applied
sciences
Article
Accurate Estimation of Bicarbonate and Acetic Acid
Concentrations with Wider Ranges in Anaerobic Media Using
Classical FOS/TAC Titration Method
Xiaojun Liu 1 , Laura André 2 , Maël Mercier-Huat 1,2,3 , Jean-Marie Grosmaître 3 , André Pauss 1
and Thierry Ribeiro 2, *






Citation: Liu, X.; André, L.;
Mercier-Huat, M.; Grosmaître, J.-M.;
Pauss, A.; Ribeiro, T. Accurate
Estimation of Bicarbonate and Acetic
Acid Concentrations with Wider
Ranges in Anaerobic Media Using
Classical FOS/TAC Titration Method.
Appl. Sci. 2021, 11, 11843. https://
doi.org/10.3390/app112411843
Academic Editor: Francisco
Jesus Fernandez-Morales
Received: 9 November 2021
Accepted: 8 December 2021
Published: 13 December 2021
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Copyright: © 2021 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
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Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Appl. Sci. 2021, 11, 11843. https://doi.org/10.3390/app112411843
1 ESCOM, TIMR (Integrated Transformations of Renewable Matter), Centre de Recherches Royallieu,
Université de Technologie de Compiègne, CS 60319, CEDEX, 60203 Compiègne, France;
xiaojun.liu@utc.fr (X.L.); mael.mercier-huat@unilasalle.fr (M.M.-H.); andre.pauss@utc.fr (A.P.)
2 Institut Polytechnique UniLaSalle, Université d’Artois, ULR 7519, Rue Pierre Waguet, BP 30313, CEDEX,
60026 Beauvais, France; laura.andre@unilasalle.fr
3 Cultimer France Producteurs Associés, ZA Les Rolandières, BP 52, 35120 Dol-de-Bretagne, France;
jeanmarie.grosmaitre@cultimer.fr
* Correspondence: thierry.ribeiro@unilasalle.fr; Tel.: +33-(0)3-44-06-76-11
Abstract: The determination of a volatile fatty acid content (FOS) and total alkalinity (TAC) can
be carried out using Nordmann’s FOS/TAC titration method developed in the 1970s. This two-
point titration (pH = 5 and 4.4) can be simply implemented and is widely employed by both the
academic and industrial worlds. However, the present study proves that Nordmann’s method is only
valid in limited ranges, since the titration of one FOS and TAC has an impact on the determination
of the other, especially in extreme conditions. The present work develops a numerical tool with
Scilab simulating the acid–base equilibria of titration. The program is efficient in predicting the
experimental equivalent volumes obtained from Nordmann’s method with different combinations
of sodium acetate and sodium bicarbonate contents. The mean absolute percentage errors (MAPE)
between the simulation and experiment are below 7%. Two new formulas are developed, considering
both equivalent volumes at pH = 5 and 4.4 to calibrate FOS and TAC values. The proposed formulas
show their good performance in predicting various combinations of FOS and TAC contents in an
anaerobic digestate at TAC ranging from 0 to 20,000 mg CaCO3 ·L−1 and FOS ranging from 0 to
31,000 mg HAc·L−1 .
Keywords: anaerobic digestion; volatile fatty acids; alkalinity; numerical simulation
1. Introduction
Anaerobic digestion (AD) is attracting increasing attention due to its environmental
benefits such as the production of renewable energy (biogas) and the valorization of organic
biomass. Four key microbial transformation steps have been identified: hydrolysis, acido-
genesis, acetogenesis and methanogenesis. During the acidogenesis stage, the molecules
produced at the end of the hydrolysis stage are degraded by acidogenic microorganisms to
produce volatile fatty acids (VFAs) such as acetic, propionic and butyric acids. The VFAs
are then consumed by acetogenic and methanogenic microorganisms for the production of
biogas and, thus, methane. The acidic nature of VFAs leads to the acidification of reactors
by lowering the pH, which is a crucial parameter for the success of AD, particularly for
methanogenic activities. As shown in Table S1 in the Supplementary Materials, the acidity
constants (pKa) of the main VFAs found in a digester are relatively close to each other. For
this reason, the VFA concentration is often expressed in an equivalent acetic acid content
(usually expressed in g HAc·L−1 ). Depending on the digestion method and the nature of
substrates, the VFA concentration can reach 3 g HAc·L−1 or much more [1].
https://www.mdpi.com/journal/applsci
Appl. Sci. 2021, 11, 11843 2 of 14

When VFAs are not consumed and, therefore, accumulate in reactors, the alkalin-
ity characterizing the buffering capacity of reactors becomes an important indicator for
ensuring a stable and optimal pH (between 6.5 and 7.5) for AD processes. Theoreti-
cally, the term “total alkalinity” (TAC) is defined as the total proton acceptance capacity
of an aqueous system by weak acids such as carbonic acid (H2 CO3 /HCO3 − /CO3 2− ),
phosphoric acid (H3 PO4 /H2 PO4 − /HPO4 2− /PO4 3− ), ammonia (NH4 + /NH3 ) and OH−
ions. In an anaerobic digester, the buffering effect of H2 CO3 /HCO3 − , H3 PO4 /H2 PO4 − ,
H2 PO4 − /HPO4 2− , HPO4 2− /PO4 3− and NH4 + /NH3 is generally negligible compared to
that of HCO3 − /CO3 2− due to their low presence in the operational pH of AD [2]. This is
justified by the pKa values of different compounds constituting alkalinity (see Table S1 in
Supplementary Materials). Alkalinity is, thus, often presented in an equivalent carbonate
alkalinity and usually expressed in g CaCO3 ·L−1 .
Many methods for determining TAC and VFA concentration in a complex solution
have been proposed since the 1960s. The simplest ones rely on the acid–base character of
the compounds and are based on titration, a simple and inexpensive method. Since the
pKa of the H2 CO3 /HCO3 − couple differs from that of acetic acid, titration with a strong
acid (HCl or H2 SO4 ) by following the pH evolution is one of the methods developed and
widely used. For a pH between 6 and 8, as shown in Figure 1, most protons are consumed
by bicarbonate. However, at a pH less than 6, the VFAs (in most cases acetate) are titrated
as well. A total of 36.5% of acetate is transformed into acetic acid at pH = 5, while more
than 95% of bicarbonate is titrated. Between pH = 5 and pH = 4, acetate becomes the main
target of titration—about 50% more acetate (i.e., 86.5% in total) is titrated. Since less than
5% of the inorganic carbon is consumed at this moment, bicarbonate has a limited effect on
the determination of VFAs. Hence, the difficulty in interpreting the titration result arises
from the fact that VFAs, mainly in their dissociated form (e.g., acetate) at a pH between 5
and 6, are also titrated and taken into account as the bicarbonate alkalinity. In summary,
during the TAC titration, VFAs are strongly involved, whereas the effect of TAC on VFA
determination exists but can be less significant.

Figure 1. Acid–base equilibria of different compounds as a function of pH at 25 ◦ C.

