Reduced iron induced nitric oxide and nitrous oxide emission

Formation of the greenhouse gas nitrous oxide in water treatment systems is predominantly studied as a biological phenomenon. There are indications that also chemical processes contribute to these emissions. Here we studied the formation of nitric oxide (NO) and nitrous oxide (N₂O) due to chemical nitrite reduction by ferrous iron (Fe(II)). Reduction of nitrite and NO coupled to Fe(II) oxidation was studied in laboratory-scale chemical experiments at different pH, nitrite and iron concentrations. The continuous measurement of both NO and N₂O emission showed that nitrite reduction and NO reduction have different kinetics. Nitrite reduction shows a linear dependency on the nitrite concentration, implying first order kinetics in nitrite. The nitrite reduction seems to be an equilibrium based reaction, leading to a constant NO concentration in the liquid. The NO reduction rate is suggested to be most dependent on reactive surface availability and the sorption of Fe(II) to the reactive surface. The importance of emission of NO and N₂O coupled to iron oxidation is exemplified by iron reduction experiments and several examples of environments where this pathway can play a role.     

Dynamics of nitric oxide and nitrous oxide emission during full-scale reject water treatment

Emission of NO and N2O from a full-scale two-reactor nitritation-anammox process was determined during a measurement campaign at the Dokhaven-Sluisjesdijk municipal WWTP (Rotterdam, NL). The NO and N2O levels in the off-gas responded to the aeration cycles and the aeration rate of the nitritation reactor, and to the nitrite and dissolved oxygen concentration. Due to the strong fluctuations in the NO and N2O levels in both the nitritation and the anammox reactor, only time-dependent measurements could yield a reliable estimate of the overall NO and N2O emissions. The NO emission from the nitritation reactor was 0.2% of the nitrogen load and the N2O emission was 1.7%. The NO emission from the anammox reactor was determined to be 0.003% of the nitrogen load and the N2O emission was 0.6%. Emission of NO2 could not be detected from the nitritation-anammox system. Denitrification by ammonia-oxidizing bacteria was considered to be the most probable cause of NO and N2O emission from the nitritation reactor. Since anammox bacteria have not been shown to produce N2O under physiological conditions, it is also suspected that ammonia-oxidizing bacteria contribute most to N2O production in the anammox reactor. The source of NO production in the anammox reactor can be either anammox bacteria or denitrification by heterotrophs or ammonia-oxidizing bacteria. Based on the results and previous work, it seems that a low dissolved oxygen or a high nitrite concentration are the most likely cause of elevated NO and N2O emission by ammonia-oxidizing bacteria. The emission was compared with measurements at other reject water technologies and with the main line of the Dokhaven-Sluisjesdijk WWTP. The N2O emission levels in the reject water treatment seem to be in the same range as for the main stream of activated sludge processes. Preliminary measurements of the N2O emission from a one-reactor nitritation-anammox system indicate that the emission is lower than in two-reactor systems.     

Nitrous oxide generation in full-scale biological nutrient removal wastewater treatment plants

International guidance for estimating emissions of the greenhouse gas, nitrous oxide (N₂O), from biological nutrient removal (BNR) wastewater systems is presently inadequate. This study has adopted a rigorous mass balance approach to provide comprehensive N₂O emission and formation results from seven full-scale BNR wastewater treatment plants (WWTP). N₂O formation was shown to be always positive, yet highly variable across the seven plants. The calculated range of N₂O generation was 0.006-0.253 kgN₂O-N per kgN denitrified (average: 0.035 ± 0.027). This paper investigated the possible mechanisms of N₂O formation, rather than the locality of emissions. Higher N₂O generation was shown to generally correspond with higher nitrite concentrations, but with many competing and parallel nitrogen transformation reactions occurring, it was very difficult to clearly identify the predominant mechanism of N₂O production. The WWTPs designed and operated for low effluent TN (i.e. <10 mgN L⁻¹) had lower and less variable N₂O generation factors than plants that only achieved partial denitrification.     

