11th International Conference on Urban Drainage, Edinburgh, Scotland, UK, 2008

Hydrogen sulfide initiated corrosion in concrete sewers a

conceptual approach for prediction
H.S. Jensen1*, A.H. Nielsen1, T. Hvitved-Jacobsen1 and J. Vollertsen1
1

Section of Environmental Engineering, Department of Biotechology, Chemistry and

Environmental Engineering, Aalborg University, Sohngaardsholmsvej 57, 9000 Aalborg,
Denmark (hsj@bio.aau.dk, ahn@bio.aau.dk, thj@bio.aau.dk, jv@bio.aau.dk)
*Corresponding author, e-mail hsj@bio.aau.dk

ABSTRACT
Concrete corrosion caused by hydrogen sulfide in sewer networks is a major economical
problem. Resent studies have provided new knowledge of the absorption of hydrogen sulfide
on concrete surfaces and of the subsequent oxidation to sulfuric acid. In this paper the
information from these studies was combined to simulate concrete corrosion in a gravity
sewer located downstream from a force main. The concrete corrosion on this section of
gravity sewer was highly dependent on the concentration of active biomass on the concrete
surface and in a worst case scenario a corrosion rate of 7 mm year-1 was predicted. The model
simulations also revealed that the concrete corrosion process can be described using saturation
type kinetics even though the removal of hydrogen sulfide from the sewer gas phase follows
nth order kinetics.

KEYWORDS
Concrete corrosion rates, corrosion kinetics, hydrogen sulfide, sewer

INTRODUCTION
Concrete corrosion due to hydrogen sulfide is a major economical problem in sewer networks
both because of renovation costs and the costs of preventive measures. Besides this, hydrogen
sulfide is both malodorous and toxic. Formation of hydrogen sulfide is therefore of major
concern when designing and operating sewer networks (ASCE, 1989).
Hydrogen sulfide is formed under anaerobic conditions in sewer biofilms, which means that
especially force mains favor the formation of hydrogen sulfide as anaerobic conditions prevail
here. When the sulfide containing wastewater from the force main is discharged into a gravity
sewer with a free water surface, hydrogen sulfide is emitted to the sewer atmosphere. This
means that concrete pipes directly downstream of force mains are potentially in high risk of
corroding (Hvitved-Jacobsen, 2002).
The emission of hydrogen sulfide to the sewer atmosphere is dependent on several processes
taking place in the wastewater. When the wastewater is discharged into a gravity sewer,
oxygen is supplied from the sewer atmosphere and sulfide can be removed by oxidation in the
wastewater and in the sewer biofilms. These processes were described in detail by Nielsen et
al. (2006). The pH of the wastewater is important for the emission of hydrogen sulfide as
hydrogen sulfide is a week acid with an acid dissociation constant of 7.0 at 25 C and it is
only the non-dissociated form of hydrogen sulfide that can be emitted to the sewer
atmosphere (Hvitved-Jacobsen, 2002; Yongsiri et al., 2004). Also the design of the discharge
manhole is important for the emission of hydrogen sulfide as turbulence in the wastewater
will increase the emission (ASCE, 1989).
Jensen et al.

11th International Conference on Urban Drainage, Edinburgh, Scotland, UK, 2008

When in the sewer atmosphere, hydrogen sulfide is absorbed by the concrete surfaces of the
sewer manholes and the sewer pipes where it is oxidized to sulfuric acid. The sulfuric acid
lowers the surface pH of the concrete and reacts with the alkaline components of the concrete,
forming gypsum, which has little structural strength (Parker, 1945).
Recently, advances have been made on the description of the removal of hydrogen sulfide in
the gas phase of concrete sewers (Vollertsen, et al., 2008) as well as in the description of the
oxidation processes for hydrogen sulfide in the corroded concrete matrix (Jensen et al.,
subm.). It is the objective of this study to simulate the oxidation of hydrogen sulfide and
production of sulfuric acid on the concrete sewer walls of a gravity sewer pipe, applying the
findings of these two studies.