Lili et al. (2011) [3] showed that the ratio of VFA concentration to the total alkalinity can
be used to assess the adequacy of the organic load in anaerobic digesters. It should be noted
that for a successful anaerobic digestion and process stability, the ratio should generally
be less than 0.4. Consequently, a wrong result of VFA and TAC contents could lead to
reactors being operated incorrectly. In the particular case of two-stage anaerobic digestion,
the digestate at the outlet of hydrolysis digesters (55 ◦ C) could have an extremely high VFA
concentration and a disproportionately low alkalinity [4]. Conversely, the digestate at the
outlet of the anaerobic digester could have a relatively low VFA concentration compared to
the alkalinity, which would be very high [5]. This would likely distort the titration result.
Appl. Sci. 2021, 11, 11843 3 of 14

The accurate determination of VFAs and TAC by minimizing the interference between
them becomes a crucial factor to ensure the right operation of anaerobic digesters.
The implementation of VFAs and alkalinity titration has been extensively studied
over the past 60 years. Many studies focus on the direct titration of samples by looking for
different pH turning points to minimize the effect of mutual interference.
The direct titration with two pH equivalent points was first developed by Nordmann
(1977) [6]. It is called the “FOS/TAC” method, and is most widely used today. In this
method, the VFA concentration is called the FOS for “Flüchtige Organische Säuren” in
German. During FOS/TAC titration, the consumption of a strong acid up to pH = 5
(denoted A, in mL) reflects the buffering capacity of the system carried by bicarbonate,
which is also called the TAC (see Figure 1). Between pH = 5 and pH = 4.4, protons are
assumed to react exclusively with organic acids [7]. The volume of titrant consumed
between these two pH values (denoted B, in mL) is used to calculate the FOS [8]. This
method is only valid for a low FOS concentration because the latter could interfere with
the TAC determination as mentioned above. The alkalinity determination at pH = 5
is inevitably biased in the case where VFA concentration is much higher. This simple,
but partially inaccurate, approach is largely used, because it is easy to implement and
allows for the evaluation of the adequacy of the organic loading in an anaerobic digester,
especially if it is used to follow the relative evolution of one specific reactor. The Nordmann
method can be implemented in Hach or METTLER TOLEDO titration devices. It is this
Nordmann FOS/TAC method (1977) that the present paper proposes to optimize but
keeping the simplicity of the experimental realization by correcting the calculation formulas,
considering the reciprocal interferences between the FOS and TAC.
Besides Nordmann (1977), Jenkins et al. (1983) [9] proposed an alternative method of
titrating the solution by a strong acid with a single stop at pH = 5.75. The method remains
approximate and is only valid for a restricted range (TAC < 2000 mg CaCO3 ·L−1 and
VFA < 500 mg HAc·L−1 ). The two-pH titration method has been modified or improved
since the 1980s. Ripley et al. (1986) [10] proposed the distinction between partial alkalinity
and intermediate alkalinity. Similarly, additional pH equivalent points have been added
for a better evaluation of FOS/TAC such as the four-point [11], five-point [12] and eight-
point [13,14] titration. The advantages and disadvantages of these different methods
have been described by many authors [3,15–19]. In general, multi-point titration has
a satisfactory accuracy for a VFA concentration below 5 g HAc·L−1 , which covers the
FOS content in most traditional anaerobic digesters. However, these methods require an
unconventional experimental design and more complex calculations.
In addition, FOS/TAC titration can also be complemented by accurately determining
one of the parameters involved (VFA or bicarbonate). DiLallo and Albertson (1961) [2]
first developed the “back titration” method for the determination of VFA and TAC in an
anaerobic digester. The solution is acidified to a low pH and then boiled to remove the
CO2 gas produced by the carbonic acid. The solution is then titrated for the second time
with a strong base (i.e., back titration) to obtain the VFA concentration. Different variant
methods have been developed, such as the studies of O’Brien and Donlan (1977) [20] and
Pauss et al. (1990) [21].
TAC is often calibrated by taking into account the concentration of VFAs. An accurate
VFA determination could be achieved by physical separation technologies such as steam
distillation, direct distillation, chromatography [22] and the total organic carbon (TOC)
analysis [23].
Approaches to simulate titration phenomena have also been investigated. Mu et al. (2018)
and Münch and Greenfield (1998) [24,25] have developed nonlinear models based on the
acid–base equilibrium theory. Coupling the pH measurement with electrical conduc-
tivity [26], the dry matter content [27] and spectrometric property [28] of the titrated
solution can give a better accuracy of VFA determination. The buffer intensity inte-
gral of different compounds allowed for a better determination of VFA content [26,29].
Møller et al. (2011) [4] gave a multiple linear model by considering the initial pH and the
Appl. Sci. 2021, 11, 11843 4 of 14

equivalent volumes of two pH points. This method showed a good efficiency of VFA con-
tent quantification with a very wide validation range between 38 and 30,056 mg HAc·L−1 .
TAC determination, however, has not been discussed.
The last 60 years of work have revealed the fact that: (1) The reciprocal impact of TAC
and FOS is often omitted, especially for the “FOS/TAC” method proposed by Nordmann;
(2) the different techniques developed are only effective for a limited range of FOS and
TAC. The determination in reactors treating special substrates that are richer in bicarbonate
and VFAs remains to be studied; (3) many studies focus on VFA determination, not on both
VFAs and TAC and (4) direct titration techniques are generally easier to perform, but lack
accuracy, while techniques that separately determine VFAs and TAC are more accurate, but
more sophisticated and require additional equipment or complex experimental protocols.
The present study is based on the most common “FOS/TAC” method of Nordmann.
It aims to develop a model for the determination of bicarbonate and VFAs that is both
accurate and simple with a very wide validation range. The objectives of the present study
are (1) the experimental demonstration of the impossibility to independently estimate FOS
and TAC in high-loading samples by Nordmann’s FOS/TAC method; (2) the simulation
of the FOS/TAC titration curve and the experimental validation of these simulations in
different artificial mixtures of pure sodium bicarbonate and sodium acetate; (3) with the
help of the simulation, the establishment of alternative formulas to the Nordmann formulas,
allowing a more accurate estimation of bicarbonate and VFA concentration in wider ranges
of FOS and TAC; (4) the experimental validation of the proposed formulas using real
digestion samples.

2. Materials and Methods

2.1. Nordmann’s FOS/TAC Titration
2.1.1. Presentation of the Method
Nordmann (1977) developed the titration technique for determining alkalinity and
VFA content of sewage sludge. This method was introduced and adapted to samples from
biogas plants by McGhee in 1968 [7,8].
The buffering capacity of the system (TAC) was determined by titrating the 20 mL
samples from their initial pH to pH = 5 with sulfuric acid. The TAC could, thus, be
calculated according to Equation (1).

TAC = A × 250 (1)

where TAC (mg CaCO3 ·L−1 ) is the total alkalinity and A (mL) is the equivalent volume of
0.1 N H2 SO4 to reach pH = 5.
The determination of FOS (VFA concentration) was based on titration of the solution
from pH = 5 to pH = 4.4. Equation (2) was then obtained by using the linear relationship of
acid consumption versus FOS as described by McGhee (1968) [8].

FOS = (B × 1.66 − 0.15) × 500 (2)

where FOS (mg HAc·L−1 ) is the VFAs content with regard to acetic acid; B (mL) is the
equivalent volume difference of 0.1 N H2 SO4 between pH = 5 and pH = 4.4.
It should be noted that Equations (1) and (2) are based on the titration of a 20 mL
sample [7]. The coefficient values in these formulas may vary if a different titration volume
is applied.

