Fos Tac

Institut für
Umwelttechnik und Energiewirtschaft
Group
Waste Resource Management
Prof. Dr.-Ing. K. Kuchta
LABORPRAKTIKUM: ABFALL- UND UMWELTCHEMIE
Determination of the FOS/TAC value of a biogas fermenter by

means of pH titration (according to Nordmann)
Introduction
According to the German Renewable Energy Act (Erneuerbare-Energien-Gesetz, EEG), opera-

tors of biogas plants receive a gratuity of about 0.16 €/kWh for electricity supplied to the power
grid which has been produced from renewable resources. Therefore, there is a strong incentive to
operate a biogas plant at its operational optimum. Overloading such plants with excessive bio-
mass may have drastic economic consequences and may even inactivate the biomass, necessitat-
ing a cost-intensive restart. Adding too little biomass also has financial consequences, as less
electricity and heat are generated and revenue is therefore lost.
The anaerobic fermentation process

The fermentation of biomass is a four step anaerobic digestion process, which is brought about
by the complementary activities of several species of bacteria (see Fig. 1). The first step is hy-
drolysis. First of all, long chain substances like carbohydrates, proteins and fats, are broken
down into smaller fragments such as simple sugars, glycerol, fatty acids and amino acids. In the
second step (acidification, acidogenesis), fermentative microorganisms convert these products
into short chain fatty acids such as acetic acid, propionic acid and butyric acid. Lactic acid, alco-
hols, hydrogen and carbon dioxide are also formed in small amounts. In the third stage of acetic
acid formation (acetogenesis), a number of final products from the acidification phase, i.e. short
chain fatty acids, propionic acid, etc, are converted into acetic acid, hydrogen and CO2. Since
acetogenic microorganisms are only viable at low hydrogen contents, but are producing hydro-
gen themselves, they are depending on a symbiosis with methanogenic bacteria. The latter are
using hydrogen, together with acetic acid and some CO2, to produce methane and more CO2,
thus providing the required low hydrogen partial pressure. In this last step, called methanogene-
sis, biogas is produced, which contains up to 70 % methane.
All the described processes run almost simultaneously in a biogas plant. They are in a sensitive
state of equilibrium, which is dependent on the pH and temperature. Changes may have a nega-
tive effect and drastically disrupt the total biogenic process.
Figure 1: Anaerobic digestion steps resulting in the production of biogas
Control parameters for optimal process performance

To achieve optimal control of the degradation process in a biogas plant, a detailed knowledge of
the key chemical and physical parameters is necessary. Besides temperature, these parameters
include the pH value, redox potential, total solids, organic acids, ammonium, and chemical oxy-
gen demand (COD).
In a well functioning biogas plant, the organic acids formed during anaerobic degradation are
consumed by the methanogenic bacteria to form biogas in the last fermentation step. In contrast,
organic acids will accumulate in a disturbed process, resulting in an inhibition of the methano-
genic bacteria.
In a single-stage biogas plant, the pH value should range from 7 to 7.7. However, knowledge of
the current value is not enough to operate a biogas plant safely. This is particularly true for plants
utilising a fermentation substrate with a high buffering capacity, since even a strong accumula-
tion of organic acids will not necessarily lead to a decrease of the pH value.
Analysis of the single organic acids is a common practice to assess the operational stability of
biogas plants; however, these analyses are quite complex and expensive.
For this reason, the FOS/TAC value has long been recognised as a guide value for assessing
fermentation processes. It describes the ratio of volatile fatty acids (German: flüchtige organ-
ische Säuren, FOS) to the total inorganic carbonate (German: totales anorganisches Carbonat,
TAC). By means of this parameter, process disturbances can be recognised at an early stage, and
countermeasures can be implemented. Figure 2 exemplarily shows the development of pH value
and FOS/TAC in a maize silage fermenter.
Figure 2: Development of pH and FOS/TAC values over time in a maize silage fermenter
Short description of the experiment
The FOS/TAC measurement is a titration test („Nordmann method“) that has been adapted by
the Federal Agricultural Research Institute for the measurement of the ratio of acid concentration
and buffering potential in the fermentation substrate. FOS is the German abbreviation for vola-
tile fatty acids (Flüchtige Organische Säuren), its unit is mg/L acetic acid equivalents. TAC rep-
resents the total inorganic carbonate (Totales Anorganisches Carbonat), its unit is mg CaCO3/L.
The method is based on the observation that during titration of a bicarbonate solution with sul-
phuric acid, the typical pH drop is shifted from 5 to 3 if organic acids are present in the solution
(Fig. 3). According to experience, the sulphuric acid consumption to reach pH 5.0 can be allo-
cated to the carbonate and bicarbonate concentration, whereas the consumption between pH 5.0
and 4.4 is due to the organic acids. The consumed millilitres of sulphuric acid are entered into
empirically derived formulae which are valid for a titration volume of 20 mL. In titration of real
samples, the ammonium/ammonia buffer system is measured as well as the carbonate buffer.
Moreover, the volatile fatty acids are measured neither completely nor exclusively, so equivalent
treatment of the FOS and TAC values with concentrations derived from specific analyses is not
acceptable.
For a stable process, a FOS/TAC value 0.3 is considered as relatively safe. However, the main
informative value of the FOS/TAC value lies in its long term development.
Figure 3: Comparison of the titration curves of a carbonate solution and a fermenter sample, the
latter also containing organic acids
Equipment
 Automatic titration unit TIM 854, Hach Lange GmbH
– Centrifuge 3-18K, Sigma
– Scales BL 1500 S, Sartorius
– 20 mL centrifuge tubes
– 50 mL sample beaker (plastic)
– Beaker for collecting waste liquids
– Variable pipette (1-5 mL)
– Pasteur pipettes
– Magnetic stir bars
– Washing bottle with deionised water
Chemicals
 Sulphuric acid standard solution (0.1 N)
Procedure
For three samples from different biogas plants, the FOS/TAC value is to be determined. If time
permits, duplicate analysis should be conducted. Subsequently, the obtained values are to be
used to give recommendations for the optimisation of the biogas plants, and sources of error
during the analysis are to be discussed.
Firstly, a sample preparation has to be conducted. For this, 25 g of each sample are weighed into
a 20 mL centrifuge tube. In order to save time during the analysis, all three samples should be
centrifuged simultaneously. In order to avoid an imbalance, the centrifuge tubes must be evenly
distributed within the centrifuge. It is important that all centrifuge tubes have the same weight
(0.05 g accuracy). Centrifugation of the samples is conducted for 10 min at 20,000 G and room
temperature. After all samples have been placed evenly spaced into the centrifuge, the rotor is
closed with the top cover, and the centrifuge lid is closed. Centrifugation is started by pressing
the green button. After the centrifugation is finished, the centrifuge can be opened using the yel-
low button. The centrifuge tubes have to be removed carefully to avoid stirring up the precipi-
tate. An aliquot of the supernatant can now be used for titration. The titration is conducted by
means of an automatic titration unit (Fig. 4).
Figure 4: Automatic titration unit TIM 854, Hach-Lange GmbH

