Yuting Pan

Nitrous oxide emissions from wastewater treatment processes

Nitrous oxide (N2O) emissions from wastewater treatment plants vary substantially between plants, ranging from negligible to substantial (a few per cent of the total nitrogen load), probably because of different designs and operational conditions. In general, plants that achieve high levels of nitrogen removal emit less N2O, indicating that no compromise is required between high water quality and lower N2O emissions. N2O emissions primarily occur in aerated zones/compartments/periods owing to active stripping, and ammonia-oxidizing bacteria, rather than heterotrophic denitrifiers, are the main contributors. However, the detailed mechanisms remain to be fully elucidated, despite strong evidence suggesting that both nitrifier denitrification and the chemical breakdown of intermediates of hydroxylamine oxidation are probably involved. With increased understanding of the fundamental reactions responsible for N2O production in wastewater treatment systems and the conditions that stimulate their occurrence, reduction of N2O emissions from wastewater treatment systems through improved plant design and operation will be achieved in the near future.

Effect of pH on N2O reduction and accumulation during denitrification by methanol utilizing denitrifiers

Acidic pH has previously been found to increase nitrous oxide (N₂O) accumulation during heterotrophic denitrification in biological wastewater treatment. However, the mechanism of this phenomenon still needs to be clarified. By using an enriched methanol utilizing denitrifying culture as an example, this paper presents a comprehensive study on the effect of pH (6.0-9.0) on N₂O reduction kinetics with N₂O as the sole electron acceptor, as well as the effect of pH on N₂O accumulation with N₂O as an intermediate of nitrate reduction. The pH dependency of nitrate and nitrite reduction was also investigated. The maximum biomass-specificN₂O reduction rate is higher than the corresponding maximum nitrate and nitrite reduction rates in the entire pH range studied. However, the maximum biomass-specific N₂O reduction rate is much more sensitive to pH variation outside of the optimal range (pH 7.5 to pH 8.0) than the maximum biomass-specific nitrate and nitrite reduction rates. The half-saturation coefficient of the N₂O reductase increased from 0.10 mg N₂O-N/L to 0.92 mg N₂O-N/L as pH increased from pH 6.0 to 9.0. At pH 6.0, approximately 20% and 40% of the denitrified nitrate accumulated as N₂O in the presence and absence of methanol (as an exogenous carbon source), respectively. However, at pH 6.5, these fractions decreased to 0% and 30%, respectively. No N₂O accumulation occurred at pH 7.0 to 9.0 independent of the availability of methanol. These results suggest that the competition for electrons among different nitrogen oxides reductases likely plays a role in N₂O accumulation at low pH conditions.

Electron competition among nitrogen oxides reduction during methanol-utilizing denitrification in wastewater treatment

Limited availability of carbon sources has been regarded as an important factor leading to N2O accumulation during denitrification in wastewater treatment. By varying the carbon (methanol) loading rate to a methanol utilizing denitrifying culture in the presence of various electron acceptors (nitrate, nitrite, N2O and their combinations), this study quantitatively investigated the electron distribution among different nitrogen oxide reductases during denitrification. The results showed that electron competition occurs under not only carbon limiting but also carbon abundant conditions. The electron distribution among the nitrogen oxide reductases is affected by the carbon loading rate, with a lower fraction of electrons distributed to the N2O reductase with reduced carbon loading rate. N2O accumulation occurs when the electron flux going to nitrite reduction is higher than that going to N2O reduction. The study also showed that, for the culture investigated, the carbon to nitrogen ratio is not a key factor leading to N2O accumulation.

Modeling electron competition among nitrogen oxides reduction and N2O accumulation in denitrification.

