Electrochimica Acta 52 (2007) 6084–6088

Effects of sulfate-reducing bacteria on the corrosion

behavior of carbon steel
Fei Kuang a,b , Jia Wang c,d,∗ , Li Yan a,b , Dun Zhang a
a Institute of Oceanology, Chinese Academic of Sciences, 7 Nanhai Road, Qingdao 266071, China
b Graduate School of the Chinese Academy of Sciences, 19 (Jia) Yuquan Road, Beijing 100039, China
c Ocean University of China, No. 238 Songling Road, Qingdao 266100, China
d State Key Laboratory for Corrosion and Protection, 62 Wencui Road, Shenyang 110015, China

Received 18 December 2006; received in revised form 15 March 2007; accepted 16 March 2007
Available online 20 March 2007

Abstract
The influences of the growing process of sulfate-reducing bacteria (SRB) in seawater system on the medium state and corrosion behavior of
carbon steel were studied by detecting solution state parameters and using corrosion electrochemical methods. The growing process of SRB in the
seawater shows the three stages of growing, death and residual phases. The solution state parameters of the concentration of sulfide, the pH value
and the redox potential changed during the three stages of the SRB growing process. And the corrosion rate of D36 carbon steel was accelerated
during the growing phase and stable during the death and residual phases. The results indicate that the medium state and the corrosion rate of the
steel do not depend on the number of active SRB, but depend on the accumulation of the metabolism products of SRB.
© 2007 Elsevier Ltd. All rights reserved.

Keywords: Sulfate-reducing bacteria; Microbiologically induced corrosion; Medium state; D36 carbon steel; Corrosion rate

1. Introduction als [5–8], and put influences on the environment parameters

The sulfate-reducing bacteria (SRB) form a specialized group
of microbes that use sulfate as terminal electron acceptor for
their respiration and generate H2 S as terminal product [1]. The
ubiquity of these bacteria leads to a variety of impressive indus-
trial, economic and ecological effects because of their proneness
to generate large quantities of H2 S. Many corrosions of indus-
trial equipment have been ascribed to microbiologically induced
corrosion (MIC) [2,3]. SRB are the main reason to cause the
MIC by accelerating corrosion rate, inducing stress corrosion
and pitting corrosion [4–8]. According to Iverson’s estimation,
more than 77% of the corrosions in the producing oil well in the
United States of America are induced by SRB [9]. Although
the corrosion induced by SRB has been studied for about a
century, the corrosion process is still debated [5,10–18]. Pre-
vious studies show that the living of SRB accelerate corrosion
rate and induce stress corrosion and pitting corrosion of met-
[19,20] which are possible factors inducing the metal corrosion.
To authors’ knowledge, no report studies the relativities among
SRB, seawater condition and corrosion behavior of metals, but
the understanding of relativities among them might be helpful
on getting a better insight of the corrosion mechanism induced
by SRB.
In this paper, the correlations among SRB, seawater condi-
tion and corrosion behavior of carbon steel were studied. The
environment parameters of the concentration of sulfide (CS2− ),
the pH values, the redox potential (Eh ) and the concentration
of oxygen dissolved in the seawater (CO2 ) were measured dur-
ing the growing process of SRB. And the corrosion rate of D36
carbon steel was investigated by the electrochemical methods
of potentiodynamic polarization curves and the electrochemical
impendence spectroscopy (EIS).
2. Experiments

2.1. The cultivation of SRB

∗ Corresponding author at: Ocean University of China, No. 238 Songling
Road, Qingdao 266100, China. Tel.: +86 532 66781903; fax: +86 532 66781903. Mixed seeds of SRB used in this study were separated
E-mail address: jwang@mail.ouc.edu.cn (J. Wang). from effluent samples collected from the mud. SRB cultures

0013-4686/$ – see front matter © 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2007.03.041
 F. Kuang et al. / Electrochimica Acta 52 (2007) 6084–6088 6085

were inoculated in a medium contained 0.5 g K2 HPO4 , 1.0 g

NH4 Cl, 2.0 g MgSO4 , 0.5 g Na2 SO4 , 0.1 g CaCl2 , 1.0 g yeast,
4 ml sodium lactate in 1 l seawater. The pH value was adjusted
to 7.2 after the deaeration using nitrogen. Then the medium
was autoclaved at 120 ◦ C for 15 min. The SRB seeds were
incubated at 30 ◦ C. The bacteria growth was monitored by
0.5 g (NH4 )2 Fe(SO4 )2 ·6H2 O and 0.1 g l-ascorbic acid. The
(NH4 )2 Fe(SO4 )2 ·6H2 O and l-ascorbic acid were sterilized by
the ultraviolet radiation for half an hour and were put into the
media together with the incubation of the SRB seeds.