Nitrous oxide emissions from secondary activated sludge in nitrifying conditions of urban wastewater treatment plants: effect of oxygenation level

In order to better understand the mechanisms of N(2)O emissions from nitrifying activated sludge of urban WWTPs, sludge from the Valenton plant (Paris conurbation) are subjected to lab-scale batch experiments under various conditions of oxygenation. The results show that the highest N(2)O emissions (7.1 microgN-N(2)OgSS(-1) h(-1) in average) occur at a dissolved oxygen (DO) concentration of around 1mgO(2)L(-1). These high emissions at low oxygenation (from 0.1 to 2 mg O(2)L(-1)) are due to two processes: autotrophic nitrifier denitrification and heterotrophic denitrification. Nitrifier denitrification always dominates, representing from 58% to 83% of the N(2)O production. This N(2)O production originating from nitrifying activated sludge becomes 8 times higher when nitrite is added at a DO of 1 mg O(2)L(-1); a decrease is observed both at higher and lower oxygenation. Heterotrophic denitrification represents less than 50% of the N(2)O production, decreasing from 42% to 17% when oxygenation increases from 0.1 to 2 mg O(2) L(-1). We show that ammonium oxidizing bacteria (AOB) can shift to nitrifier denitrification when oxygen is depleted in the environments including in the WWTPs, nitrite then plays the role of oxygen as the final electron acceptor. As opposed to what happens in nitrification, the end products of nitrifier denitrification are gaseous forms of nitrogen, where N(2)O is not negligible compared to N(2). Overall, N(2)O emissions represent 0.1-0.4% of oxidized NH(4)(+), depending on the oxygenation level. N(2)O emissions would range from 0.11 to 0.42 TN-N(2)O day(-1) for a tertiary treatment of the Paris wastewater effluents, consisting exclusively of activated sludge nitrification.     

Nitrous oxide production kinetics during nitrate reduction in river sediments

A significant amount of nitrogen entering river basins is denitrified in riparian zones. The aim of this study was to evaluate the influence of nitrate and carbon concentrations on the kinetic parameters of nitrate reduction as well as nitrous oxide emissions in river sediments in a tributary of the Marne (the Seine basin, France). In order to determine these rates, we used flow-through reactors (FTRs) and slurry incubations; flow-through reactors allow determination of rates on intact sediment slices under controlled conditions compared to sediment homogenization in the often used slurry technique. Maximum nitrate reduction rates (R_m) ranged between 3.0 and 7.1 μg N g⁻¹ h⁻¹, and affinity constant (K_m) ranged from 7.4 to 30.7 mg N-NO₃⁻ L⁻¹. These values were higher in slurry incubations with an R_m of 37.9 μg N g⁻¹ h⁻¹ and a K_m of 104 mg N-NO₃⁻ L⁻¹. Nitrous oxide production rates did not follow Michaelis-Menten kinetics, and we deduced a rate constant with an average of 0.7 and 5.4 ng N g⁻¹ h⁻¹ for FTR and slurry experiments respectively. The addition of carbon (as acetate) showed that carbon was not limiting nitrate reduction rates in these sediments. Similar rates were obtained for FTR and slurries with carbon addition, confirming the hypothesis that homogenization increases rates due to release of and increasing access to carbon in slurries. Nitrous oxide production rates in FTR with carbon additions were low and represented less than 0.01% of the nitrate reduction rates and were even negligible in slurries. Maximum nitrate reduction rates revealed seasonality with high potential rates in fall and winter and low rates in late spring and summer. Under optimal conditions (anoxia, non-limiting nitrate and carbon), nitrous oxide emission rates were low, but significant (0.01% of the nitrate reduction rates).     

