Yingyu Law

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.

N2O production rate of an enriched ammonia-oxidising bacteria culture exponentially correlates to its ammonia oxidation rate.

The relationship between the ammonia oxidation rate (AOR) and nitrous oxide production rate (N(2)OR) of an enriched ammonia-oxidising bacteria (AOB) culture was investigated. The AOB culture was enriched in a nitritation system fed with synthetic anaerobic digester liquor. The AOR was controlled by adjusting the dissolved oxygen (DO) and pH levels and also by varying the initial ammonium (NH(4)(+)) concentration in batch experiments. Tests were also performed directly on the parent reactor where a stepwise decrease/increase in DO was implemented to alter AOR. The experimental data indicated a clear exponential relationship between the biomass specific N(2)OR and AOR. Four metabolic models were used to analyse the experimental data. The metabolic model formulated based on aerobic N(2)O production from the decomposition of nitrosyl radical (NOH) predicted the exponential correlation observed experimentally. The experimental data could not be reproduced by models developed on the basis of N(2)O production through nitrite (NO(2)(-)) and nitric oxide (NO) reduction by AOB.

The effect of pH on N2O production under aerobic conditions in a partial nitritation system

Ammonia-oxidising bacteria (AOB) are a major contributor to nitrous oxide (N(2)O) emissions during nitrogen transformation. N(2)O production was observed under both anoxic and aerobic conditions in a lab-scale partial nitritation system operated as a sequencing batch reactor (SBR). The system achieved 55 ± 5% conversion of the 1g NH(4)(+)-N/L contained in a synthetic anaerobic digester liquor to nitrite. The N(2)O emission factor was 1.0 ± 0.1% of the ammonium converted. pH was shown to have a major impact on the N(2)O production rate of the AOB enriched culture. In the investigated pH range of 6.0-8.5, the specific N(2)O production was the lowest between pH 6.0 and 7.0 at a rate of 0.15 ± 0.01 mg N(2)O-N/h/g VSS, but increased with pH to a maximum of 0.53 ± 0.04 mg N(2)O-N/h/g VSS at pH 8.0. The same trend was also observed for the specific ammonium oxidation rate (AOR) with the maximum AOR reached at pH 8.0. A linear relationship between the N(2)O production rate and AOR was observed suggesting that increased ammonium oxidation activity may have promoted N(2)O production. The N(2)O production rate was constant across free ammonia (FA) and free nitrous acid (FNA) concentrations of 5-78 mg NH(3)-N/L and 0.15-4.6 mg HNO(2)-N/L, respectively, indicating that the observed pH effect was not due to changes in FA or FNA concentrations.

Ammonium as a sustainable proton shuttle in bioelectrochemical systems.

This work examines a pH control method using ammonium (NH(4)(+)) as a sustainable proton shuttle in a CEM-equipped BES. Current generation was sustained by adding NH(3) or ammonium hydroxide (NH(4)OH) to the anolyte, controlling its pH at 7. Ammonium ion migration maintained the catholyte pH at approximately 9.25. Such NH(4)(+)/NH(3) migration accounted for 90±10% of the ionic flux in the BES. Reintroducing the volatilized NH(3) from the cathode into the anolyte maintained a suitable anolyte pH for sustained microbial-driven current generation. Hence, NH(4)(+)/NH(3) acted as a proton shuttle that is not consumed in the process.

Modeling of Nitrous Oxide Production by Autotrophic Ammonia-Oxidizing Bacteria with Multiple Production Pathways

Autotrophic ammonia oxidizing bacteria (AOB) have been recognized as a major contributor to N2O production in wastewater treatment systems. However, so far N2O models have been proposed based on a single N2O production pathway by AOB, and there is still a lack of effective approach for the integration of these models. In this work, an integrated mathematical model that considers multiple production pathways is developed to describe N2O production by AOB. The pathways considered include the nitrifier denitrification pathway (N2O as the final product of AOB denitrification with NO2(-) as the terminal electron acceptor) and the hydroxylamine (NH2OH) pathway (N2O as a byproduct of incomplete oxidation of NH2OH to NO2(-)). In this model, the oxidation and reduction processes are modeled separately, with intracellular electron carriers introduced to link the two types of processes. The model is calibrated and validated using experimental data obtained with two independent nitrifying cultures. The model satisfactorily describes the N2O data from both systems. The model also predicts shifts of the dominating pathway at various dissolved oxygen (DO) and nitrite levels, consistent with previous hypotheses. This unified model is expected to enhance our ability to predict N2O production by AOB in wastewater treatment systems under varying operational conditions.

The Confounding Effect of Nitrite on N2O Production by an Enriched Ammonia-Oxidizing Culture

The effect of nitrite (NO2(-)) on the nitrous oxide (N2O) production rate of an enriched ammonia-oxidizing bacteria (AOB) culture was characterized over a concentration range of 0-1000 mg N/L. The AOB culture was enriched in a nitritation system fed with synthetic anaerobic digester liquor. The N2O production rate was highest at NO2(-) concentrations of less than 50 mg N/L. At dissolved oxygen (DO) concentration of 0.55 mg O2/L, further increases in NO2(-) concentration from 50 to 500 mg N/L resulted in a gradual decrease in N2O production rate, which maintained at its lowest level of 0.20 mg N2O-N/h/g VSS in the NO2(-) concentration range of 500-1000 mg N/L. The observed NO2(-)-induced decrease in N2O production was even more apparent at increased DO concentration. At DO concentrations of 1.30 and 2.30 mg O2/L, the lowest N2O production rate (0.25 mg N2O-N/h/g VSS) was attained at a lower NO2(-) concentration of 200-250 mg N/L. These observations suggest that N2O production by the culture is diminished by both high NO2(-) and high DO concentrations. Collectively, the findings show that exceedingly high NO2(-) concentrations in nitritation systems could lead to decreased N2O production. Further studies are required to determine the extent to which the same response to NO2(-) is observed across different AOB cultures.