2.1.2. Preparation of Sodium Bicarbonate and Sodium Acetate Solutions for FOS/TAC Titration
To verify the accuracy of the method developed by Nordmann (1977), sodium acetate
trihydrate (ASC, ISO, Reag. Ph. Eur., Merck, Darmstadt, Germany), sodium bicarbonate
(99.5%, Sigma, St. Louis, MO, USA) and deionized water at 18 MΩ·cm were used to
prepare the solutions of different combinations of FOS and TAC contents. Eight acetic
acid concentrations (FOS = 0, 145, 536, 1126, 3138, 5044, 10,315 and 20,472 mg HAc·L−1 )
Appl. Sci. 2021, 11, 11843 5 of 14

and nine alkalinity concentrations (TAC = 0, 510, 1487, 2517, 4010, 5999, 7523, 10,005 and
12,492 mg CaCO3 ·L−1 ) were selected. A total of 72 solutions was used for this work.

2.1.3. Experimental Realization

The HACH AT1102 potentiometric titrator with 1 syringe (HACH, Loveland, CO, USA)
was used to perform the titration of the above 72 solutions. The pH electrode was calibrated
at pH = 4, 7 and 10. The titrator application kit “FOS/TAC (BIOGAS)” (AP0006.AT1102)
was used to obtain the FOS and TAC values using Nordmann’s method.
It should be noted that according to the HACH protocol, the titrator determines the
FOS/TAC for a 5 mL sample instead of 20 mL. Thus, 5 mL of sample is diluted in 15 mL of
deionized water in a specific beaker. A stirring rod and the pH electrode were introduced
into the beaker. The 0.1 N standard sulfuric acid (0.05 mol H2 SO4 ·L−1 , Ref. 20253, HACH)
was used as the titrant. At the end of the titration, the Nordmann’s FOS, TAC and equivalent
volumes were displayed on the titrator screen. The formulas to calculate FOS and TAC
were adapted to the 5 mL titration as shown in Equations (3) and (4).

A × Ctit ×50045
TACemp = (3)
Vsample

FOSemp = (B × 1.66 − 0.15) × 500 (4)

where TACemp (mg CaCO3 ·L−1 ) is the total empirical alkalinity content using Nordmann’s
method; A (mL) is the equivalent volume of 0.1 N H2 SO4 to obtain pH = 5; Ctit (moleq ·L−1
or N) is the concentration of sulfuric acid as titrant (Ctit = 0.1 N); Vsample (mL) is the volume
of titrated sample (Vsample = 5 mL); FOSemp (mg HAc·L−1 ) is the empirical VFA content
using Nordmann’s method and B (mL) is the difference of two equivalent volumes at
pH = 5 and pH = 4.4.
Sodium bicarbonate (NaHCO3 ) was used to simulate different alkalinity in the solu-
tions. Its titrated concentration [NaHCO3 ] (mg NaHCO3 ·L−1 ) could, therefore, be recalcu-
lated from the TAC value given by the titrator:

TAC × 84 × 2 TAC
[NaHCO3 ] = = (5)
100 0.595
The titration results were recorded and then further treated using Scilab software
(ESI Group, Rungis, France).

2.2. Simulation of FOS/TAC Titration Curve

It was possible to numerically simulate the titration curves based on the acid–base
equilibrium theory. This allowed finding the relations that determined FOS and TAC
accurately (see Section 2.3). The simulations were developed with the Scilab software
(ESI Group, Rungis, France). The simulated results were validated experimentally with
the titration of various solutions of pure sodium bicarbonate and sodium acetate mixture
as presented in Section 2.1. The buffering effect of H2 CO3 /HCO3 − , H3 PO4 /H2 PO4 − ,
H2 PO4 − /HPO4 2− , HPO4 2− /PO4 3− and NH4 + /NH3 was ignored since these acid/base
couples were much less present at pH below 8 for most anaerobic digested samples.
The simulation code is available in Supplementary Materials, as well as the flowchart
of programming (Figure S1).

2.3. Multiple Linear Regression of Simulated Results

In the Nordmann method, Equations (1) and (3) above show that TAC is a linear
function of the first equivalent volume (i.e., A in mL). Equations (2) and (4) show that FOS
is a linear function of the difference of the two equivalent volumes (i.e., B in mL). Since
FOS and TAC interfere in the titration of each other, two new 3-parameter models were
proposed in the present work to calibrate the determination of TAC and FOS. This was a
multiple linear regression assuming that TAC and FOS depended on both A and B.
Appl. Sci. 2021, 11, 11843 6 of 14

With the simulated data to be validated by experiments, and by using the Scilab solver
for multiple linear regression, it was possible to identify the model coefficients to calculate
the bicarbonate (or equivalent TAC) and acetic acid concentrations:

[NaHCO 3 ]new = α1 ×A+α2 ×B+α3 (6)

[HAc]new = FOSnew = β 1 ×A+ β 2 ×B+ β 3 (7)

where [NaHCO3 ]new (mg NaHCO3 · L−1 )
is the new sodium bicarbonate content; [HAc]new
(mg HAc·L−1 ) is the new acetic acid content, namely, FOS; A (mL) is the equivalent volume
of 0.1 N H2 SO4 to obtain pH = 5; B (mL) is the difference of two equivalent volumes at
pH = 5 and pH = 4.4; α1 , α2 and α3 and β 1 , β 2 and β 3 are the model parameters for multiple
linear regression.
The simulation range of sodium bicarbonate and acetic acid contents was both extended to
40,000 mg·L−1 equivalent to TAC = 23,800 mg CaCO3 ·L−1 and FOS = 40,000 mg HAc·L−1 ,
since the simulation was proved to accurately predict the experimental results (see
Sections 3.1 and 3.2).
By applying Equation (5), [NaHCO3 ] could be converted to the equivalent alkalinity
(TACnew ). One could also use the FOS and TAC values calculated with the Nordmann
formulas (i.e., TACemp and FOSemp ), recalculate the values of “A” and “B” and then
reinject these values into the above formulas in order to correct the initial FOS and TAC
(see Section 3.3).

2.4. Experimental Validation of the Proposed New Formulas

The anaerobic digestate collected from a local biogas plant (Coudun, Oise, France)
receiving agricultural waste was used as real medium for experimental validation of the
proposed new FOS and TAC formulas. The digestate, after being filtered through a 1 mm
sieve, had a total solids content (TS) of 6.5% and a volatile solids content (VS/TS) of 65%.
The FOS/TAC titration was performed using the automatic titrator. Its empirical FOS and
TAC with Nordmann’s method were, respectively, found at 11,009 ± 674 mg CaCO3 ·L−1
and 2452 ± 64 mg HAc·L−1 .
In order to remove as much bicarbonate as possible, 200 mL of the digestate and a
stirring rod were put into an Erlenmeyer flask. The initial pH of the digestate was measured
(pH = 7.74). Sulfuric acid (40%w /w ) was introduced dropwise to obtain pH = 4.03 on a
magnetic stirrer. Two drops of anti-foaming agent were added to prevent foam production.
The flask was then sealed and put in vacuum condition by a vacuum pump for 10 min
(1.6 × 104 Pa, Bioblock scientific, Illkirch-Graffenstaden, France). It is considered that a
majority of the bicarbonate could be destroyed at pH = 4 and, therefore, transformed into
CO2 that was extracted in vacuum condition [21]. The flask was then opened. NaOH
(3 mol·L−1 ) was added dropwise into the digestate to bring the pH back to approximately
its initial value (final pH = 7.86).
The degassed digestate was tested again in terms of its empirical TAC and FOS
(denoted X and Y mg·L−1 , respectively). Different combinations of total bicarbonate
content (put as TAC) and total acetic acid content (put as FOS) were prepared using this
degassed digestate by adding additional NaHCO3 and NaAc·3H2 O. The tested FOS and
TAC conditions are shown in Table 1. Each condition was realized by the Hach automatic
titrator in duplicate. The empirical FOS and TAC values from Equations (3) and (4) were
recorded and then converted into new FOS and TAC using Equations (6) and (7). All
empirical and new FOS and TAC values were compared with the real FOS and TAC values
to see the difference, interpreted by mean absolute percentage error (MAPE).
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Y + 1000 ✓ Y + 5000 Y + 1000
FOS

