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WHAT BUBBLES CAN TELL ABOUT WATER –

CONTROL OF WASTEWATER TREATMENT


BASINS USING OFF-GAS ANALYSES

Wouter Michiels
Student number: 01809314

Promoters: Prof. dr. ir. Eveline Volcke, ir. Janis Baeten


Tutor: ir. Laurence Strubbe

A dissertation submitted to Ghent University in partial fulfilment of the requirements for the degree of
Master of Science in Bioscience Engineering: Chemistry and Bioprocess Technology

Academic year: 2019 – 2020


Deze pagina is niet beschikbaar omdat ze persoonsgegevens bevat.
Universiteitsbibliotheek Gent, 2021.

This page is not available because it contains personal information.


Ghent University, Library, 2021.
Table of contents
Abstract ....................................................................................................................................................... 5
1. Introduction and thesis outline ............................................................................................................... 7
2. Literature review ..................................................................................................................................... 8
2.1. Continuous wastewater treatment systems ................................................................................... 8
2.1.1. Operation and biochemical reactions ..................................................................................... 8
2.1.2. Monitoring and control ........................................................................................................... 9
2.2. Sequencing batch reactors ............................................................................................................ 12
2.2.1. Operation and biochemical reactions ................................................................................... 12
2.2.2. Monitoring and control ......................................................................................................... 14
2.3. Off-gas analysis .............................................................................................................................. 19
2.3.1. Gas-liquid mass transfer principles ....................................................................................... 19
2.3.2. Monitoring ............................................................................................................................. 20
2.4. Conclusions and thesis objectives ................................................................................................. 26
3. Material and methods ........................................................................................................................... 27
3.1. Model description.......................................................................................................................... 27
3.1.1. Biochemical processes and liquid-phase concentrations ...................................................... 27
3.1.2. Speciation model ................................................................................................................... 28
3.1.3. Liquid-gas transfer ................................................................................................................. 29
3.2. Simulations .................................................................................................................................... 30
3.2.1. Reference case....................................................................................................................... 30
3.2.2. Varying influent composition ................................................................................................ 31
4. Results and discussion ........................................................................................................................... 32
4.1. Reference case............................................................................................................................... 32
4.1.1. Liquid phase ........................................................................................................................... 32
4.1.2. Gas phase............................................................................................................................... 33
4.1.3. Endpoint detection ................................................................................................................ 33
4.2. Varying influent compositions ....................................................................................................... 36
4.2.1. Endpoint detection via oxygen off-gas analysis .................................................................... 36
4.2.2. Information derived from off-gas carbon dioxide ................................................................. 41
4.2.3. Endpoint detection via oxygen and carbon dioxide off-gas analysis..................................... 42
4.3. Proposition of control strategy ...................................................................................................... 48
5. Conclusions ............................................................................................................................................ 50
6. Recommendations for further research ................................................................................................ 51
7. References ............................................................................................................................................. 52

3
List of abbreviations
Abbreviation Description
COD Chemical oxygen demand
HLC High N-load controller
LLC Low N-load controller
ORP Oxidation-reduction potential
PAO Phosphate-accumulating organisms
PP Polyphosphate
SBR Sequencing batch reactor
TOC Total organic carbon
VFA Volatile fatty acids
XANO Autotrophic biomass
XOHO Heterotrophic biomass

List of symbols
Symbol Description Units
ṁL−G
A Mass transfer of compound A across liquid-gas interface m.h-1
Ṙ CO2 Carbon dioxide production rate g.h-1
Ṙ O2 Oxygen consumption rate g.h-1
k 𝑃A Mass transfer coefficient of compound A in phase P m.h-1
𝐶𝐴𝑃 Concentration of compound A in phase P g.m-3
𝐶𝐴𝑃∗ Equilibrium concentration of compound A in phase P g.m-3
𝐾A𝑃 Overall mass transfer coefficient of compound A in phase P m.h-1
a Gas-liquid interfacial area per liquid volume m-1
HA Dimensionless Henry’s law constant for A (-)
Q Flow rate m³.h-1
V Volume m³
Vfill Volume added to SBR during fill phase m³
Vmin Remaining volume in SBR after the draw phase m³

List of super- and subscripts


Subscript Description
AE In aerobic reactor
AN In anoxic reactor
SP Setpoint
in Into the reactor
out Out of the reactor
Superscript Description
L Liquid phase
G Gas phase

4
Abstract
Nederlands

Deze thesis gaat over het monitoren en regelen van afvalwaterzuiveringsprocessen op basis van metingen
in de gasfase. Er werden afvalwaterzuiveringsprocessen bestudeerd die als batch systeem opereren, met
als doel de lengte van de aerobe fases te regelen door metingen in het afgas, d.w.z. het gas dat de reactor
verlaat. Meer specifiek werd onderzocht of specifieke vormen in de dynamische profielen van de zuurstof-
en koolstofdioxide-afgasconcentratie kunnen worden gebruikt om het einde van nitrificatie te detecteren
voor verschillend samenstellingen van het influent. Verder werd onderzocht of de lengte van de aerobe
fase met enkel deze metingen kon worden geregeld.

Hiertoe werd een Matlab/Simulink model van een ‘sequencing batch reactor’ gebouwd. Dit model omvat
de verwijdering van nutriënten en organische stoffen, speciatie van koolstofdioxide in de vloeistoffase en
gas-vloeistof masaoverdracht van zuurstof en koolstofdioxide in een batch reactor.

De behandeling van een constant influent werd gesimuleerd en de afgasprofielen werden onderzocht onder
stationaire werking. Het einde van nitrificatie kwam overeen met een plotselinge stijging van de
concentratie zuurstof in het afgas die wiskundig kon worden gedefinieerd als een stijgend buigpunt. Deze
relatie werd onderzocht voor een brede waaier aan influentcomposities die varieerden in concentraties van
ammonium, fosfaat, en organische stoffen. Dit werd gedaan door de automatische detectie van deze vorm
in de simulatieresultaten, en het onderzoek van de ammoniumconcentratie in de reactor op het moment
van detectie. Het einde van de fosfaatopname bleek de detectie bij hoge influentconcentraties aan
organische stoffen te kunnen verstoren.

Om een betrouwbaardere detectie te bereiken, werd naast de zuurstofconcentratie ook rekening gehouden
met de koolstofdioxideconcentratie in het gas. Het einde van nitrificatie leek overeen te komen met een
afnemende koolstofdioxide-afgasconcentratie. Deze informatie werd gebruikt om een nauwkeurigere
detectiemethode te ontwikkelen die het einde van nitrificatie correct kon aangeven bij 98% van de
onderzochte constante influent composities.

Ten slotte werd een strategie voor de controle van de aerobe faselengte op basis van zuurstof- en
kooldioxide-afgasanalyse voorgesteld en gedemonstreerd voor één steady-state cyclus en een
samenstelling met constant influent. De beluchting werd op deze manier beëindigd toen het einde van
nitrificatie werd gedetecteerd, wat resulteerde in zowel een verkorting van de aeratieduur (en dus een
afname van het energieverbruik) als een toename van de behandelingscapaciteit van het systeem met
behoud van de bijna volledige ammoniumverwijdering van de cyclus.

Globaal werd aangetoond dat afgasanalyse van zuurstof en koolstofdioxide in batchprocessen theoretisch
gezien nuttig is voor de detectie van het einde van de nitrificatie voor een breed bereik aan constante
influentcomposities. Dit wijst erop dat deze metingen ook gebruikt kunnen worden voor real-time regeling
van sequencing batch reactors, maar dit moet nog worden aangetoond.

5
English

This thesis focuses on the monitoring and control of wastewater treatment processes based on
measurements in the gas phase. Batch-wisely operated wastewater treatment processes were studied,
aiming to control the length of the aerobic phase by measurements in the off-gas, i.e. the gas leaving the
reactor. More specifically, it was examined whether specific shapes in the dynamic profiles of the oxygen
and carbon dioxide off-gas concentration could be used to detect the end of nitrification over different
influent conditions. Further, it was explored if the aerobic phase length could be controlled using only these
measurements.

To this end, a Matlab/Simulink model of a sequencing batch reactor was built. The model includes the
removal of nutrients and organics, carbon dioxide speciation in the liquid phase and gas-liquid mass transfer
of oxygen and carbon dioxide in a batch reactor.

The treatment of a constant influent was simulated and the off-gas profiles were investigated under steady-
state operation. The end of nitrification corresponded to a sudden rise in oxygen off-gas concentration that
could be mathematically defined as a rising inflection point. This relation was investigated for a wide range
of influent conditions that were varied in the concentration of influent ammonium, phosphate and organics,
by automatic detection of this shape in the simulation results, and the investigation of the ammonium
concentration in the reactor at the time of detection. It was found that the end of phosphate uptake can
interfere with the detection at high influent organics concentrations.

In order to achieve a more reliable detection, the off-gas carbon dioxide concentration was taken into
account in addition to the oxygen concentration. The end of nitrification seemed to correspond to a
decreasing carbon dioxide off-gas concentration. This information was used to develop a more accurate
detection method that was able to correctly indicate the end of nitrification in 98% of the investigated
constant influents.

Finally, an aerobic phase length control strategy based on oxygen and carbon dioxide off-gas analysis was
proposed and demonstrated for one steady-state cycle and a constant influent composition. This way
aeration was ended when the end of nitrification was detected, resulting in both a shortening of aerobic
phase length (and thus a decrease in energy consumption) and an increase in treatment capacity of the
system while retaining the cycle’s near complete ammonium removal.

Overall, it was demonstrated that, theoretically, oxygen and carbon dioxide off-gas analysis in batch
processes can be valuable to detect the end nitrification over a wide range of different constant influent
compositions. This indicates that these measurements could also be used for real-time control of
sequencing batch reactors, although this still remains to be proven.

6
1. Introduction and thesis outline
The activated sludge process is a wastewater treatment process that uses a liquid culture of micro-
organisms which remove nutrients (nitrogen and phosphorus) and organics before discharge in natural
waters, to prevent eutrophication and oxygen depletion. It can be a continuous or a batch-type process,
called a sequencing batch reactor (SBR). In both cases, the complexity of the system and the large variations
in influent flowrate and composition make process control crucial for the proper functioning of a
wastewater treatment plant, which can be defined as the achievement of the imposed effluent quality
norms. Moreover, ever more stringent effluent standards and a larger societal emphasis on energy
efficiency further increase its importance (Olsson et al., 2005). Real-time control is usually performed by
estimating the nutrient concentrations and using this information to adapt some property of the system
(like aeration or liquid flowrate) if necessary. Most measurements to achieve this take place in the
wastewater itself and are either direct (nutrient sensors) or indirect (measurements of other variables, like
oxygen).

Measurements can also take place in the gas leaving the reactor, called off-gas. Off-gas analysis has the
advantage of representing an overall reactor performance, versus the point measurements made by
sensors in the liquid phase. Other advantages versus liquid-phase measurements are simple pre-treatment,
a small maintenance cost and no requirements for chemical reagents (Hellinga et al., 1996). A major
application of off-gas analysis in wastewater treatment is the monitoring of the emission of greenhouse
gases like nitrous oxide (N2O) and methane (CH4). Another application is the analysis of off-gas oxygen
content to determine aeration, and thus energy, efficiency (Redmon et al., 1983; Chandran et al., 2016).

The goal of this thesis is to investigate if oxygen and carbon dioxide off-gas analysis alone can be used to
estimate the ammonium concentration, in order to control the process of nitrification (ammonium
oxidation) in SBRs. This type of system is gaining significance in recent years because of the implementation
of aerobic granular sludge, a new type of activated sludge with a more compact morphology (granules),
where SBR systems are used (Nancharaiah & Reddy, 2018). Because oxygen and carbon dioxide take part
in several biochemical conversion processes, it is reasonable to assume that the oxygen and carbon dioxide
content in the off-gas are influenced by these processes. If process control based on off-gas oxygen and
carbon dioxide measurements alone is possible, one type of measurement, off-gas analysis, could then be
used for a whole range of purposes: control, monitoring of greenhouse gas emissions and the monitoring
of aeration efficiency.

In chapter 1, the general principles of continuous and SBR systems and the applications of off-gas analysis
in wastewater treatment are introduced to the reader. Chapter 3 explains the mathematical model used to
describe the gas-liquid transfer and the removal of organics, nitrogen and phosphorus in an SBR system.
Also, the simulations that were done to investigate if oxygen and carbon dioxide off-gas analysis could
signify the end of nitrification under a wide range of influent conditions are explained. In chapter 4, the
results of these simulations are presented and discussed, and a control strategy based on off-gas
measurements is proposed and tested for a specific case. The final conclusions are given in chapter 5, and
chapter 6 gives some recommendations for further research.

7
2. Literature review
In this chapter, the general principles of wastewater treatment and off-gas analysis are introduced to the
reader. The operation and control of two types of wastewater treatment systems are described: continuous
systems in section 2.1 and sequencing batch reactors in section 2.2. In section 2.3, the theoretical
background and application of off-gas analysis is elaborated, followed by concluding remarks on this
chapter in section 2.4.

2.1. Continuous wastewater treatment systems


Most wastewater treatment systems operate continuously: fresh wastewater is continuously added and
treated wastewater is continuously removed. It is the most common type of wastewater treatment process
that uses activated sludge nowadays (Hreiz et al., 2015). In this section, the first part will explore the basics
of operation and biochemical reactions. Secondly, the monitoring and control of a continuous wastewater
treatment plant will be explained.

2.1.1. Operation and biochemical reactions


The influent wastewater is, after primary treatment (the removal of large materials and of settleable or
floating organic and inorganic solids), mixed with the activated sludge. The water is subsequently led into
an anaerobic, an anoxic and an aerobic zone, followed by a clarifier (Figure 2.1). In these different zones,
different microbial conversions occur (Pell & Wörman, 2008).

Figure 2.1: Typical layout of a continuous wastewater treatment plant with pre-denitrification and enhanced biological phosphorus
removal. All reactions are schematic and not stoichiometrically correct (Pell & Wörman, 2008).

In the aerobic zone, air is bubbled trough the water. Here, heterotrophic bacteria oxidise organic pollutants,
often expressed in units of chemical oxygen demand (COD), to form carbon dioxide and grow extra
heterotrophic biomass (XOHO). In the same compartment, autotrophic nitrifying bacteria oxidise ammonium
to nitrate. New autotrophic biomass (XANO) is also formed, using carbon dioxide as a carbon source. Part of
the water that has passed through the aerobic compartment is recycled to the anoxic zone. Here,
heterotrophic bacteria use nitrate from the recycled stream as an electron acceptor to oxidise the influent
organics during the denitrification reaction. This forms nitrogen gas, carbon dioxide and heterotrophic
biomass. The other part of the water is sent to a clarifier, where the biomass settles. Part of the sludge is
wasted to compensate for the excess biomass growth. The other part is recycled to the anaerobic

8
compartment to maintain a high biomass concentration in the system (Gerba & Pepper, 2015; Pell &
Wörman, 2008).

