Modelling the long-term effect of wastewater compositions on maximum sulfide and methane production rates of sewer biofilm.

Reliable modelling of sulfide and methane production in sewer systems is required for efficient sewer emission management. Wastewater compositions affect sulfide and methane production kinetics through both its short-term variation influencing the substrate availability to sewer biofilms, and its long-term variation affecting the sewer biofilm structure. While the short-term effect is well considered in existing sewer models with the use of Monod or half-order equations, the long-term effect has not been explicitly considered in current sewer models suitable for network modelling. In this study, the long-term effect of wastewater compositions on sulfide and methane production activities in rising main sewers was investigated. A detailed biofilm model was firstly developed, and then calibrated and validated using experimental data measured during the entire biofilm development period of a laboratory sewer reactor. Based on scenario simulations using the detailed biofilm model, empirical equations describing the long-term effect of sulfate and sCOD (soluble chemical oxygen demand) concentrations on kH2S (the maximum sulfide production rate of sewer biofilm) and kCH4 (the maximum methane production rate of sewer biofilm) were proposed. These equations require further verification in future studies before their potential integration into network-wide sewer models.

Impact of reduced water consumption on sulfide and methane production in rising main sewers.

Reduced water consumption (RWC), for water conservation purposes, is expected to change the wastewater composition and flow conditions in sewer networks and affect the in-sewer transformation processes. In this study, the impact of reduced water consumption on sulfide and methane production in rising main sewers was investigated. Two lab-scale rising main sewer systems fed with wastewater of different strength and flow rates were operated to mimic sewers under normal and RWC conditions (water consumption reduced by 40%). Sulfide concentration under the RWC condition increased by 0.7-8.0 mg-S/L, depending on the time of a day. Batch test results showed that the RWC did not change the sulfate-reducing activity of sewer biofilms, the increased sulfide production being mainly due to longer hydraulic retention time (HRT). pH in the RWC system was about 0.2 units lower than that in the normal system, indicating that more sulfide would be in molecular form under the RWC condition, which would result in increased sulfide emission to the atmosphere as confirmed by the model simulation. Model based analysis showed that the cost for chemical dosage for sulfide mitigation would increase significantly per unit volume of sewage, although the total cost would decrease due to a lower sewage flow. The dissolved methane concentration under the RWC condition was over two times higher than that under the normal flow condition and the total methane discharge was about 1.5 times higher, which would potentially result in higher greenhouse gas emissions. Batch tests showed that the methanogenic activity of sewer biofilms increased under the RWC condition, which along with the longer HRT, led to increased methane production.

Feasibility of sulfide control in sewers by reuse of iron rich drinking water treatment sludge.

Dosage of iron salt is the most commonly used method for sulfide control in sewer networks but incurs high chemical costs. In this study, we experimentally investigate the feasibility of using iron rich drinking water treatment sludge for sulfide control in sewers. A lab-scale rising main sewer biofilm reactor was used. The sulfide concentration in the effluent decreased from 15.5 to 19.8 mgS/L (without dosing) to below 0.7-2.3 mgS/L at a sludge dosing rate achieving an iron to total dissolved inorganic sulfur molar ratio (Fe:S) of 1:1, with further removal of sulfide possible by prolonging the reaction time. In fact, batch tests revealed an Fe consumption to sulfide removal ratio of 0.5 ± 0.02 (mole:mole), suggesting the possible occurrence of other reactions involving the removal of sulfide. Modelling revealed that the reaction between iron in sludge and sulfide has reaction orders of 0.65 ± 0.01 and 0.77 ± 0.02 with respect to the Fe and sulfide concentrations, respectively. The addition of sludge slightly increased the total chemical oxidation demand (tCOD) concentration (by approximately 12%) as expected, but decreased the soluble chemical oxidation demand (sCOD) concentration and methane formation by 7% and 20%, respectively. Some phosphate removal (13%) was also observed at the sludge dosing rate of 1:1 (Fe:S), which is beneficial to nutrient removal from the wastewater. Overall, this study suggests that dosing iron-rich drinking water sludge to sewers could be an effective strategy for sulfide removal in sewer systems, which would also reduce the sludge disposal costs for drinking water treatment works. However, its potential side-effects on sewer sedimentation and on the wastewater treatment plant effluent remain to be investigated.

