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.     

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.     

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.     

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.     

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.     

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.     

Simultaneous removal of nitrate and arsenic from drinking water sources utilizing a fixed-bed bioreactor system

A novel bioreactor system, consisting of two biologically active carbon (BAC) reactors in series, was developed for the simultaneous removal of nitrate and arsenic from a synthetic groundwater supplemented with acetic acid. A mixed biofilm microbial community that developed on the BAC was capable of utilizing dissolved oxygen, nitrate, arsenate, and sulfate as the electron acceptors. Nitrate was removed from a concentration of approximately 50 mg/L in the influent to below the detection limit of 0.2 mg/L. Biologically generated sulfides resulted in the precipitation of the iron sulfides mackinawite and greigite, which concomitantly removed arsenic from an influent concentration of approximately 200 ug/L to below 20 ug/L through arsenic sulfide precipitation and surface precipitation on iron sulfides. This study showed for the first time that arsenic and nitrate can be simultaneously removed from drinking water sources utilizing a bioreactor system.     

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.     

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.     

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.     

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.     

Nitrate removal and biofilm characteristics in methanotrophic membrane biofilm reactors with various gas supply regimes

Aerobic methanotrophs can contribute to nitrate removal from contaminated waters, wastewaters, or landfill leachate by assimilatory reduction and by producing soluble organics that can be utilized by coexisting denitrifiers. The goal of this study was to investigate nitrate removal and biofilm characteristics in membrane biofilm reactors (MBfR) with various supply regimes of oxygen and methane gas. Three MBfR configurations were developed and they achieved significantly higher nitrate removal efficiencies in terms of methane utilization (values ranging from 0.25 to 0.36 mol N mol⁻¹ CH₄) than have previously been observed with suspended cultures. The biofilm characteristics were investigated in two MBfRs with varying modes of oxygen supply. The biofilms differed in structure, but both were dominated by Type I methanotrophs growing close to the membrane surface. Detection of the nitrite reductase genes, nirS and nirK, suggested genetic potential for denitrification was present in the mixed culture biofilms.     

The strong biocidal effect of free nitrous acid on anaerobic sewer biofilms

Several recent studies showed that nitrite dosage to wastewater results in long-lasting reduction of the sulfate-reducing and methanogenic activities of anaerobic sewer biofilms. In this study, we revealed that the quick reduction in these activities is due to the biocidal effect of free nitrous acid (FNA), the protonated form of nitrite, on biofilm microorganisms. The microbial viability was assessed after sewer biofilms being exposed to wastewater containing nitrite at concentrations of 0-120 mg-N/L under pH levels of 5-7 for 6-24 h. The viable fraction of microorganisms was found to decrease substantially from approximately 80% prior to the treatment to 5-15% after 6-24 h treatment at FNA levels above 0.2 mg-N/L. The level of the biocidal effect has a much stronger correlation with the FNA concentration, which is well described by an exponential function, than with the nitrite concentration or with the pH level, suggesting that FNA is the actual biocidal agent. An increase of the treatment from 6 to 12 and 24 h resulted in only slight decreases in microbial viability. Physical disrupted biofilm was more susceptible to FNA in comparison with intact biofilms, indicating that the biocidal effect of FNA on biofilms was somewhat reduced by mass transfer limitations. The inability to achieve 2-log killing even in the case of disrupted biofilms suggests that some microorganisms may be more resistant to FNA than others. The recovery of biofilm activities in anaerobic reactors after being exposed to FNA at 0.18 and 0.36 mg-N/L, respectively, resembled the regrowth of residual sulfate-reducing bacteria and methanogens, further confirming the biocidal effects of FNA on microorganisms in biofilms.     

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.     

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.     

Sources, nature, and fate of heavy metal-bearing particles in the sewer system

A preliminary insight into metal cycling within the urban sewer was obtained by determining both the heavy metal concentrations (Cu, Zn, Pb, Cd, Ni, Cr) in sewage and sediments, and the nature of metal-bearing particles using TEM–EDX, SEM–EDX and XRD. Particles collected from tap water, sump-pit deposits, and washbasin siphons, were also examined to trace back the origin of some mineral species. The results show that the total levels in Cu, Pb, Zn, Ni, and Cr in sewage are similar to that reported in the literature, thus suggesting that a time-averaged heavy metal fingerprint of domestic sewage can be defined for most developed cities at the urban catchment scale. Household activities represent the main source of Zn and Pb, the water supply system is a significant source of Cu, and in our case, groundwater infiltration in the sewer system provides a supplementary source of Ni and Cd. Concentrations in heavy metals were much higher in sewer sediments than in sewage suspended solids, the enrichment being due to the preferential settling of metal-bearing particles of high density and/or the precipitation of neoformed mineral phases. TEM and SEM–EDX analyses indicated that suspended solids, biofilms, and sewer sediments contained similar heavy metal-bearing particles including alloys and metal fragments, oxidized metals and sulfides. Copper fragments, metal carbonates (Cu, Zn, Pb), and oxidized soldering materials are released from the erosion of domestic plumbing, whereas the precipitation of sulfides and the sulfurization of metal phases occur primarily within the household connections to the sewer trunk. Close examination of sulfide phases also revealed in most cases a complex growth history recorded in the texture of particles, which likely reflects changes in physicochemical conditions associated with successive resuspension and settling of particles within the sewer system.     