In the case of biological phosphorus removal, in the anaerobic zone, a specific type of heterotrophs, namely
phosphate-accumulating organisms (PAO), store volatile fatty acids (VFA), such as acetate, intracellularly as
poly-hydroxy-alkanoates (PHA). The energy for this step originates from the breakdown of intracellular
polyphosphate (PP), resulting in the release of phosphate into the water. When the PAO enter the anoxic
and aerobic compartments, they oxidise the stored PHA with nitrate or oxygen respectively as electron
acceptor. Simultaneously, phosphate uptake takes place to replenish the PP store. In this way even more
phosphate is taken up than was released (Pell & Wörman, 2008).

2.1.2. Monitoring and control


A wastewater treatment plant faces extremely large fluctuations in the influent composition and flow rate,
a high complexity of the process and a limited number of manipulatable variables. To keep a constant
effluent concentration with a fluctuating influent, different control strategies can be employed (Olsson et
al., 2005). In the following section, different ways in which continuous wastewater treatment plants can be
controlled are explored. More specifically, the control of aeration, nitrate recycling and the addition of
external COD are elaborated.
2.1.2.1. Aeration control

The control of aeration in a wastewater treatment plant has two main goals. To reduce energy consumption
in a plant, aeration should be minimised. However, enough aeration should be provided to obtain sufficient
removal of ammonium and organics in the aerobic zone. The setpoint for the dissolved oxygen
𝐿
concentration, 𝐶𝑂2 (in g.m-3) is either kept constant, or, is adapted to the amount of oxygen that is needed
at that time (Olsson et al., 2005).

Completely mixed reactor


𝐿
Dissolved oxygen control with a fixed setpoint is performed with a 𝐶𝑂2 sensor in the water and a feedback
𝐿
control loop. An on-off controller can be applied which turns the aeration off whenever the 𝐶𝑂2 level
exceeds a fixed maximum and which turns the aeration back on when it drops below a fixed minimum. PI
𝐿
and PID controllers can also be used. These decrease the aeration rate if the 𝐶𝑂2 is above its setpoint and
𝐿
increase it when it is below its setpoint, aiming to keep it at a constant value. An upper limit for the 𝐶𝑂2
setpoint is advisable, as an increase only has a marginal effect on reaction rates from a certain point, while
more energy is still required. A lower limit is also advisable for the airflow rate to ensure sufficient mixing,
even when the pollutant load is low. The controller sends a signal to a valve or variable speed pump (the
aerator) to alter the air flow rate. This strategy is shown in Figure 2.2 (Olsson et al., 2005; Åmand et al.,
2013).

9
𝐿 𝐿
Figure 2.2: Dissolved oxygen (𝐶𝑂2 ) feedback control with fixed setpoint (𝐶𝑂2,𝑆𝑃 ) and PI controller (Åmand, Olsson and Carlsson,
2013).

𝐿
To adapt the 𝐶𝑂2 setpoint according to the ammonium load, a cascade control system is employed, shown
in Figure 2.3. The master control loop consists of an ammonium sensor of which measured value is
𝐿
compared to a fixed setpoint. The controller action raises the 𝐶𝑂2 setpoint if the measured ammonium
𝐿 𝐿
concentration (𝐶𝑁𝐻4) is higher than the setpoint; if it is less it lowers the 𝐶𝑂2 setpoint. The slave control
𝐿
loop is the same as the one described in the section above, the only difference being the variable 𝐶𝑂2
setpoint (Olsson et al., 2005; Åmand et al., 2013).

Figure 2.3: Cascaded aeration control, with fixed ammonium setpoint (𝐶𝐿𝑁𝐻4,𝑆𝑃 ) (Åmand et al., 2013).

Plug-flow like reactor


To implement aeration control in a plug-flow like reactor, it needs to be divided in several zones. Each zone
L
has its own CO2 (and ammonium) sensor and feedback control mechanism. If the ammonium sensor is
placed near the end of the reactor, it is associated with a lag time; the control action comes too late to
oxidise all the ammonium. Therefore the ammonium sensor is best placed somewhere in the middle, to
allow corrective action at the end of the reactor (Olsson et al., 2005).

2.1.2.2. Nitrate recirculation flow control

Because denitrification is often limited by the availability of COD, the anoxic zone is mostly placed before
the aerobic zone so that the influent organics can be used for denitrification (Ni et al., 2017). In addition to
the achievement of nitrogen effluent norms, there are several other reasons for which denitrification
should be maximised. For example, more aeration energy is needed to remove the organics that were not
removed anoxically. If the recirculation flow transporting nitrate to the anoxic zone is too low
(underloading), the rate of denitrification is limited by the amount of nitrate recirculated, resulting in too
high effluent nitrate concentrations. It also results in nitrate not being present in parts of the anoxic reactor
and thus anaerobic conditions, inducing phosphate release. In contrast, a flow that is too high requires

10
more pumping energy and transports too much oxygen to this zone (overloading), which hinders
denitrification. Therefore, an optimal recirculation rate exists, which depends on the time-varying influent
wastewater characteristics (Yuan et al., 2002).

Most wastewater treatment systems keep the recirculation rate near its optimal value with a PID control
loop with a fixed setpoint for the measured nitrate concentration at the end of the anoxic zone which is
low but not zero (e.g. 1-2 g N.m-3) (Olsson et al., 2005). As such, it is certain that not all nitrate is consumed
in the anoxic zone (no underloading), while there is only a little bit more electron acceptor recirculation
(nitrate and oxygen) than the anoxic reactor can remove (minimal overloading) (Zhiguo Yuan et al., 2002).
This strategy is shown in Figure 2.4.

𝐿
Figure 2.4: Nitrate recirculation control with low but non-zero setpoint at the end of the anoxic zone (𝐶𝑁𝑂3,𝐴𝑁,𝑆𝑃 ) (Olsson et al.,
2005).

2.1.2.3. Control of external COD addition

Even though the above-described nitrate recirculation control strategy ensures maximal use of influent COD
for denitrification; it cannot ensure that the effluent nitrate is below legal limits in case the influent COD/N
ratio is too low for complete denitrification.

In case denitrification is limited by COD, the addition of external COD sources may be required to meet the
effluent total nitrogen standard. The addition of external COD increases the denitrification capacity i.e. the
amount of nitrate that can be reduced (Yuan et al., 2002). However, too much addition should be avoided
to prevent extra chemical costs, aeration requirements and sludge production (Yuan & Keller, 2004).

Control of external COD addition to the denitrification zone is based on a control loop that controls the
nitrate concentration at the end of the anoxic zone at a low but non-zero level. This control loop is thus
analogous to the one explained in section 2.1.2.2., with external COD addition instead of nitrate
recirculation as manipulated variable. This ensures that all added COD will be used for denitrification.
Together, another control loop manipulates the nitrate recirculation flow, controlling the nitrate
concentration at the end of the aerobic zone at a set-point based on the discharge limits. The two loops
together constitute the control strategy called the ‘High N-load controller’ (HLC) and is shown in Figure 2.5
(Yuan & Keller, 2004).

11
Figure 2.5: High N-load controller. The subscripts AE, AN, REC and EX stand for anaerobic, anoxic, recirculating and external
respectively (adapted from Yuan & Keller (2004)).

A plant using the HLC can also use a control loop such as the one described in section 2.1.2.2., which is
called the ‘Low N-load controller’ (LLC) if a HLC is present. The HLC is only active if the discharge limits
cannot be met using only recirculation. When the nitrate sensor in the aerobic zone indicates the discharge
limit is met again, the LLC becomes active again and so, external COD addition and associated costs are
minimised (Yuan & Keller, 2004; Smith, 2019).

2.2. Sequencing batch reactors


In a sequencing batch reactor (SBR), wastewater comes into contact with activated sludge
discontinuously, as opposed to continuous wastewater treatment systems (Dutta & Sarkar, 2015). In this
chapter, the first part will explore the basics of operation and biochemical reactions. Secondly, the
monitoring and control of an SBR system will be explained.

2.2.1. Operation and biochemical reactions


In sequencing batch reactors, all the same biochemical reactions take place as in continuous systems. The
difference is that the conditions and corresponding reactions are now separated in time instead of in space
(over different reactor compartments). In the same manner as in continuous systems, which reactions take
place is dependent on the conditions that the reactor provides. If the reactor is aerated, aerobic conditions
occur and the corresponding reactions take place (nitrification and COD removal). If it is not aerated, the
conditions, anaerobic or anoxic, depend on the presence of nitrate. Under anaerobic conditions,
phosphorus release takes place and under anoxic conditions, denitrification occurs. An SBR system operates
in cycles, subdivided most often in five phases: fill, react, settle, draw and idle, shown in Figure 2.6 (Al-
Rekabi et al., 2007).

Most of the biochemical reactions take place during the first two phases, fill and react. In the filling phase,
influent is added that comes into contact with the activated sludge and, potentially, wastewater from the
previous cycle. Three types of filling can take place, or any combination of them: static fill, mixed fill and
aerated fill. During static fill, both aeration and mixing are absent, causing a high substrate to

12
microorganisms ratio. This promotes the growth of floc-forming organisms as opposed to filamentous ones.
During mixed fill the wastewater and activated sludge are mixed mechanically but remain unaerated. During
aerated fill aeration is on, which also provides mixing (Dutta & Sarkar, 2015). The reaction phase is actually
an extension of the previous phase, where the reactions initiated during filling are completed. The only
differences are that now there is no more fresh wastewater flowing into the reactor and mixing is always
on, either mechanically or by aeration (Vives Fabregas, 2004). The variation of aeration, provides the
desired conditions. The duration of these conditions determines the degree of treatment required (Singh
& Srivastava, 2010). Because the reaction phase is a continuation of the fill phase, the time required to
achieve the degree of treatment needed will be determined by the durations of the fill and reaction phases.
(Vives Fabregas, 2004). Also, more than one filling event and even continuous filling can occur, making the
reaction and filling phases unidentifiable from each other. Because of these reasons, a ‘process phase’ has
been proposed, that covers both (Figure 2.6) (Artan & Orhon, 2005).

In the settling phase aeration and mixing are stopped and the whole tank will act as a clarifier, allowing the
sludge and other solid materials to settle on the bottom. After the settling phase, the clear supernatant is
discharged from the reactor in the draw phase. A part of the treated wastewater can remain in the reactor,
above the settled sludge. The period between the end of the draw phase and the beginning of the next
cycle (filling phase) is called the idle phase. This phase is often needed for the coordination of several SBRs
operated in parallel. Also, sludge wasting can be done during this phase (Dutta & Sarkar, 2015). It is
commonly assumed that during the settle, draw and idle phases, no biological conversions take place (Artan
& Orhon, 2005).

Figure 2.6: Typical SBR operation cycle with static fill. Everything inside the dashed circle is part of the process phase (Artan et al.,
2006; Dutta & Sarkar, 2015)

13
To remove nitrogen from wastewater, COD should be consumed anoxically instead of aerobically. Different
strategies can be applied to achieve this in SBR systems. One possibility is to add external COD when the
wastewater is anoxic. Another possibility is to choose the sequence of reaction conditions in the reactor by
choosing smartly when to aerate, and when not to (Broch, 2008). In the simplest of these cycle structures,
the first part of the process phase is unaerated, removing nitrate present in the non-removed wastewater
from the previous cycle using COD from the new wastewater. This is followed by aeration, oxidising the
remaining COD and the influent ammonium. Thus, the amount of nitrogen removed is limited by the
amount of nitrate present in non-removed volume. Using this strategy on wastewater that has no influent
nitrate and a constant ammonium load, only a part of the total nitrogen can be removed (Artan & Orhon,
2005) (Equation 2.1):
Vmin
fraction of total N removed = V (2.1)
min +Vfill
where Vmin (m3) is the remaining volume in the reactor, while Vfill (m³) is the filled volume per cycle. This
strategy is analogous to nitrate recirculation, the nitrate recirculation flow being similar to the non-removed
volume (Artan & Orhon, 2005).

By using intermittent aeration during the reaction phase, more nitrogen can be removed from the
wastewater. If the aeration is stopped when there is still influent COD present, the nitrate formed in the
previous phase can be removed with this COD. Analogous to the many possible reactor configurations
possible in continuous systems, there are a lot of other cycle strategies possible, for example intermittent
feeding followed by anoxic reacting phases, where the newly added COD is used for denitrification (Artan
& Orhon, 2005).

2.2.2. Monitoring and control


Whereas the distribution of anoxic and aerobic capacity in continuous systems is affected by the volume of
the corresponding compartments, in SBR systems it is affected by the duration of the corresponding phases
(Artan & Orhon, 2005). These durations are easily adaptable, as the process can quickly change from
completely anoxic to completely aerobic and back. It is often stated that this gives SBR systems a more
flexible operation than continuous ones (Gerardi, 2010).

The duration of aerobic and anoxic phases can be fixed or are dynamic. When applied to nitrogen removal,
the basic principle is that the end of nitrification and denitrification is detected when the respective
concentrations of ammonium and nitrate ions are low (Figure 2.7A). The following phase can then be
started by starting or stopping aeration (Zanetti et al., 2012).

The latter can be based on an open-loop control scheme, where the lengths of the phases are based on
predictions of load variations (night/day, week/weekend etc.), with safety margins (Yang et al., 2010).
Otherwise, the phase lengths can also be controlled in real time based on on-line measurements to adapt
to the actual influent characteristics. This can improve effluent quality, decrease energy consumption by
unnecessary aeration and increase the amount of wastewater that can be treated per time unit, thereby
reducing the space required for newly built systems (Dries, 2016). Real-time control is usually based on the
detection of the start and end of the biological reactions taking place within the SBR.

14
Direct nutrient measurements have several shortcoming such as high sensor cost and complex
maintenance. Because of this, a lot of research has been done concerning the measurement of other
variables, to indirectly detect the start or end of the biochemical processes taking place. These include
L
oxidation-reduction potential (ORP), oxygen concentration in the liquid phase (CO2 ) and pH, whose sensors
are cheaper and easier to use (Zanetti et al., 2012). Both ORP and pH are strongly influenced by influent
variations and sensor drift is commonly observed in ORP, pH and DO probes (Schneider et al., 2019).
Therefore, it is difficult to use absolute values for process control. Instead, biochemical events are detected
by several characteristic points in the indirect parameter-time graphs (‘breakpoints’). Figure 2.7B shows
these breakpoints that are linked to the ends of nitrification and denitrification (Rubio et al., 2004).