Mathematical modeling of nitrous oxide (N2O) emissions from full-scale wastewater treatment plants

Mathematical modeling of N2O emissions is of great importance toward understanding the whole environmental impact of wastewater treatment systems. However, information on modeling of N2O emissions from full-scale wastewater treatment plants (WWTP) is still sparse. In this work, a mathematical model based on currently known or hypothesized metabolic pathways for N2O productions by heterotrophic denitrifiers and ammonia-oxidizing bacteria (AOB) is developed and calibrated to describe the N2O emissions from full-scale WWTPs. The model described well the dynamic ammonium, nitrite, nitrate, dissolved oxygen (DO) and N2O data collected from both an open oxidation ditch (OD) system with surface aerators and a sequencing batch reactor (SBR) system with bubbling aeration. The obtained kinetic parameters for N2O production are found to be reasonable as the 95% confidence regions of the estimates are all small with mean values approximately at the center. The model is further validated with independent data sets collected from the same two WWTPs. This is the first time that mathematical modeling of N2O emissions is conducted successfully for full-scale WWTPs. While clearly showing that the NH2OH related pathways could well explain N2O production and emission in the two full-scale plants studied, the modeling results do not prove the dominance of the NH2OH pathways in these plants, nor rule out the possibility of AOB denitrification being a potentially dominating pathway in other WWTPs that are designed or operated differently.

Fossil organic carbon in wastewater and its fate in treatment plants

This study reports the presence of fossil organic carbon in wastewater and its fate in wastewater treatment plants. The findings pinpoint the inaccuracy of current greenhouse gas accounting guidelines which defines all organic carbon in wastewater to be of biogenic origin. Stable and radiocarbon isotopes ((13)C and (14)C) were measured throughout the process train in four municipal wastewater treatment plants equipped with secondary activated sludge treatment. Isotopic mass balance analyses indicate that 4-14% of influent total organic carbon (TOC) is of fossil origin with concentrations between 6 and 35 mg/L; 88-98% of this is removed from the wastewater. The TOC mass balance analysis suggests that 39-65% of the fossil organic carbon from the influent is incorporated into the activated sludge through adsorption or from cell assimilation while 29-50% is likely transformed to carbon dioxide (CO2) during secondary treatment. The fossil organic carbon fraction in the sludge undergoes further biodegradation during anaerobic digestion with a 12% decrease in mass. 1.4-6.3% of the influent TOC consists of both biogenic and fossil carbon is estimated to be emitted as fossil CO2 from activated sludge treatment alone. The results suggest that current greenhouse gas accounting guidelines, which assume that all CO2 emission from wastewater is biogenic may lead to underestimation of emissions.

A novel methodology to quantify nitrous oxide emissions from full-scale wastewater treatment systems with surface aerators

The quantification of nitrous oxide (N2O) emissions from open-surface wastewater treatment systems with surface aerators is difficult as emissions from the surface aerator zone cannot be easily captured by floating hoods. In this study, we propose and demonstrate a novel methodology to estimate N2O emissions from such systems through determination of the N2O transfer coefficient (kLa) induced by surface aerators based on oxygen balance for the entire system. The methodology is demonstrated through its application to a full-scale open oxidation ditch wastewater treatment plant with surface aerators. The estimated kLa profile based on a month-long measurement campaign for oxygen balance, intensive monitoring of dissolved N2O profiles along the oxidation ditch over a period of four days, together with mathematical modelling, enabled to determine the N2O emission factor from this treatment plant (0.52 ± 0.16%). Majority of the N2O emission was found to occur in the surface aerator zone, which would be missed if the gas hood method was applied alone.

Integrative microbial community analysis reveals full-scale enhanced biological phosphorus removal under tropical conditions

Management of phosphorus discharge from human waste is essential for the control of eutrophication in surface waters. Enhanced biological phosphorus removal (EBPR) is a sustainable, efficient way of removing phosphorus from waste water without employing chemical precipitation, but is assumed unachievable in tropical temperatures due to conditions that favour glycogen accumulating organisms (GAOs) over polyphosphate accumulating organisms (PAOs). Here, we show these assumptions are unfounded by studying comparative community dynamics in a full-scale plant following systematic perturbation of operational conditions, which modified community abundance, function and physicochemical state. A statistically significant increase in the relative abundance of the PAO Accumulibacter was associated with improved EBPR activity. GAO relative abundance also increased, challenging the assumption of competition. An Accumulibacter bin-genome was identified from a whole community metagenomic survey, and comparative analysis against extant Accumulibacter genomes suggests a close relationship to Type II. Analysis of the associated metatranscriptome data revealed that genes encoding proteins involved in the tricarboxylic acid cycle and glycolysis pathways were highly expressed, consistent with metabolic modelling results. Our findings show that tropical EBPR is indeed possible, highlight the translational potential of studying competition dynamics in full-scale waste water communities and carry implications for plant design in tropical regions.