dosage. The findings are pertinent for optimizing nitrate dosing to control sulfide in rising main sewers.     

Nitrite effectively inhibits sulfide and methane production in a laboratory scale sewer reactor

The production and emission of hydrogen sulfide and methane by anaerobic microoganisms in sewer systems is a well-documented problem. The effectiveness of nitrite in controlling sulfide and methane production was tested in a laboratory scale sewer reactor. Nitrite was continuously dosed in the reactor for 25 days at concentrations of 20-140mgN/L. No sulfide and methane accumulation was observed in the reactor in the presence of nitrite. A significant reduction was observed in the sulfate reduction and methane production capabilities of the biofilm. Nitrite also stimulated biological sulfide oxidation within the biofilm. The nitrite uptake rate of the reactor increased over the nitrite dosing period and nitrous oxide production was observed within the biofilm. When nitrite addition was stopped, sulfate reduction and methane production gradually resumed, and reached pre-nitrite addition levels after 2.5 months. The slow recovery suggests that nitrite can be applied intermittently for sulfide and methane control, which represents a key advantage over similar chemicals such as nitrate and oxygen. The study demonstrates nitrite addition as a promising and effective strategy for the management of sulfide and methane in sewers. Further investigation and optimization are still required before application in the field.     

Chemical and biological technologies for hydrogen sulfide emission control in sewer systems: a review

Biogenic corrosion of sewers represents a cost of about 10% of total sewage treatment cost in Flanders (Belgium) and is further increasing. In the past, research has resulted in a number of prevention methods, such as injection of air, oxygen, H(2)O(2), NaClO, FeCl(3) and FeSO(4). The possibility of biological oxidation of sulfide using nitrate as the electron acceptor has also been explored in sewer systems. However, all of these methods have a problem with the high cost (euro 1.9-7.2 kg(-1)S removal). In this review, new approaches for hydrogen sulfide emission control in sewer systems are discussed. The control of hydrogen sulfide emission by using a microbial fuel cell (MFC) can be cost-effective while the BOD is removed partially. The use of phages that target sulfate-reducing bacteria (SRB) can possibly inhibit sulfide formation. Novel inhibitors, such as slow release solid-phase oxygen (MgO(2)/CaO(2)) and formaldehyde, warrant further study to control hydrogen sulfide emission in sewer systems.     

Microbial community structures and in situ sulfate-reducing and sulfur-oxidizing activities in biofilms developed on mortar specimens in a corroded sewer system

Microbially induced concrete corrosion (MICC) caused by sulfuric acid attack in sewer systems has been a serious problem for a long time. A better understanding of microbial community structures of sulfate-reducing bacteria (SRB) and sulfur-oxidizing bacteria (SOB) and their in situ activities is essential for the efficient control of MICC. In this study, the microbial community structures and the in situ hydrogen sulfide production and consumption rates within biofilms and corroded materials developed on mortar specimens placed in a corroded manhole was investigated by culture-independent 16S rRNA gene-based molecular techniques and microsensors for hydrogen sulfide, oxygen, pH and the oxidation-reduction potential. The dark-gray gel-like biofilm was developed in the bottom (from the bottom to 4 cm) and the middle (4–20 cm from the bottom of the manhole) parts of the mortar specimens. White filamentous biofilms covered the gel-like biofilm in the middle part. The mortar specimens placed in the upper part (30 cm above the bottom of the manhole) were corroded. The 16S rRNA gene-cloning analysis revealed that one clone retrieved from the bottom biofilm sample was related to an SRB, 12 clones and 6 clones retrieved from the middle biofilm and the corroded material samples, respectively, were related to SOB. In situ hybridization results showed that the SRB were detected throughout the bottom biofilm and filamentous SOB cells were mainly detected in the upper oxic layer of the middle biofilm. Microsensor measurements demonstrated that hydrogen sulfide was produced in and diffused out of the bottom biofilms. In contrast, in the middle biofilm the hydrogen sulfide produced in the deeper parts of the biofilm was oxidized in the upper filamentous biofilm. pH was around 3 in the corroded materials developed in the upper part of the mortar specimens. Therefore, it can be concluded that hydrogen sulfide provided from the bottom biofilms and the sludge settling tank was emitted to the sewer atmosphere, then oxidized to corrosive compounds in the upper and middle parts of the manhole, and only the upper part of the mortar specimens were corroded, because in the middle part of the manhole the generated corrosive compounds (e.g., sulfuric acid) was reduced in the deeper parts of the biofilm.     