L L
The CO2 breakpoint in the aerobic phase is a point at which the CO2 suddenly increases. This corresponds
to the end of nitrification, when the oxygen demand suddenly decreases because of the depletion of
L
ammonium. Mathematically, the CO2 breakpoint corresponds to an inflection point: the second derivative
L
of the CO2 -time profile is equal to zero, and this is how it is detected, as is presented in Table 2.1.

The ORP indicates if the wastewater constitutes an oxidising or reducing environment. It is expressed in
millivolts, with positive values indicating a tendency to oxidise compounds and negative values a tendency
to reduce them. The ORP is the influenced by the potentials of all half-reactions of the compounds in the
system, and by the relative abundancies of these compounds. The presence of oxidising compounds, with
a positive half-reaction potential, such as oxygen or nitrate increases ORP, and the presence of reducing
compounds such as COD or ammonium decreases it (Meijer, 2004). During aeration, the ORP rises because
of oxygen input, the formation of nitrate and the removal of reducing compounds, such as ammonium and
organics. When the ammonium ions are depleted, ORP suddenly rises a lot faster (Plisson-Saune et al.,
1996). This first ORP bending point, called the ‘ammonium breakpoint’, occurs because of the
𝐿
corresponding sudden rise in 𝐶𝑂2 , which has a much larger positive influence on ORP than nitrate (Meijer,
𝐿
2004). When aeration stops, ORP decreases, because of the decrease in 𝐶𝑂2 and nitrate concentration.
When the nitrate ions get depleted, a second ORP bending point occurs, at which the ORP suddenly
decreases much faster. This “nitrate knee” is a result of the main electron acceptor changing from nitrate
to sulphate or other components. This produces sulphides, which have a large impact on the ORP values
𝐿
(Plisson-Saune et al., 1996). As with the 𝐶𝑂2 breakpoint, the two ORP bending points are detected and
defined mathematically as the second-order derivative being equal to zero (Table 2.1)(Kim & Hao, 2001).

pH is influenced by several processes, both during unaerated and aerated processes. At the beginning of
aeration, the pH of the wastewater rapidly increases because of CO2 stripping and phosphate uptake, but
it quickly starts decreasing when the nitrification rate becomes high enough to compensate for the stripping
effect (which also decreases) and when phosphate uptake ends. The pH rises again once ammonium is
depleted, mostly due to of ammonification (ammonium production from the degradation of organic
nitrogen) (Sötemann et al., 2006). The resulting local pH minimum thus indicates the end of nitrification
and is called the ‘ammonium valley’. However, it has been reported that the pH profile behaves differently
if phosphate uptake ends after nitrification. In this case, the pH decreasing effect caused by nitrification is
counteracted by a stronger pH increasing effect caused by the combination of CO2 stripping and phosphate
uptake. The end of nitrification is then visible as a sudden change of slope (steeper) in an increasing pH
profile (Spagni et al., 2001; Marsili-Libelli et al., 2008). Denitrification, and thus hydrogen ion consumption,

15
in the subsequent anoxic phase will cause the pH to rise. When nitrate ions are depleted, the pH will again
drop steadily because of a range of other reactions taking place in the anaerobic medium, such as
phosphate release (Chang & Hao, 1996). The resulting maximum thus indicates the end of denitrification
and is called the ‘nitrate apex’. The pH breakpoints can be detected as the first-order derivative being equal
to zero (Table 2.1) (Chang & Hao, 1996; Dutta & Sarkar, 2015).

Table 2.1: Overview of indirect control parameter breakpoints, The use of these derivative signals requires data filtering (Hegg et
al., 2000; Kim & Hao, 2001; Marsili-Libelli, 2006; Marsili-Libelli et al., 2008)
Event Breakpoint Description Mathematical
definition
End of Nitrate knee Inflection point in ORP profile d²ORP
=0
denitrification dt²
Nitrate apex Maximum in pH profile dpH
=0
dt
End of nitrification Ammonium Inflection point in ORP profile d²ORP
=0
breakpoint dt²
Ammonium valley Minimum in pH profile dpH
=0
dt
𝐿 𝐿 L
𝐶𝑂2 breakpoint Inflection point in 𝐶𝑂2 profile d²CO2
=0
dt²

16
Figure 2.7: 2.7A shows the schematic representation of nitrate and ammonium profiles in a sequencing batch reactor with an
intermittent filling event at the start of the unaerated phase. 2.7B shows the schematic representation of the schematic
𝐿
representation of the ORP, 𝐶𝑂2 and pH profiles in the same experiment. The grey-shaded zones in both figures shows the periods of
the ends of nitrification and end of nitrification. The grey rectangles below the two figures show whether aeration is on (light grey)
or off (dark grey). Adapted from Olsson et al. (2005).

Each of the three indirect parameters has its own weaknesses in detecting the endpoints however. Because
𝐿
the 𝐶𝑂2 is practically zero during unaerated phases, no information can be derived from unaerated phases
(Yang et al., 2010). ORP measurements on the other hand can in theory detect events in both phases.
However the ammonium breakpoint based on ORP is hard to detect (Chang & Hao, 1996; Kim & Hao, 2001).
Finally, pH is most often reported as being the most reliable single control parameter (Yang et al., 2010),
because both nitrification and denitrification can be accurately detected. Nonetheless, a problem with pH
measurements to detect these events can be the alkalinity present in the wastewater, strongly buffering
the variations in the pH and the fact that the ammonium valley is not always visible if phosphate uptake
ends after nitrification. (Casellas et al., 2006; Yang et al., 2010; Dutta & Sarkar, 2015).

During some cycles the end of nitrification or denitrification can therefore not be detected using only one
measured variable. Figure 2.8 gives a generalised flow-chart of control strategies based on the
measurement of one variable. Because of the shortcomings associated with control strategies based on one
measured variable, they are reported as less reliable (Yang et al., 2010). To overcome this, many studies

17
have tried to integrate several control parameters into control strategies using multiple control parameters.
Control strategies based on both pH and ORP are most commonly used and researched (Basu et al., 2006;
Kim & Hao, 2001; Yang et al., 2010).

Figure 2.8: Simplified flow-chart for single-parameter control strategy.

18
2.3. Off-gas analysis
Gas-liquid mass transfer constitutes the transfer of volatile molecules from a gas phase into a liquid phase,
i.e. absorption, and the other way around, i.e. stripping. During aerobic wastewater treatment, the former
will typically occur with oxygen, a process critical to provide the necessary oxygen to the microorganisms.
Carbon dioxide and also other gases such as nitrogen, methane and nitrous oxides will mostly be subject to
stripping (Doran, 2013). In this section, only the applications of O2 and CO2 measurements in the bubbles
that reach the liquid surface will be considered.

2.3.1. Gas-liquid mass transfer principles


The transfer of any volatile substance A between the liquid and gas phases occurs by diffusion through the
two stationary films on either side of the gas-liquid interface (see Figure 2.9). The mass transfer rate can
therefore be calculated by Equation 2.2, which follows from Fick’s law on the liquid side of the interface
(Lewis & Whitman, 1924):

𝑚̇𝐴𝐿−𝐺 = 𝐾𝐴𝐿 𝑎(𝐶𝐴𝐿∗ − 𝐶𝐴𝐿 )𝑉 𝐿 (2.2)

where ṁL−G
A is the transfer rate of A (g.h-1). VL denotes the volume of the liquid phase in m³, CAL the
concentration of substance A in the liquid phase and CAL∗ the saturation concentration in the liquid phase,
both expressed in g.m-3. The difference between the two concentrations represents the driving force for
mass transfer. If it is positive, absorption into the liquid will occur, and if it is negative, stripping from the
solution will occur. K LA is the overall mass transfer coefficient (m.h-1) and a is the interfacial area per liquid
volume in m-1. Because the independent determination of the parameters a and K LA is difficult, they are
usually grouped together as one (K LA a, in h-1) (Doran, 2013).

Figure 2.9: Concentration profile of compound A across liquid-gas interface (Doran, 2013).

19
K LA is dependent on diffusion resistance trough both the liquid (k LA , in m.h-1) and gas-phase (k GA , in m.h-1)
film (Amaral et al., 2019):
1 1 𝐻𝐴
= + (2.3)
𝐾𝐴𝐿 𝑘𝐴𝐿 𝐺
𝑘𝐴

where HA is the dimensionless Henry’s law constant for A, expressed in g A.m-3 in the liquid phase per g A.m-3
in the gas phase. It expresses the solubility of compound A in the liquid phase, and can be used to calculate
its saturation concentration CAL∗ (Sander, 2015):
𝐶𝐴𝐿∗ = 𝐶𝐴𝐺 𝐻𝐴 (2.4)

where CAG is the concentration of A in the gas phase. If the gas is poorly soluble, its Henry’s law constant
will be low, and the first term in Equation 2.3 will be larger than the second. Most gases in wastewater
treatment are poorly soluble, with the notable exception of ammonium, which is highly soluble (Amaral et
al., 2019). Using Equation 2.3 with a small HA, the overall mass transfer coefficient will approach k LA and
Equation 2.2 will simplify to Equation 2.5:
𝑚̇𝐴𝐿−𝐺 = 𝑘𝐴𝐿 𝑎(𝐶𝐴𝐿∗ − 𝐶𝐴𝐿 )𝑉 𝐿 (2.5)

Most data in literature concerning the k LA a and CAL∗ are however only valid for standard operating
conditions, being 20 °C and clean water. A liquid temperature that is different from 20 °C influences k LA a.
Also, the wastewater composition influences the k LA a, especially surfactants. The wastewater composition
also influences the Henry coefficient and thus the saturation concentration CAL∗ (Stenstrom & Gilbert, 1981).
To calculate the oxygen transfer rate in process conditions using data that is only valid for standard
conditions, correction factors exist that account for the previously described differences (Amaral et al.,
2019).

2.3.2. Monitoring
Measurements of oxygen and carbon dioxide content in off-gas can be a good tool to monitor processes
taking place in the reactor if these processes are well understood (Chandran et al., 2016; Spanjers &
Vanrolleghem, 2016; Baeten et al., 2020). They have many advantages over measurements in the liquid
phase, such as reflecting an overall reactor performance, simple pre-treatment, small maintenance cost
and no requirements for chemical reagents (Hellinga et al., 1996). However, most research concerning off-
gas analysis has focused on the emissions of greenhouse gases such as methane and nitrous oxide (N2O)
(Van Loosdrecht et al., 2016). First a summary of what can be monitored with off-gas analysis of oxygen will
be given, then the same will be done for carbon dioxide and the final part will explain what information can
be obtained from a combination of both.

2.3.2.1. Oxygen

The measurement of oxygen content in off-gas is the best method to monitor the effectiveness of aeration
in real time and under process conditions. Given that this is the most energy-intensive and therefore costly
operation in wastewater treatment, quantifying the effectiveness of it is a common application of off-gas
analysis in wastewater treatment (Leu et al., 2009). This can be done by calculating 2 values: the liquid-gas
transfer coefficient of oxygen (k LO2 a) and the oxygen transfer efficiency (OTE).

20
The value of the liquid-gas transfer coefficient of oxygen k LO2 a, is an assessment of aeration performance.
Under process conditions, it can be calculated from the gas-phase mass balance of oxygen. The change of
total oxygen in the gas phase is determined by the oxygen gas flow in and out of the reactor and the oxygen
transfer to the liquid phase:
𝐺
𝑑𝑚𝑂2 𝐺 𝐺 𝐺 𝐺 𝐿−𝐺
𝑑𝑡
= (𝑄𝑖𝑛 𝐶𝑂2,𝑖𝑛 − 𝑄𝑜𝑢𝑡 𝐶𝑂2,𝑜𝑢𝑡 ) − 𝑚̇𝑂2 (2.6)

where mO2G is the total mass of the oxygen present in the gas bubbles (g) and ṁL−GO2 the oxygen transfer
-1 G - -1 G
rate (g.h ). Q is the volumetric gas flow rate (g.m ³.h ), CO2 the oxygen concentration in the gas phase.
The subscripts in and out stand for the inlet and outlet gas flow. Using gas-phase measurements, the gas
flow rate and oxygen concentration can be quantified (Redmon et al., 1983). Often, no accumulation of the
measured component is assumed in the gas phase, since the reaction rate does not change rapidly (Oeggerli
et al, 1995). With this steady state assumption, the mass balance (Equation 2.6) can be rearranged to
Equation 2.7 after substitution of ṁL−G L
O2 via Equation 2.5. The value of k O2 a can be calculated if
measurements are made of the inlet and outlet oxygen concentrations and gas flow rates, and the oxygen
L∗
concentration in the liquid phase. In addition, an estimation must be made of CO2 (ASCE, 1997).
𝐺 𝐺 𝐺 𝐺
𝐿 1 𝑄𝑖𝑛 𝐶𝑂2,𝑖𝑛 −𝑄𝑜𝑢𝑡 𝐶𝑂2,𝑜𝑢𝑡
𝑘𝑂2 𝑎 = 𝑉𝐿 𝐿∗ −𝐶 𝐿
𝐶𝑂2
(2.7)
𝑂2

The OTE (Equation 2.8) is also a way of quantifying aeration performance. It is the fraction of the injected
oxygen that is effectively absorbed into the water (Redmon et al., 1983):
𝐺 𝐺 𝐺 𝐺
𝑄𝑖𝑛 𝐶𝑂2,𝑖𝑛 −𝑄𝑜𝑢𝑡 𝐶𝑂2,𝑜𝑢𝑡
𝑂𝑇𝐸 = 𝐺 𝐺 (2.8)
𝑄𝑖𝑛 𝐶𝑂2,𝑖𝑛

This is a value that can thus be calculated using only gas-phase measurements. Both Equation 2.7 and
Equation 2.8 can be simplified if the inlet and outlet gas flow rate are assumed to be equal (Redmon et al.,
1983).

Another application of off-gas analysis is respirometry, which is generally defined as the measurement and
interpretation of the rate of biological consumption of an inorganic electron acceptor (Spanjers &
Vanrolleghem, 2016). During aerobic biological respiration (of organics and nitrogen compounds; Figure
2.1), oxygen is the main electron acceptor. The respiration rate is typically measured in terms of the oxygen
consumption rate in the liquid phase, Ṙ O2 (g.h-1). If a suitable model exists that describes the contributions
of biological carbon and nitrogen removal, these processes can be monitored by measuring Ṙ O2 (Pratt et
al., 2003).