Degradation of methanethiol in anaerobic sewers and its correlation with methanogenic activities.

Methanethiol (MT) is considered one of the predominant odorants in sewer systems. Therefore, understanding MT transformation in sewers is essential to sewer odor assessment and abatement. In this study, we investigated the degradation of MT in laboratory anaerobic sewers. Experiments were carried out in seven anaerobic sewer reactors with biofilms at different stages of development. MT degradation was found to be strongly dependent on the methanogenic activity of sewer biofilms. The MT degradation rate accelerated with the increase of methanogenic activity of sewer biofilms, resulting in MT accumulation (i.e. net production) in sewer reactors with relatively low methanogenic activities, and MT removal in reactors with higher methanogenic activities. A Monod-type kinetic expression was developed to describe MT degradation kinetics in anaerobic sewers, in which the maximum degradation rate was modeled as a function of the maximum methane production rate through a power function. It was also found that MT concentration had a linear relationship with acetate concentration, which may be used for preliminary assessment of MT presence in anaerobic sewers.

Stratified microbial structure and activity in sulfide- and methane-producing anaerobic sewer biofilms.

Simultaneous production of sulfide and methane by anaerobic sewer biofilms has recently been observed, suggesting that sulfate-reducing bacteria (SRB) and methanogenic archaea (MA), microorganisms known to compete for the same substrates, can coexist in this environment. This study investigated the community structures and activities of SRB and MA in anaerobic sewer biofilms (average thickness of 800 µm) using a combination of microelectrode measurements, molecular techniques, and mathematical modeling. It was seen that sulfide was mainly produced in the outer layer of the biofilm, between the depths of 0 and 300 µm, which is in good agreement with the distribution of SRB population as revealed by cryosection-fluorescence in situ hybridization (FISH). SRB had a higher relative abundance of 20% on the surface layer, which decreased gradually to below 3% at a depth of 400 µm. In contrast, MA mainly inhabited the inner layer of the biofilm. Their relative abundances increased from 10% to 75% at depths of 200 µm and 700 µm, respectively, from the biofilm surface layer. High-throughput pyrosequencing of 16S rRNA amplicons showed that SRB in the biofilm were mainly affiliated with five genera, Desulfobulbus, Desulfomicrobium, Desulfovibrio, Desulfatiferula, and Desulforegula, while about 90% of the MA population belonged to the genus Methanosaeta. The spatial organizations of SRB and MA revealed by pyrosequencing were consistent with the FISH results. A biofilm model was constructed to simulate the SRB and MA distributions in the anaerobic sewer biofilm. The good fit between model predictions and the experimental data indicate that the coexistence and spatial structure of SRB and MA in the biofilm resulted from the microbial types and their metabolic transformations and interactions with substrates.

An efficient method for measuring dissolved VOSCs in wastewater using GC-SCD with static headspace technique.

Volatile organic sulfur compounds (VOSCs) are important sources of unpleasant odor in wastewater systems. However, the study of VOSCs is usually hindered by their complicated measurement method and highly reactive nature. In this work, a static headspace method utilising gas chromatography (GC) with a sulfur chemiluminescence detector (SCD) was developed to quantitatively analyze VOSCs in wastewater matrices. The method has low detection limits and requires no pre-concentration treatment. Three typical VOSCs, namely methanethiol (MT), dimethyl sulfide (DMS) and dimethyl disulfide (DMDS), were chosen as examples for this study. The calibration curves of all three compounds covering a wide range from 0.5 ppb to 500 ppb showed good linearity (R(2) > 0.999). The method detection limits (MDL) were 0.08, 0.12 and 0.21 ppb for MT, DMS and DMDS, respectively. The reproducibility (relative standard deviation) was approximately 2%. The recovery ratio of MT, DMS and DMDS in spiked wastewater samples were 83 ± 4%, 103 ± 4% and 102 ± 3%, respectively. Sample preservation tests showed that VOSCs in wastewater samples could be preserved in vials without headspace under acidified conditions (pH ∼1.1) for at least 24 h without significant changes (<1.8 ppb). The analysis of real wastewater samples from both a laboratory-scale sewer system and a full-scale sewer pipe demonstrated the suitability of this method for routine wastewater VOSC measurement.