Total FOS
HAc·

(mg HAc·
3. Results and Discussion ✓ 3. Results ✓ and 3.
Discussion
Results and Discussion ✓✓
Total

50003. Results and Discussion ✓

YY++10,000 Y + 30,000 Y + ✓20,000 Y + 10,000 Y + 5000
(mg(mg

3. Results ✓ and Discussion Y✓✓NaHCO ✓+ 10,000

Total

3.1. FOS/TAC Titration

20,000
Y + 10,000 of Artificial Solutions with Pure NaHCO
Y +✓ 30,000 3.1.
3 and
FOS/TAC
NaAc Titration
3.1.
+ 20,000 and Y FOS/TAC of Artificial
Titration Solutions
of Artificial
with Pure
Soluti N
3.1. FOS/TAC Titration of Artificial Solutions with Pure 3 NaAc
TheY accuracy
+ 30,0003.1. FOS/TAC
20,000 of the ✓ “FOS/TAC” 3. Results
Titration and Discussion
ofdetermination
Artificial Solutions method with Pure TheYNaHCO
developed ✓ + 30,000
accuracy by3 andNordmann
of
The Y✓accuracy
NaAc
✓
the + “FOS/TAC”
20,000 of the ✓determination
“FOS/TAC” d
The accuracy of the “FOS/TAC” determination method developed by Nordmann
(1977) [6]Y +was30,000 The✓
studied.
(1977)
Solutions
accuracy
[6]
at
of eight
3.1. FOS/TAC
was studied. theSolutions 3.
“FOS/TAC” Results
equivalent
Titration ofacetic
at eight
and
ArtificialDiscussion
(1977)
determinationacidSolutions
concentrations
equivalentmethod
[6] waswith (1977)
studied.
acetic acid
Pure and
[6]
developed✓ Solutions
YNaHCO+was
nine
concentrations30,000 studied.
by3 andat NaAc ✓Solutions
eight
Nordmann and
equivalent
nine
at eiga
alkalinity
3. Results concentrations
and (1977)
Discussion [6] werestudied.
was prepared to
Solutions
The accuracy simulate
3.1. at different
eight
FOS/TAC
of the “FOS/TAC” alkalinity
3.
equivalenttrue
Results
Titration FOS
of concentrations
and
acetic and
Artificial
determinationalkalinity
TAC
Discussion
acid concen- concentrations
concentrations
Solutions were
method with prepared
Pure and
developed NaHCOwere
to
nine simulate
prepared
and
by Nordm
3 NaAdi
alkalinity concentrations were prepared to simulate different true FOS and TAC concentra-
trations.
3. Results Some
and experimental
alkalinity
Discussion values
concentrations
(1977) were
[6] was missing
were prepared
studied. at extremely
to
Solutions trations.
simulate low
at or
Some
different
eight high trations.
experimental
3. [HAc]
equivalent true
Results FOSdue
Some and to
and values
experimental
TAC
Discussion were
concen- missing
values at
wer ex
3.1. FOS/TAC Titration tions. Some of Artificial Solutions
experimental with
values Pure
The
were NaHCO
accuracy
missing 3.1.
3 andFOS/TAC
NaAc
of extremely
at the “FOS/TAC” low orofacetic
Titration Artificial
determination
high acidSolutions
[HAc] concentrations
duemethod to thewith Pure and
develo N
the detection
3.1. FOS/TAC limits of
trations.
Titration theSome
of automatic
experimental
alkalinity
Artificial titrator.
Solutions The
values
concentrations
(1977)
with instrument
Pure were
[6] NaHCO were
was the
missing did detection
prepared
studied.
and not
atNaAc allow
extremely
to
Solutions limits
the
the
simulate
3.1. detection
addition
atof
low theor
different
eight
FOS/TAC automatic
high of
limits[HAc]
equivalenttrue
Titration of titrator.
the
due
FOS
of automatic
acetic to
and
ArtificialTheTAC
acid instru
titr
con
conc
Soluti
The accuracy detection
of the limits “FOS/TAC” of the automatic
determination titrator. The instrument
method 3 developed
The accuracy didby notNordmann
ofallowthe the addition of
“FOS/TAC” more
determination
more than 25 mL of the titrant as preset by the FOS/TAC titration
more than program.25 mLmore of
Sometimes,
than
theextremely
titrant
25 mL asof preset
thedifferent
ortitrant
byofthe as FOS/T
prese
(1977)The was the
[6] accuracy detection
than
studied.
of 25
the mL
Solutionslimits
of trations.
“FOS/TAC”the at ofeight
the
titrant Some automatic
alkalinity
asequivalent
preset
determination bytitrator.
experimental the
acetic The
values
concentrations
FOS/TAC
method (1977) instrument
aciddevelopedwere
titration
concentrations
[6] was missing
were did
prepared
program.
studied.
by
not
at
and
Nordmann
The
allow to
Sometimes,
Solutions
nine
accuracy
the
simulate addition
low
at
of even
eight
the highthe [HAc]
equivalent
“FOS/TAC” true FOdad
even the addition moreof a
addition small
than 25 amount
mLthe
of a small of of
the
detection titrant
titrant to
limitsas a
trations. depleted
preset
of the Some by even
FOS
the
automatic and
the
FOS/TAC
experimental addition
TAC
titrator. solution
even
titration
The
values of the
a small
would
addition
program.
instrument
were amount
missing did of a of
Sometimes,
not small
atcause titrant
allow
extremely amount
to
the a depl
additi
low of or t
alkalinity
(1977)
cause the
concentrations
[6] equivalent
was studied. point
were
Solutions
to be atamount
prepared
exceeded,
of
eighttoequivalent
making
titrant different
simulate
the
to a depleted
acetic alkalinity
acid
calculation
cause
true
the
FOS
FOS
of FOS
and
equivalent
TAC
concentrations
concentrations and TACand
(1977)
or
causeTAC
solution
concen-
[6]
the
point
impos-
were
was
nine
equivalent
to
would
prepared
studied.
be exceeded,
point
to the
Solutions
to
simulate
making
be at eig
exceed the
di
trations. Some even the
equivalent
experimental addition more
point
values of abesmall
to than
were 25
exceeded,amount
mL
the of of
detection
making titrant
thedifferent
titrant to
limits
the as a depleted
preset
of FOS
calculation the by FOS
ofthe
automatic FOS and
FOS/TAC
or TAC
titrator.
TAC solution
titration
The instrument
impossible. would
program. did Someti
not a
alkalinity
sible. concentrations were prepared tomissing
simulate at extremely trations.
low
true
sible.
or
Some high
and experimental
[HAc]
alkalinity
TAC
sible.
due
concen- tovalues
concentrations were missing
were prepared at ex
the detection cause
limits the
Figure equivalent
of the automatic 2 even
shows point
the the
titrator. to
addition be
experimental
more exceeded,
of a small
than
The instrument sodium
25 making
amount
mLthe the
of
bicarbonate
of the
diddetection
notor calculation
titrant
titrant
allow to a
concentration
limits
the as of
depleted
preset
addition
of the FOS by
automaticor
FOS TAC and