METHODS
The corrosion process was simulated combining the findings of Vollertsen et al. (2008) and
Jensen et al. (subm.). These studies describe the removal of hydrogen sulfide in a concrete
sewer atmosphere and the oxidation of hydrogen sulfide within concrete corrosion products of
a heavily corroded sewer pipe, respectively. The corroded concrete matrix consists mainly of
gypsum, sand, water and small amounts of organic matter and it is the underlying hypothesis
in this study that the matrix of corroded concrete can be described as a biofilm subject to
diffusion of compounds. The processes in the corroded concrete matrix are outlined in Figure
1.

Figure 1. Schematic outline of the processes taking place in the corroded concrete matrix.
After Vollertsen et al. (2008) (left part of the figure) and Jensen et al. (subm.) (right part of
the figure).
Hydrogen sulfide absorption from the sewer atmosphere by the concrete surface
Hydrogen sulfide can be removed from the sewer atmosphere both by adsorption to the
surface of the concrete pipe and by diffusion into the pore water of the corrosion products on
the pipe surface. The overall removal of hydrogen sulfide from a sewer atmosphere was
described as following nth order kinetics by Vollertsen et al. (2008), Equation (1).

FH 2 S

k F p Hn 2 S

(1)

All parameters in this and the following equations are defined in Table 2.

Hydrogen sulfide initiated corrosion in concrete sewers

11th International Conference on Urban Drainage, Edinburgh, Scotland, UK, 2008

The parameter kF is reported to vary between 0.002 and 0.010 mg S m-2 s-1 (ppm H2S)-n and
the reaction order n is correlated with kF, with n approximately 0.5 for low kF-values and 0.7
for high kF-values (Vollertsen et al., 2008).
Transformations in the corroded concrete matrix
The oxidation pathway for hydrogen sulfide suggested by Jensen et al. (subm.) was that
hydrogen sulfide initially is oxidized to readily biodegradable elemental sulfur. This
elemental sulfur is partly aged to slowly biodegradable elemental sulfur and partly oxidized to
sulfuric acid. The slowly biodegradable elemental sulfur is also oxidized to sulfuric acid, only
at a lower rate (Figure 1). This oxidation pathway was studied in suspensions of the corrosion
products replicating the conditions found in a matrix of corroded concrete. Kleinjan et al.
(2005) also suggested the existence of a nascent form of biologically produced elemental
sulfur that is more reactive than aged elemental sulfur.
Oxidation of hydrogen sulfide
The oxidation of hydrogen sulfide on the heavily corroded concrete is mainly a microbial
process with Acidithiobacillus thiooxidans as main responsible organism (Parker, 1945;
Okabe et al., 2007) hence the abiotic oxidation of hydrogen sulfide is not taken into account
in this study. Acitithiobacillus thiooxidans is reported to be dominant when the pH of the
corrosion products is below 2 (Okabe et al., 2007; Islander et al., 1991). Such pH value has
been found in corrosion products on heavily corroded concrete surfaces in several studies
(Parker, 1945; Mori et al., (1992)). The oxidation rate of hydrogen sulfide to fast
biodegradable elemental sulfur was described by (Jensen et al., subm.), Equation (2).

RH 2 S

ox

wbio X TS

S H 2S
SO2
K H 2 S S H 2 S K O 2 ,H 2 S S O 2

(2)

Assuming that the concentration of biomass is a constant fraction of the total solids, XTS is
proportional to concentration of active sulfur oxidizing biomass in the corroded concrete.
Oxidation of readily biodegradable elemental sulfur
The oxidation of readily biodegradable elemental sulfur is expected to be carried out by the
same bacterial population as the oxidation of hydrogen sulfide. Acidithiobacillus thiooxidans
has been shown to oxidize elemental sulfur (Gourdon and Funtowicz, 1998; Konishi et al.,
1995). The oxidation kinetics of readily biodegradable elemental sulfur was described by
(Jensen et al., subm.), Equation (3).

