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Applied

Microbiology
Biotechnology

Appl Microbiol Biotechnol (1987)26:294--298

Springer-Verlag 1987

Bacterial corrosion of mild steel under the condition


of simultaneous formation of ferrous and sulphide ions
C. O. Obuekwe ~, D. W. S. Westlake 2, and J. A. Plambeck 3
1 Department of Microbiology, University of Benin, Benin City, Nigeria
2 Department of Microbiology, University of Alberta, Edmonton, Alberta, Canada
3 Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada

Summary. Corrosion of mild steel in cultures of a


Pseudomonas species under the condition of simultaneous formation of Fe(II) and S 2- was initially inhibited by inhibiting the anodic reaction,
but after long incubation the corrosion process
was allowed to continue. When only S 2- was produced, the initial corrosion rate increased for up
to 60 h but later declined, probably due to a protective FeS film formed on the metal. Cathodic
reactions were affected in a similar fashion as the
anode.
Extensive pitting corrosion was observed
when the mild steel coupons were immersed in
bacterial culture producing Fe(II) and S 2-, but
not in the uninoculated control.

Introduction
Coatings formed by the oxidation of iron and
steel to ferric compounds have been used for the
protection of steel against corrosion (Uhlig 1979;
Lumsden and Szklarska-Smialowska 1978), and
the removal of such films can cause the corrosion
of the metal they protect. Obuekwe et al. (1981a)
demonstrated that a Pseudomonas species isolated
from a corroding crude oil pipeline caused corrosion of mild steel by the depolarization of the
anode. Such corrosion of mild steel by the bacterium arose from the reduction of insoluble ferric
film to soluble ferrous compounds (Obuekwe et
al. 1981b). The presence of large amounts of soluble iron compounds in culture solutions is
known to increase the corrosion of mild steel
(Booth et al. 1967a), and a high content of soluble
iron compounds increases the aggressiveness of
Offprint requests to: C. O. Obuekwe

soils, augmenting the corrosion of iron and steel


buried in them (Booth et al. 1967b).
Apart from the ability to transform protective
ferric films on steel surfaces to nonprotective soluble ferrous compounds, bacteria can cause corrosion of iron and steel by generating sulphide,
which reacts with the metal to cause corrosion
(Von Wolzogen Kuhr 1961; Booth et al. 1968).
Sulphide production in a pipeline system has
been associated with the corrosion of the pipeline
(Obuekwe et al. 1983).
Although it has been shown that the reduction
of Fe(III) to Fe(II) or the formation of S 2- by
bacteria can cause the corrosion of iron and steel,
no work has been done on the corrosion of iron
and steel when Fe(II) and S 2- are being produced
simultaneously. The aim of this investigation is to
determine the bacterial corrosion of mild steel under the condition of simultaneous production of
Fe(II) and S 2-.

Materials and methods


Bacterial culture and inoculum preparation. The organism employed for this study was Pseudomonas sp. no. 200, which reduces Fe(III) to Fe(II) and also reduces thiosulphate and sulphite to sulphide. The organism was originally isolated from a
corroded crude oil pipeline (Obuekwe et al. 1981a). The bacterium was grown for 18 h in a complex medium of Torriani and
Rothman (1961), washed and resuspended in 0.1 M phosphate
buffer, pH 7.2, to a final concentration of 1 g wet weight per
80 ml buffer, yielding approximately 3.0 x 108 colony-forming
units per millilitre.
Medium for polarization, The medium for polarization and
growth of the bacteria in the corrosion cell was an Fe(IIl)-rich
Blo medium described previously (Obuekwe et al. 1981a) and
modified by the addition of 0.7 g Na2S203 per litre medium.
Potentiostatic polarization. The polarization of the sterile working electrode (AISI 10-18 mild steel coupon; dimensions