A mass balance of oxygen in the liquid phase (Equation 2.9) of an aerated batch reactor is determined by
the oxygen consumption and the oxygen transfer to the liquid phase (Spanjers & Vanrolleghem, 2016):
𝐿
𝑑𝑚𝑂2
𝑑𝑡
𝐿−𝐺
= 𝑚̇𝑂2 − 𝑅̇𝑂2 (2.9)

where Ṙ O2 is the oxygen consumption rate (g.h-1). The Ṙ O2 is mostly measured only in the liquid phase
(Pratt et al., 2003), by the so-called ‘dynamic method’ (Garcia-Ochoa et al., 2010). In this case, the aeration
and thus oxygen mass transfer is stopped, and Equation 2.9 reduces to Equation 2.10:
𝐿
𝑑𝑚𝑂2
𝑑𝑡
= −𝑅̇𝑂2 (2.10)

21
Thus, measuring the decrease of the oxygen concentration in a known volume can be used to determine
Ṙ O2 .

The gas-phase mass balance of oxygen (Equation 2.6) can also be used to determine Ṙ O2 (Pratt et al., 2003).
The first term on the right hand side of Equation 2.9 is the oxygen transfer rate, which can be calculated
using off-gas measurements if steady state is assumed in the gas-phase, as explained above:
𝐿−𝐺 𝐺 𝐺 𝐺 𝐺
𝑚̇𝑂2 = (𝑄𝑖𝑛 𝐶𝑂2,𝑖𝑛 − 𝑄𝑜𝑢𝑡 𝐶𝑂2,𝑜𝑢𝑡 ) (2.11)

To calculate Ṙ O2 using off-gas measurements, Equation 2.11 is substituted in Equation 2.9 and, after
rearranging, Equation 2.12 is obtained:
𝐿
𝐺 𝐺 𝑑𝑚
𝑅̇𝑂2 = (𝑄𝑖𝑛 𝐶𝑂2,𝑖𝑛 𝐺
− 𝑄𝑜𝑢𝑡 𝐺
𝐶𝑂2,𝑜𝑢𝑡 ) − 𝑂2 (2.12)
𝑑𝑡

measurements are however still needed in the liquid phase, to determine the left-hand side of Equation 2.9
(Spanjers & Vanrolleghem, 2016). To overcome this and use only gas-phase data to determine the oxygen
consumption rate, a steady state of the oxygen concentration in the liquid phase must be assumed. It can
L
also be imposed by controlling CO2 at a constant setpoint, which will however need liquid-phase
measurements too (Gapes & Keller, 2001).

2.3.2.2. Carbon dioxide

The rate at which carbon dioxide is being produced biologically can be a valuable indicator of biological
activity of the activated sludge, in a similar way as the oxygen consumption rate. The difference with oxygen
is that carbon dioxide is part of an acid-base equilibrium, that has to be accurately accounted for if the off-
gas data is used to determine the carbon dioxide production rate (Weissenbacher et al., 2007).

The liquid-phase mass balance of carbon dioxide (Figure 2.10) is given by Equation 2.13:
𝐿
𝑑𝑚𝐶𝑂2
= 𝑅̇𝐶𝑂2 − 𝑅̇𝐶𝑂𝑁 − 𝑚̇𝐶𝑂2
𝐿−𝐺
(2.13)
𝑑𝑡

where Ṙ CO2 is the net carbon dioxide production rate by microorganisms (g.h-1), ṁL−G
CO2 the carbon transfer
-1 ̇
rate from the liquid to the gas phase (g.h ) and R CON the rate of carbon dioxide conversion to other
inorganic carbon species (g.h-1). The hydration reaction of carbon dioxide produces carbonic acid (H2CO3),
one of the three species in an acid/bas system, the other two being bicarbonate (HCO3-) and carbonate
(CO32-). Carbon dioxide can also undergo a direct reaction with a hydroxide ion, producing bicarbonate
(HCO3-) (Stumm & Morgan, 1995). The only species that is substantially transferred to the gas phase is non-
hydrated carbon dioxide (CO2), the transfer rate of which follows the same principles as the oxygen transfer
rate (Spérandio & Paul, 1997).

22
Figure 2.10: Transformations and mass transfer of different inorganic carbon species during biological wastewater treatment. The
two reactions inside the dashed circle make up 𝑅̇𝐶𝑂𝑁 (adapted from Spérandio and Paul (1997)).

Several simplifications can be applied to the above model. At the typical wastewater pH of 6-8, the
dissociation of bicarbonate to carbonate can be ignored (pKa = 10.43) (Spérandio & Paul, 1997; Stumm &
Morgan, 1995). Also, at a pH below 8 the reaction of hydroxide with carbon dioxide is insignificant (Stumm
& Morgan, 1995). Further, the ratio between non-hydrated carbon dioxide (CO2) and hydrated carbon
dioxide (H2CO3) is very large, and uninfluenced by pH. The two species are therefore mostly grouped as one
species: H2CO3* (Pratt et al., 2003). These simplifications are summarized in Figure 2.11.

Figure 2.11: Transformations and mass transfer of different inorganic carbon species during biological wastewater treatment:
simplified scheme in a pH range typical for wastewater.

If the H2CO3* and HCO3- concentrations are in equilibrium, no net conversion takes place and Ṙ CON is equal
to zero. The equilibrium between H2CO3* and HCO3- is however very sensitive to pH in the pH range that is
typical for wastewater treatment. If the pH rises, the equilibrium will shift to the bicarbonate side and thus,
Ṙ CON will become larger than zero until the new equilibrium is attained. This will affect the H2CO3*
concentration negatively and consequently also the carbon dioxide mass transfer rate. Therefore, the
carbon dioxide mass transfer rate is lower than what would be expected by not taking Ṙ CON into account.
The reverse is true for a drop in pH (Figure 2.12). Because pH is influenced by a lot of processes in
wastewater treatment (Lijklema, 1969), a change in carbon dioxide transfer rate could be wrongly
attributed to changes in carbon dioxide production rate (Weissenbacher et al., 2007).

23
Figure 2.12: Influence of pH change on carbon dioxide transfer rate in an aerated batch reactor with respiring activated sludge in a
culture medium at 20°C. The unmeasurable carbon dioxide production rate stays constant. Adapted from (Spérandio & Paul, 1997).

Several authors were able to correctly calculate the Ṙ CO2 based on pH measurements, off-gas analysis and
models that describe the influence of pH shifts on ṁL−GCO2 (Spérandio & Paul, 1997; Weissenbacher et al.,
2007). The use of these models are said to be more important for batch systems, as the pH shifts tend to
be larger there (Weissenbacher et al., 2007).

2.3.2.3. Combination of carbon dioxide and oxygen

Hellinga et al. (1996) calculated that the ratio of total organic carbon (TOC) to COD of the carbonaceous
substrate, which can vary with the wastewater composition, is a linear function of the ratio of Ṙ CO2 to Ṙ O2 ,
if oxidation of carbonaceous substrate is the only conversion taking place (Equation 2.14):
𝑇𝑂𝐶𝑆 𝑅̇𝐶𝑂2 𝐶
= 𝐴( ) +𝐵 (2.14)
𝐶𝑂𝐷𝑆 𝑅̇𝑂2

where A and B are dimensionless and dependent on the observed yield, the ratio of the measured rates of
biomass production to substrate uptake. The superscript C stands for only COD oxidation. According to
simulations of a continuous system, the ratio of CO2 to O2 concentration in the gas phase was still a good
indicator of the ratio of COD to total organic carbon (TOC), even with nitrification and denitrification. The
gas-phase data could however not be used to monitor N-removal versus C-removal (Hellinga et al., 1996).

By comparing the mass transfer of oxygen (ṁL−G L−G


O2 ) and carbon dioxide (ṁCO2 ) using off-gas data, Leu et al.
(2010) were able to indicate failure of nitrification in a continuously fed wastewater treatment plant. When
all the ammonium was completely oxidised, the ratio ṁL−G L−G
O2 /ṁCO2 was lower than during periods of
incomplete nitrification (Figure 2.13). Thus, when the measured ṁL−G L−G
O2 /ṁCO2 is higher than expected, it can
be an indication of a high ammonium concentration in the effluent (‘NH4 breakthrough’) (Leu et al., 2010).

24
Figure 2.13: Relationship between the CTR and OTR measured via off-gas analyses in case of incomplete (red) and complete (black)
nitrification (Leu et al., 2010).

2.3.3. Off-gas analysis in SBR systems


Because sequencing batch reactors are constantly in a transient state, off-gas analysis seems to be more
suitable for the control and monitoring of these kind of systems than for continuous ones. Measurements
of a system in transient state will always give more information than measurements of a system in semi-
steady state such as continuous wastewater treatment systems (Olsson & Newell, 2005). In batch systems,
the changes in the different reaction rates will be more easily visible in time profiles of the measured
variable, direct or indirect. This makes breakpoint-based control possible only in SBRs (Meijer, 2004). This
L
is already used for the monitoring and control with indirect parameters such as CO2 , ORP and pH. If the
different biological conversion mechanisms have an influence on the off-gas carbon dioxide and oxygen
concentrations, as several authors have suggested (Hellinga et al., 1996; Gapes et al., 2003; Leu et al., 2010),
the endpoints of the reactions would be visible in SBRs and not in continuous ones. The application of
oxygen and carbon dioxide off-gas analysis for monitoring and control has however mostly focused on
continuous systems (Hellinga et al., 1996; Leu et al., 2010; Weissenbacher et al., 2007)(Hellinga et al., 1996;
S. Y. Leu et al., 2010; Weissenbacher et al., 2007).

25
2.4. Conclusions and thesis objectives
Real-time control of continuous and SBR wastewater treatment systems both aim to maintain a good
effluent quality with minimal energy use and maximal volumetric capacity, but the way this is done is
different for both systems. For control of continuous systems, nutrient measurements in the effluent are
done to determine if the system is operating as desired at that time by comparing it to the required effluent
concentration. If this is not the case, feedback control loops change some aspect of the operation, until the
system does operate as desired. Thus, in an ideally operating continuous system, the nutrient
measurements remain constant and under the desired level. This is not the case for SBR systems, which are
inherently operating in a transient state. In these kinds of systems, nutrient measurements are used to
determine the end of their removal processes, after which the system alters its operation to enable other
processes (phase-switch). Thus, in an ideally operating SBR system, nutrient measurements do not remain
constant.

The nutrient measurements in SBR systems can be replaced by indirect measurements like pH, oxidation-
reduction potential and dissolved oxygen. These measurements indicate the end of nutrient removal
processes by typical associated shapes in their time profile. Another indirect measurement of nutrient
removal processes in SBR systems could be the off-gas oxygen and carbon dioxide content. However, most
research concerning oxygen and carbon dioxide off-gas analysis for process monitoring and control has
focused on continuous systems.

In the following parts, it will be investigated if the end of nitrification can be detected by off-gas analysis
alone. It will be examined if the influent composition influences the possible correct detection. If
nitrification can be correctly detected over a wide range of influence conditions, this could result in an SBR
control strategy that would turn off aeration in case the end of nitrification is ended, saving time and energy
while guaranteeing near complete ammonium removal in an aerobic phase. The application of such an off-
gas based SBR control strategy will also be investigated. The research questions to be answered are:
1) Can the end of nitrification be detected via measurements of the off-gas oxygen concentration
alone?
2) Can the end of nitrification be detected via a combination of off-gas oxygen and carbon dioxide
concentration measurements alone?
3) Can the aerobic phase length be controlled via oxygen and carbon dioxide off-gas concentration
measurements alone?

26
3. Material and methods

3.1. Model description


The model describing biochemical processes and substance concentrations in the liquid phase of an SBR
system is described in section 3.1.1, section 3.1.2 describes the model used to determine the chemical
speciation of the different substances in the liquid phase of the reactor. In section 3.1.3, the equations
used to determine liquid-gas transfer and gas-phase oxygen and carbon dioxide concentrations are
explained.
3.1.1. Biochemical processes and liquid-phase concentrations
The Activated Sludge Model No. 2d (ASM2d) developed by Henze et al. (2000) and adapted by Flores-Alsina
et al. (2015) was used to describe the biochemical processes taking place in the reactor, as implemented in
Matlab/Simulink by Flores-Alsina et al. (2015). In this model, hydrolysis, denitrification, nitrification, COD
conversion and lysis processes are all included. In total, 19 different biochemical processes, designated with
index j, are considered. The rates of these processes, ρj, are dependent on the concentrations of 19 different
substances that are state variables in the model, and constant kinetic parameters. The state variables
included the three biomass concentrations (OHO, PAO, ANO). The nutrients included were ammonium,
nitrate plus nitrite, phosphate and several fractionations of COD. Several inorganic substances were also
state variables: oxygen, total inorganic carbon (TIC), nitrogen (N2), potassium and magnesium, as was the
concentration of particulate matter and the changing liquid volume. An overview of these processes and
state variables is given in appendix A1.

The rate at which substance A is produced by process j (ṙ j,A ; g.m-3.d-1) is calculated as the product of the
stoichiometric coefficient νA,j and the process rate ρj (Equation 3.1). The overall reaction rate of of A, rA, is
then calculated as the sum of these separate reaction rates over all 19 processes (Equation 3.2) (Henze et
al., 2000). The reaction rate equations were taken from Flores-Alsina et al. (2015).
𝑟̇𝑗,𝐴 = 𝑣𝑗,𝐴 𝜌𝑗 (3.1)

𝑟̇𝐴 = ∑ 𝑣𝐴,𝑗 𝜌𝑗 over all processes j (3.2)

For each substance A, a mass balance was set-up over the reactor to calculate the change of its
concentration over time. For a soluble substance, the mass balance took the form of Equation 3.3:
𝑑(𝑉 𝐿 ∗𝐶𝐴𝐿 ) 𝐿 𝐿
= (𝑄𝑖𝑛 𝐿
𝐶𝐴,𝑖𝑛 − 𝑄𝑜𝑢𝑡 𝐶𝐴𝐿 ) + 𝑟̇𝐴 𝑉 𝐿 + 𝑚̇𝐴𝐿−𝐺 (3.3)
𝑑𝑡

L
where V L is the liquid volume (m³), CAL the concentration of compound A (g.m-3) in the reactor and CA,in
the concentration of compound A in the influent. QLin an QLout are the liquid in and outflow (m³.d-1) and ṁL-
G -1 L−G
A is the transfer rate from the gas to the liquid phase (g.d ). ṁA was equal to zero for substances that
were non-transferable to the gas phase. For oxygen and total inorganic carbon, the liquid-gas transfer was
non-zero during aeration, its calculation is explained in section 3.1.3.