Effects of nitrate dosing on methanogenic activity in a sulfide-producing sewer biofilm reactor.

Nitrate dosing is widely used by water industry to control hydrogen sulfide production in sewers. This study assessed the impact of nitrate addition on methane generation by sewer biofilms using a lab-scale rising main sewer reactor. It was found that methanogenesis could coexist with denitrification and sulfate reduction in sewers dosed with nitrate. However, methane production was substantially reduced by nitrate addition. Methanogenic rates remained below 10% of its baseline level, with 30 mg-N/L of nitrate dosing for each pump event. By calculating the substrate penetration depth in biofilms, it is suggested that methanogenesis may persist in deeper biofilms due to the limited penetration of nitrate and sulfate, and better penetration of soluble organic substrates. The control of methane and sulfide production was found to be determined by the nitrate penetration depth in biofilms and nitrate presence time in sewers, respectively. The presence of nitrous oxide after nitrate addition was transient, with a negligible discharge of nitrous oxide from the sewer reactor due to its further reduction by denitrifiers after nitrate depletion.

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 12h. 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.

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.

Variation in biofilm structure and activity along the length of a rising main sewer.

Sewers systems are dynamic in nature, with periodic variation of hydraulic flow and wastewater substrate concentrations. While various models are currently available for predicting hydrogen sulfide (H2S) production in rising mains, they assume constant biofilm activities along the length and ignore the effect of substrate availability on biofilm development. To investigate variation in rising main biofilm structure and activity, detailed studies were carried out on a Robbins device setup, which was established in parallel to a real rising main that it simulated. The changes in wastewater characteristics, as wastewater traveled through both the experimental setup and the real sewer system, were monitored. The study revealed that the biofilm activities varied significantly with locations, with biofilm corresponding to the start of the rising main capable of greater sulfide and volatile fatty acid production than biofilm downstream. Analysis of microbial community composition of these biofilms showed a difference in diversity and abundance, both with regard to general bacterial populations and sulfate reducers. These differences were hypothesized to be a consequence of varying substrate types and availability along the sewer line. The results suggest that the biofilm structure and activity may vary considerably along the length of rising mains and should be taken into consideration for improved sewer modeling and when considering the overall effect of different hydrogen sulfide management options.

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 (S(0)) and the oxidation of S(0) to sulfate (SO(4)(2-)). 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 S(0) reduction. The relatively slower S(0) oxidation and reduction rates implied that S(0) 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.

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 H(2)S 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 H(2)S and CH(4) 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.

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 (15-25mg O(2)/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.

Dynamics and dynamic modelling of H2S production in sewer systems.

Accurate and reliable predictions of sulfide production in a sewer system greatly benefit formulation of appropriate strategies for optimal sewer management. Sewer systems, rising main systems in particular, are highly dynamic in terms of both flow and wastewater composition. In order to get an insight in sulfide production as a response to the dynamic changes in sewer conditions, several measurement campaigns were conducted in two rising mains in Gold Coast, Australia. The levels of various sulfur species and volatile fatty acids (VFAs) were monitored through hourly sampling for periods ranging from 8 to 29 h. The results of these field studies showed large temporal as well as spatial variations in sulfide generation. A dynamic sewer model taking into account the hydraulics and the biochemical transformation processes was formulated and calibrated and validated using the data collected during the four measurement campaigns at the two sites. The model was demonstrated to reasonably well describe the temporal and spatial variations in sulfide, sulfate and VFA concentrations. Application of the model was illustrated with a case study aimed to optimize oxygen injection to one of the two mains studied, which is being used as a means to control sulfide production on this site. The model predicted that, moving the current oxygen injection point to a location close to the end of the sewer line could achieve the same degree of sulfide control with only 50% of the current oxygen use. This study highlighted that the location at which oxygen is injected plays a major role in sulfide control and a dynamic model could be used to make a proper choice of the location.