C. O. Obuekwe et al.: Bacterial corrosion during Fe(II) and S 2 production


50 12 x 1.0 mm) was undertaken in B10 medium in a twochambered polarization cell described previously (Obuekwe et
al. 1981a). The auxiliary electrode was a platinum flag of large
surface area, while the potentiostat was a Princeton Applied
Research (PAR) Potentiostat/Galvanostat Model 173 coupled
to a PAR Model 175 Universal Programmer to provide the desired potential. The potential between the working electrode
(mild steel coupon) and the reference electrode (saturated Calomel Electrode, Fischer Scientific) was measured using an
Electrometer Probe Model 178. The current output was recorded on a Houston Instrument Omnigraphic Recorder,
Model 2000.
Polarization was undertaken after inoculation of polarization medium with 1 ml of the bacteria suspension, de-aeration
with deoxygenated N2 and blanketing of the surface of the medium with the nitrogen gas. The mild steel working electrode
was polarized anodically (positive direction) and cathodically
(negative direction) with reference to the open-circuit potential at 25 C. The potentiostat rate was 2 mV s -1 and chart
speeds were 25 mV c m - 1 (x axis) and 0.5 mV c m - t (y axis).

Immersion of mild steel coupon in culture medium. Immersion


experiments were carried out in 500-ml corrosion chambers
(Erlenmeyer flasks with overflow side arm) connected to 44litre capacity B~o medium reservoir (Fig. 1). Each corrosion
chamber, filled with 400 ml medium, was inoculated with the
bacterial culture (1 ml cell suspension) and growth was allowed at 25 C for 24 h before opening the medium feedline.
This procedure allowed the culture to establish to prevent
wash-out. The dilution rate was 0.012 h - ' . This low rate was
chosen to simulate the slow bacterial growth observed under
natural conditions.

295

108

-03

-05

-0.6

//~/~/

V
i i

-0.5 "0

AnodicPolarization

i i 1.0i i I i 2_0
I i

-0.6 -'~Cathodic
-0.7

Polarization

-08
-0.9

",~N,~08

_1ol
I

0.2
0.4
Current Density (mA cm-2)

Fig. 2. Polarization curves of mild steel coupons in cultures of


Pseudomonas sp. no. 200 in Blo medium lacking Fe(III) but
containing Na2S203. The numbers O, 12, 24, 60 and 108 denote
incubation time in hours at 25 C. The curves with broken lines
also show the polarization of mild steel at the designated periods

Results and discussion


)2

"--3

~///////~//y////////////y~

"//,~

Fig. 1. Setup for continuous culture of Pseudomonas sp. no.


200 during the corrosion of mild steel coupons in the culture
of the bacterium. 1, Filter-tipped aspirator; 2, Flow breaker;
3, Medium reservoir; 4, Corrosion chamber; 5, Mild steel
coupons; 6, Effluent

To investigate the corrosion of mild steel (AISI


10-18) in bacterial cultures under conditions of simultaneous formation of Fe(II) and S 2-, the electrochemical (polarization) characteristics of mild
steel coupons and the behaviour of the metal under immersion in cultures containing $20 2without Fe(III) were determined.
The polarization characteristics of mild steel
coupons in bacterial cultures during S 2- production alone and during simultaneous Fe(II) and
S 2- production are shown in Figs. 2 and 3 respectively. When only S 2- was produced by the bacteria, there was an initial stimulation of the anodic
reaction (Fig. 2) up to 12 h. However, with subsequent reaction the anode became polarized, probably due to the formation of a protective FeS film
in the absence of high Fe(II) level in the culture.
A similar observation was made by Booth and
Tiller (1960). Working with cultures of sulphatereducing bacteria, these authors observed that an