27
For an insoluble substance A, such as biomass, storage products, particulate organics and other particulate
matter’ (see appendix A1), a slightly different mass-balance was used to account for the retention inside
the system due to settling. During the waste phases with duration tw (d), the output rate of the particulates
was set to obtain a predefined solids retention time SRT (d-1) (Equation 3.4).
𝑑(𝑉 𝐿 ∗𝐶𝐴𝐿 ) 𝐿 𝐿 𝑉 𝐿 ∗𝐶𝐴𝐿 𝑡𝑡𝑜𝑡
𝑑𝑡
= 𝑄𝑖𝑛 𝐶𝐴,𝑖𝑛 − 𝑆𝑅𝑇 𝑡𝑤
+ 𝑟̇𝐴 𝑉 𝐿 (3.4)

Here, the ratio of the waste duration tw (d) to the total cycle duration ttot (d) was multiplied with the typical
term used to obtain a fixed SRT in continuously operated reactors (Batstone et al., 2002) to compensate for
the short fraction of the total time where wasting takes place. During the rest of the cycle, the output rate
was set to zero (Equation 3.5).
d(VL ∗CL
A)
dt
= QLin CA,in
L
+ ṙ A V L (3.5)
L
As an SBR was considered, the liquid volume in the reactor V was also a state variable, of which the changes
were calculated via a mass balance considering the inflow QLin and outflow QLout (Equation 3.6):
dVL
dt
= QLin − QLout (3.6)
To solve the mass balances (Equation 3.3-3.5) to the concentrations of soluble and particulate substances
with a variable liquid volume, the product rule was applied to obtain an explicit expression for the derivative
of the concentration (Equation 3.7), as demonstrated for Equation 3.3 (Equation 3.7-3.8).
dVL dCL
CAL + V L A = (QLin CA,in
L
− QLout CAL ) + ṙ A V L + ṁL−G
A (3.7)
dt dt
dCL 1 ṁ L−G
CL
dVL
A
= L (QLin CA,in
L
− QLout CAL ) + ṙ A + AL − AL (3.8)
dt V V V dt

3.1.2. Speciation model


To correctly describe carbon dioxide mass transfer across the liquid/gas interface, the fraction of TIC in the
liquid phase that is in the H2CO3* form, which is the aggregate of non-hydrated (COL2 ) and hydrated carbon
dioxide (H2CO3), should be calculated. This is necessary because the carbon dioxide off-gas concentration is
dependent on the concentration of the transferable H2CO3*, which in itself is not only dependent on its
biological production, but also on its chemical production trough pH shifts (see section 2.3.2.2). The
calculation was done in a separate speciation model developed by Flores-Alsina et al. (2015). In this model,
the output concentrations of the ASM2d model were used to estimate pH and substance speciation at each
time step. The model uses chemical equilibrium, mass balance and charge balance equations, in which
chemical activities are used instead of concentrations to correct for the effect of the ionic strength. These
result in a nonlinear algebraic system which was solved by a multi-dimensional version of the Newton-
Raphson method. The concentration of undissociated carbon dioxide, 𝐶𝐻𝐿2 𝐶𝑂3∗ , was then used to calculate
𝐿−𝐺
the transfer rate of carbon dioxide to the gas phase (𝑚̇𝐶𝑂2 ), as in Floris-Alsina et al. 2015, but with a
different liquid-gas transfer model, as described in the following section.

28
3.1.3. Liquid-gas transfer
The liquid-gas transfer rate of substance A during aerated phases was calculated according Equation 3.9,
which considers the effects of the mean hydraulic pressure and composition of the gas-phase along the
reactor height (Baeten et al., 2020)
VL
(pG
atm +ρg )MA
2S
HA xGin,A −CA
L
ṁL−G
A = k LA a RT
G V L VL (3.9)
kL
A aHA (patm +ρg 2S )V
L
1+
[ 2pG G
atm Qin ]
In this equation,k LA a -1
is the mass transfer coefficient of A (d ), HA its dimensionless Henry’s law constant
for A, expressed in g A.m-3 in the liquid phase per g A.m-3 in the gas phase. R (J.mole-1.K-1) is the universal
gas constant, T (K) the temperature, S (m2) the cross-sectional area of the reactor, pGatm (Pa) the atmospheric
pressure, MA (g.mole-1) the molar mass of A, ρ (kg.m-3) the density of the water, g (m.s-2) the gravitational
acceleration, QGin (m3.d-1) the inlet gas flow rate and HR (m) the reactor height. When aeration was off, the
liquid-gas transfer was set to zero.

The aeration rate QG was calculated via an empirical correlation with the oxygen mass transfer coefficient
𝐿
𝑘𝑂2 𝑎 (Equation 3.10) (Baeten et al., 2020). It was assumed that the volumetric flowrate didn’t change
𝐺 𝐺
between the bottom and top of the reactor (𝑄𝑖𝑛 = 𝑄𝑜𝑢𝑡 ).
VL
kL G
O2 a(patm +ρg )A
G 2A
Q = 0.6pG
(3.10)
atm
The carbon dioxide mass transfer coefficient k LCO2 a was calculated via Equation 3.11 (Baeten et al., 2020):
DCO2
k LCO2 a = k LO2 a√ (3.11)
DO2
where DCO2 and DO2 are the diffusivities of carbon dioxide and oxygen respectively (cm².s-1).

The gas-phase concentrations of oxygen and carbon dioxide (g.m-3) were calculated each time step of the
simulation. This was done by assuming no accumulation in the gas-phase (see section 2.3.2). For example,
if the oxygen concentration in the gas phase was to be calculated, following mass balance could be used:
d(VG ∗CG
O2 ) G G
dt
= 0 = QG (CO2,in − CO2,out ) − ṁL−G
O2 (3.12)
G G ṁL−G
O2
CO2,out = CO2,in − QG
(3.13)
For the carbon dioxide concentration in the gas phase, an analogous equation was used:
G G ṁL−G
CO2
CCO 2,out
= CCO 2,in
− QG
(3.14)
The resulting off-gas concentrations in g.m-3 (Equations 3.13 and 3.14) were converted to concentrations
in ppmv via Equations 3.15 and 3.16:
G RT G
CO2,out,[ppmv] = pG CO2,out,[g.m−3 ] (3.15)
atm MO2
RT
G
CCO2,out,[ppmv] = CG
pG MCO2 CO2,out,[g.m ]
−3 (3.16)
atm
𝐿
The parameters in these gas-phase equations were assumed to be constant, except for 𝑘𝑂2 𝑎 and the
liquid-phase concentrations, and can be found in appendix A2.

29
3.2. Simulations
3.2.1. Reference case
SBR cycle
The reactor operation with fixed phase lengths described by Casellas et al. (2006) was chosen as a reference
case (Figure 3.1). The total duration of the cycle with fixed phase lengths is 22.5h, subdivided into several
phases. First, an unaerated filling phase of 3h occurred, providing anaerobic circumstances needed for
phosphorus removal. Subsequently, a 6h aerobic phase for nitrification occurred, followed by an anoxic
phase with extra addition of wastewater of 4h. This new filling event was needed to provide COD for
denitrification: as explained in section 2.2.1. Hereafter, three extra phases followed: aerobic (3h), anoxic
(5h) and aerobic (0.5h). The 1.5h settling phase used in the cited reference was omitted in the simulations,
because settling was not modelled mechanistically, but with a fixed SRT (Equation 3.4). Finally, a drawing
and an idle phase occurs, each with a 0.5h duration (Casellas et al., 2006). The maximal and minimal liquid
volume corresponded to 1.320 and 0.660 m³, so the volume added each filling event was 0.330 m³. The
sludge retention time SRT was 30 days.

For aerated phases, the measured maximum k LO2 a of 264 d-1 was used. No dissolved oxygen control was
implemented to facilitate the examination of the relationship between off-gas composition and the
biochemical processes taking place. Namely, if aeration remained constant during a period, the off-gas
composition was more directly related to what happens in the liquid phase during this period than if
aeration was varied due to control actions.

Figure 3.1: Illustration of the reference SBR cycle structure. Each rectangle represents a distinct phase with its phase length in and
𝐿
its 𝑘𝑂2 𝑎 below it. Three shades of grey express, from dark to light, anaerobic, anoxic and aerobic conditions. Filling and drawing
events are represented by the blue arrows, with the corresponding displaced volumes. Wasting is represented by a brown arrow.
The amount of wasting was dependent on the sludge concentration and thus variable, but a constant SRT of 30 days was used
(Equation 3.4).

Influent composition and steady-state simulations


A constant influent composition was assumed, based on the values provided by Alex et al. (2008) for
municipal wastewater and Solon et al. (2017)(for CLTIC, CLPP, CLPAO, CLK, CLMg, which were not considered in the
former). The influent composition for the reference case is given in appendix A3. Each simulation was run
for 90 (3*SRT) days to approach steady state, which corresponded to exactly 96 cycles. Only this final cycle
was used to investigate the relation between the biochemical processes and off-gas composition.

30
Analysis
The relation between the nitrification endpoints and off-gas composition was subsequently investigated for
this specific influent composition in the final cycle. More specifically, it was investigated if specific shapes
in the off-gas the off-gas oxygen and carbon dioxide profiles matched to the ends of nitrification in the two
aerobic phases. If such a match was found, a strategy was proposed, based on a mathematical translation
of this shape (as in Table 2.1), to enable the automatic detection of nitrification ending in an aerated phase.

3.2.2. Varying influent composition


If a potential strategy was found for the automatic detection of the nitrification endpoint in the aerated
phase, this strategy was tested for different influent conditions and the same reference SBR cycle. In this
way the robustness of the detection strategy could be checked for different influent conditions.

Influent composition
Three influent characteristics were varied widely to cover the complete range of their average
concentrations found for municipal wastewater on different locations (Henze et al., 2008). The ammonium
concentration was varied between 20 and 75 g N.m-3 in 20 equal steps, phosphate between 4 and 15 g P.m-3
in 20 equal steps and total COD was set at 500, 750 and 1200 g COD.m-³. The other influent concentrations
were kept at their reference value. Because total COD was not a separate state variable, the fraction of
each contributing state variable was kept the same as in the reference simulation (see appendix A3). The
combination of the three variable influent properties resulted in 1200 (3*20*20) different influent
compositions.

Analysis
The off-gas based endpoint detection strategy for nitrification proposed after analysis of the reference case
was then applied to the simulation results of the 96th cycle for the 1200 different influent compositions. It
was investigated if the detection indeed corresponded to the end of nitrification. This typically happens
with low ammonium concentrations, due to the low saturation coefficient for ammonium as a substrate for
autotrophs (1 g N.m-3 in the model). Thus, a detection was defined as correct if the ammonium
concentration in the reactor was below 1 g N.m-3. Errors in the detection of the end of nitrification could
belong to one of two classes: false negatives and false positives. A false positive error was defined as the
detection of the end of nitrification, while the ammonium concentration was higher than 1 g N.m-3. A false
negative error was defined as no detection of the end of nitrification, while the ammonium concentration
fell below 1 g N.m-3 in the examined time period. If such errors were found, their cause was investigated. If
it was found that the errors were not due to the arbitrariness of the used ammonium threshold, but due to
a fundamental fault in the detection strategy, a new strategy was proposed to resolve this.

31
4. Results and discussion
In this chapter the results of the simulations are presented and discussed. In section 4.1, the relevant time
profiles of the reference case are examined, and a detection strategy is developed based on the derived
findings. In section 4.2, this strategy is tested for different influent compositions, after which a second
detection strategy is proposed and investigated in the same way. In the final section, a control strategy
based on off-gas analysis is proposed and briefly investigated for the reference case.
4.1. Reference case
4.1.1. Liquid phase
After 96 cycles, the SBR reached a steady state under the reference conditions, with a constant influent
composition (Figure 4.1).

Figure 4.1: Evolution of biomass concentrations during 96 cycles with a constant influent composition as given in appendix A3.

Qualitatively, the concentration profiles of ammonium, nitrate, phosphorus and oxygen within the last
simulated cycle agreed to experimental observations in an SBR (Figure 2.7A). The profiles are shown in
Figure 4.3A. Ammonium decreased during the aerated phase due to nitrification, increased during
unaerated filling events due to the addition of influent ammonium and increased slowly during other
unaerated phases due to the release of organically bound ammonium via hydrolysis. The ammonium
concentration in the effluent was 0.11 g N.m-3, well below the used quality limit of 4 g N.m-3. Nitrate
decreased during the unaerated phases due to denitrification, the rate of which was dependent on the
amount of biodegradable COD present. After filling events, the amount of biodegradable COD was high,
and so was the denitrification rate. In the third unaerated phase however, no filling event occurred and
the amount of available COD for denitrification was consequently a lot lower, which translates into a slower

32
denitrification rate. Net phosphate release took place under anaerobic circumstances, and net uptake took
place under anoxic and aerobic circumstances. This was visible in the first unaerated phase: the phosphate
concentration rose, except for the very beginning, where it declined slowly. This short decline can be
explained by the presence of nitrate, which was quickly removed in the absence of oxygen and the presence
of biodegradable COD.

The dissolved oxygen concentration rose whenever aeration was on and decreased due to the aerobic
𝐿
conversions during other phases. Two 𝐶𝑂2 breakpoints were visible during the first and second aerated
phases, as expected (see Figure 2.7 and Table 2.1). These breakpoints, occurring in the first and second
aerated phase, corresponded to the end of nitrification, as visible in the ammonium profile. This was due
to the low ammonium concentration causing the rate of nitrification to drop, thereby decreasing the oxygen
L
consumption and increasing the oxygen concentration. Another shape similar to, but smaller than, the CO2
breakpoint was visible in the first aerobic phase around t = 5h, coincident with the end of phosphate uptake.
In the ASM2d model, phosphate uptake in this phase is described by the process ‘Aerobic storage of
polyphosphate’, which uses oxygen (Henze et al., 2008). In a similar way as the end of nitrification, the low
phosphate concentration causes the process rate to drop, which increases the oxygen concentration.

4.1.2. Gas phase


The simulated off-gas concentration profile of oxygen and carbon dioxide were plotted in Figure 4.3B, to
investigate whether the end of nitrification corresponded to specific shapes in the profiles.