The titration unit is switched on and the filling level of the standard solution (0.1 N H2SO4) in
the storage vessel is checked. The electrode is removed from the protective cap filled with
electrolyte solution (3 molar KCl solution) and flushed with deionised water (use beaker for
collecting waste liquids!). The fill hole cap is removed from the electrode. The burette tip is
flushed with deionised water as well. Furthermore, the tubing and the burette have to be
checked for air bubbles. If necessary, the burette has to be emptied and refilled to remove air
bubbles. For this, “Bürettenfunktionen” (burette functions) is selected in the “Reagenzien-
Menü” (reagents menu), and the appropriate commands selected at the display (Entleeren –
empty; Füllen – fill). After everything is checked, the desired method (FOS/TAC Prak.) can
be selected in the main menu.
For the titration, 5 mL of the supernatant from the centrifuge tubes are pipetted into the sam-
ple beaker using a variable Eppendorf pipette. A magnetic stir bar is put into the beaker with
the sample, which is then placed onto the magnetic stirrer of the titration unit. Now, the beak-
er is filled with deionised water up to the marking (approx. 50 mL). The electrode and burette
are now lowered until the diaphragm of the electrode is submerged to a level above the dia-
phragm. The magnetic stir bar must not be touched under any circumstances.
After entering the sample ID (“ProbenID“) and the sample volume (“Probenvolumen”), the
titration can be started. The titration curve is displayed directly at the titration unit. The con-
sumption of the sulphuric acid standard solution is recorded automatically by the unit and re-
ported as the result. The values have to be noted down.
The volume of the sample has to be selected in a way that no less than 3 mL and no more than
20 mL of sulphuric acid standard solution are consumed. Normally, 5 mL of sample are OK.
The titration will be stopped automatically after a pH of 4.4 is reached.
After the End of the titration, the sample beaker is removed and the electrode and the tip of
the burette are flushed with deionised water (use beaker for collecting waste liquids!). The
burette will be refilled automatically.
After the end of the experiment, the electrode is reinserted into the protective cap. The level of
electrolyte solution in the cap must be sufficient to keep the glass bulb of the electrode moist.
The fill hole cap is put in place again. All solutions are disposed in the chemicals sink con-
nected to the neutralisation unit. Used beakers and stir bars are flushed with deionised water
and put in place for the next group. Used centrifuge tubes are flushed with tap water and
placed into the white washtub.
Assessment and interpretation of the results
The FOS/TAC value is calculated using the following empirically determined equations:
20 mL
TAC (mg/L)   VTAC  250
VSample
 20 mL 
FOS (mg/L)    VFOS  1,66  0,15   500
 VSample 
FOS (mg/L)
FOS/TAC 
TAC (mg/L)
VTAC = Volume of sulphuric acid standard solution consumed during the TAC titration (mL)
VFOS = Volume of sulphuric acid standard solution consumed during the FOS titration (mL)
VSample = Volume of the sample used for the titration (mL)
In practice, a FOS/TAC ratio of 0.3 to 0.4 is normal, although each plant has its own optimal
ratio. This can only be determined by long-term observation and regular checks, as there is a
strong dependence on the substrate. For example, plants that make use of renewable raw materi-
als usually require a FOS/TAC ratio of 0.4 to 0.6 for stable operation.
Table 1: Rules of thumb for the interpretation of FOS/TAC values

FOS/TAC value background measure
>0.6 highly excessive biomass input stop feed
0.3-0.4 biogas production at a maximum keep feed constant
<0.2 plant is starving increase feed rapidly

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Institut für

Umwelttechnik und Energiewirtschaft

LABORPRAKTIKUM: ABFALL- UND UMWELTCHEMIE

Determination of the FOS/TAC value of a biogas fermenter by

According to the German Renewable Energy Act (Erneuerbare-Energien-Gesetz, EEG), opera-

The anaerobic fermentation process

Control parameters for optimal process performance

Figure 4: Automatic titration unit TIM 854, Hach-Lange GmbH

Assessment and interpretation of the results

Table 1: Rules of thumb for the interpretation of FOS/TAC values

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