2.2. The detection of the number of active SRB and

environment parameters

The 50 ml SRB culture was diluted into 500 ml purified sea-

water. The number of active SRB (NSRB ) value in the system was
calculated in most probable number (MPN) method according to Fig. 1. The SRB growing process in seawater system.
the American Society of Testing Materials (ASTM) Standard D
4412-84. The concentration of sulfide in the system is detected the 3rd stage: residual phase. During this stage, the number of
by sulfide-selective electrode according to the ASTM Standard SRB backs to the original number and the active SRB almost
D 4658-03. The values of pH, the redox potential and the con- disappeared.
centration of oxygen dissolved in the seawater were detected by
YSI6600 Multi-parameter Water Quality Monitor. All experi-
3.2. The effects of the SRB growth on the environment
ments were carried out at 28 ◦ C and in airtight system.
parameters
2.3. Electrochemical measurement systems
Hydrogen sulfide generated by the metabolism of SRB during
its growing process caused the change of environment parame-
D36 carbon steel composed of the following elements with
ters was confirmed by the results shown in Figs. 2–5. Figs. 2–5
a mass ratio of 0.4% C, 0.50% Mn, 0.17% Si, 0.035% P, 0.
illustrate the variation of CS2− , Eh , pH and CO2 values with the
25% Cr, 0.00104% Mo, 0.25% Ni, 0.015% Al, 0.0053% Co,
growing process of SRB, respectively. During the exponential
0.25% Cu, 0.015% Nb, 0.02% V, 0.010% W, 0.02% Ti, 0.014%
phase, the CS2− value increases with increasing the NSRB value.
Sn, 0.035% S and 98.0% Fe was used as a working electrode
When the NSRB value reaches the maximum value, the nutrient
in this study. The steel electrode was polished with silicon
substance and the sulfate are almost exhausted. And then the
carbide waterproof electro-coated abrasive paper no. 800, and
CS2− almost keeps a value of 1.5 mM which is the original con-
then it was degreased with ethanol and dried in cool air before
centration of sulfate in the culture medium system during the
experiment. A platinum plate and a saturated calomel elec-
declining process of the active SRB number.
trode (SCE) were used as a counter electrode and a reference
The Eh value of the study system depends on the redox quality
electrode, respectively. The corrosion potential (Ecorr ), potentio-
substances in the solution. Therefore, the change of the Eh value
dynamic polarization curves and the electrochemical impedance
shows the same way as that of the CS2− value. Fig. 3 indicates
spectroscopy were performed with Solartron SI1287 Electro-
the Eh decreases with the increase of NSRB value and maintains
chemical Interface and SI1260 Impedance/Gain-Phase Analyzer
control systems.