Methane emission during municipal wastewater treatment

Municipal wastewater treatment plants emit methane. Since methane is a potent greenhouse gas that contributes to climate change, the abatement of the emission is necessary to achieve a more sustainable urban water management. This requires thorough knowledge of the amount of methane that is emitted from a plant, but also of the possible sources and sinks of methane on the plant. In this study, the methane emission from a full-scale municipal wastewater facility with sludge digestion was evaluated during one year. At this plant the contribution of methane emissions to the greenhouse gas footprint were slightly higher than the CO₂ emissions related to direct and indirect fossil fuel consumption for energy requirements. By setting up mass balances over the different unit processes, it could be established that three quarters of the total methane emission originated from the anaerobic digestion of primary and secondary sludge. This amount exceeded the carbon dioxide emission that was avoided by utilizing the biogas. About 80% of the methane entering the activated sludge reactor was biologically oxidized. This knowledge led to the identification of possible measures for the abatement of the methane emission.     

Nitrous oxide emissions for early warning of biological nitrification failure in activated sludge

Experiments were carried out to establish whether nitrous oxide (N₂O) could be used as a non-invasive early warning indicator for nitrification failure. Eight experiments were undertaken; duplicate shocks DO depletion, influent ammonia increases, allylthiourea (ATU) shocks and sodium azide (NaN₃) shocks were conducted on a pilot-scale activated sludge plant which consisted of a 315 L completely mixed aeration tank and 100 L clarifier. The process performed well during pre-shock stable operation; ammonia removals were up to 97.8% and N₂O emissions were of low variability (<0.5 ppm). However, toxic shock loads produced an N₂O response of a rise in off-gas concentrations ranging from 16.5 to 186.3 ppm, followed by a lag-time ranging from 3 to 5 h ((0.43-0.71) × HRT) of increased NH₃-N and/or NO₂⁻ in the effluent ranging from 3.4 to 41.2 mg L⁻¹. It is this lag-time that provides the early warning for process failure, thus mitigating action can be taken to avoid nitrogen contamination of receiving waters.     

Predicting odour emissions from wastewater treatment plants by means of odour emission factors

In this study, the results of odour concentration measurements on different wastewater treatment plants are presented and used in order to estimate the odour emission factors relevant to single odour sources. An odour emission factor is a representative value that relates the quantity of odour released to the atmosphere to a specific activity index, which in this case was the plant treatment capacity, resulting in an odour emission factor expressed in odour units per cubic metre of treated sewage. The results show that the major odour source of a wastewater treatment plant is represented by the primary sedimentation (with an OEF equal to 1.9 × 10⁵ ou_E m⁻³). In general, the highest OEFs are observed in correspondence of the first steps of the wastewater depuration cycle (OEF between 1.1 × 10⁴ ou_E m⁻³ and 1.9 × 10⁵ ou_E m⁻³) and tend to decrease along the depuration process (OEF between 7.4 × 10³ ou_E m⁻³ and 4.3 × 10⁴ ou_E m⁻³). In general, the OEFs calculated according to this approach represent a model for a rough prediction of odour emissions independently from the specific characteristics of the different plants.     

DNA microarray detection of nitrifying bacterial 16S rRNA in wastewater treatment plant samples

A small scale DNA microarray containing a set of oligonucleotide probes targeting the 16S rRNAs of several groups of nitrifying bacteria was developed for the monitoring of wastewater treatment plant samples. The microarray was tested using reference rRNAs from pure cultures of nitrifying bacteria. Characterization of samples collected from an industrial wastewater treatment facility demonstrated that nitrifying bacteria could be detected directly by microarray hybridization without the need for PCR amplification. Specifically, the microarray detected Nitrosomonas spp. but did not detect Nitrobacter. The specificity and sensitivity of direct detection was evaluated using on-chip dissociation analysis, and by two independent analyses--an established membrane hybridization format and terminal restriction fragment length polymorphism fingerprinting (T-RFLP). The latter two analyses also revealed Nitrospira and Nitrobacter to be contributing populations in the treatment plant samples. The application of DNA microarrays to wastewater treatment systems, which has been demonstrated in the current work, should offer improved monitoring capabilities and process control for treatment systems, which are susceptible to periodic failures.     