𝐿
A steep rise in the off-gas oxygen profile can be seen, around the end of nitrification. Because the 𝑘𝑂2 𝑎,
𝐺 G 𝐺
𝐶𝑂2,𝑖𝑛 and Q in were constant during aerated phases, the off-gas oxygen concentration 𝐶𝑂2 was only
𝐿
dependent on the liquid phase oxygen concentration 𝐶𝑂2 , (Equations 3.9 and 3.13). Therefore, the steep
𝐿
rises in the oxygen off-gas profile can be explained by the 𝐶𝑂2 breakpoints at the end of nitrification (Figure
4.3A). The other, smaller shape in the oxygen liquid-phase profile in the first aerated phase can also be seen
in the oxygen off-gas profile, according to the same principle.

The carbon dioxide off-gas profile showed, as expected, a strong link to the pH profile. As aeration started,
the pH rose quickly because of CO2 stripping, as can be seen by the high off-gas CO2 concentration. After
this, a period of dropping pH levels would be expected, followed by a subsequent rise resulting in a pH
minimum. However, this minimum was not visible. Still, there was a change of slope visible in the pH profile,
which ended together with nitrification. As explained in the literature review, because nitrification ends
before phosphorus uptake this corresponds to experimental observations (see section 2.2.2). This faster
increase in the pH caused the liquid-phase concentration of the transferable H2CO3* to drop faster, and thus
also the carbon dioxide concentration in the off-gas (see section 2.3.2.2).

4.1.3. Endpoint detection


A first, uncomplicated, detection strategy for the endpoint of nitrification was searched that was only based
on the off-gas oxygen concentration. For this purpose, an adequate mathematical definition for the steep
rise in the off-gas oxygen profile was needed to enable its automatic detection, to check the applicability

33
for different influent compositions (section 3.2.2) and ultimately for control purposes. Inspired by the
conventional techniques for detecting endpoints based on the time derivatives of the ORP, pH and/or
dissolved oxygen (section 2.2.2), the first and second time derivatives of the off-gas oxygen concentration
were investigated (Figure 4.3C). The steep rise corresponded to a maximum in the first derivative and thus
to a zero (from positive to negative values) in the second derivative. This shows that the steep rise in the
oxygen concentrations corresponded to a rising inflection point, i.e. the graph changes from convex to
concave. The proposed detection strategy was therefore chosen as the first crossing from positive to
G
negative values in the second derivative of the CO2 profile, after ten minutes in the investigated aerobic
phase. The ten-minute buffer was chosen to exclude the potential transitional effects caused by the sudden
start of aeration. The detection strategy is depicted as a decision tree in Figure 4.2.

G
Another CO2 rising inflection point was visible in the first aerated phase, corresponding to the end of
phosphate uptake (see section 4.1.2). This point came after the nitrification inflection point for these
specific conditions, but the sequence of the two points may switch place for different influent compositions.
If the end point of nitrification is defined as the first inflection point, this would lead to a false positive
detection. Therefore, the effect of the influent composition on the applicability of this detection strategy
G
for specifically the first aerobic phase (where a phosphate-related CO2 rising inflection point was visible)
was investigated in the following section.

Figure 4.2: Proposed detection strategy based on the first rising inflection point in the aerobic phase, starting at tstart and ending at
tend. The simulation time steps are designated with index i. In the reference case, detection would happen at a time t(i) somewhere
in the first red-coloured area in Figure 4.3.

34
Figure 4.3: Several profiles during the 96th cycle with a constant influent (appendix A3). The SBR phases are shown below the profiles
(see Figure 3.1), with the first and second aerated phases indicated with AE 1 and AE 2. The transitions between the phases are
shown as black vertical lines within the profiles. The approximate end of nitrification is highlighted light red in both aerated phases.
Figure 4.3A shows the ammonium, nitrate, phosphate and oxygen concentration profiles in the liquid phase. Figure 4.3B shows the
off-gas oxygen and carbon dioxide and pH profiles. Figure 4.3C shows the first and second derivatives of the off-gas oxygen profile.
Two similar shapes can be discerned in the first aerobic phase: one corresponding to the end of nitrification, and one corresponding
to the end of phosphate uptake.

35
4.2. Varying influent compositions
4.2.1. Endpoint detection via oxygen off-gas analysis
The detection strategy proposed in the previous section (see section 4.1.3), was tested for different influent
compositions, in the first aerobic phase of the final cycle. To this end, the ammonium concentration at the
moment of detection for each influent was investigated to determine if there were false positive or false
negative errors (see section 3.2.2). First, the results will be presented for each influent COD concentration,
followed by an overall assessment of the detection strategy and an investigation of the potential errors.

Effect of influent ammonium and phosphate concentrations for different influent COD concentrations
For an influent COD concentration of 500 g COD.m-3, no false negative errors were recorded. No false
positive errors were recorded either, as can be seen in Figure 4.4: for all influent combinations the
ammonium concentrations at the time of detection were below 1 g N.m-3. They were independent of
influent phosphate and dependent on influent ammonium concentration. However, the dependency on
influent ammonium concentration was also limited, as the ammonium concentrations at the time of
detection were always far below the limit (between 0.12 and 0.22 g.m-3).

𝐺
Figure 4.4: Ammonium concentration in the reactor at the time of the first 𝐶𝑂2 rising inflection point in the first aerobic phase (Figure
4.2) as a function of the influent ammonium concentration, for different influent phosphate concentrations (grey scale) and a fixed
influent COD concentration of 500 g COD/m³. The ammonium limit for a correct detection (1 g N.m-3) is highlighted red.

For an influent COD concentration of 750 g COD.m-3, again no false negative or false positive errors were
recorded (Figure 4.5). For combinations of low influent phosphate (4-6 g P.m-3) and low influent ammonium,
the ammonium concentration at the time of detection was clearly dependent on both influent phosphate
and influent ammonium. The lower the influent phosphate concentration, the higher the range over which
the strong dependency on influent ammonium was, and the stronger the dependency on influent
phosphate concentration. For most influent combinations however, the ammonium concentration at the

36
time of detection was much less dependent on influent ammonium and independent on influent
phosphate. If there was dependency on influent phosphate or influent ammonium, the ammonium
concentrations at the time of detection were higher than if there was no dependency.

𝐺
Figure 4.5: Ammonium concentration in the reactor at the time of the first 𝐶𝑂2 rising inflection point in the first aerobic phase (Figure
4.2) as a function of the influent ammonium concentration, for different influent phosphate concentrations (grey scale) and a fixed
influent COD concentration of 750 g COD/m³. The ammonium limit for a correct detection (1 g N.m-3) is highlighted red.

For an influent COD concentration of 1200 g COD.m-3, the majority of detections were false positives
(81.51%), as can be seen on Figure 3.7. Also, the majority of the influent combinations show a stronger
dependency on influent phosphate and ammonium. In general, a lower influent phosphate and a higher
influent ammonium concentration corresponded to higher ammonium concentrations at the time of
detection. Only for high influent phosphate (>14 g P.m-3), the ammonium concentrations were quasi-
independent on both influent phosphate and influent ammonium. No false negative errors were recorded.

37
𝐺
Figure 4.6: Ammonium concentration in the reactor at the time of the first 𝐶𝑂2 rising inflection point in the first aerobic phase (Figure
4.2) as a function of the influent ammonium concentration, for different influent phosphate concentrations (grey scale) and a fixed
influent COD concentration of 750 g COD/m³. The ammonium limit for a correct detection (1 g N.m-3) is highlighted red.

Assessment of detection strategy:


The end of nitrification, according to the used definition, was correctly detected in 73% of the cases. The
incorrect detections were all false positive errors. This means that for this detection strategy, for 27% of
the influent conditions, the end of nitrification was detected too early: the ammonium concentration was
still above the threshold of 1 g N.m-3. The results are summarized in Figure 4.7: green squares are correct
detections, and red squares are false positive errors. The false positive results can be explained by
examining the worst-case scenario (the highest ammonium concentration at a detection), which is circled
in blue in Figure 4.7.

In the worst-case scenario, the phosphate and nitrification endpoints have switched place in the first
𝐺
aerobic phase (Figure 4.8), compared to the reference case (Figure 4.3). This causes the first 𝐶𝑂2 upward
inflection point associated with the end of phosphate uptake to occur before nitrification is ended, causing
the threshold of 1 g N.m-3 to be exceeded. This was also the case for the other false positive results. These
errors only happened with high influent COD, as high influent VFA (acetate) concentrations can sustain a
higher PAO biomass concentration, leading to higher phosphate uptake rates during the aerobic phases.
Autotrophs are not aided by higher influent COD concentrations in the same way. As a consequence, the
end of phosphate uptake could happen earlier than the end of nitrification. This is shown in Figure 4.9,
where the ammonium and phosphate concentrations in the reactor during the first aerobic phase are
compared between the worst-case scenario and an influent composition that is the same, except for a lower
influent COD (750 g.m3 brown circle in Figure 4.7). The higher PAO biomass concentration in the case of
high influent COD (2700 vs 570 g COD.m-3) results in a higher phosphate uptake rate (steeper slope), and
an earlier end of phosphate uptake, even with an initial phosphate concentration that was higher.

38
In case of a false positive error, the ammonium concentration at the time of faulty detection was dependent
on both influent ammonium and phosphate. This was because, the higher the influent ammonium, the later
the end of nitrification occurred and the lower the influent phosphate, the quicker the end of phosphate
uptake occurred. Therefore, the higher the influent ammonium and the lower the influent phosphate, the
larger the time interval was between the two and the larger the ammonium concentration still was at the
time of the first inflection point.

In most cases of correct detection, the ammonium concentration at the time of detection was independent
of influent phosphate and largely independent of influent ammonium. This was not the case in some
influent combinations with 750 and 1200 g COD.m-3 however. They are the lighter green squares in Figure
4.7, which indicate a higher ammonium concentration than most correct detections (left bottom for 750 g
COD.m-3 and around the edges of the red color for 1200 g COD.m-3). In these cases, the phosphate-related
upward inflection point also came before the ammonium-related inflection point, but the ammonium
concentration was already lower than 1 g N.m-3 at the time of detection. Therefore, they were classified as
correct detections, although the detection was not due to the end of nitrification, but due to the end of
phosphate uptake.

To correctly detect the nitrification endpoint, extra information is needed to distinguish it from the end of
phosphate uptake. This extra information could be extracted from the off-gas carbon dioxide profile. If
there is a specific shape that corresponds to the end of nitrification and not to the end of phosphate uptake,
or vice versa, this can be used to determine whether or not an oxygen rising inflection point indicates the
end of nitrification.

𝐺
Figure 4.7: Ammonium concentration in the reactor at time of the first upward 𝐶𝑂2 inflection point in the first aerobic phase (Figure
4.2) of the final cycle of a 90-day simulation, for different influent COD, phosphate and ammonium influent compositions. Influent
compositions that lead to correct detections are represented by a green square, with darker green corresponding to lower
ammonium concentrations in the reactor at the time of detection. False positive detections are represented by a red square, with
darker red corresponding to higher ammonium concentrations. Especially higher influent COD concentrations complicate automatic
detection of the end of nitrification by oxygen off-gas analysis. The colored circles indicate the cases that are further investigated in
Figure 4.8 (blue) and Figure 4.9 (blue and brown).

39
Figure 4.8: Ammonium concentration, phosphate concentration, off-gas oxygen concentration and its second derivative in the first
aerated phase of the final cycle for the worst-case scenario (highest ammonium concentration at the time of false positive
detection). The influent composition is indicated by the blue circle in Figure 4.7 (75 g N.m-3, 4 g P.m-3 and 1200 g COD.m-3). The first
oxygen rising inflection point corresponds not to the end of nitrification, but to the end of phosphate uptake, resulting in a faulty
detection (red line) and the ammonium concentration seen in Figure 4.7. The actual end of nitrification takes place in the period
that is highlighted light red.

Figure 4.9: Evolution of ammonium and phosphate concentration in first aerated phase of the final cycle. Comparison between two
influent compositions (indicated by the brown and blue circles in Figure 4.7) that are the same, except for influent COD. The brown
lines show the profiles for an influent composition of 75 g N.m-3, 4 g P.m-3 and 750 g COD.m-3, the blue lines show the profiles for an
influent composition of 75 g N.m-3, 4 g P.m-3 and 1200 g COD.m-3.

40
4.2.2. Information derived from off-gas carbon dioxide
The carbon dioxide off-gas profile in the first aerobic phase for the worst case (indicated blue in Figure 4.7)
was examined, to investigate whether carbon dioxide off-gas measurements could provide additional
information to distinguish the end of nitrification from the end of phosphate uptake. In Figure 4.10, the
ammonium concentration, second derivative of the off-gas oxygen profile, the off-gas carbon dioxide profile
and the pH are shown. In this case, a minimum in pH was visible, roughly coincident with the end of
nitrification. This is in accordance with what has been reported in literature (the ammonium valley is visible
𝐺
if phosphate uptake ends before nitrification). The end of phosphate uptake corresponded to a rising 𝐶𝐶𝑂2
(positive first derivative), which can be explained by the pH profile: the drop in pH caused by the end of
phosphate uptake and continuing nitrification causes the liquid-phase concentration of the transferable
𝐺
H2CO3* to rise, and thus also the 𝐶𝐶𝑂2 (see section 2.3.2.2). The reverse is true for the pH rise caused by the
* 𝐺
end of nitrification: the H2CO3 concentration decreases and so does the 𝐶𝐶𝑂2 (negative first derivative).

𝐺 𝐺 𝐺
Figure 4.10: Profiles of the ammonium concentration, phosphate concentration, 𝐶𝑂2 second derivative, 𝐶𝐶𝑂2 and 𝐶𝐶𝑂2 first derivative
in the first aerated phase of the final cycle. The influent composition is taken from the worst-case scenario (indicated by the blue
𝐺
circle in Figure 4.7: 75 g N.m-3, 4 g P.m-3 and 1200 g COD.m-3). Two 𝐶𝑂2 rising inflection points are recognizable by the two crossings
𝐺
from positive to negative in the 𝐶𝑂2 second derivative. The first corresponded to the end of phosphate uptake, and the second
corresponded to the end of nitrification (in the period that is highlighted light red).

𝐺
A new nitrification endpoint detection strategy was proposed based on the first 𝐶𝑂2 rising inflection point
𝐺 𝐺
(as in the first strategy) coincident with a negative 𝐶𝐶𝑂2 first derivative (decreasing 𝐶𝐶𝑂2 ). There was some
𝐺
noise on the 𝐶𝐶𝑂2 signal, which was amplified in its first derivative.(Figure 4.10) Because only the sign of
the first derivative was used, this was no problem for the new strategy, as long as the noise didn’t change
the sign. The new detection strategy is depicted as a decision tree in Figure 4.11 and was again tested for
different influent compositions.