296

C . O . Obuekwe et al.: Bacterial corrosion during Fe(II) and S 2 production

initial stimulation of the anodic reaction was always followed by inhibition, regardless of
whether the organism was hydrogenase-positive
or hydrogenase-negative.
Under the conditions of simultaneous production of S 2- and Fe(II) by the bacteria, the polarization characteristics showed that the reaction at
the anode was initially stifled for up to 60 h but
was later followed by an increased anodic dissolution (anodic depolarization). This observation is
the reverse of what was observed only S 2- was
produced in the medium. A high concentration of
Fe(III) in the form of Fe3PO4 inhibited mild steel
(Obuekwe et al. 1981a), and it was not until Fe(II)
and S 2- were produced that corrosion resumed.
In the cathode, the changes in the corrosion characteristics of the mild steel coupons were similar
to what was observed in the anode, as shown by
the polarization characteristics.
High amounts of soluble iron have been reported to prevent the formation of a protective
sulphide film on ferrous metal (Booth et al.
1967a) and will also cause a high corrosion rate of

60/

-O2

24

110
j 0

12 . pt.1"

9~

-0.2

//

/ ///..-

-0.3

~ 2

//-'"

- - ~ f

~v

-0.~
-0.5 f ~ Z

Anodic Polarization

-> -0.6

-0.5 0

0.4

~- -0.6
-0.7

0.8

1.2

[afhodic Po[arizahon

-08

-0.9
-to
i

I 011 J i

i 0.2r I

f 013

Eurrenf Densify (mA cm4)


Fig. 4. Polarization curves of mild steel coupons in uninoculated Blo medium (control) containing Fe(III) and Na2S203.
The numbers O, 12, 24, 60 and 98 denote incubation time in
hours at 25 C. The curves with broken lines also show the polarization curves of mild steel at the designated periods

-(13

SjJ Sr
-0.4

-0.3

-0,~

Anodic Polarization
-05

-0.5 7

-06 1
I

-o

Anodk Polarization

> -0.5 , I

-~

=
g -0.5

-0.5

.I 4

,I

08

1.2

~-" -Q6

-0.6

Cathodic Polarization

-0.7

-0.7

-0.8

-0.8

-0.9

~'
I

60 ~

-0.9

.O! 0

-1.0 ~

Eafhodic Potarization

- 1.0

12
I

Q2
04
Current Density (mAcm

2/+x~60
t

0.6
-2)

Fig. 3. Polarization Curves of mild steel coupons in cultures of


Pseudomonas sp. no. 200 in B~o medium containing Fe(III)
and Na2S203. The numbers 0, 12, 24, 60 and 110 denote incubation time in hours at 25 C. The curves with broken lines
show the polarization of mild steel at the designated periods

0/ 8

0.
0.16
024
Eurrent Density (mAcm-2)
Fig. 5. Polarization curves of mild steel coupons in uninoculated B]o medium (control) containing Na2S2Oa but not
Fe(III). The numbers 0, 12, 24, 60 and 98 denote incubation
time in hours at 25 o C. The curves with broken lines also show
the polarization curves of the mild steel at the designated periods

C. O. Obuekwe et al.: Bacterial corrosion during Fe(II) and S 2 production

297

Fig. 6a, b. Pit formation on mild


steel coupons immersed for 9
weeks in S2- and Fe(II)-producing cultures of P s e u d o m o n a s sp.
no. 200. Magnification x 52.5. a
Pits (p) on coupon immersed in
cultures
during
simultaneous
Fe(II) and S 2 formation, b Control (uninoculated)

such metal in soils (Booth et al. 1967b). In this


investigation, the soluble iron compounds (Fell)
were formed in situ by the reduction of Fe(III)
and the simultaneous production of S 2- would
eventually prevent the formation of protective
FeS film on the metal. In the case where only S 2was produced by the organism, the initial increase
in anodic reaction was due to the reaction of S : produced by the bacterium with the metal. The resultant FeS eventually protected the metal, as
seen from the polarization curve in Fig. 2.
In the condition of simultaneous production
of S 2- and Fe(II), it was possible that the large
amount of FeS formed in the medium also contributed to increased corrosion by depolarization
of the cathode, as seen in Fig. 3, after 60 h incubation. It has been reported that FeS, in the absence
of bacteria, can cause corrosion of ferrous metal
by increasing the cathodic reaction (depolarization of the cathode), as was similarly observed in
Fig. 3 after long incubation.
In the control experiments (Figs. 4, 5) both the
anodic and cathodic reactions were inhibited (polarized) in the absence of bacterial reduction of
Fe(III) and $2032- to Fe(II) and S 2- respectively.