determined
the FOS/TAC
of experimental impos-
TAC with
titrator.values solution
titration
The instru w
pr
trations. Some
Figure experimental
2 shows the experimental values were sodium missing at extremely
bicarbonate low high trations.
[HAc] due
Some 2to wer
more
the than 25limits
detection
sible.
mL Nordmann’s
ofofthe the titrant cause
empirical
automatic the
as preset equivalent
formula
titrator. by theeven
The point
(Equation
the
FOS/TAC
instrument toconcentration
addition be
(3)) ofFigure
exceeded,
at
titration
more
did different
athan
not small
program.
allow
2determined
shows
25making
acetic
amount
mLthe
the of
Figure
the of experimental
the
acid
Sometimes,
the
detection
addition
with
titrant
titrant
shows
calculation
levelsof to
limits against
as
the
apreset
of ofsodium
depleted
the
experimental
FOS
its by or
real bicarbon
FOS
the
automatic TAC and
FOS/T
soT
im
titr
Nordmann’s empirical formula (Equation (3)) at different acetic
Nordmann’s
acid levels empirical
Nordmann’s
against its
formula real empirical
(Equation formula (3)) at
(Equatio
differe
even the
more thanaddition
25 mL ofFigure
concentration.
athesmall 2 amount
titrant
shows
sible.
The the
as presetof experimental
empirically
titrant
by thetocalculated
cause the
a depleted
FOS/TAC
sodium
equivalent bicarbonate
concentrations
even
FOS
titration and
thepoint addition
TAC
program. toconcentration
of
be bicarbonate
exceeded,
solution
more of athan
Sometimes,small
would determined
25makingobviously
amount
mL the with
varied
calculation
of titrant
ofempirically
the titrant toasaprese of
depl
concentration. The empirically
Nordmann’s
linearly with calculated
empirical
the Figure
real formula2
values,concentrations
shows (Equation
highly
sible. the of
(3))
experimental
dependent concentration.
bicarbonate
at different
on sodium
the obviously
aceticconcentration.
The
acetic empirically
acid
bicarbonate
acid varied
levels
concentration. Thecalculated
against
concentration its
For concentratio
real calculate
determined
low
cause
even the equivalent
thewith
addition point
of a values, to
small amount be exceeded,
of making
titrant to on the
a depleted calculation
cause
FOS andtheof FOS
equivalent
TACthe or TAC
solution
even thepoint
impos-
would
addition to be exceeded,
of a values,
small amount making the
of t
linearly the real
concentration.
acetic acidto highly
Nordmann’s
concentrations dependent
The empirically calculated
empirical
(i.e., [HAc] the
Figure acetic
formula
= linearly
0,shows
145,acid
2concentrations
(Equation
536
the concentration.
with
and of
(3)) linearly
1126
experimental real
bicarbonate
atTAC values,
For
different
mg Lwith
−1low
·impos-
sodium thehighly
),obviously
acetic
the realacid
average
bicarbonate dependent
varied
levels
error highly on the
against
concentrati depits
sible.
cause the equivalent point be exceeded, making the sible.
calculation of FOS or
cause the equivalent point to be exceed
acetic acid concentrations
linearly (i.e., [HAc] = 0, 145, 536 andthe 1126 acetic mg· acid
Lformula
−1 ),method
concentrations
theacetic
average acid errorconcentrations
(i.e., at[HAc] =3 low
]0,(i.e.,
145,[HAc]536
acidan vl=
sible.Figure 2 shows thewith
between the the
experimental real values,
concentration.
[NaHCO sodium highly
The
3 ] determined
Nordmann’s
bicarbonate dependent
empirically
by empirical on
calculated
FOS/TAC
concentration the
Figure acetic acid
2concentrations
and
(Equation
determined
shows
sible. the concentration.
the of bicarbonate
real
(3))
experimental
with [NaHCO For
differentsodium obviously
was
acetic
bicarbon
between the [NaHCO acetic ]
acid determined
concentrations by the FOS/TAC
for(i.e., method between
and the the real [NaHCO
[NaHCO
between ] determined
the
] was [NaHCO by ] determined
−the
1 FOS/TAC by m t
at[HAc] = 0,itacetic
145, 536 and 1126 mg· L ),acetic
the average ·L error
−1
less than 3 3%, whereas
linearly with larger
the real[HAc],
concentration. values, was
The3138,
highly 5044,
dependent
empirically 10,315 on
calculated 3and
the 3 20,472 mgconcentration.
acid 3 ; (3))
this For
Nordmann’s
Figure
less than 3%, 2 empirical
shows
whereas thefor formula
experimental
larger
(Equation
[HAc], sodiumit
(3))
was
different
bicarbonate
3138, 5044,
Nordmann’s
10,315
less
acid
concentration
than and
levels
3%,
empirical
20,472
against
determined
whereas
less mg· Figure
than L
its
formula
for
−13%,;with2concentrations
real
this shows
larger
(Equation
whereas thefor
[HAc], it
of bicarbona
experimental
larger
was
at differe
3138,
[HAc] so5
between
concentration.empiricaldiscrepancy
The the [NaHCO
empirically increased
acetic 3] determined
acid
calculated from 26% toby247%.
concentrations
linearly
concentrations the(i.e.,
with FOS/TAC
of This
the realmeant
[HAc]
concentration.
bicarbonate method
= 0,
values, that 145, and
the
highly
obviously
The 536 the
higher and
dependent
empirically
variedreal the
1126 [NaHCO
acetic
mg·
on the
calculated 3]),was
Lacid
−1 con-average
the
acetic acid
concentratio con
Nordmann’s
discrepancy increased formula
from 26% (Equation
to accurate
247%. (3))
This atmeant
different that acetic
the acid
discrepancy
higher levels
the Nordmann’s
against
increased
acetic
discrepancy acid its
from real
con- empirical
increased
26% to 247%. formula
from This
26% (Equatio
meant
to 247%
linearly with less
the than
centration,
real 3%,
values, whereas
the less
between
highly for
the
dependent largerthe
[NaHCO
acetic [HAc],
bicarbonate
on ]
acid
3
the it was
determined 3138,
determination.
concentrations
acetic linearly
acid by 5044,
the
concentration.
with 10,315
(i.e.,
the The
FOS/TAC [HAc]
real and
bicarbonate
method
=
values,
For 20,472
0,
low 145,
highly mg·
536 L
concentration
and the −1; this
and real
dependent [NaHCO
1126 mg·
on L−13]
the
concentration.
centration, the less The accurate
empirically the calculated
bicarbonate concentrations
determination. ofThe bicarbonate
centration,
bicarbonate the obviously
concentration.
less
centration,
concentration
accurate varied the the The
less empirically