Impact of process design on greenhouse gas (GHG) generation by wastewater treatment plants

The overall on-site and off-site greenhouse gas emissions by wastewater treatment plants (WWTPs) of food processing industry were estimated by using an elaborate mathematical model. Three different types of treatment processes including aerobic, anaerobic and hybrid anaerobic/aerobic processes were examined in this study. The overall on-site emissions were 1952, 1992, and 2435 kg CO₂e/d while the off-site emissions were 1313, 4631, and 5205 kg CO₂e/d for the aerobic, anaerobic and hybrid treatment systems, respectively, when treating a wastewater at 2000 kg BOD/d. The on-site biological processes made the highest contribution to GHG emissions in the aerobic treatment system while the highest emissions in anaerobic and hybrid treatment systems were obtained by off-site GHG emissions, mainly due to on-site material usage. Biogas recovery and reuse as fuel cover the total energy needs of the treatment plants for aeration, heating and electricity for all three types of operations, and considerably reduce GHG emissions by 512, 673, and 988 kg CO₂e/d from a total of 3265, 6625, and 7640 kg CO₂e/d for aerobic, anaerobic, and hybrid treatment systems, respectively. Considering the off-site GHG emissions, aerobic treatment is the least GHG producing type of treatment contrary to what has been reported in the literature.     

Mechanisms of N2O production in biological wastewater treatment under nitrifying and denitrifying conditions

Nitrous oxide (N₂O) is an important greenhouse gas and a major sink for stratospheric ozone. In biological wastewater treatment, microbial processes such as autotrophic nitrification and heterotrophic denitrification have been identified as major sources; however, the underlying pathways remain unclear. In this study, the mechanisms of N₂O production were investigated in a laboratory batch-scale system with activated sludge for treating municipal wastewater. This relatively complex mixed population system is well representative for full-scale activated sludge treatment under nitrifying and denitrifying conditions.Under aerobic conditions, the addition of nitrite resulted in strongly nitrite-dependent N₂O production, mainly by nitrifier denitrification of ammonia-oxidizing bacteria (AOB). Furthermore, N₂O is produced via hydroxylamine oxidation, as has been shown by the addition of hydroxylamine. In both sets of experiments, N₂O production was highest at the beginning of the experiment, then decreased continuously and ceased when the substrate (nitrite, hydroxylamine) had been completely consumed. In ammonia oxidation experiments, N₂O peaked at the beginning of the experiment when the nitrite concentration was lowest. This indicates that N₂O production via hydroxylamine oxidation is favored at high ammonia and low nitrite concentrations, and in combination with a high metabolic activity of ammonia-oxidizing bacteria (at 2 to 3 mgO₂/l); the contribution of nitrifier denitrification by AOB increased at higher nitrite and lower ammonia concentrations towards the end of the experiment.Under anoxic conditions, nitrate reducing experiments confirmed that N₂O emission is low under optimal growth conditions for heterotrophic denitrifiers (e.g. no oxygen input and no limitation of readily biodegradable organic carbon). However, N₂O and nitric oxide (NO) production rates increased significantly in the presence of nitrite or low dissolved oxygen concentrations.     

Greenhouse gas production: a comparison between aerobic and anaerobic wastewater treatment technology

Anaerobic wastewater treatment offers improved energy conservation with potential reduction in greenhouse gas emissions. Pitfalls exist in that the methane produced in anaerobic treatment can offset any reductions in carbon dioxide emissions, if it is released to the environment. This paper analyzes greenhouse gas emissions from both aerobic and anaerobic treatment systems, including sludge digestion and the losses of dissolved methane in digested biosolids and process effluents. There exists cross over points, ranging from 300 to 700 mg/L influent wastewater BODu, which are functions of the efficiency of the aerobic treatment system. Anaerobic treatment becomes favorable when treating influents higher in concentrations than the cross over values. A technology to recover dissolved methane would make anaerobic treatment favorable at nearly all influent strengths.     