RSf

ox

y Sf X TS

S Sf
K Sf

SO2
S Sf K O 2 ,Sf

SO2

(3)

Ageing of fast biodegradable elemental sulfur to slowly biodegradable elemental sulfur

The formation of slowly biodegradable elemental sulfur from readily biodegradable elemental
sulfur is described using first order kinetics (Jensen et al., subm.), Equation (4).
RSf

Ss

z S S Sf

Jensen et al.

(4)

11th International Conference on Urban Drainage, Edinburgh, Scotland, UK, 2008

Oxidation of slowly biodegradable elemental sulfur
The oxidation of slowly biodegradable elemental sulfur is described using nth order kinetics,
dependent only on the oxygen concentration (Jensen et al., subm.), and the total solids
concentration i.e. the concentration of active biomass (Equation (5)). This equation is
expected only to represent conditions where slowly elemental sulfur is present in high
concentrations and the process therefore is solely limited by the available oxygen and the
biomass concentration.

RSs

ox

q Ss X TS S Oc 2

(5)

Corrosion depth
The potential corrosion depth is evaluated by assuming that all the produced sulfuric acid
reacts with calcium carbonate in the concrete. The concrete is assumed to be produced
according to Danish national standards and having a specific density of 2,340 kg m-3 with an
alkalinity of 0.181 gCaCO3 (g concrete)-1 (Vollertsen et al., 2008). The corrosion depth could
then be calculated using Equation (6).

d corr

n H 2 SO 4 M CaCO 3
Alk conc conc

(6)

Transformations in the sewer bulk water and sewer biofilms

The transformations of e.g. organic matter, oxygen, and hydrogen sulfide in the sewer bulk
water and sewer biofilms was simulated using the WATS model concept (Hvitved-Jacobsen,
2002, Nielsen et al., 2006). The transformations of hydrogen sulfide in the sewer bulk water
and sewer biofilms is described in details by Nielsen et al. (2006). This includes processes
such as production of hydrogen sulfide in pressure mains, oxidation of hydrogen sulfide in
sewer bulk water and sewer biofilms in the downstream gravity sewer and the transfer of
hydrogen sulfide between the sewer bulk water and the sewer atmosphere.
Model scenarios
The WATS model concept combined with the equations for removal of hydrogen sulfide from
the sewer atmosphere and sulfide transformations on the concrete sewer wall was used to
predict the concrete corrosion as a result of different hydrogen sulfide emission scenarios. The
simulated scenarios replicate an intercepting sewer line 1 km of gravity sewer downstream of
a force main. The hydraulic conditions for the simulations as well as initial sulfide
concentrations in the gravity sewer are based on the findings by Nielsen et al. (2008), only the
gas phase velocity was increased to 35 % of the wastewater velocity based on the findings by
(Madsen et al., in prep) (Table 1). The force main had an inner diameter of 300 mm and a
length of 2012 meter. The hydraulic retention time in the force main was 3.63 to 4.66 h.
Table 1. Physical parameters for the gravity sewer pipe.
Pipe diameter
0.5 m

Slope
0.3 %

Wastewater flow
0.01 m s-1

Wastewater pH
7.5

Gas phase velocity

35 % of wastewater velocity

In the studied interceptor, the force main discharges into the gravity sewer without turbulence.
Nielsen et al. (2008) reported the findings of typical sulfide concentrations in the wastewater
directly downstream of a force main between 1 and 5 g S m-3.