41
Figure 4.11: Proposed detection strategy based on the first rising inflection point in an aerobic phase coincident with a negative
𝐺
𝐶𝐶𝑂2 first derivative, starting at tstart and ending at tend. The simulation time steps are designated with index i, with i=1 corresponding
to the first time step in the concerned aerobic phase. In the worst-case scenario, detection would happen at a time t(i) somewhere
in the first red-coloured area in Figure 4.10.

4.2.3. Endpoint detection via oxygen and carbon dioxide off-gas analysis
The new detection strategy based on the off-gas oxygen and carbon dioxide profile (Figure 4.11) was tested
in the same way and for the same 1200 influent conditions as the first detection strategy (section 4.2.1).
The main goal of the new strategy was to suppress the largely false positive results of the influent with large
COD content. It was also tested to make sure that its more stringent condition did not generate false
negative results for influent compositions for which the first detection strategy worked correctly. In these
simulations, the new detection strategy was also investigated for the second aerobic phase. First, the results
will be presented for each influent COD concentration, followed by an overall assessment of the detection
strategy and an investigation of the potential errors.

42
Effect of influent ammonium and phosphate concentrations for different influent COD concentrations
For both aerobic phases with an influent COD concentration of 500 g COD.m-3, no false negative errors were
recorded. No false positive errors were recorded either (Figure 4.12). Ammonium concentrations at the
time of detection were independent of influent phosphate and only limitedly dependent on influent
ammonium concentration, as the ammonium concentrations at the time of detection were always far
below the limit (between 0.12 and 0.45 g N.m-3). The ammonium concentrations were lower for the first
aerobic phase (0.12-0.22 g N.m-3) than for the second (0.25-0.40 g N.m-3).

𝐺
Figure 4.12: Ammonium concentration in the reactor at the time of the first 𝐶𝑂2 rising inflection point coincident with a decreasing
𝐺
𝐶𝐶𝑂2 (Figure 4.11) in the first and second aerobic phase as a function of the influent ammonium concentration, for different influent
phosphate concentrations (grey scale) and a fixed influent COD concentration of 500 g COD/m³. The ammonium limit for a correct
detection (1 g N.m-3) is highlighted red.

No false negative or false positive errors were recorded for influent combinations of 750 g COD.m-3 in either
of the aerobic phases. The same observations could be made as for the cases with 500 g.m-3 influent COD:
there was no and limited dependency on influent phosphate and ammonium respectively. The ammonium
concentrations were again lower for the first aerobic phase (0.05-0.10 g N.m-3) than for the second (0.15-
0.30 g N.m-3).

43
𝐺
Figure 4.13: Ammonium concentration in the reactor at the time of the first 𝐶𝑂2 rising inflection point coincident with a decreasing
𝐺
𝐶𝐶𝑂2 (Figure 4.11) in the first and second aerobic phase as a function of the influent ammonium concentration, for different influent
phosphate concentrations (grey scale) and a fixed influent COD concentration of 750 g COD/m³. The ammonium limit for a correct
detection (1 g N.m-3) is highlighted red.

In the first aerobic phase of the simulations with 1200 g.m-3 influent COD, no false positives were detected
(Figure 4.14, upper panel). However, 10 false negative errors were recorded (not shown): no detection
happened, but nitrification was ended. In the other cases, the ammonium concentrations were more
variable for low influent ammonium concentrations (< 40 g N.m-3), but no clear trends could be discerned.

In the second aerobic phase, no false negative and 26 false positive cases were detected (Figure 4.14, lower
panel). The ammonium concentrations at the time of detection are independent from the influent
ammonium concentrations, until a certain threshold influent ammonium concentration. This threshold is
dependent on the influent phosphate, with lower concentrations corresponding to a lower threshold. If the
influent phosphate was larger than 8.5 g P.m-3, the ammonium concentrations at the time of detection were
independent of influent phosphate and limitedly dependent on influent ammonium, around 0.1 g N.m-3.

44
𝐺
Figure 4.14: Ammonium concentration in the reactor at the time of the first 𝐶𝑂2 rising inflection point coincident with a decreasing
𝐺
𝐶𝐶𝑂2 (Figure 4.11) in the first and second aerobic phase as a function of the influent ammonium concentration, for different influent
phosphate concentrations (grey scale) and a fixed influent COD concentration of 1200 g COD/m³. The ammonium limit for a correct
detection (1 g N.m-3) is highlighted red.

Assessment of detection strategy:


The end of nitrification in the first aerobic phase was correctly detected in 99% of the cases (Figure 4.15).
The incorrect detections in this phase were false negative errors, which means that no end of nitrification
was detected, while it occurred. Thus, the second detection strategy succeeded in its goal of avoiding the
false positives of the influent with large COD content, with only a limited increase of false negatives (1%).
In the second aerobic phase, the end of nitrification was correctly detected in 98% of the cases (Figure
4.16). The incorrect detections in this phase were false positive errors, all for influent compositions with
1200 g COD.m-3. Thus, as for the first detection strategy, the only errors were recorded for high influent
COD.

A random false negative error (encircled blue in Figure 4.15) was investigated, to determine its cause (Figure
4.17). The endpoints of phosphate uptake and nitrification happened almost simultaneously. This led to
𝐺 𝐺
only one upward 𝐶𝑂2 inflection point: there was only one zero crossing from positive to negative in the 𝐶𝑂2
second derivative. This inflection point was probably the one associated with the end of phosphate uptake,
as the pH was decreasing, causing the off-gas carbon dioxide to increase and leaving the inflection point
𝐺
undetected. There was a second minimum visible in the 𝐶𝑂2 second derivative, shortly after the upward
𝐺
𝐶𝑂2 inflection point, which was not visible for cases for which the ends of phosphate and nitrification uptake
were more separated in time (Figure 4.3, Figure 4.10). Therefore, this shape was probably related to the
end of nitrification, as the pH was increasing at the time of this shape, which is typical for this event (see
section 2.3.2.2). These remarks were also valid for the other false negative errors.

45
The worst case of a false positive error (encircled red in Figure 4.15) was also investigated. Like in the false
𝐺
positive cases of the first detection strategy, the phosphate-related upward 𝐶𝑂2 inflection point was
𝐺
detected instead of the end of nitrification. The extra condition of a negative 𝐶𝐶𝑂2 did not prevent this, as
𝐺
the 𝐶𝐶𝑂2 was indeed decreasing. This decrease was caused by a slightly increasing pH, which is atypical for
the end of phosphate uptake. This was the case for all the false positive errors and for the correct detections
that are indicated by a light green colour in Figure 4.16. No adequate explanation for this behaviour of the
pH profile was found.

𝐺
Figure 4.15: Ammonium concentration in the reactor at time of the first upward 𝐶𝑂2 inflection point in the first aerobic phase,
𝐺
coincident with a decreasing 𝐶𝐶𝑂2 (Figure 4.2) of the final cycle of a 90-day simulation, for different influent COD, phosphate and
ammonium influent compositions. Influent compositions that lead to correct detections are represented by a green square, with
darker green corresponding to lower ammonium concentrations in the reactor at the time of detection. False negative detections
are represented by a black cross. The blue circle indicates the false negative error that is further investigated (Figure 4.17).

𝐺
Figure 4.16: Ammonium concentration in the reactor at time of the first upward 𝐶𝑂2 inflection point in the second aerobic phase,
𝐺
coincident with a decreasing 𝐶𝐶𝑂2 (Figure 4.2) of the final cycle of a 90-day simulation, for different influent COD, phosphate and
ammonium influent compositions. Influent compositions that lead to correct detections are represented by a green square, with
darker green corresponding to lower ammonium concentrations in the reactor at the time of detection. False positive detections are
represented by a red square, with the darkest red corresponding to the highest ammonium concentration recorded (with detection
strategy 1).

46
𝐺 𝐺 𝐺
Figure 4.17: Profiles of the ammonium concentration, phosphate concentration, 𝐶𝑂2 second derivative, 𝐶𝐶𝑂2 and 𝐶𝐶𝑂2 first derivative
in the first aerated phase of the final cycle. The influent composition is taken from a random false negative error (indicated by the
blue circle in Figure 4.15: 32 g N.m-3, 14 g P.m-3 and 1200 g COD.m-3). The nitrification endpoint (which was not detected) takes
place in the period that is highlighted light red.

𝐺 𝐺 𝐺
Figure 4.18: Profiles of the ammonium concentration, phosphate concentration, 𝐶𝑂2 second derivative, 𝐶𝐶𝑂2 and 𝐶𝐶𝑂2 first derivative
in the second aerated phase of the final cycle. The influent composition is taken from the worst false positive error (indicated by the
red circle in Figure 4.16: 75 g N.m-3, 4 g P.m-3 and 1200 g COD.m-3). The time of faulty detection is indicated by the red line. The
actual end of nitrification takes place in the period that is highlighted light red.

47
4.3. Proposition of control strategy
The detection strategy that combines oxygen and carbon dioxide measurements (Figure 4.11) could be used
to turn off aeration in the reference cycle if the end of nitrification is detected. In case of a correct detection,
the effluent ammonium concentration would stay low, while the duration of aeration shortens, decreasing
the energy consumption and increasing the daily capacity. To prevent ongoing aeration in case of a false
negative error, a maximal duration of aeration, tmax (d) would also be needed, after which aeration is
automatically switched off. This control strategy is shown as a decision tree in Figure 4.19, and was
implemented for the reference case in each aerated phase of the final cycle (Figure 4.20). The total duration
of the aerated phases was reduced from 9.5 to 1.75 hours, reducing the aeration-related energy
consumption by 82%. Moreover, the total cycle time was reduced from 22.5 to 15.5 hours, increasing the
treating capacity by 45%. The effluent concentration of ammonium did not change significantly. The
ammonium profile changed a little from the end of the first aerobic phase compared to the original cycle,
as an earlier end of aeration affected the course of the biochemical processes from this point onward.

Figure 4.19: Proposed strategy for aerobic phase length control. The detections happens by the strategy depicted in Figure 4.11.

48
Figure 4.20: Ammonium concentration profiles in the final cycle for the uncontrolled reference case (top) and with control of the
aerobic phase length (Figure 4.19Figure 4.11) (bottom). The SBR phases are shown below the profiles (see Figure 3.1), with the first
and second aerated phases indicated with AE 1 and AE 2.

The previous simulation was not repeated for different influent compositions, but it is reasonable to assume
that similar results would be obtained for other influent compositions for which there was a correct
detection (Figure 4.15, Figure 4.16). The effect of the first control action on the detection in the second
aerobic phase was not investigated for other influent compositions however, so this assumption is not
completely certain. In case of a false negative error, the aerobic phase length would not be changed, so
there would be no negative effect on the SBR ammonium removal performance, energy use or treating
capacity. In case of a false positive error in the second aerobic phase, the effluent ammonium concentration
would be higher than for the uncontrolled cycle. This elevated effluent ammonium concentration would
not be a significant problem for the investigated influents, as the concentrations at the time of these false
positive detections were always lower than a typical effluent ammonium limit of 4 g N.m-3 (Alex et al., 2008).

49
5. Conclusions
Sequencing batch reactor (SBRs) are a type of wastewater treatment process that operates batch wise and
aims to remove organics, nitrogen and phosphorus trough biochemical conversion processes by activated
sludge. Which processes take place is determined by the conditions the reactor provides, which is in its turn
mostly determined by the degree of aeration of the reactor. The oxidation of ammonium in SBRs
(nitrification) takes place when the reactor is aerated, which is energy-intensive. In order to limit the
amount of aeration, liquid-phase measurements are normally employed, that detect if nitrification is ended.
They can be either direct (ammonium) or indirect (pH, ORP, dissolved oxygen) measurements.

In this thesis, a model of an SBR reactor treating wastewater was built and used to determine if the end of
nitrification can be correctly detected by using only off-gas O2 and CO2 measurements, instead of the more
conventional liquid-phase measurements. To this end, the off-gas composition of a reference SBR cycle with
two aerated phases that operated in stationary state was simulated for a wide range of constant influents
that were varied in ammonium, phosphate and total COD concentrations. The following results were found:

• A steep rise in the oxygen off-gas profile corresponded to the end of nitrification, which could be
defined mathematically as an upward inflection point. A detection strategy was developed that
automatically detects the first time this shape occurred. However, for influent wastewater with
high influent COD, this first inflection point mostly corresponded to the end of phosphate uptake
instead, resulting in an ammonium concentration that is too high.

• When an inflection point in the oxygen off-gas profile coincided with a decreasing carbon dioxide
concentration, it almost always (98% of the investigated influent compositions) corresponded with
the end of nitrification. The 2% incorrect detections were the results of interference from the end
of phosphate uptake in case of high influent COD.

• An aerobic phase length control strategy based on oxygen and carbon dioxide off-gas analysis was
proposed and implemented in one steady state cycle of the reference case in both aerobic phases.
Aeration was stopped when nitrification ended, decreasing energy consumption and increasing the
daily capacity of the system while retaining the ammonium removal capacity. This control strategy
was not tested for other influent conditions, but it is reasonable to assume that similar results
would be obtained for constant influents where the detection strategy was shown to work
correctly.

50
6. Recommendations for further research
• A logical next step would be to further test the control strategy that uses only carbon dioxide and
off-gas analysis. This could be done by applying it to steady state reference cycles for other influent
compositions, or to a reactor with a variable influent composition, which is closer to the actual
application of controllers.

• The application of off-gas analysis could be further extended towards the detection of the
denitrification endpoint. According to the same principles used in this thesis, the end of
denitrification could be visible as a specific shape in the off-gas oxygen and carbon dioxide profiles.
If correct detection trough off-gas analysis is possible, an anoxic phase length control could be
developed that is similar to the aerobic phase length control proposed in this thesis, further
increasing the daily capacity of the system. Aeration would need to be not completely off during
the anoxic phases, as in this thesis, but on a low level, to be able to do off-gas analysis during these
phases.

• An explanation for the wrong detections caused by the unexpected pH profile in the second aerobic
phase has not been found: the behavior of the pH profile in these cases can be further investigated.

• The application of off-gas analysis for the control of processes that use aerobic granular sludge can
also be further researched, as this type of process is an SBR process that is quickly gaining
importance. This can be done by implementing greater saturation coefficients (Baeten et al., 2018)
and considering a typical aerobic granular sludge cycle and reactor, which is higher (>5m) and thus
influences the off-gas O2 and CO2 concentrations (Baeten et al., 2020).

• The detection of nitrification endpoint by oxygen and carbon dioxide off-gas analysis and the
proposed control strategy could be tested in experimental work on batch reactors equipped with
an online oxygen and carbon dioxide analyzer.

