Synergies from off-gas analysis and mass balances for wastewater treatment - Some personal reflections on our experiences.

Looking back at over a decade of research by herself and her group, the author advocates the added value of gas phase measurements and the application of mass balances, as well as the synergetic benefits obtained when combining both. The increased application of off-gas measurements for greenhouse gas emission monitoring offers a great opportunity to look at other components in the gas phase, particularly oxygen. Mass balances should not be strictly reserved for modellers but also prove useful while conducting lab experiments and studying full-scale measurement data. Combining off-gas measurements with mass balances may serve not only to quantify greenhouse gas emission factors and aeration efficiency but also to follow dynamic concentration profiles of dissolved components without dedicated sensors and/or to calculate other unmeasured variables. Mass-balance-based data reconciliation allows for obtaining reliable and accurate data, and even more when combined with off-gas analysis.

Impact of primary treatment methods on sludge characteristics and digestibility, and wastewater treatment plant-wide economics.

Biogas production from anaerobic sludge digestion plays a central role for wastewater treatment plants to become more energy-efficient or even energy-neutral. Dedicated configurations have been developed to maximize the diversion of soluble and suspended organic matter to sludge streams for energy production through anaerobic digestion, such as A-stage treatment or chemically enhanced primary treatment (CEPT) instead of primary clarifiers. Still, it remains to be investigated to what extent these different treatment steps affect the sludge characteristics and digestibility, which may also impact the economic feasibility of the integrated systems. In this study, a detailed characterization has been performed for sludge obtained from primary clarification (primary sludge), A-stage treatment (A-sludge) and CEPT. The characteristics of all sludges differed significantly from each other. The organic compounds in primary sludge consisted mainly of 40% of carbohydrates, 23% of lipids, and 21% of proteins. A-sludge was characterized by a high amount of proteins (40%) and a moderate amount of carbohydrates (23%), and lipids (16%), while in CEPT sludge, organic compounds were mainly 26% of proteins, 18% of carbohydrates, 18% of lignin, and 12% of lipids. The highest methane yield was obtained from anaerobic digestion of primary sludge (347 ± 16 mL CH4/g VS) and A-sludge (333 ± 6 mL CH4/g VS), while it was lower for CEPT sludge (245 ± 5 mL CH4/g VS). Furthermore, an economic evaluation has been carried out for the three systems, considering energy consumption and recovery, as well as effluent quality and chemical costs. Energy consumption of A-stage was the highest among the three configurations due to aeration energy demand, while CEPT had the highest operational costs due to chemical use. Energy surplus was the highest by the use of CEPT, resulting from the highest fraction of recovered organic matter. By considering the effluent quality of the three systems, CEPT had the highest benefits, followed by A-stage. Integration of CEPT or A-stage, instead of primary clarification in existing wastewater treatment plants, would potentially improve the effluent quality and energy recovery.

Life Cycle Environmental Impacts of Wastewater-Derived Phosphorus Products: An Agricultural End-User Perspective.

Recovering phosphorus from wastewater in more concentrated forms has potential to sustainably recirculate phosphorus from cities to agriculture. The environmental sustainability of wastewater-based phosphorus recovery processes or wastewater-derived phosphorus products can be evaluated using life cycle assessment (LCA). Many LCA studies used a process perspective to account for the impacts of integrating phosphorus recovery processes at wastewater treatment plants, while some used a product perspective to assess the impacts of producing wastewater-derived phosphorus products. We demonstrated the application of an end-user perspective by assessing life cycle environmental impacts of substituting half of the conventional phosphorus rock-based fertilizers used in three crop production systems with wastewater-derived phosphorus products from six recovery pathways (RPs). The consequential LCA results show that the substitution reduces global warming potential, eutrophication potential, ecotoxicity potential, and acidification potential of the assessed crop production systems in most RPs and scenarios. The end-user perspective introduced in this study can (i) complement with the process perspective and the product perspective to give a more holistic picture of environmental impacts along the "circular economy value chains" of wastewater-based resource recovery, (ii) enable systemwide assessment of wide uptake of wastewater-derived products, and (iii) draw attention to understanding the long-term environmental impacts of using wastewater-derived products.