Hydrogen sulfide initiated corrosion in concrete sewers

11th International Conference on Urban Drainage, Edinburgh, Scotland, UK, 2008

The sulfur transformation processes in the corroded concrete matrix developing on the
concrete sewer walls were assumed to take place in the outermost millimeter of the matrix.
The solids in the corroded concrete were regarded as being suspended in the pore water of the
matrix. The oxygen concentration in the matrix was assumed to be constant at 0.5 g O2 m-3
based on the oxygen profile measured by Okabe et al. (2007) in the outermost part of the
heavily corroded concrete.
Table 2. Definition of model parameters
Parameter
FH2S
pH2S
n
kF
RH2S-ox
wbio
XTS
SH2S
KH2S
SO2
KO2,H2S
RSf-ox
ySf
SSf
KSf
KO2,Sf
RSf-Ss
zS
RSs-ox
qSs
c
dcorr
nH2SO4
MCaCO3
Alkconc
conc

Definition
Surface-specific hydrogen sulfide removal rate
Partial pressure of hydrogen sulfide
Reaction order for gas phase removal
Surface specific process rate constant
Oxidation rate of hydrogen sulfide in corroded
concrete matrix
Rate constant for the biotic oxidation of hydrogen
sulfide
Total solids concentration
Hydrogen sulfide concentration in the pore water
of the corroded concrete matrix
Half saturation constant for hydrogen sulfide
Concentration of dissolved oxygen in the pore
water of the corroded concrete matrix
Half saturation constant for oxygen in the
oxidation of hydrogen sulfide
Oxidation rate of readily biodegradable elemental
sulfur
Rate constant for the oxidation of fast
biodegradable elemental sulfur
Concentration readily biodegradable elemental
sulfur
Half saturation constant for fast biodegradable
elemental sulfur
Half saturation constant for oxygen in the
oxidation of fast biodegradable elemental sulfur
Ageing rate of readily biodegradable elemental
sulfur
Rate constant for the ageing of readily
biodegradable elemental sulfur
Oxidation rate of slowly biodegradable elemental
sulfur
Rate constant for the oxidation of slowly
biodegradable elemental sulfur
Reaction order for the oxidation of slowly
biodegradable elemental sulfur
Corrosion depth
Molar concentration of sulfuric acid formed in
the concrete matrix
Molar mass of calcium carbonat
Alkalinity of concrete
Specific density of concrete

Unit
mg S m-2 s-1
ppm
mg S m-2 s-1 (ppm H2S)-n

Value
0.5 0.7
0.002 0.010

g H2S-S m-3 h-1

g H2S-S (g TS h)-1

3.94 10-5

g TS m-3

1941176

-3

-3

g H2S-S m

1.35 10-3

g O2 m-3

0.5

g O2 m-3

0.1

gS m-3 h-1

g S (g TS h)-1

1.5 10-5

gS m-3

g S m-3

0.9

g O2 m-3

0.45

gS m-3 h-1

h-1

0.1

gS m-3 h-1

gS m3c ((gO2)c gTS h)-1

3.5 10-8

gH2S-S m

1.3
mm

-2

-1

100
0.181
2340

mol m

g mol
gCaCO3 (g concrete)-1
kg m-3

Simulation of hydrogen sulfide profiles in the gravity sewer

The corrosion process was simulated at hydrogen sulfide concentrations considered high (5 g
S m-3) bulk water concentrations of sulfide and at high, low and medium hydrogen sulfide gas
phase removal rates (Table 3). After simulating 24 hours of continuous hydrogen sulfide
supply from the sewer bulk water to the sewer gas phase and subsequently to the concrete

Jensen et al.