bicarbonate
accurate the calculate
determinat
bicarbon
acetic acid discrepancy
and,
concentrations thus, increased
the
(i.e., corresponding
less than
[HAc] from
=3%, 26%
0, 145, TAC
whereas
between to 247%.
536thewerefor
the
and This
[NaHCO
1126 aceticmeant
systematically
larger [HAc],
mg· that
] −1determined
acid
3L the the
overestimated
),itconcentrations
was higher
3138,
average by 5044,
thethe
error by acetic
(i.e.,the
10,315
FOS/TAC [HAc] acid
Nordmann’s
and con-
= 20,472
method0, 145, mg·
and
536the Lan−1
linearly
and, thus, with
thethe real values,
corresponding highly
TAC dependent
were systematically on acetic
overestimated
and,acid thus,concentration.
by
the thelinearly
corresponding
and,Nordmann’s
thus,Forwith low
the the real
corresponding
TAC were values, highly
systematically
TAC weredep
centration,
FOS/TAC the less
formulas. accurate
discrepancy This the
justifiedbicarbonate
the remark determination.
in the previous The bicarbonate
section that concentration
the acetate reacts
between
acetic
FOS/TAC
theconcentrations
acid [NaHCO3] determined
formulas. This (i.e.,
justified [HAc] by =the
the remark 0,increased
less 536
FOS/TAC
145,
in the
thanfromand3%,1126
method
previous
26%
whereas
between
FOS/TAC
to 247%.
and
mg·
section Lfor
the the
−1
that
real This
larger
[NaHCO
[NaHCO
),formulas.
the
the aceticmeant
[HAc],
average
FOS/TAC
acetate acid
This
]that
3] 3determined
was
error
reacts
formulas.
justified
higher
itconcentrations
was 3138,
the
by5044,
This remark
the
the acetic
10,315
FOS/TAC
(i.e.,
justified in [HAc]
the
acid
and
thepre rem
m =
less than the and,
3%,[NaHCO with thus,
whereas3]forthe the
protoncorresponding
during
centration,
larger [HAc], the
it wasTAC
discrepancywere
determination
less accurate
3138, method systematically
the of
increased
5044, 10,315 less the
bicarbonate
than from
and3%, overestimated
bicarbonate 26%
20,472
whereas to alkalinity.
determination.
mg·Lfor247%. −1 by
; was
this the
This
largerThe Nordmann’s
Thismeant additional
bicarbonate
[HAc], that theconcentr
it was 3138, higher 5t
between
with the proton during the determined
determination by the FOS/TAC
of thetakenbicarbonate with and the
alkalinity.
the real [NaHCO
between 3the
] [NaHCO 3] determined by
consumption
FOS/TAC formulas. of the
and, Thistitrant was
justified the remarkinto account
in the inproton
previous thethe This
with
TAC during
section additional
thethat
calculationproton
the determination
the during
and,
acetate the
therefore,
reacts determinat
of the bica
discrepancy
less than 3%, increased
whereas from
for 26%
larger tothus,
247%.
[HAc], the
it corresponding
This
wascentration,
meant
3138, 5044, the TAC
that less
the
10,315 were
accurate
discrepancy
higher and systematically
the
20,472 bicarbonate
increased
acetic
less mg· acid
than L from
−13%,;overestimated
con-
this determination.
26%
whereas to 247%. for bylarger
the
The
This Nordma
bicarb
meant
[HAc]
consumption ofwith the titrant
distorted
the protonwas
the takenespecially
result,
during
FOS/TAC into
the account forthus,
determination
formulas.and, in the
the
This theTAC of
justified consumption
determination thecalculation
the
corresponding remarkof TAC
bicarbonate ofconsumption
and,
in
TAC the
with therefore,
titrant
alkalinity.
the were a high
previous was of
FOS
Thisthe
taken
section
systematically titrant
content. into
additional
that was
account
the
overestimated taken
acetate inin rt
centration,
discrepancy the less accurate fromthe bicarbonate determination. The
centration,
bicarbonate theacetic
less
concentration
accurate the bicarbonate determinat
distorted theincreased
result, especially
consumption
26%
of for
the
with
tothe247%.
titrant
the proton
This
determination
was
meant
taken
during the
FOS/TAC of
into
that
TAC the
account
higher
distorted
with
determination
formulas. a
in highthe
the
This justified
the FOS
TAC
of
discrepancy
result,
distorted
the
acid
content.
especially
calculation
the the
bicarbonate
remark
con- increased
result,
for
and,
in the the from
especially 26%
determination
therefore,
alkalinity.
previous for
This
tothe
section
247%
addit of
de
th
and, thus, the
centration, thecorresponding
less accurate the TAC were
bicarbonate systematically
determination. overestimated
and,bicarbonate
The thus, by
thethe corresponding
Nordmann’s
centration,
concentration the TAC less were
accurate systematically
the bicarbon
FOS/TAC distorted the result, especially
consumption of for
withthe the
the determination
titrant proton was taken
during of
intothe TAC with
account
determination a
in high
the FOS
TACof content.
thecalculation
bicarbonate and, there
alkalin
and, thus, formulas. This justified
the corresponding TACthe were remark in the previous
systematically FOS/TAC
section that
overestimated formulas.
by the the acetate
and, Thisreacts
Nordmann’s
thus, justified
the corresponding the remarkTAC in the pre
were
with the proton
FOS/TAC formulas. during
Thisthe justifieddistorted
determination
the remark the result, inthetheespecially
ofconsumptionbicarbonate
previous for
ofwith
the the
titrant
alkalinity.
section the determination
proton
that was
theThis taken
during
FOS/TAC
acetate of
into
additional theTAC
reacts account
formulas. withThis
determination ainhighthe FOS
TAC
of the
justified conten
calcula
the bica
rem
consumption
with the proton of the titrant
during thewas taken into account
determination ofdistorted in the
the bicarbonate the TAC result,
consumptionespecially
calculation
alkalinity. of for
thethe
and,
This
with determination
therefore,
titrant
additional
the proton was duringtaken of into TAC
the with ainhit
account
determinat
distorted
consumption the result,
of the especially
titrant wasfor the determination
taken into account inofthe TAC TAC distorted
with a high
calculation the FOS result, content.
consumption
and, especially
therefore, offorthethe determination
titrant was taken of in
distorted the result, especially for the determination of TAC with a high FOS distorted
content. the result, especially for the de