Effects of nitrite concentration and exposure time on sulfide and methane production in sewer systems

Nitrite dosing is a promising technology to prevent sulfide and methane formation in sewers, due to the known inhibitory/toxic effect of nitrite on sulfate-reducing bacteria (SRB) and methanogenic Archaea (MA). The dependency of nitrite-induced inhibition on sulfide and methane producing activities of anaerobic sewer biofilms on nitrite levels and exposure time is investigated using a range of nitrite concentrations (40, 80, 120 mg-N/L) and exposure time up to 24 days. The recovery of these activities after the 24-day nitrite dosage was also monitored for more than two months. The inhibition level was found to be dependent on both nitrite concentration and exposure time, with stronger inhibition observed at higher nitrite concentrations and/or longer exposure time. However, the time required for achieving 50% recovery of both sulfate-reducing and methanogenic activities after the cessation of nitrite dosage only marginally depended on nitrite concentration. Model-based analysis of the recovery data showed that the recovery was likely due to the regrowth of SRB and methanogens. The lab studies and mathematical analysis supported the development of an intermittent dosing strategy, which was tested in a 1-km long rising main sewer. The field trial confirmed that intermittent dosing of nitrite can effectively reduce/prevent the formation of both sulfide and methane.     

Inhibition of sulfate-reducing and methanogenic activities of anaerobic sewer biofilms by ferric iron dosing

Ferric iron is commonly used for sulfide precipitation in sewers, thus achieving corrosion and odour control. Its impact on the activities of sulfate-reducing bacteria and methanogens in anaerobic sewer biofilms is investigated in this study. Two lab-scale rising main sewer systems fed with real sewage were operated for 8 months. One received Fe³⁺ dosage (experimental system) and the other was used as a control. In addition to precipitating sulfide from bulk water, Fe³⁺ dosage was found to significantly inhibit sulfate reduction and methane production by sewer biofilms. The experimental reactor discharged an effluent containing a higher concentration of sulfate and a lower concentration of methane in comparison with the reference reactor. Batch experiments showed that the addition of ferric ions reduced the sulfate reduction and methane production rates of the sewer biofilms by 60% and 80%, respectively. The batch experiments further showed that Fe³⁺ dosage changed the final products of sulfate reduction with sulfide accounting for only 54% of the sulfate reduced. The other products could not be confirmed, but were not dissolved inorganic sulfur species such as sulfite or thiosulfate. The results suggest the addition of Fe³⁺ at upstream locations would minimize the ferric salts required for achieving the same level of sulfide removal. Fe³⁺ dosing could also substantially reduce the formation of methane, a potent greenhouse gas, in sewers.     

Methane formation in sewer systems

Methane formation and emission in sewer systems has not received as much attention as hydrogen sulphide formation. Through field measurements from two rising mains, with an average sewage temperature of 28.4 and 26.6 degrees C, respectively, at the time of sampling, this study shows that a significant amount of methane can be produced in sewer systems, and that this production is positively correlated with the hydraulic retention time of wastewater in these systems. The experimental results from a laboratory-scale sewer system fed with real sewage with a temperature of approximately 21 degrees C confirmed these field observations and further revealed that methanogenesis and sulphate reduction occur simultaneously in sewers, with methane production contributing considerably more to the loss of soluble COD in sewers than sulphate reduction. The production of methane in sewers at levels revealed by this study is a serious environmental concern as it potentially results in greenhouse emissions that is comparable to that caused by the energy consumption for the treatment of the same wastewater. Further, methane production in sewers influences sulphide production and its management due to the competition between methanogens and sulphate-reducing bacteria for potentially the same electron donors. The potential interactions between sulphate-reducing and methanogenic bacteria in sewer networks are discussed.     