11th International Conference on Urban Drainage, Edinburgh, Scotland, UK, 2008

surface, the hydrogen sulfide supply was terminated in order to evaluate the potential
corrosion due to the consumption of stored elemental sulfur.
Table 3. Scenarios for simulation of hydrogen sulfide profiles in the gravity sewer pipe.
Scenario
low rate
medium rate
high rate

Wastewater sulfide
concentration
g S m-3
5

kF
-2

-1

mg S m s (ppm H2S)
0.002
0.006
0.010

n
-n

0.5
0.6
0.7

Determination of concrete corrosion kinetics

The variation in hydrogen sulfide removal rate is likely to be affected by variations in the
concentration of active biomass in the corroded concrete matrix. The biomass concentration in
the study by Jensen et al. (subm.) was evaluated to be relatively low as the samples were
taken in a sewer manhole rather than in the sewer pipe it self, where the supply of moisture
and nutrients would be higher. This means that the parameter values suggested by Jensen et
al. (subm.) are likely to correspond to the lower range of hydrogen sulfide gas phase removal
rates.
In order to investigate the potential concrete corrosion rate at varying concentrations of active
biomass the scenarios outlined in Table 4 were simulated. Other studies have reported a broad
range of corrosion rates for sewer pipes (e.g. Zhang et al., 2008). Initial model simulations
showed that a range in biomass concentration from 1 to 40 times the biomass reported by
Jensen et al. (subm.) (XTS) would cover the range of reported corrosion rates. In the
simulations, hydrogen sulfide was supplied continuously for 24 hours.
Table 4. Scenarios for evaluation of the corrosion kinetics
Scenario

Hydrogen sulfide
concentration, gas phase

kF

XTS

g m-3

0.7
0.7
0.7
0.7
0.7

XTS
XTS10
XTS20
XTS30
XTS40

-2 -1

mg S m s (ppm
H2S)-n
0.010
0.010
0.010
0.010
0.010

ppm
1100
1100
1100
1100
1100

RESULTS AND DISCUSSION

Potential corrosion rates
The dynamics of the concrete corrosion was simulated in a scenario where hydrogen sulfide
was supplied continuously at a constant gas phase concentration for 24 hours after which the
hydrogen sulfide supply was ended (gas phase concentration: 0 ppm). These simulations
showed that the corrosion of the concrete could be divided into two stages: High corrosion
rate due to oxidations of readily biodegradable elemental sulfur and low corrosion rate due to
slowly biodegradable elemental sulfur (Figure 2). The corrosion rate can be calculated as the
slope of the curve. As it can be seen in Figure 2, the corrosion rate due to the oxidation of
slowly biodegradable elemental sulfur was very low. Calculations have shown that it was in a
magnitude of m per year. In gravity sewers that are full flowing with regular intervals, the
corrosion products are washed off, as they are attached only loosely to the concrete surface.
This is likely to remove the slowly biodegradable elemental sulfur fraction before it can cause

Hydrogen sulfide initiated corrosion in concrete sewers

11th International Conference on Urban Drainage, Edinburgh, Scotland, UK, 2008

significant corrosion of the sewer pipes, which means that this sulfur fraction in practice can
be considered as an inert sulfur fraction.

Figure 2. Corrosion depth over time exemplified at a hydrogen sulfide gas phase
concentration of 1 ppm.
Distribution of hydrogen sulfide in the gravity sewer pipe
The removal rate of hydrogen sulfide by the concrete surfaces effects how hydrogen sulfide is
distributed in the sewer atmosphere throughout the gravity sewer pipe.

Figure 3. Concentration profile for hydrogen sulfide in the sewer atmosphere and the bulk
wastewater through the gravity sewer pipe. The concentration profile is calculated for high,
medium and low rates of hydrogen sulfide removal from the sewer atmosphere, respectively
(Table 3).
The simulated concentration profile changed with changing gas phase removal rates (Figure
3). The higher the removal rate, the closer to the force main discharge the maximum
concentration of hydrogen sulfide was found. At low hydrogen sulfide removal rate, hydrogen
sulfide was transported further downstream from the force main than for high removal rates.
At high removal rates, the hydrogen sulfide concentrations in the sewer atmosphere becomes
low because more of the hydrogen sulfide is taken up by the concrete matrix and thereby
removed from the sewer atmosphere.
Corrosion in the sewer pipe
Based on the hydrogen sulfide concentration profiles showed in Figure 3, the corrosion rates
through the gravity sewer pipe were simulated for both low and high gas phase removal rate
(Figure 4, left side). These simulations were performed for the biomass concentration reported
Jensen et al.