Mainstream short-cut N removal modelling: current status and perspectives.

This work gives an overview of the state-of-the-art in modelling of short-cut processes for nitrogen removal in mainstream wastewater treatment and presents future perspectives for directing research efforts in line with the needs of practice. The modelling status for deammonification (i.e., anammox-based) and nitrite-shunt processes is presented with its challenges and limitations. The importance of mathematical models for considering N2O emissions in the design and operation of short-cut nitrogen removal processes is considered as well. Modelling goals and potential benefits are presented and the needs for new and more advanced approaches are identified. Overall, this contribution presents how existing and future mathematical models can accelerate successful full-scale mainstream short-cut nitrogen removal applications.

Primary and A-sludge treatment by anaerobic membrane bioreactors in view of energy-positive wastewater treatment plants.

Energy-rich sludge can be obtained from primary clarifiers preceding biological reactors. Alternatively, the incoming wastewater can be sent to a very-high-loaded activated sludge system, i.e., a so-called A-stage. However, the effects of applying an A-stage instead of a primary clarifier, on the subsequent sludge digestion for long-term operation is still unknown. In this study, biogas production and permeate quality, and filterability characteristics were investigated in a lab-scale anaerobic membrane bioreactor for primary sludge and A-stage sludge (A-sludge) treatment. A higher specific methane yield was obtained from digestion of A-sludge compared to primary sludge. Similarly, specific methanogenic activity was higher when the anaerobic membrane bioreactor was fed with A-sludge compared to primary sludge. Plant-wide mass balance analysis indicated that about 35% of the organic matter in wastewater was recovered as methane by including an A-stage, compared to about 20% with a primary clarifier.

Dynamic modelling of N2 O emissions from a full-scale granular sludge partial nitritation-anammox reactor.

Partial nitration-anammox is a resource-efficient pathway for nitrogen removal from wastewater. However, the advantages of this nitrogen removal technology may be counter-acted by the emission of N2 O, a potent greenhouse gas. In this study, mathematical modelling was applied to analyse N2 O formation and emission dynamics and to develop N2 O mitigation strategies for a one-stage partial nitritation-anammox granular sludge reactor. Dynamic model calibration for such a full-scale reactor was performed, applying a one-dimensional biofilm model and including several N2 O formation pathways. Simultaneous calibration of liquid phase concentrations and N2 O emissions leads to improved model fit compared to their consecutive calibration. The model could quantitatively predict the average N2 O emissions and qualitatively characterize the N2 O dynamics, adjusting only seven parameter values. The model was validated with N2 O data from an independent data set at different aeration conditions. Nitrifier nitrification was identified as the dominating N2 O formation pathway. Off-gas recirculation as a potential N2 O emission reduction strategy was tested by simulation and showed indeed some improvement, be it at the cost of higher aeration energy consumption.

Unaerated feeding alters the fate of dissolved methane during aerobic wastewater treatment.

In municipal wastewater treatment plants, some dissolved methane can enter the aerobic bioreactors. This greenhouse gas originates from sewers and return flows from anaerobic sludge treatment. In well-mixed conventional activated sludge reactors, methane emissions are largely avoided because methane oxidizing bacteria consume a large fraction, even without optimizing for this purpose. In this work, the fate of dissolved methane is studied in aerobic granular sludge reactors, as they become increasingly popular. The influence of the characteristic design and operating conditions of these reactors are studied with a mathematical model with apparent conversion kinetics and stripping: the separation of feeding and aeration in time, a higher substrate transport resistance, a high retention time of granular biomass and a taller water column. Even for a best-case scenario combining an unrealistically low intragranule substrate transport resistance, a high retention time, a tall reactor, an extremely high influent methane concentration and no oxygen limitation, the methane conversion efficiency was only 12% when feeding and aeration were separated in time, which is lower than for continuous activated sludge reactors under typical conditions. A more rigorous model was used to confirm the limited conversion, considering the multi-species and multi-substrate biofilm kinetics, anoxic methane consumers and the high substrate concentration at the bottom during upward plug flow feeding. The observed limited methane conversion is mainly due to the high concentration that accumulates during unaerated feeding phases, which favours stripping more than conversion in the subsequent aeration phase. Based on these findings, strategies were proposed to mitigate methane emissions from wastewater treatment plants with sequentially operated reactors.