Quantification of oxygen fluxes in a long gravity sewer

Quantification of the oxygen fluxes in the sewer system is at present the optimal methodology to obtain information about the influence of sewers on transformations and mass balances in the urban drainage system. However, the relative and absolute values of these fluxes are practically unknown. In this work, the oxygen fluxes were quantified experimentally in a full-scale aerobic main sewer. The sewer biofilm respiration was determined with an in situ flow cell, a method that has not been used before in the sewer. The surface reaeration was determined with a gas tracer method based on the inert, non-radio-active and non-toxic gas tracer sulphur hexafluoride. In addition, the wastewater biomass respiration rate was measured. The validity of the applied methods was verified with redundant oxygen balances over a 2-km-long section. Measurement campaigns under different hydrodynamic conditions showed that the relative contribution of the biofilm, the wastewater, the reaeration and the in- and outflow with the water, all contributed significantly. However, the absolute contributions varied extensively and depended especially on the discharge. The COD conversion in the sewer could be estimated from the aerobic activity. The aerobic total degradation in the study reach was 3%. However, when extrapolated to the entire sewer net of the catchment area with 5000 PE, the COD conversion was estimated as high as 30% of the dissolved COD during the night. This indicates that the wastewater composition at the treatment plant will be strongly affected by the sewer system.     

Iron salts dosage for sulfide control in sewers induces chemical phosphorus removal during wastewater treatment

Chemical phosphorus (P) removal during aerobic wastewater treatment induced by iron salt addition in sewer systems for sulfide control is investigated. Aerobic batch tests with activated sludge fed with wastewater containing iron sulfide precipitates showed that iron sulfide was rapidly reoxidised in aerobic conditions, resulting in phosphate precipitation. The amount of P removed was proportional to the amount of iron salts added, and for the sludge used, ratios of 0.44 and 0.37 mgP/mgFe were obtained for ferric and ferrous dosages, respectively. The hydraulic retention time (HRT) of iron sulfide in sewers was found to have a crucial impact on the settling of iron sulfide precipitates during primary settling, with a shorter HRT resulting in a higher concentration of iron sulfide in the primary effluent and thus enabling higher P removal. A mathematical model was developed to describe iron sulfide oxidation in aerated activated sludge and the subsequent iron phosphate precipitation. The model was used to optimise FeCl₃ dosing in a real wastewater collection and treatment system. Simulation studies revealed that, by moving FeCl₃ dosing from the WWTP, which is the current practice, to a sewer location upstream of the plant, both sulfide control and phosphate removal could be achieved with the current ferric salt consumption. This work highlights the importance of integrated management of sewer networks and wastewater treatment plants.     

Optimization of intermittent, simultaneous dosage of nitrite and hydrochloric acid to control sulfide and methane productions in sewers

Free nitrous acid (FNA) was previously demonstrated to be biocidal to anaerobic sewer biofilms. The intermittent dosing of FNA as a measure for controlling sulfide and methane productions in sewers is investigated. The impact of three key operational parameters namely the dosing concentration, dosing duration and dosing interval on the suppression and subsequent recovery of sulfide and methane production was examined experimentally using lab-scale sewer reactors. FNA as low as 0.26 mg-N/L was able to suppress sulfide production after an exposure of 12 h. In comparison, 0.09 mg-N/L of FNA with 6-h exposure was adequate to restrain methanogenesis effectively. The recovery of sulfide production was well described by an exponential recovery equation. Model-based analysis revealed that 12-h dosage at an FNA concentration of 0.26 mg-N/L every 5 days can reduce the average sulfide production by >80%. Economic analysis showed that intermittent FNA dosage is potentially a cost-effective strategy for sulfide and methane control in sewers.     