3. Results and discussion

3.1. Growing process of SRB

Fig. 1 illustrates the growing process of SRB in the seawa-

ter system which was added small amounts of culture medium
and SRB seeds. The results indicated that the growing process
of SRB can be divided into three stages. One to four-day is the
1st stage called exponential phase. During this stage, the num-
ber of active SRB increases quickly and the number of SRB
achieves the maximum value at the 4th day. After the 4th day,
the growing process of SRB reaches the 2nd stage naming death
phase. The number of active SRB decreases quickly during this
stage. After the 14th day, the growing process of SRB reaches Fig. 2. The change of CS2− values in seawater system with the SRB growth.
6086 F. Kuang et al. / Electrochimica Acta 52 (2007) 6084–6088
Fig. 3. The change of Eh values with the SRB growth.
Fig. 4. The change of pH values in the seawater system with the SRB growth.
at a stable value when the growing process of SRB comes to the
death phase and the residual phase.
Fig. 4 suggests that the pH values decrease slightly during the
exponential phase of SRB growth and maintain at a stable value
Fig. 5. The change of CO2 values in the seawater system with the SRB growth.
Fig. 6. The Ecorr values of D36 carbon steel with the SRB growth.
during the later phases. The reason is considered that the sulfide
and organic acid generated by the metabolism of SRB increase
during the exponential phase of SRB and stabilize during the
later stages. But in general, the pH value changes slightly. Com-
paring with the change of redox quality, the seawater system has
a greater influence than the change of acidity. The buffer quality
of the seawater perhaps is one of the reasons.
Fig. 5 shows that the CO2 value in the study system does
not depend on the number of active SRB and their metabolism
products in the open purified seawater system.
These results indicate that the growing process of SRB can
induce the changes of solution condition in limited culture
medium. The first of the changes is the increase of the CS2− value
and the decrease of Eh value. It represents that the reduction
ability of the system increased. The second one is the changes
appear during the exponential phase and stabilize during the
later phases. In another words, the redox quality caused by the
metabolism products of SRB can be preserved in the solution.
The third one is the influences on the redox quality caused by
the metabolism products of SRB do not depend on time but on
the amount of nutrient substances in the solution.
3.3. The effects of the SRB growth on the corrosion process
of carbon steel
Figs. 6–8 show the Ecorr , polarization curve and EIS of carbon
steel at different growth stages of SRB in the seawater system,
respectively. Similar to the change of the CS2− value, the Ecorr
value of carbon steel shifts to negative direction with the increase
of the NSRB value, and reaches a stable value at the death and
residual phases. It is clearly that both the enhancement of reduc-
tion quality of the medium and the acceleration of the anode
reaction as shown in Fig. 7 shift the Ecorr of carbon steel to
negative direction with a value of 35 mV as shown in Fig. 6.
Fig. 7 illustrates that the shapes of potentiodynamic polariza-
tion curve are not essential differenced in the systems with or
without SRB. Indicating that the mechanisms of anode process
and cathode process on carbon steel electrode do not change
essentially in the study system containing SRB. However, it can
be seen that the anode process increases largely and the cathode
 F. Kuang et al. / Electrochimica Acta 52 (2007) 6084–6088 6087

Fig. 9. EIS of D36 carbon steel in purified seawater and sweater system at
different growing stages of SRB (impedance modulus (|Z|) vs. frequency and
phase angle (θ) vs. frequency).
Fig. 7. Potentiodynamic polarization curves of D36 carbon steel in purified
seawater and seawater system at different growing stages of SRB.

process increases slightly with the increasing of NSRB value. And

the shapes of the potentiodynamic polarization curve are almost
the same after the 4th day, at which time the NSRB value stopped
increasing. This behavior is consistent with the change of the
redox quality of the study system. In addition, these features are
also consistent with the potentiodynamic polarization curves in
the medium containing different concentrations of Na2 S [21].
The changes of corrosion rate with the SRB growing process,
which were calculated from Fig. 7 are shown in Fig. 8. The intro-
duced SRB increases the corrosion rate of carbon steel largely
comparing with that in pure seawater. And the corrosion rate
of carbon steel increases during the exponential phase and are
stable during the later phases as the same way as the change of
CS2− . This suggested that the electrochemical corrosion behav-
ior of carbon steel is influenced mainly by the redox quality, Fig. 10. The Rp values of D36 carbon steel in seawater and seawater system at
which depends on the concentration of sulfide generated by the different growing stages of SRB calculated from Fig. 9.
metabolisms of SRB. And the corrosion rate hardly relates on
the SRB itself and the biology activity of SRB. Therefore, the corrosion mechanisms of carbon steel do not
The EIS shown in Fig. 9 further verified the reliability of the change with the growing process of SRB. The resistence por-
above results. The main structure of the EIS does not change. larization (Rp ) calculated from Fig. 9 are shown in Fig. 10. The
change of Rp values is consistent to the change of CS2− value.
In another words, the Rp value decreases with the increase of
the NSRB value and maintains at a stable value during the death
and residual phases. In addition, this is in concordance with the
change of corrosion rate which is shown in Fig. 8.

4. Conclusions

The growing process of SRB in the seawater system con-

Fig. 8. Corrosion current density of D36 carbon steel in purified seawater and
seawater system at different growing stages of SRB calculated from Fig. 7.
taining limited culture medium shows three different stages:
exponential, death and residual phases.
The main effects of the SRB growing process on the environ-
ment parameters are that the concentration of sulfide generated
by the metabolisms of SRB increases quickly during the expo-
nential phase and stabilizes during the death phase and the
residual phase. The changes of redox potential during the SRB
growing process are consistent with the changes of the sulfide
concentration.
6088 F. Kuang et al. / Electrochimica Acta 52 (2007) 6084–6088
The corrosion behavior of carbon steel in the study system
containing SRB hardly relates on the active SRB number. But
it depends on the accumulation of the metabolism products of
SRB. And the anode process and the corrosion rate are accel-
erated during the exponential phase and stable during the death
and the residual phases.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China under the contract no. 50499335-3 and
Chinese Academy of Sciences (Grant KZCX2-YW-210).
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