Biological and chemical interactions with U(VI) during anaerobic enrichment in the presence of iron oxide coated quartz

Microcosm experiments were performed to understand chemical and biological interactions with hexavalent uranium (U(VI)) in the presence of iron oxide bearing minerals and trichloroethylene (TCE) as a co-contaminant. Interactions of U(VI) and hydrous iron oxide moieties on the mineral oxide surfaces were studied during enrichments for dissimilatory iron reducing (DIRB) and sulfate reducing bacteria (SRB). Microbes enriched from groundwater taken from the Test Area North (TAN) site at the Idaho National Laboratory (INL) were able to reduce the U(VI) in the adsorption medium as well as the iron on quartz surfaces. Early in the experiment disappearance of U(VI) from solution was a function of chemical interactions since no microbial activity was evident. Abiotic removal of U(VI) was enhanced in the presence of carbonate. As the experiment proceeded, further removal of U(VI) from solution was associated with the fermentation of lactate to propionate and acetate. During later phases of the experiment when lactate was depleted from the growth medium in the microcosm containing the DIRB enrichments, U(VI) concentrations in the solution phase increased until additional lactate was added. When additional lactate was added and fermentation proceeded, U(VI) concentrations in the liquid phase again returned to near zero. Similar results were shown for the SRB enrichment but lower uranium concentrations were seen in the liquid phase, while in the enrichment with carbonate a similar increase in uranium concentration was not seen. Chemical and biological interactions appear to be important on the mobilization/immobilization of U(VI) in an iron oxide system when TCE is present as a co-contaminant. Interestingly, TCE present in the microcosm experiments was not dechlorinated which was probably an effect of redox conditions that were unsuitable for reductive dechlorination by the microbial culture tested.     

Removal of sulfate and heavy metals by sulfate reducing bacteria in short-term bench scale upflow anaerobic packed bed reactor runs

Mildly acidic metal (Cu, Zn, Ni, Fe, Al and Mg), arsenic and sulfate contaminated waters were treated, over a 14 day period at 25 degrees C, in a bench-scale upflow anaerobic packed bed reactor filled with silica sand and employing a mixed population of sulfate-reducing bacteria (SRB). The activity of SRB increased the water pH from approximately 4.5 to 7.0, and enhanced the removal of sulfate and metals in comparison to controls not inoculated with SRB. Addition of organic substrate and sulfate at loading rates of 7.43 and 3.71 kg d(-1) m(-3), respectively, resulted in >82% reduction in sulfate concentration. The reactor removed more than 97.5% of the initial concentrations of Cu, Zn and Ni, while only >77.5% and >82% of As and Fe were removed, respectively. In contrast, Mg and Al levels remained unchanged during the whole treatment process. The removal patterns for Cu, Zn, Ni and Fe reflected the trend in their solubility for their respective metal sulfides, while As removal appeared to coincide with decreasing Cu, Zn, Ni and Fe concentrations, which suggests adsorption or concomitant precipitation with the other metal sulfides.     

Captured streams and springs in combined sewers: A review of the evidence,consequences and opportunities

Captured streams and springs may be flowing in combined sewers, increasing clean baseflow in pipes and wastewater treatment works (WwTWs), reducing pipe capacity and increasing treatment costs. The UK water industry is aware of this in principle, but there has been no explicit discussion of this in the published literature, nor have there been any known attempts to manage it. Instead, the current focus is on the similar intrusion of groundwater infiltration through pipe cracks and joints. We have conducted a thorough review of literature and international case studies to investigate stream and spring capture, finding several examples with convincing evidence that this occurs. We identify three modes of entry: capture by conversion, capture by interception, and direct spring capture. Methods to identify and quantify capture are limited, but the experience in Zurich suggests that it contributed 7–16% of the baseflow reaching WwTWs. There are negative impacts for the water industry in capital and operational expenditure, as well as environmental and social impacts of loss of urban streams. For a typical WwTW (Esholt, Bradford) with 16% of baseflow from captured streams and springs, we conservatively estimate annual costs of £2 million to £7 million. A detailed case study from Zurich is considered that has successfully separated captured baseflow into daylighted streams through the urban area, with multiple economic, environmental and social benefits. We conclude that there is a strong case for the UK water industry to consider captured streams and springs, quantify them, and assess the merits of managing them.     

Applying global sensitivity analysis to the modelling of flow and water quality in sewers

While several approaches for global sensitivity analysis (GSA) have been proposed in literature, only few applications exist in urban drainage modelling. This contribution discusses two GSA methods applied to a sewer flow and sewer water quality model: Standardised Regression Coefficients (SRCs) using Monte-Carlo simulation as well as the Morris Screening method. For selected model variables we evaluate how the sensitivities are influenced by the choice of the rainfall event. The aims are to i) compare both methods concerning the similarity of results and their applicability, ii) discuss the implications for factor fixing (identifying non-influential parameters) and factor prioritisation (identifying important parameters) and iii) rank the important parameters for the investigated model. It was shown that both methods lead to similar results for the hydraulic model. Parameter interactions and non-linearity were identified for the water quality model and the parameter ranking differs between the methods. For the investigated model the results allow a sound choice of output variables and rainfall events in view of detailed uncertainty analysis or model calibration. We advocate the simultaneous use of both methods for a first model assessment as they allow answering both factor fixing and factor prioritisation at low computational cost.