Long term competition between sulfate-reducing and methane-producing bacteria for acetate in anaerobic biofilm

A long term competition between sulfate-reducing bacteria (SRB) and methane-producing bacteria (MPB) for acetate was investigated using a laboratory scale anaerobic fluidized bed. When the synthetic wastewater composed of acetate and sulfate was fed at a low organic loading rate, averages of the remaining acetate and sulfate concentrations were 1.7 mg Cl⁻¹ and 78.5 mg l⁻¹, respectively. During several months of this acetate limited operation the methane production rate as well as the microbial mass of MPB declined gradually, whereas the amount of reduced sulfate along with the microbial mass of SRB increased, which apparently indicates that SRB out-compete MPB in the biofilm at lower acetate concentrations. On the other hand, MPB were able to form a biofilm faster than SRB at higher acetate concentrations presumably due to MPB's higher ability to adhere carrier surfaces compared with SRB. Kinetic constants for both species in the biofilm were determined and compared with those reported for pure MPB and SRB cultures. Based on the kinetic mechanism of this competition, operational conditions which would support methanogenesis by suppressing sulfate reduction were identified.     

Influence of pipe material and surfaces on sulfide related odor and corrosion in sewers

Hydrogen sulfide oxidation on sewer pipe surfaces was investigated in a pilot scale experimental setup. The experiments were aimed at replicating conditions in a gravity sewer located immediately downstream of a force main where sulfide related concrete corrosion and odor is often observed. During the experiments, hydrogen sulfide gas was injected intermittently into the headspace of partially filled concrete and plastic (PVC and HDPE) sewer pipes in concentrations of approximately 1000 ppm_v. Between each injection, the hydrogen sulfide concentration was monitored while it decreased because of adsorption and subsequent oxidation on the pipe surfaces. The experiments showed that the rate of hydrogen sulfide oxidation was approximately two orders of magnitude faster on the concrete pipe surfaces than on the plastic pipe surfaces. Removal of the layer of reaction (corrosion) products from the concrete pipes was found to reduce the rate of hydrogen sulfide oxidation significantly. However, the rate of sulfide oxidation was restored to its background level within 10-20 days. A similar treatment had no observable effect on hydrogen sulfide removal in the plastic pipe reactors. The experimental results were used to model hydrogen sulfide oxidation under field conditions. This showed that the gas-phase hydrogen sulfide concentration in concrete sewers would typically amount to a few percent of the equilibrium concentration calculated from Henry's law. In the plastic pipe sewers, significantly higher concentrations were predicted because of the slower adsorption and oxidation kinetics on such surfaces.     

Dosing free nitrous acid for sulfide control in sewers: Results of field trials in Australia

Intermittent dosing of free nitrous acid (FNA), with or without the simultaneous dosing of hydrogen peroxide, is a new strategy developed recently for the control of sulfide production in sewers. Six-month field trials have been carried out in a rising main sewer in Australia (150 mm in diameter and 1080 m in length) to evaluate the performance of the strategy that was previously demonstrated in laboratory studies. In each trial, FNA was dosed at a pumping station for a period of 8 or 24 h, some with simultaneous hydrogen peroxide dosing. The sulfide control effectiveness was monitored by measuring, on-line, the dissolved sulfide concentration at a downstream location of the pipeline (828 m from the pumping station) and the gaseous H₂S concentration at the discharge manhole. Effective sulfide control was achieved in all nine consecutive trials, with sulfide production reduced by more than 80% in 10 days following each dose. Later trials achieved better control efficiency than the first few trials possibly due to the disrupting effects of FNA on sewer biofilms. This suggests that an initial strong dose (more chemical consumption) followed by maintenance dosing (less chemical consumption) could be a very cost-effective way to achieve consistent control efficiency. It was also found that heavy rainfall slowed the recovery of sulfide production after dosing, likely due to the dilution effects and reduced retention time. Overall, intermittent dose of FNA or FNA in combination with H₂O₂ was successfully demonstrated to be a cost-effective method for sulfide control in rising main sewers.     