Impact of organics, aeration and flocs on N2O emissions during granular-based partial nitritation-anammox.

Partial nitration-anammox is a resource-efficient technology for nitrogen removal from wastewater. However, the advantages of this nitrogen removal technology are challenged by the emission of N2O, a potent greenhouse gas. In this study, a granular sludge one-stage partial nitritation-anammox reactor comprising granules and flocs was run for 337 days in the presence of influent organics to investigate its effect on N removal and N2O emissions. Besides, the effect of aeration control strategies and flocs removal was investigated as well. The interpretation of the experimental results was complemented with modelling and simulation. The presence of influent organics (1 g COD g-1 N) helped to suppress NOB and significantly reduced the overall N2O emissions while having no significant effect on anammox activity. Besides, long-term monitoring of the reactor indicated that constant airflow rate control resulted in more stable effluent quality and less N2O emissions than DO control. Still, floc removal reduced N2O emissions at DO control but increased N2O emissions at constant airflow rate. Furthermore, anammox bacteria could significantly reduce N2O production during heterotrophic denitrification, likely via competition for NO with heterotrophs. Overall, this study demonstrated that the presence of influent organics together with proper aeration control strategies and floc management could significantly reduce the N2O emissions without compromising nitrogen removal efficiency during one-stage partial nitritation-anammox processes.

Potential of off-gas analyses for sequentially operated reactors demonstrated on full-scale aerobic granular sludge technology.

This work shows how more variables can be monitored with a single off-gas sampler on sequentially operated than on continuously fed and aerated reactors and applies the methods to data from a full-scale aerobic granular sludge reactor as a demonstration and to obtain insight in this technology. First, liquid-gas transfer rates were calculated. Oxygen (O2) absorption and carbon dioxide (CO2) emission rates showed comparable cyclic trends due to the coupling of O2 consumption and CO2 production. Methane (CH4) emissions showed a stripping profile and nitrous oxide (N2O) emissions showed two peaks each cycle, which were attributed to different production pathways. Secondly, aeration characteristics were calculated, of which the gradual improvement within cycles was explained by surfactants degradation. Thirdly, liquid phase concentrations were estimated from off-gas measurements via a novel calculation procedure. As such, an average influent CH4 concentration of 0.7 g·m-3 was found. Fourthly, reaction rates could be estimated from off-gas data because no feeding or discharge occurred during reaction phases. The O2 consumption rate increased with increasing dissolved oxygen and decreased once nitrification was complete. Fifthly, greenhouse gas emissions could be derived, indicating a 0.06% N2O emission factor. Sixthly, off-gas gave an indication of influent characteristics. The CO2 emitted per kg COD catabolized corresponded with the TOC/COD ratio of typical wastewater organics in cycles with balanced nitrification and denitrification. High nitrogen removal efficiencies were associated with high catabolized COD/N ratios as estimated from the O2 absorption. Finally, mass balances could be closed using off-gas O2 data. As such, an observed yield of 0.27 g COD/g COD was found. All these variables could be estimated with a single sampler because aeration without feeding creates a more homogeneous off-gas composition and simplifies liquid-phase mass balances. Therefore, off-gas analyzers may have a broader application potential for sequentially operated reactors than currently acknowledged.

Ammonium-based aeration control improves nitrogen removal efficiency and reduces N2O emissions for partial nitritation-anammox reactors.