Competition for electrons among different steps of denitrification has previously been shown to occur, and to play an important role in the accumulation and emission of N2O in wastewater treatment. However, this electron competition is not recognized in the current denitrification models, limiting their ability to predict N2O accumulation during denitrification. In this work, a new denitrification model is developed for wastewater treatment processes. It describes electron competition among the four steps of denitrification, through modeling the carbon oxidation and nitrogen reduction processes separately, in contrast to the existing models that directly couple these two types of processes. Electron carriers are introduced to link carbon oxidation, which donates electrons to carriers, and nitrogen oxides reduction, which receives electrons from these carriers. The relative ability of each denitrification step to compete for electrons is modeled through the use of different affinity constants with reduced carriers. Model calibration and validation results demonstrate that the developed model is able to reasonably describe the nitrate, nitrite, and N2O reduction rates of a methanol-utilizing denitrifying culture under various carbon and nitrogen oxides supplying conditions. The model proposed, while subject to further validation, is expected to enhance our ability to predict N2O accumulation in denitrification.

Effect of H2S on N2O reduction and accumulation during denitrification by methanol utilizing denitrifiers.

Sulfide is produced in sewer networks, and previous studies suggest that sulfide in sewage could alter the activity of heterotrophic denitrification and lead to N2O accumulation during biological wastewater treatment. However, the details of this phenomenon are poorly understood. In this study, the potential inhibitory effects of sulfide on nitrate, nitrite, and N2O reduction were assessed with a methanol-utilizing denitrifying culture both prior to and after its exposure and adaptation to sulfide. Hydrogen sulfide was found to be strongly inhibitory to N2O reduction, with 50% inhibition observed at H2S concentrations of 0.04 mg H2S-S/L and 0.1 mg H2S-S/L for the unadapted and adapted cultures, respectively. In comparison, both nitrate and nitrite reduction was more tolerant to H2S. A 50% inhibition of nitrite reduction was observed at approximately 2.0 mg H2S-S/L for both unadapted and adapted cultures, while no inhibition of nitrate reduction occurred at the highest H2S concentrations applied (2.0 mg H2S-S/L) to either culture. N2O accumulation was observed during nitrate and nitrite reduction by the adapted culture when H2S concentrations were above 0.5 and 0.2 mg H2S-S/L, respectively. Additionally, we reveal that hydrogen sulfide (H2S), rather than sulfide, was likely the true inhibitor of N2O reduction, and the inhibitory effect was reversible. These findings suggest that sulfide management in sewers could potentially have a significant impact on N2O emission from wastewater treatment plants.

Full-scale modeling explaining large spatial variations of nitrous oxide fluxes in a step-feed plug-flow wastewater treatment reactor

Nitrous oxide (N2O) emission data collected from wastewater treatment plants (WWTPs) show huge variations between plants and within one plant (both spatially and temporarily). Such variations and the relative contributions of various N2O production pathways are not fully understood. This study applied a previously established N2O model incorporating two currently known N2O production pathways by ammonia-oxidizing bacteria (AOB) (namely the AOB denitrification and the hydroxylamine pathways) and the N2O production pathway by heterotrophic denitrifiers to describe and provide insights into the large spatial variations of N2O fluxes in a step-feed full-scale activated sludge plant. The model was calibrated and validated by comparing simulation results with 40 days of N2O emission monitoring data as well as other water quality parameters from the plant. The model demonstrated that the relatively high biomass specific nitrogen loading rate in the Second Step of the reactor was responsible for the much higher N2O fluxes from this section. The results further revealed the AOB denitrification pathway decreased and the NH2OH oxidation pathway increased along the path of both Steps due to the increasing dissolved oxygen concentration. The overall N2O emission from this step-feed WWTP would be largely mitigated if 30% of the returned sludge were returned to the Second Step to reduce its biomass nitrogen loading rate.

Unravelling the spatial variation of nitrous oxide emissions from a step-feed plug-flow full scale wastewater treatment plant

Plug-flow activated sludge reactors (ASR) that are step-feed with wastewater are widely adopted in wastewater treatment plants (WWTPs) due to their ability to maximise the use of the organic carbon in wastewater for denitrification. Nitrous oxide (N2O) emissions are expected to vary along these reactors due to pronounced spatial variations in both biomass and substrate concentrations. However, to date, no detailed studies have characterised the impact of the step-feed configuration on emission variability. Here we report on the results from a comprehensive online N2O monitoring campaign, which used multiple gas collection hoods to simultaneously measure emission along the length of a full-scale, step-fed, plug-flow ASR in Australia. The measured N2O fluxes exhibited strong spatial-temporal variation along the reactor path. The step-feed configuration had a substantial influence on the N2O emissions, where the N2O emission factors in sections following the first and second step feed were 0.68% ± 0.09% and 3.5% ± 0.49% of the nitrogen load applied to each section. The relatively high biomass-specific nitrogen loading rate in the second section of the reactor was most likely cause of the high emissions from this section.