Figure 2. Experimental (points) and simulated (lines) sodium bicarbonate concentrations versus true
sodium bicarbonate concentrations at different acetic acid concentration levels.
Appl. Sci. 2021, 11, 11843 8 of 14

Similarly, the [HAc] determined by Nordmann’s method at different bicarbonate con-

centrations was compared with the real [HAc] in the solutions. As illustrated in Figure 3A,
the average error between the measured [HAc] and the true value in the solution was
much smaller than that of the bicarbonate determination. This implied that the presence of
bicarbonate had a less significant effect on the determination of [HAc]. Nevertheless, when
zooming in on the [HAc] = 0 to 5000 mg HAc·L−1 part (see Figure 3B), one can note that a
systematic overestimation of [HAc] could also be observed. The difference between the
experiment and reality could be as high as 684%. It means bicarbonate concentration also
interferes with the determination of FOS, especially when [HAc] (or FOS) is very low and
[NaHCO3 ] (or TAC) is much higher.

Figure 3. (A) Experimental (points) and simulated (lines) acetic acid concentrations versus true acetic
acid concentrations at different sodium bicarbonate concentrations; (B) Figure 3A zoomed for [HAc]
between 0 and 5000 mg·L−1 .

The determination of the sodium bicarbonate and acetic acid concentration by the
Nordmann method was highly dependent on each other. The results of FOS and TAC
with Nordmann empirical formulas were only acceptable for a limited combination of
moderate [HAc] and [NaHCO3 ], which meant both FOS and TAC must be neither too
low nor too high. This reduces the applicability of Nordmann’s FOS/TAC method in
determining the alkalinity and VFAs of a digester, especially for digesters with a high
loading of organic matter (e.g., hydrolysis tank of two-stage anaerobic digestion) and
bicarbonate (e.g., digestion of certain shellfish substrates).

3.2. Simulation of Titration Curves

It was possible to simulate the curves of FOS/TAC titration with Scilab, which then
allowed finding the relationships to distinctly identify bicarbonate and acetic acid contents.
The lines in different colors in Figures 2 and 3A,B represent the simulated concentra-
tions of two compounds (sodium bicarbonate and acetic acid) using the FOS/TAC titration
of Nordmann. Comparing them with the experimental results, it was shown that the
simulation of the titration from the acid–base equilibria allowed a good prediction of the
concentrations of bicarbonate and acetic acid when the Nordmann method was used. The
R2 of 0.991 and 0.997 was, respectively, obtained. The mean absolute percentage errors
(MAPE) were found at 5% and 7%, respectively. This indicated that by using the numerical
tool, we could safely simulate the titration of the two compounds by avoiding the material
and experimental constraints (e.g., detection limit of the titrator, uncertainties related to
the preparation of solutions at low concentrations of FOS and TAC).
Consequently, the results of the simulation instead of the experiment were used to
calibrate the Nordmann FOS/TAC method and, accordingly propose new formulas to
calculate the FOS and TAC more precisely.
Appl. Sci. 2021, 11, 11843 9 of 14

3.3. Proposing New Formulas for FOS and TAC Estimation

Since the determination of both [NaHCO3 ] and [HAc] depends on each other, it was
found that the formulas according to the FOS/TAC method had a lower accuracy when the
bicarbonate and/or VFAs concentration was in the average conditions (either low or high).
Two new formulas (Equations (6) and (7)) were proposed to recalculate FOS and TAC
in a more accurate way. Using the equivalent volumes at pH = 5.0 and 4.4 obtained by the
simulation at different conditions (12 × 12 = 144 datasets of [NaHCO3 ] and [HAc] ranging
from 0 to 40 g·L−1 ), a multiple linear regression with Scilab was performed in search of
their relationships with the true values of [NaHCO3 ] and [HAc]. The two new formulas
with the identified model parameters are shown in Equations (8) and (9).

[NaHCO 3 ]new = 1822 × A − 2010 × B + 8.166 (8)

FOSnew = [HAc]new = −125.8 × A + 3763 × B − 22.05 (9)

Figure 4A,B shows the recalculated values, denoted [NaHCO3]new and [HAc]new ,
using the new formulas compared to the theoretical values. In these figures, all of the
points at the same bicarbonate or acetic acid level were mixed up, superimposed and,
thus, not visible. It appeared that the two proposed formulas made possible the accurate
determination of bicarbonate and acetic acid concentrations by equivalent volumes at
pH = 5.0 and 4.4. The mean absolute percentage error (MAPE) was reduced from 1346%
to 0.33% for the bicarbonate content and from 159% to 0.37% for the acetic acid content in
the simulation ranges concerned (see Table 2). This implied that without modifying the
experimental protocol of the FOS/TAC method, it would be possible to more precisely
estimate the concentration of bicarbonate and acetic acid and, therefore, FOS and TAC, for
wider ranges (from 0 to 40 g·L−1 ) thanks to these two formulas.

Figure 4. (A) Recalculated sodium bicarbonate concentrations (points) using Equation (8) versus
true sodium bicarbonate concentrations at different acetic acid levels; (B) recalculated acetic acid
concentrations (points) using Equation (9) versus true acetic acid concentrations at different sodium
bicarbonate levels.

Table 2. MAPE (mean absolute percentage error) of the simulated concentrations with Nordmann’s
formulas versus respective real values and MAPE of the simulated concentrations with new for-
mulas versus respective real values ([NaHCO3 ] and [HAc] ranging from 0 to 40,000 mg·L−1 in
water solutions).

MAPE [NaHCO3 ]Nordmann [NaHCO3 ]new [NaHCO3 ]corr

[NaHCO3 ]real 1346% 0.33% 0.33%
MAPE [HAc]Nordmann [HAc]new [HAc]corr
[HAc]real 159% 0.37% 0.41%
Appl. Sci. 2021, 11, 11843 10 of 14

We could also, from the empirical FOS and TAC calculated with the Nordmann
equations, recalculate the equivalent volumes A and B from previous experiments and
then reinject these values into Equations (8) and (9) so as to obtain the corresponding new
FOS and TAC, as shown in Equations (10) and (11). This allowed us to correct previous
values without repeating the experiments. The dilution level can change the acid–base
equilibrium of acetate and bicarbonate. Therefore, it has to be noted that one should apply
the same dilution protocol as we did (5 mL of sample + 15 mL of water) when using the
new formulas.

[NaHCO 3 ]corr = 1.820 × TACNordmann − 0.606 × FOSNordmann − 37.24 (10)

TACcorr = 0.595 × [NaHCO 3 ]corr = 1.083 × TACNordmann − 0.360 × FOSNordmann −22.16 (11)

FOScorr = −0.126 × TACNordmann + 1.133 × FOSNordmann +62.95 (12)

In Table 2, it is shown that very low MAPEs were obtained by correcting the Nordmann
FOS and TAC values using our new formulas.
Knowing that the simulation with Scilab allowed a good prediction of the equivalent
volumes of the two pH points and, thus, of the FOS and TAC values, it was possible to use
the same program to estimate the equivalent volumes at the other pH points without doing
the experiments (not shown). The developed Scilab code allowed to directly perform the
multiple linear regression by finding the relations between [NaHCO3 ] or [HAc] and the
equivalent volumes of the titrant. Thanks to the numerical tool, identifying the proper pH
equivalent points would no longer be a main factor impacting the accuracy of the FOS and
TAC determination.

3.4. Experimental Validation of the Proposed Formulas

After acidification and degasification, the empirical TAC and FOS of the digestate
were reduced from 11,009 mg CaCO3 ·L−1 to 2802 ± 181 mg CaCO3 ·L−1 in terms of TAC
and from 2452 mg HAc·L−1 to 1152 mg HAc·L−1 in terms of FOS. These values were both
put into new formulas (Equations (11) and (12)) to obtain the corresponding corrected TAC
(2598 mg CaCO3 ·L−1 ) and FOS (1016 mg HAc·L−1 ). The latter was considered as the X
and Y values that were explained in the Materials and Methods section, and taken into
account in calculating different true TAC and FOS combinations shown in Table 1.
Ten conditions with different TAC and FOS combinations were tested using the real
anaerobic digestate. Both the empirical FOS and TAC calculated with Nordmann’s method
and the new values corrected with new formulas were recorded and put against their
corresponding real concentrations in the digestate (see Figure 5).