This study deals with the effect of aeration control strategies on the nitrogen removal efficiency and nitrous oxide (N2O) emissions in a partial nitritation-anammox reactor with granular sludge. More specifically, dissolved oxygen (DO) control, constant airflow and effluent ammonium (NH4+) control strategies were compared through a simulation study. Particular attention was paid to the effect of flocs, which are deliberately or unavoidable present besides granules in this type of reactor. When applying DO control, DO setpoints had to be adjusted to the amount of flocs present in the reactor to maintain high nitrogen removal and reduce N2O emissions, which is difficult to realize in practice because of variable floc fractions. Constant airflow rate control could maintain a good nitrogen removal efficiency independent of the floc fraction in the reactor, but failed in N2O mitigation. Controlling aeration based on the effluent ammonium concentration results in both high nitrogen removal and relatively low N2O emissions, also in the presence of flocs. Fluctuations in floc fractions caused significant upsets in nitrogen removal and N2O emissions under DO control but had less effect at constant airflow and effluent ammonium control. Still, rapid and sharp drops in flocs led to a peak in N2O emissions at constant airflow and effluent ammonium control. Overall, effluent ammonium control reached the highest average nitrogen removal and lowest N2O emissions and consumed the lowest aeration energy under fluctuating floc concentrations.

Elucidating the Competition between Heterotrophic Denitrification and DNRA Using the Resource-Ratio Theory.

Heterotrophic denitrification and dissimilatory nitrate reduction to ammonium (DNRA) are two microbial processes competing for two shared resources, namely, nitrate and organic carbon (COD). Their competition has great implications for nitrogen loss, conservation, and greenhouse gas emissions. Nevertheless, a comprehensive and mechanistic understanding of the governing factors for this competition is still lacking. We applied the resource-ratio theory to study this competition and validated the theory with experimental data from continuous cultures reported in the literature. Based on this theory, we revealed that influent COD/N ratio alone was not sufficient to predict the competition outcome as the boundary values for different competition outcomes changed substantially with influent resource concentrations. The stoichiometry of the two processes was determinative for the boundaries, whereas the affinity for the shared resources (KS), maximum specific growth rate (µmax) of the two species, and the dilution rate had significant impacts as well but mainly at low influent resource concentrations (e.g., <100 µM nitrate). The presented approach allows for a more comprehensive understanding of the parameters controlling microbial competition. The computational comparison between continuous and batch cultures could explain seemingly conflicting experimental results as to the impact of the COD/N ratio. The results also include testable hypotheses and tools for understanding and managing the fate of nitrate in ecosystems, which could also be applied more widely to other species competing for two shared resources.

When and why do gradients of the gas phase composition and pressure affect liquid-gas transfer?

Gas bubbles are introduced in water to absorb or strip volatile substances in a variety of unit operations, for example during (waste)water treatment. To calculate the transfer rate of substances between the liquid phase and the gas phase, different assumptions have been made in literature regarding the gas phase composition and hydraulic pressure, which both vary along the reactor height. In this study, analytical expressions were derived for the total (macroscopic) liquid-gas transfer rate, using either the complete gradients of the mole fraction and pressure (comprehensive approach) or a uniform value, for one or both of them. Simulations with the comprehensive model were performed to understand the effect of the type of volatile substance and of the reactor design and operating conditions on the total liquid-gas transfer rate. These effects were found to be highly interactive and often non-linear. Next, the simulation results of the comprehensive model were compared with those from models that assume either a uniform mole fraction or a uniform pressure in the complete reactor volume. This illustrated that for soluble substances, the mole fraction gradient strongly affects the total liquid-gas transfer rate, while the pressure gradient became only important under operating conditions that promote stripping (i.e., for a high concentration in the liquid phase and low concentration in the inlet gas). For very poorly soluble substances, the pressure became more important under conditions that promote absorption. These results on the importance of the mole fraction and pressure gradients remained equally valid when explicitly considering a typical variation of the volumetric overall transfer coefficient (KLa) along the reactor height. Finally, a simple and fast procedure was made available through a spreadsheet to select appropriate simplifying assumptions in reactor or plant-wide models. By applying the procedure to oxygen (O2), carbon dioxide (CO2), methane (CH4), nitrous oxide (N2O) and nitrogen gas (N2) in an aerobic biological wastewater treatment reactor, it was demonstrated that some common simplifications can lead to significant errors, for which corrections were proposed.

Process schemes for future energy-positive water resource recovery facilities.