Acetate removal in sewer biofilms under aerobic conditions

Removal of acetate has been investigated in sewer biofilms by continuous-flow biofilm reactor studies simulating the conditions in a gravity sewer. Non-steady-state conditions are prevailing in sewers, due to periodic variations in substrate concentrations. In order to simulate two extreme situations in a gravity sewer, biofilms defined as high-loaded and low-loaded, respectively, were grown by continuously feeding wastewater to the reactors with and without supplementary addition of acetate. During short-term experiments with high acetate concentrations (1-2 h), surface removal rates of acetate and dissolved oxygen (DO) and observed yield coefficients were determined, as well as the influence of DO concentration on acetate removal rates. The low-loaded biofilms showed very high acetate removal rates in short-term experiments at high acetate concentrations. The DO uptake rates were low, resulting in an average observed yield coefficient of 0.79 g biomass produced per gram acetate (as chemical oxygen demand, COD) consumed. This indicated a luxury uptake by the cells probably for storage inside the cells or for production of extracellular polymeric substances. The high-loaded biofilms showed lower acetate removal rates during the short-term experiments, with an average yield coefficient of 0.49 g biomass produced per gram acetate (as COD) consumed. The level of the acetate removal rates seemed to be related to the structure of the biofilm. The highest acetate removal rates were found for the low-loaded biofilm, where the biofilm was very hairy with 'streamers" with a length of 8-9 mm. At low acetate removal rates (high-loaded biofilm), the "streamer" lengths were only 3-5 mm. The surface removal rates for acetate and DO seemed to follow 1/2 order approximations to biofilm kinetics. For a DO of 0.8 and 6.0 g/m3, the limiting acetate concentrations were about 34 and 20 g-COD/m3, respectively. Under real gravity sewer conditions, the typical concentration ranges for acetate and DO are at levels where any of them may be rate-limiting for microbial acetate removal.     

Development of a model for assessing methane formation in rising main sewers

Significant methane formation in sewers has been reported recently, which may contribute significantly to the overall greenhouse gas emission from wastewater systems. The understanding of the biological conversions occurring in sewers, particularly the competition between methanogenic and sulfate-reducing populations for electron donors, is an essential step for minimising methane emissions from sewers. This work proposes an extension to the current state-of-the-art models characterising biological and physicochemical processes in sewers. This extended model includes the competitive interactions of sulfate-reducing bacteria and methanogenic archaea in sewers for various substrates available. The most relevant parameters of the model were calibrated with lab-scale experimental data. The calibrated model described field data reasonably well. The model was then used to investigate the effect of several key sewer design and operational parameters on methane formation. The simulation results showed that methane production was highly correlated with the hydraulic residence time (HRT) and pipe area to volume (A/V) ratio showing higher methane concentrations at a long HRT or a larger A/V ratio.     

pH dynamics in sewers and its modeling

pH variation in sewers has a significant effect on hydrogen sulfide production and emissions, and hence its accurate prediction is critical for the optimization of mitigation strategies. In this study, the nature and dynamics of pH variation in a sewer system is examined. Three sewer systems collecting domestic wastewater were monitored, with pH in all cases showing large diurnal variations. pH in fresh sewage in all three cases had a very similar trend with maximum pH in the range of 8.5–8.7. pH variation in fresh sewage followed the same pattern as the sewage flow rate, suggesting that sewage pH is influenced by household water use. Nitrogen content of the wastewater was found to be the most influential factor causing pH variation in fresh sewage, with the total ammonium concentration variation well correlated with the pH variation. A methodology for predicting pH variation in sewers is developed and calibration protocols proposed. The methodology, which is based on the concept of charge balance, was validated using titration curves and field pH data. Measurement of the total ammonium concentration in fresh sewage was found necessary and adequate for the calibration of the charge balance-based pH model.