Moisture effects on greenhouse gases generation in nitrifying gas-phase compost biofilters

Gas-phase compost biofilters are extensively used in concentrated animal feeding operations to remove odors and, in some cases, ammonia from air sources. The expected biochemical pathway for these predominantly aerobic systems is nitrification. However, non-uniform media with low oxygen levels can shift biofilter microbial pathways to denitrification, a source of greenhouse gases. Several factors contribute to the formation of anoxic/anaerobic zones: media aging, media and particle structure, air velocity distribution, compaction, biofilm thickness, and moisture content (MC) distribution. The present work studies the effects of media moisture conditions on ammonia (NH₃) removal and greenhouse gas generation (nitrous oxide, N₂O and methane, CH₄) for gas-phase compost biofilters subject to a 100-day controlled drying process. Continuous recordings were made for the three gases and water vapor (2.21-h sampling cycle, each cycle consisted of three gas species, and water vapor, for a total of 10,050 data points). Media moisture conditions were classified into three corresponding media drying rate (DR) stages: Constant DR (wetter media), falling DR, and stable-dry system. The first-half of the constant DR period (0-750 h; MC = 65-52%, w.b.) facilitated high NH₃ removal rates, but higher N₂O generation and no CH₄ generation. At the drier stages of the constant DR (750-950 h; MC = 52-48%, w.b.) NH₃ removal remained high but N₂O net generation decreased to near zero. In the falling DR stage (1200-1480 h; MC = 44-13%) N₂O generation decreased, CH₄ increased, and NH₃ was no longer removed. No ammonia removal or greenhouse gas generation was observed in the stable-dry system (1500-2500 h; MC = 13%). These results indicate that media should remain toward the drier region of the constant DR (in close proximity to the falling DR stage; MC = 50%, approx.), to maintain high levels of NH₃ removal, reduced levels of N₂O generation, and nullify levels of CH₄ generation.     

Identifying key sources of uncertainty in the modelling of greenhouse gas emissions from wastewater treatment

This study investigates sources of uncertainty in the modelling of greenhouse gas emissions from wastewater treatment, through the use of local and global sensitivity analysis tools, and contributes to an in-depth understanding of wastewater treatment modelling by revealing critical parameters and parameter interactions. One-factor-at-a-time sensitivity analysis is used to screen model parameters and identify those with significant individual effects on three performance indicators: total greenhouse gas emissions, effluent quality and operational cost. Sobol's method enables identification of parameters with significant higher order effects and of particular parameter pairs to which model outputs are sensitive. Use of a variance-based global sensitivity analysis tool to investigate parameter interactions enables identification of important parameters not revealed in one-factor-at-a-time sensitivity analysis. These interaction effects have not been considered in previous studies and thus provide a better understanding wastewater treatment plant model characterisation. It was found that uncertainty in modelled nitrous oxide emissions is the primary contributor to uncertainty in total greenhouse gas emissions, due largely to the interaction effects of three nitrogen conversion modelling parameters. The higher order effects of these parameters are also shown to be a key source of uncertainty in effluent quality.     

Long term partial nitritation of anaerobically treated black water and the emission of nitrous oxide

Black water (toilet water) contains half the load of organic material and the major fraction of the nutrients nitrogen and phosphorus in a household and is 25 times more concentrated, when collected with a vacuum toilet, than the total wastewater stream from a Dutch household. This research focuses on the partial nitritation of anaerobically treated black water to produce an effluent suitable to feed to the anammox process. Successful partial nitritation was achieved at 34 °C and 25 °C and for a long period (almost 400 days in the second period at 25 °C) without strict process control a stable effluent at a ratio of 1.3 NO₂-N/NH₄-N was produced which is suitable to feed to the anammox process. Nitrite oxidizers were successfully outcompeted due to inhibition by free ammonia and nitrous acid and due to fluctuating conditions in SRT (1.0-17 days) and pH (from 6.3 to 7.7) in the reactor. Microbial analysis of the sludge confirmed the presence of mainly ammonium oxidizers. The emission of nitrous oxide (N₂O) is of growing concern and it corresponded to 0.6-2.6% (average 1.9%) of the total nitrogen load.     