There are numerous successful studies on optimizing the performance of conventional activated sludge (CAS)-based wastewater treatment plants. However, recent studies have shown that a more significant improvement of the plant performance is achievable through integration of established technologies in novel process schemes. High-rate activated sludge system, chemically enhanced primary treatment, partial nitritation-anammox, partial nitrification-denitrification over nitrite and anaerobic digestion are integrated in two process schemes to determine to which extent energy savings and energy production can be achieved with these new process layouts compared to a CAS-based process scheme. The results presented in this paper show that there is potential for achieving future energy-positive water resource recovery facilities through novel integration of mature technologies for municipal wastewater treatment.

Long-term microbial community dynamics at two full-scale biotrickling filters treating pig house exhaust air.

In this study, the microbial community structure of two full-scale biotrickling filters treating exhaust air from a pig housing facility were evaluated using 16S metabarcoding. The effect of inoculation with activated sludge of a nearby domestic waste water treatment plant was investigated, which is a cheap procedure and easy to apply in practice. The study was performed at a three-stage and a two-stage full-scale biotrickling filter; of which, only the latter was inoculated. Both biotrickling filters evolved towards a rather similar community over time, which differed from the one in the activated sludge used for inoculation. However, the bacterial population at both biotrickling filters showed small differences on the family level. A large population of heterotrophic bacteria, including denitrifying bacteria, was present in both biotrickling filters. In the non-inoculated biotrickling filter, nitrite-oxidizing bacteria (NOB) could not be detected, which corresponded with the incomplete nitrification leading to high nitrite accumulation observed in this system. Inoculation with the wide spectrum inoculum activated sludge had in this study a positive effect on the biotrickling filter performance (higher ammonia removal and lower nitrous oxide production). It could thus be beneficial to inoculate biotrickling filters in order to enrich NOB at the start-up, making it easier to keep the free nitrous acid concentration low enough to not be inhibited by it.

The future of WRRF modelling - outlook and challenges.

The wastewater industry is currently facing dramatic changes, shifting away from energy-intensive wastewater treatment towards low-energy, sustainable technologies capable of achieving energy positive operation and resource recovery. The latter will shift the focus of the wastewater industry to how one could manage and extract resources from the wastewater, as opposed to the conventional paradigm of treatment. Debatable questions arise: can the more complex models be calibrated, or will additional unknowns be introduced? After almost 30 years using well-known International Water Association (IWA) models, should the community move to other components, processes, or model structures like 'black box' models, computational fluid dynamics techniques, etc.? Can new data sources - e.g. on-line sensor data, chemical and molecular analyses, new analytical techniques, off-gas analysis - keep up with the increasing process complexity? Are different methods for data management, data reconciliation, and fault detection mature enough for coping with such a large amount of information? Are the available calibration techniques able to cope with such complex models? This paper describes the thoughts and opinions collected during the closing session of the 6th IWA/WEF Water Resource Recovery Modelling Seminar 2018. It presents a concerted and collective effort by individuals from many different sectors of the wastewater industry to offer past and present insights, as well as an outlook into the future of wastewater modelling.

Modelling anaerobic, aerobic and partial nitritation-anammox granular sludge reactors - A review.

Wastewater treatment processes with granular sludge are compact and are becoming increasingly popular. Interest has been accompanied by the development of mathematical models. This contribution simultaneously reviews available models in the scientific literature for anaerobic, aerobic and partial nitritation-anammox granular sludge reactors because they comprise common phenomena (e.g. liquid, gas and granule transport) and thus pose similar challenges. Many of the publications were found to have no clearly defined goal. The importance of a goal is stressed because it determines the appropriate model complexity and helps other potential users to find a suitable model in the vast amount of literature. Secondly, a wide variety was found in the model features. This review explains the chosen modelling assumptions based on the different reactor types and goals wherever possible, but some assumptions appeared to be habitual within fields of research, without clear reason. We therefore suggest further research to more clearly define the range of operational conditions and goals for which certain simplifying assumptions can be made, e.g. when intragranule solute transport can be lumped in apparent kinetics and when biofilm models are needed, which explicitly calculate substrate concentration gradients inside granules. Furthermore, research is needed to better mechanistically understand detachment, removal of influent particulate matter and changes in the mixing behaviour inside anaerobic systems, before these phenomena can be adequately incorporated in models. Finally, it is suggested to perform full-scale model validation studies for aerobic and anammox reactors. A spreadsheet in the supplementary information provides an overview of the features in the 167 reviewed models.