11th International Conference on Urban Drainage, Edinburgh, Scotland, UK, 2008

by Jensen et al., (subm.) (XTS). They revealed that the corrosion rate was almost independent
on the gas phase removal rate, with corrosion rates of about 0.4 mm year-1 through the entire
simulated sewer pipe section. As the biomass concentration in the study by Jensen et al.
(subm.) was evaluated to be low, a scenario replicating a situation with a biomass
concentration 20 times higher than that of Jensen et al. (subm.) was simulated (Figure 4, right
side). This showed corrosion rates changing with the distance from the force main and
therefore dependent on the hydrogen sulfide gas phase concentration, and the rates varied
from 2 mm year-1 to 7 mm year-1. The results were simulated with an initial concentration of 5
g S m-3 sulfide in the discharge from the force main. This concentration is in the upper end of
the range of concentrations reported by Nielsen et al. (2008) thus these corrosion rates can be
considered as a worst case scenario.

Figure 4. Corrosion rates in a gravity sewer downstream from a force main. Corrosion rates at
low and high hydrogen sulfide removal rates and a scenario with high removal rate where the
active biomass is increased 20 times are shown (right side).
Corrosion kinetics
The kinetics of the concrete corrosion was investigated by simulating the scenarios outlined in
Table 4. For each biomass concentration the high corrosion rate at hydrogen sulfide gas phase
concentration varying from 1 to 100 ppm was simulated (Figure 5). This showed that the high
corrosion rate could be described using saturation type kinetics, and thus does not follow the
same type of kinetics as the removal of hydrogen sulfide from the sewer gas phase.

Figure 5. Kinetics of the concrete corrosion at varying biomass concentration

The half saturation constants and maximum specific corrosion rates are shown in Table 5. The
values of these parameters were in the same order of magnitude as those reported by soy et
al. (2002), who found a half saturation constant of 2 ppm and a maximum specific corrosion
8

Hydrogen sulfide initiated corrosion in concrete sewers

11th International Conference on Urban Drainage, Edinburgh, Scotland, UK, 2008

rate of 16 mm/year. Comparing the maximum specific corrosion rate and half saturation
constant found by soy et al. (2002) with the values in Table 5 indicates that the biomass in
their study was between 20 and 30 times higher than the biomass in the study by Jensen et al.
(subm.).
Table 5. Half saturation constants and maximum specific corrosion rates.
Biomass increase
x1
x 10
x 20
x 30
x 40

Half saturation constant

ppm
0
1
2
4
6

Maximum specific corrosion rate

mm year-1
0.4
4.8
9.8
15.1
20.8

Conclusion
Corrosion rates were simulated in a gravity sewer downstream of a force main. The corrosion
was found to take place in two stages. The first stage was due to the oxidation of readily
biodegradable elemental sulfur and the second due to the oxidation of slowly biodegradable
elemental sulfur. The oxidation rate and subsequently corrosion rate due to the oxidation of
slowly biodegradable elemental sulfur was so low, that this sulfur fraction could be
considered inert.
Simulation of corrosion rates through the gravity sewer showed that with a low biomass
concentration, the highest corrosion rates were limited at 0.4 mm year-1 regardless of the gas
phase concentration of hydrogen sulfide; however, with an increase in the biomass
concentration, the corrosion profile followed the gas phase concentration profile. A worst case
scenario predicted corrosion rates of up to 7 mm year-1.
Determinations of the kinetics of the concrete corrosion revealed that the corrosion could be
described using saturation type kinetics even though the uptake of hydrogen sulfide on the
concrete surface follows nth order kinetics. This difference in kinetics is important when
aiming to predict hydrogen sulfide induced concrete of sewer networks.

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Hydrogen sulfide initiated corrosion in concrete sewers