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 (¹³C and ¹⁴C) 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.     

Particulate-biofilm, expanded-bed technology for high-rate, low-cost wastewater treatment: nitrification

The performance of a particulate-biofilm, expanded-bed process for nitrification of activated sludge final effluent (ASFE) is reported for a plant receiving mixed industrial and domestic wastewater. The support material for the particulate-biofilms was glassy coke, to which the nitrifying bacteria attached and formed a highly active biofilm. An average nitrification rate of 1.7+/-0.6 kg m(expanded bed)(-3)d(-1) was recorded during operation of the bioreactor, which had a hydraulic residence time of 15 min. On average, the ASFE contained 12.6+/-3.7 g m(-3) NH3-N, which was reduced to 2.6+/-3.3 g m(-3) NH3-N. Furthermore, transfer of 10-12% of the oxygen in air was achieved using counter-current aeration. This investigation has demonstrated that a high rate of nitrification can be achieved with a particulate-biofilm, expanded-bed process. It has also demonstrated that the process can operate without backwashing and still remove particulate material from the ASFE feed.     

Effects of selected pharmaceutically active compounds on treatment performance in sequencing batch reactors mimicking wastewater treatment plants operations

The impact of four pharmaceutically active compounds (PhACs) introduced both individually and in mixtures was ascertained on the performance of laboratory-scale wastewater treatment sequencing batch reactors (SBRs). When introduced individually at concentrations of 0.1, 1 and 10 μM, no significant differences were observed with respect to chemical oxygen demand (COD) and ammonia removal. Microbial community analyses reveal that although similarity index values generally decreased over time with an increase in PhAC concentrations as compared to the controls, no major microbial community shifts were observed for total bacteria and ammonia-oxidizing bacteria (AOB) communities. However, when some PhACs were introduced in mixtures, they were found to both inhibit nitrification and alter AOB community structure. Ammonia removal decreased by up to 45% in the presence of 0.25 μM gemfibrozil and 0.75 μM naproxen. PhAC mixtures did not however affect COD removal performance suggesting that heterotrophic bacteria are more robust to PhACs than AOB. These results highlight that the joint action of PhACs in mixtures may have significantly different effects on nitrification than the individual PhACs. This phenomenon should be further investigated with a wider range of PhACs so that toxicity effects can more accurately be predicted.     

Occurrence, partition and removal of pharmaceuticals in sewage water and sludge during wastewater treatment

During 8 sampling campaigns carried out over a period of two years, 72 samples, including influent and effluent wastewater, and sludge samples from three conventional wastewater treatment plants (WWTPs), were analyzed to assess the occurrence and fate of 43 pharmaceutical compounds. The selected pharmaceuticals belong to different therapeutic classes, i.e. non-steroidal anti-inflammatory drugs, lipid modifying agents (fibrates and statins), psychiatric drugs (benzodiazepine derivative drugs and antiepileptics), histamine H2-receptor antagonists, antibacterials for systemic use, beta blocking agents, beta-agonists, diuretics, angiotensin converting enzyme (ACE) inhibitors and anti-diabetics. The obtained results showed the presence of 32 target compounds in wastewater influent and 29 in effluent, in concentrations ranging from low ng/L to a few μg/L (e.g. NSAIDs). The analysis of sludge samples showed that 21 pharmaceuticals accumulated in sewage sludge from all three WWTPs in concentrations up to 100 ng/g. This indicates that even good removal rates obtained in aqueous phase (i.e. comparison of influent and effluent wastewater concentrations) do not imply degradation to the same extent. For this reason, the overall removal was estimated as a sum of all the losses of a parent compound produces by different mechanisms of chemical and physical transformation, biodegradation and sorption to solid matter. The target compounds showed very different removal rates and no logical pattern in behaviour even if they belong to the same therapeutic groups. What is clear is that the elimination of most of the substances is incomplete and improvements of the wastewater treatment and subsequent treatments of the produced sludge are required to prevent the introduction of these micro-pollutants in the environment.