• The influent organic carbon (TIC) was set at 150 g C.m-3 for all investigated influent compositions,
so the influence of this state on the correct endpoint detection has not been investigated.
Nonetheless, it can influence the carbon dioxide off-gas concentration in three ways. Firstly, it
includes the species of inorganic carbon that is transferred to the gas phase. Secondly, it acts as a
pH buffer and as such influences the carbon dioxide transfer rate, which is very much influenced by
pH. Finally, nitrifying organisms use inorganic carbon as a carbon source and hence the end of
nitrification (and its effect on carbon dioxide transfer) is influenced by the concentration of TIC. The
effect of influent TIC on the correct off-gas detection is therefore an interesting topic for future
research.

51
7. References
Al-Rekabi, W. S., Qiang, H., & Qiang, W. W. (2007). Review on sequencing batch reactors. Pakistan Journal
of Nutrition, 6(1), 11–19.
Alex, J., Benedetti, L., Copp, J., Gernaey, K. V, Jeppsson, U., Nopens, I., … Vanrolleghem, P. (2008).
Benchmark Simulation Model No. 2 (BSM2), Tech. rep.
Åmand, L., Olsson, G., & Carlsson, B. (2013). Aeration control – a review. Water Science and Technology,
67(11), 2374–2398.
Amaral, A., Gillot, S., Garrido-Baserba, M., Filali, A., Karpinska, A. M., Plósz, B. G., … Rosso, D. (2019).
Modelling gas-liquid mass transfer in wastewater treatment: when current knowledge needs to
encounter engineering practice and vice versa. Water Science and Technology, 80(4), 607–619.
Artan, N., Tasli, R., & Orhon, D. (2006). Rational basis for optimal design of sequencing batch reactors with
multiple anoxic filling for nitrogen removal. Process Biochemistry, 41(4), 901–908.
Artan, Nazik, & Orhon, D. (2005). Mechanism and Design of Sequencing Batch Reactors for Nutrient
Removal. London: IWA Publishing.
ASCE. (1997). Standard Guidelines for In-Process Oxygen Transfer Testing (ASCE 18-96). New York:
American Society of Civil Engineers.
Baeten, J. E., van Loosdrecht, M. C. M., & Volcke, E. I. P. (2018). Modelling aerobic granular sludge
reactors through apparent half-saturation coefficients. Water Research, 146, 134–145.
Baeten, J. E., van Loosdrecht, M. C. M., & Volcke, E. I. P. (2020). When and why do gradients of the gas
phase composition and pressure affect liquid-gas transfer ? Water Research, 178, 115844.
Basu, S., Pilgram, S. K., Keck, D. W., & Painter, C. (2006). ORP and pH Based Control of SBR Cycles for
Nutrient Removal from Wastewater. Water Environment Research, 78(1), 5890–5900.
Batstone, D. J., Keller, J., Angelidaki, I., Kalyuzhnyi, S. V., Pavlostathis, S. G., Rozzi, A., … Vavilin, V. A.
(2002). Anaerobic Digestion Model no1. London: IWA Publishing.
Broch, S. P. (2008). Operation and Control of Sbr Processes for Enhanced Biological Nutrient Removal From
Wastewater. University of Girona.
Casellas, M., Dagot, C., & Baudu, M. (2006). Set up and assessment of a control strategy in a SBR in order
to enhance nitrogen and phosphorus removal. Process Biochemistry, 41(9), 1994–2001.
Chandran, K., Volcke, E. I. P., & Van Loosdrecht, M. (2016). Off-Gas Emission Tests. In Experimental
Methods in Wastewater Treatment (1st ed.). London: IWA Publishing.
Chang, C. H., & Hao, O. J. (1996). Sequencing Batch Reactor System for Nutrient Removal: ORP and pH
Profiles. Journal of Chemical Technology & Biotechnology, 67(1), 27–38.
Doran, P. M. (2013). Mass Transfer. In Bioprocess Engineering Principles (2nd ed., Vol. 58, pp. 379–444).
London: Academic Press.
Dries, J. (2016). Dynamic control of nutrient-removal from industrial wastewater in a sequencing batch
reactor, using common and low-cost online sensors. Water Science and Technology, 73(4), 740–745.
Dutta, A., & Sarkar, S. (2015). Sequencing Batch Reactor for Wastewater Treatment: Recent Advances.
Current Pollution Reports, 1(3), 177–190.
Flores-Alsina, X., Kazadi Mbamba, C., Solon, K., Vrecko, D., Tait, S., Batstone, D. J., … Gernaey, K. V. (2015).
A plant-wide aqueous phase chemistry module describing pH variations and ion speciation/pairing in
wastewater treatment process models. Water Research, 85, 255–265.
Gapes, D., & Keller, J. (2001). Analysis of biological wastewater treatment processes using
multicomponent gas phase mass balancing. Biotechnology and Bioengineering, 76(4), 361–375.
Gapes, D., Pratt, S., Yuan, Z., & Keller, J. (2003). Online titrimetric and off-gas analysis for examining
nitrification processes in wastewater treatment. Water Research, 37(11), 2678–2690.
Garcia-Ochoa, F., Gomez, E., Santos, V. E., & Merchuk, J. C. (2010). Oxygen uptake rate in microbial

52
processes: An overview. Biochemical Engineering Journal, 49(3), 289–307.
Gerardi, M. H. (2010). Sequencing Batch Reactor Technology. Hoboken: John Wiley and Sons.
Gerba, C. P., & Pepper, I. L. (2015). Municipal Wastewater Treatment. In Environmental Microbiology (3rd
ed., pp. 583–606). Elsevier Inc.
Hegg, D., Cohen, T., Song, Q., & Kasabov, N. (2000). Intelligent Control of Sequencing Batch Reactors
(SBRs) for Biological Nitrogen Removal.
Hellinga, C., Vanrolleghem, P., Van Loosdrecht, M. C. M., & Heijnen, J. J. (1996). The potential of off-gas
analyses for monitoring wastewater treatment plants. Water Science and Technology, 33(1), 13–23.
Henze, M., & Comeau, Y. (2008). Wastewater characterization. Biol. Wastewater Treat. Princ. Model. Des.,
33–52.
Henze, M., Gujer, W., Mino, T., & Van Loosdrecht, M. (2000). Activated sludge models ASM1, ASM2,
ASM2d and ASM3. IWA Publishing.
Hreiz, R., Latifi, M. A., & Roche, N. (2015). Optimal design and operation of activated sludge processes:
State-of-the-art. Chemical Engineering Journal, 281(1), 900–920.
Kim, H., & Hao, O. J. (2001). pH and Oxidation-Reduction Potential Control Strategy for Optimization of
Nitrogen Removal in an Alternating Aerobic-Anoxic System. Water Environment Research, 73(1), 95–
102.
Leu, S., Rosso, D., Stenstrom, M. K., & Angeles, L. (2009). Real-Time Aeration Efficiency Monitoring in the
Activated Sludge Process and Methods to Reduce Energy Consumption and Operating Costs. Water
Environment Research, 81(12).
Leu, S. Y., Libra, J. A., & Stenstrom, M. K. (2010). Monitoring off-gas O2/CO2 to predict nitrification
performance in activated sludge processes. Water Research, 44(11), 3434–3444.
Lewis, W. K., & Whitman, W. G. (1924). Principles of gas absorption. Industrial and Engineering Chemistry,
16(12), 1215–1220.
Lijklema, L. (1969). Factors affecting pH change in alkaline waste water treatment—I. Water Research,
3(12), 913–930.
Marsili-Libelli, S. (2006). Control of SBR switching by fuzzy pattern recognition. Water Research, 40(5),
1095–1107.
Marsili-Libelli, S., Spagni, A., & Susini, R. (2008). Intelligent monitoring system for long-term control of
sequencing batch reactors. Water Science and Technology, 57(3), 431–438.
Meijer, S. (2004). Theoretical and practical aspects of modelling activated sludge processes. Delft
University of Technology.
Nancharaiah, Y. V., & Kiran Kumar Reddy, G. (2018). Aerobic granular sludge technology: Mechanisms of
granulation and biotechnological applications. Bioresource Technology, 247(September 2017), 1128–
1143.
Ni, B. J., Pan, Y., Guo, J., Virdis, B., Hu, S., Chen, X., & Yuan, Z. (2017). Denitrification Processes for
Wastewater Treatment. In Metalloenzymes in Denitrification: Applications and Environmental
Impacts (Vol. 2017-Janua, pp. 368–418). The Royal Society of Chemistry.
Oeggerli, A., Eyer, K., & Heinzle, E. (1995). On‐line gas analysis in animal cell cultivation: I. Control of
dissolved oxygen and pH. Biotechnology and Bioengineering, 45(1), 42–53.
Olsson, G, Nielsen, M., Yuan, Z., Lynggaard-Jensen, A., & Steyer, J.-P. (2005). Instrumentation, Control and
Automation in Wastewater Systems. In Water Intelligence Online. London: IWA Publishing.
Olsson, Gustaf, & Newell, B. (2005). Wastewater Treatment Systems: Modelling, Diagnosis and Control.
London: IWA Publishing.
Pell, M., & Wörman, A. (2008). Biological Wastewater Treatment Systems. In Encyclopedia of ecology (2nd
ed., Vol. 6, pp. 426–441). Oxford: Elsevier Inc.
Plisson-Saune, S., Capdeville, B., Mauret, M., Deguin, A., & Baptiste, P. (1996). Real-time control of

53
nitrogen removal using three ORP bending-points: Signification, control strategy and results. Water
Science and Technology, 33(1), 275–280.
Pratt, S., Yuan, Z., Gapes, D., Dorigo, M., Zeng, R. J., & Keller, J. (2003). Development of a novel titration
and off-gas analysis (TOGA) sensor for study of biological processes in wastewater treatment
systems. Biotechnology and Bioengineering, 81(4), 482–495.
Redmon, D., Boyle, W. C., & Ewing, L. (1983). Oxygen Transfer Efficiency Measurements in Mixed Liquor
Using Off-Gas Techniques. Water Science and Technology, 55(11), 1338–1347.
Rubio, M., Colomer, J., Ruiz, M. L., & Colprim, J. (2004). Qualitative Trends for Situation Assessment in SBR
Wastewater Treatment Process. In Proceedings of the 4th ECAI Workshop on Binding Environmental
Sciences and Artificial Intelligence (BESAI). Valencia.
Sander, R. (2015). Compilation of Henry’s law constants (version 4.0) for water as solvent. Atmospheric
Chemistry and Physics, 15(8), 4399–4981.
Schneider, M. Y., Carbajal, J. P., Furrer, V., Sterkele, B., Maurer, M., & Villez, K. (2019). Beyond signal
quality: The value of unmaintained pH, dissolved oxygen, and oxidation-reduction potential sensors
for remote performance monitoring of on-site sequencing batch reactors. Water Research, 161(1),
639–651.
Singh, M., & Srivastava, R. K. (2010). Sequencing batch reactor technology for biological wastewater
treatment: a review. Asia-Pacific Journal Of Chemical Engineering, 6(1), 3–13.
Smith, R. (2018). How to Control Denitrification Using Online Nitrate Sensors. Retrieved December 5,
2019, from http://www.waterworld.com/whitepapers/2015/08/how-to-control-denitrification-
using-online-nitrate-sensors.html
Solon, K., Flores-Alsina, X., Kazadi Mbamba, C., Ikumi, D., Volcke, E. I. P., Vaneeckhaute, C., … Jeppsson, U.
(2017). Plant-wide modelling of phosphorus transformations in wastewater treatment systems:
Impacts of control and operational strategies.
Sötemann, S., Musvoto, E., Wentzel, M., & Ekama, G. (2006). Integrated biological , chemical and physical
processes kinetic modelling Part 1 – Anoxic-aerobic C and N removal in the activated sludge system.
Water SA, 31(4), 529–544.
Spagni, A., Buday, J., Ratini, P., & Bortone, G. (2001). Experimental considerations on monitoring ORP , pH
, conductivity and dissolved oxygen in nitrogen and phosphorus biological removal processes. Water
Science and Technology, 43(11), 197–204.
Spanjers, H., & Vanrolleghem, P. (2016). Respirometry. In Experimental Methods in Wastewater
Treatment (1st ed., Vol. 9781780404). London: IWA Publishing.
Spérandio, M., & Paul, E. (1997). Determination of carbon dioxide evolution rate using on-line gas analysis
during dynamic biodegradation experiments. Biotechnology and Bioengineering, 53(3), 243–252.
Stenstrom, M. K., & Gilbert, R. G. (1981). Effects of alpha, beta and theta factor upon the design,
specification and operation of aeration systems. Water Research, 15(6), 643–654.
Stumm, W., & Morgan, J. J. (1995). Dissolved Carbon Dioxide. In Aquatic Chemistry : Chemical Equilibria
and Rates in Natural Waters (3rd ed., pp. 148–205). Somerset: John Wiley and Sons.
Van Loosdrecht, M. C. M., Nielsen, P. H., López Vázquez, C. M., & Brdjanovic, D. (2016). Experimental
Methods in Wastewater Treatment (1st ed.). London: IWA Publishing.
Vives Fabregas, M. T. (2004). SBR technology for wastewater treatment suitable operational conditions
for a nutrient removal. University of Girona.
Weissenbacher, N., Lenz, K., Mahnik, S. N., Wett, B., & Fuerhacker, M. (2007a). Determination of activated
sludge biological activity using model corrected CO2 off-gas data. Water Research, 41(7), 1587–
1595.
Weissenbacher, N., Lenz, K., Mahnik, S. N., Wett, B., & Fuerhacker, M. (2007b). Determination of activated
sludge biological activity using model corrected CO2 off-gas data. Water Research, 41(7), 1587–

54
1595. https://doi.org/10.1016/j.watres.2006.12.037
Yang, Q., Gu, S., Peng, Y., Wang, S., & Liu, X. (2010). Progress in the development of control strategies for
the SBR process. Clean - Soil, Air, Water, 38(8), 732–749.
Yuan, Z., & Keller, J. (2004). Integrated control of nitrate recirculation and external carbon addition in a
predenitrification system. Water Science and Technology, 48(11–12), 345–354.
Yuan, Zhiguo, Oehmen, A., & Ingildsen, P. (2002). Control of nitrate recirculation flow in predenitrification
systems. Water Science and Technology, 45(4–5), 29–36.
Zanetti, L., Frison, N., Nota, E., Tomizioli, M., Bolzonella, D., & Fatone, F. (2012). Progress in real-time
control applied to biological nitrogen removal from wastewater. A short-review. Desalination, 286,
1–7.

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