Thus, both the production of S 2 and Fe(II) simultaneously (Fig. 3) and the production of
Fe(II) alone by the bacteria (Fig. 2) were responsible for the anodic dissolution (corrosion) of the
mild steel coupons, and in the absence of production of Fe(II) and S 2- no dissolution of the anode
was observed, as shown in the controls (Figs. 4,
5).
Mild steel coupons immersed in the bacterial
cultures showing simultaneous production of
Fe(II) and S 2- showed extensive pitting corrosion
(Fig. 6a) and was covered by a loose deposit of
FeS. No such pit formation was found on control
coupons (Fig. 6b). In real life, the problems of the
Pembina pipeline system, from which the bacterium was isolated, have been associated with pitting corrosion.
In conclusion, it was observed that the corrosion of mild steel (AISI 10-18) in cultures of
Pseudomonas sp. no. 200 was sustained and led to
extensive ptting of the coupons when Fe(II) and
S 2- were produced simultaneously. In the presence of S 2- alone, the corrosion was inhibited
soon. Undoubtedly, the combined effects of destabilization of FeS film on the coupon and ca-

298

C.O. Obuekwe et al.: Bacterial corrosion during Fe(II) and S2- production

thodic depolarization by a large quantity of FeS


formed in the culture would contribute effectively
to the sustained corrosion of the mild steel under
the condition of simultaneous Fe(II) and S 2- production in the culture.

References
Booth GH, Tiller AK (1960) Polarization studies of mild steel
in cultures of sulphate-reducing bacteria. Trans Faraday
Soc 56:1689--1696
Booth GH, Elford L, Wakerley DS (1968) Corrosion of mild
steel by sulphate-reducing bacteria: an alternative mechanism. Br Corrosion J 3:242--245
Booth GH, Cooper AW, Cooper PM (1967a) Rates of microbial corrosion in continuous culture. Chem Industr
86:2084--2085
Booth GH, Cooper AW, Cooper PM (1967b) Criteria of soil
aggressiveness towards buried metals. II. Assessment of
various soils. Br Corrosion J 2:109--115
Lumsden JB, Szklarska-Smialowska Z (1978) The properties of
films formed on iron exposed to inhibitive solutions. Corrosion 34:169-- 176

Obuekwe O, Westlake DWS, Plambeck JA, Cook FD (1981a)


Corrosion of mild steel in cultures of ferric iron reducing
bacterium isolated from crude oil. I. Polarization characteristics. Corrosion 37:461--467
Obuekwe CO, Westlake DWS, Plambeck JA, Cook FD
(1981b) Corrosion of mild steel in cultures of ferric iron
reducing bacterium isolated from crude oil. 11. Mechanisms of anodic depolarization. Corrosion 37:632--637
Obuekwe CO, Westlake DWS, Cook FD (1983) Corrosion of
Pembina crude oil pipeline. The origin and mode of formation of hydrogen sulphide. Eur J Appl Microbiol Biotechnol 17:173--177
Torriani A, Rothman F (1961) Mutants of Escherichia coli constitutive for alkaline phosphatase. J Bacteriol 81:835-836
Uhlig HH (1979) Passivity of metals and alloys. Corr Sci
19:777--791
Von Wolzogen Kuhr CAH (1961) Unity of anaerobic and
aerobic iron corrosion process in the soil. Corrosion
17:119--125

Received July 9, 1986/Revised January 19, 1987

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