Evaluation of Nitrous Oxide Emission from Sulfide- and Sulfur-Based Autotrophic Denitrification Processes

Recent studies have shown that sulfide- and sulfur-based autotrophic denitrification (AD) processes play an important role in contributing to nitrous oxide (N2O) production and emissions. However, N2O production is not recognized in the current AD models, limiting their ability to predict N2O accumulation during AD. In this work, a mathematical model is developed to describe N2O dynamics during sulfide- and sulfur-based AD processes for the first time. The model is successfully calibrated and validated using N2O data from two independent experimental systems with sulfide or sulfur as electron donors for AD. The model satisfactorily describes nitrogen reductions, sulfide/sulfur oxidation, and N2O accumulation in both systems. Modeling results revealed substantial N2O accumulation due to the relatively low N2O reduction rate during both sulfide- and sulfur-based AD processes. Application of the model to simulate long-term operations of activated sludge systems performing sulfide- and sulfur-based AD processes indicates longer sludge retention time reduced N2O emission. For sulfide-based AD process, higher initial S/N ratio also decreased N2O emission but with a higher operational cost. This model can be a useful tool to support process operation optimization for N2O mitigation during AD with sulfide or sulfur as electron donor.

Modelling methane production and sulfate reduction in anaerobic granular sludge reactor with ethanol as electron donor

In this work, a mathematical model based on growth kinetics of microorganisms and substrates transportation through biofilms was developed to describe methane production and sulfate reduction with ethanol being a key electron donor. The model was calibrated and validated using experimental data from two case studies conducted in granule-based Upflow Anaerobic Sludge Blanket reactors. The results suggest that the developed model could satisfactorily describe methane and sulfide productions as well as ethanol and sulfate removals in both systems. The modeling results reveal a stratified distribution of methanogenic archaea, sulfate-reducing bacteria and fermentative bacteria in the anaerobic granular sludge and the relative abundances of these microorganisms vary with substrate concentrations. It also indicates sulfate-reducing bacteria can successfully outcompete fermentative bacteria for ethanol utilization when COD/SO42− ratio reaches 0.5. Model simulation suggests that an optimal granule diameter for the maximum methane production efficiency can be achieved while the sulfate reduction efficiency is not significantly affected by variation in granule size. It also indicates that the methane production and sulfate reduction can be affected by ethanol and sulfate loading rates, and the microbial community development stage in the reactor, which provided comprehensive insights into the system for its practical operation.

Modeling Electron Competition among Nitrogen Oxides Reduction and N2O Accumulation in Hydrogenotrophic Denitrification

Hydrogenotrophic denitrification is a novel and sustainable process for nitrogen removal, which utilizes hydrogen as electron donor, and carbon dioxide as carbon source. Recent studies have shown that nitrous oxide (N2O), a highly undesirable intermediate and potent greenhouse gas, can accumulate during this process. In this work, a new mathematical model is developed to describe nitrogen oxides dynamics, especially N2O, during hydrogenotrophic denitrification for the first time. The model describes electron competition among the four steps of hydrogenotrophic denitrification through decoupling hydrogen oxidation and nitrogen reduction processes using electron carriers, in contrast to the existing models that couple these two processes and also do not consider N2O accumulation. The developed model satisfactorily describes experimental data on nitrogen oxides dynamics obtained from two independent hydrogenotrophic denitrifying cultures under various hydrogen and nitrogen oxides supplying conditions, suggesting the validity and applicability of the model. The results indicated that N2O accumulation would not be intensified under hydrogen limiting conditions, due to the higher electron competition capacity of N2O reduction in comparison to nitrate and nitrite reduction during hydrogenotrophic denitrification. The model is expected to enhance our understanding of the process during hydrogenotrophic denitrification and the ability to predict N2O accumulation.