Figure 5. (A) Nordmann’s FOS and TAC versus real FOS and TAC values in the tested anaerobic
digestate; (B) FOS and TAC calculated from new formulas versus real FOS and TAC values in the
tested anaerobic digestate.
Appl. Sci. 2021, 11, 11843 11 of 14

Results show that by Nordmann’s method, the TAC was systematically overestimated
as compared to the FOS, of which Nordmann’s equations showed a relevantly acceptable
estimation (Figure 5A). As show in Table 3, the absolute relative errors of TAC and FOS
with Nordmann’s formula varied from 1% to 302% and from 1% to 215% with MAPE of
74% and 46%, respectively.

Table 3. MAPE (mean absolute percentage errors) for TAC/FOS with Nordmann’s method (first line) and with new
formulas (second line) for each sodium bicarbonate and sodium acetate condition in the digestate.

Total TAC (mg CaCO3 ·L−1 )

Xa X + 596 X + 2979 X + 5958 X + 11,916 X + 17,874
NA c 3%/153% 3%/215%
Yb
NA 1%/14% 3%/13%
22%/18% d
Y + 1000
8%/13% e
(mg HAc·L−1 )
Total FOS

28%/7%
Y + 5000
5%/7%
30%/1%
Y + 10,000
7%/2%
211%/8% 33%/1%
Y + 20,000
40%/1% 9%/1%
302%/9% 35%/1%
Y + 30,000
61%/1% 8%/2%
a Initial TAC value of degassed digestate using Equation (11), X = 2598 mg CaCO3 ·L−1 . b Initial FOS value of degassed digestate using
Equation (12), Y = 1016 mg HAc·L−1 . c MAPE is not available since X and Y calculated with new formulas were considered as real values
in degassed digestate. d MAPE for TACNordmann /MAPE for FOSNordmann . e MAPE for TACnew /MAPE for FOSnew .

When it came to the TAC and FOS values recalculated with the newly proposed
formulas (see Figure 5B), the absolute relative error ranged from 1% to 61% and 1% to 13%
for the estimation of TAC and FOS contents (Table 3). The global MAPE for TAC and FOS
was, respectively, found at 15.6% and 6%. The major prediction errors for TAC came from
the estimation of TAC in very extreme conditions (X/Y + 20,000 and X/Y + 30,000), where
highly charged FOS interfered greatly with the determination of a very low TAC. Similarly,
the major errors for FOS determination came from the extreme cases where TAC was very
high but FOS was very low (X + 11,916/Y and X + 17,874/Y).
When these extreme conditions were not considered (X/Y + 20,000, X/Y + 30,000,
X + 11,916/Y and X + 17,874/Y), the MAPE covering moderate conditions (still including
digestate with a very high loading of both TAC and FOS) dropped to 5.6% for TAC and
3.7% for FOS. The major difference between the modeled and true values may be attributed
to the presence of other impacting factors in the digestate, which could interfere with the
titration process of bicarbonate and acetic acid (such as particulates and proteins, etc.). The
presence of various types of fatty acids (short-chain and other long-chain acids) in complex
media could also contribute to the performance of titration.
The experimental confrontation of both Nordmann’s formulas [6,7] and the newly
proposed formulas in the present study confirmed the fact that the former would only
be efficient and accurate in a very limited range, while the new formulas could give
satisfactory estimation of both TAC and FOS up to, respectively, 20,000 mg CaCO3 ·L−1 and
31,000 HAc·L−1 , except for certain very extreme conditions.
The experiments and the simulation were performed only with acetate. The inclusion
of other VFA (propionic, butyric and valeric acids) in the simulation is possible. The original
Scilab code is given in Supplementary Materials. One could vary the concentrations of
these VFAs to see their respective impact on the final results.
The pKa values of propionic, butyric and valeric acids were so close (around 4.7–4.8,
cf Table S1) that the consideration of these species in the titration process had a limited
Appl. Sci. 2021, 11, 11843 12 of 14

effect on the output results (i.e., A and B values). However, one should be fully conscious
of the fact that there exist different calculation methods to report the total VFA content;
VFA could be calculated at first in the molar concentration and converted to an equivalent
acetic acid mass concentration; the total VFA content could also be a simple sum of all mass
concentrations of the concerned acids. The first method did not modify the FOS calculation,
for the original Nordmann’s method as well as the proposed model, while the effect of the
second one could be significant.

4. Conclusions
The reciprocal impact of TAC and FOS on the determination of each other by the
classical FOS/TAC method of Nordmann (1977) was experimentally confirmed both in a
synthetic water solution and in anaerobic media. High loading in FOS could greatly impact
the determination of TAC and vice versa (relative errors up to 35% in moderate conditions
and over 300% in extreme conditions). The present paper proposed two new formulas with
which this reciprocal effect was taken into account in order to calibrate the concentration
of each. With the help of new formulas, the mean absolute percentage errors between the
estimated and the real values were significantly reduced to less than 6% in real anaerobic
medium, with a moderate loading of VFAs or bicarbonate.
Wrong FOS/TAC results may lead to an inappropriate operation and, thus, cause
digestion failure. The question that arose is the interest and the importance of correcting
FOS/TAC calculation formulas. In another word, if, in practice, the correction would be
necessary. In Table S2 in the Supplementary Materials, two sets of literature FOS and TAC
data of organic waste [16] were collected and recalculated using new formulas. Results
showed that the calibration by new formulas could significantly change the judgement on
the reactor state; thus, proving it is necessary. The newly proposed equations could allow a
more accurate characterization of alkalinity and VFA content in anaerobic digesters, which
contributes to a better monitoring of the reactor performance during anaerobic digestion.

Supplementary Materials: The following are available online at https://www.mdpi.com/article/10

.3390/app112411843/s1, Figure S1: programming flowchart for the simulation of FOS/TAC titration
curves, Table S1: pKa of main compounds in an anaerobic digester at 25 ◦ C (data extracted from Sun
et al., 2016 [18]), Table S2: TAC and FOS values reported in literature and calculated using Nordmann
method versus the respective corrected values using new formulas (raw data collected from [16]),
Scilab code 1: Scilab code for calculation of the sodium bicarbonate contents at different acetic acid
concentrations, Scilab code 2: Scilab code for calculation of the acetic acid contents at different sodium
bicarbonate concentrations.
Author Contributions: Conceptualization, X.L., A.P., L.A. and T.R.; methodology, X.L., A.P., L.A.
and T.R.; software, A.P. and X.L.; validation, A.P. and T.R.; formal analysis, X.L.; investigation,
X.L.; resources, M.M.-H. and J.-M.G.; writing—original draft preparation, X.L.; writing—review
and editing, A.P., L.A. and T.R.; visualization, X.L. and A.P.; supervision, A.P. and T.R.; project
administration, J.-M.G., A.P. and T.R.; funding acquisition, J.-M.G., A.P. and T.R. All authors have
read and agreed to the published version of the manuscript.
Funding: This research was funded by the ANRT (Association Nationale de la Recherche et de la
Technologie, France, CIFRE no. 2017/1298) and Cultimer France Producteurs Associés for the Ph.D.
thesis of Maël Mercier-Huat.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Acknowledgments: The authors would like to extend their thanks to Stéphane Mottelet (TIMR,
université de technologie de Compiègne) for his valuable support on Scilab code realization.
Conflicts of Interest: The authors declare no conflict of interest.
Appl. Sci. 2021, 11, 11843 13 of 14

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