Final products and kinetics of biochemical and chemical sulfide oxidation under microaerobic conditions.

Hydrogen sulfide is a toxic and usually undesirable by-product of the anaerobic treatment of sulfate-containing wastewater. It can be removed through microaeration, a simple and cost-effective method involving the application of oxygen-limiting conditions (i.e., dissolved oxygen below 0.1 mg L-1). However, the exact transformation pathways of sulfide under microaerobic conditions are still unclear. In this paper, batch experiments were performed to study biochemical and chemical sulfide oxidation under microaerobic conditions. The biochemical experiments were conducted using a strain of Sulfuricurvum kujiense. Under microaerobic conditions, the biochemical sulfide oxidation rate (in mg S L-1 d-1) was approximately 2.5 times faster than the chemical sulfide oxidation rate. Elemental sulfur was the major end-product of both biochemical and chemical sulfide oxidation. During biochemical sulfide oxidation elemental sulfur was in the form of white flakes, while during chemical sulfide oxidation elemental sulfur created a white suspension. Moreover, a mathematical model describing biochemical and chemical sulfide oxidation was developed and calibrated by the experimental results.

Modelling aerobic granular sludge reactors through apparent half-saturation coefficients.

During biological wastewater treatment, substrates undergo simultaneous diffusion and reactions inside microbial aggregates, creating microscale spatial substrate gradients and limiting the macroscale reaction rates. For flocculent and anaerobic granular sludge, this rate-limiting effect of diffusion is often lumped in model parameters, like the half-saturation coefficients of Monod kinetics in activated sludge models (ASM). Yet, an explicit description of the reaction-diffusion process with biofilm models is more common for aerobic granular sludge. This work investigates whether apparent half-saturation coefficients could have applications for aerobic granular sludge as well and examines the implications of this simplification. To this end, the macroscopic reaction rates predicted with a one-dimensional biofilm (1D) model were fitted with Monod kinetics. The results showed that the macroscale rates could indeed be described using apparent kinetics, at the very least over a time scale where the microbial population distribution stays fixed. However, the coefficients were sensitive to changes in the microbial population distribution, which can be affected by long-term changes in operating conditions. Also the activity of organisms that compete for the same substrates affect the parameter value. Be that as it may, apparent kinetics also depend on the operating conditions for flocculent and anaerobic granular sludge, but they have still been used successfully for design and optimization. Therefore, the last section of this work illustrates that they may also have applications for aerobic granular sludge. A simple model for ammonium removal using apparent half-saturation coefficients for oxygen and ammonium is applied to a full-scale reactor, taking advantage of the batch-wise operation and on-line monitoring data for regular recalibration.

Experimental design for evaluating WWTP data by linear mass balances.

A stepwise experimental design procedure to obtain reliable data from wastewater treatment plants (WWTPs) was developed. The proposed procedure aims at determining sets of additional measurements (besides available ones) that guarantee the identifiability of key process variables, which means that their value can be calculated from other, measured variables, based on available constraints in the form of linear mass balances. Among all solutions, i.e. all possible sets of additional measurements allowing the identifiability of all key process variables, the optimal solutions were found taking into account two objectives, namely the accuracy of the identified key variables and the cost of additional measurements. The results of this multi-objective optimization problem were represented in a Pareto-optimal front. The presented procedure was applied to a full-scale WWTP. Detailed analysis of the relation between measurements allowed the determination of groups of overlapping mass balances. Adding measured variables could only serve in identifying key variables that appear in the same group of mass balances. Besides, the application of the experimental design procedure to these individual groups significantly reduced the computational effort in evaluating available measurements and planning additional monitoring campaigns. The proposed procedure is straightforward and can be applied to other WWTPs with or without prior data collection.