Corrosion Science 146 (2019) 99–111

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Review

Mechanistic microbiologically influenced corrosion modeling—A review T

a b a,⁎ a b
A. Marciales , Y. Peralta , T. Haile , T. Crosby , J. Wolodko
a
InnoTech Alberta, Devon Research Center, 1 Oil Patch Drive, Devon, Alberta, T9G 1A8, Canada
b
Department of Agricultural, Food and Nutritional Sciences, University of Alberta 4-10 Agricultural/Forestry Centre, Edmonton, Alberta, T6G 2P5, Canada

ARTICLE INFO ABSTRACT

Keywords: At present, most Microbiologically Influenced Corrosion (MIC) models used in the petroleum industry are risk
MIC based, and predict the likelihood of MIC. It is imperative that the industry adopts mechanistic models to ac-
Biofilms curately quantify MIC in pipes/facilities. This paper summarizes the findings of a literature review of me-
Mechanistic model chanistic MIC models available in the public domain. The results indicated that most of the models reviewed
Sessile bacteria
consider Sulphate Reducing Bacteria (SRB) as the main players in MIC, and very few models consider biofilm
Electrochemistry
formation and transport phenomena. Furthermore, no models were found to accurately correlate sessile and
planktonic bacteria.

1. Introduction strong heterogeneity. It is well known that the metabolic activity of

About 20–40% of localized corrosion related failures are attributed
directly or indirectly to Microbiologically Influenced Corrosion (MIC)
[1,2]. MIC is manifested in areas where the fluid shear stress at the pipe
wall, the force responsible for mobilizing such solids, is reduced [3].
Biologically active sludge can contain microbial communities which
cause corrosion, including sulphate reducing bacteria (SRB), sulphate
reducing archaea (SRA), methanogen, acetogens, fermenters, iron re-
ducing bacteria (IRB), iron reducing archaea (IRA), iron oxidizing
bacteria (IOB), manganese oxidizing bacteria (MOB), acid producing
bacteria (APB), and slime formers, among others. It is important to note
that MIC may occur in a wide range of pipeline environments and op-
erating conditions which support microbial growth.
Corrosion is an interfacial process. The kinetics of corrosion are
determined by the physicochemical environment at the interface in-
cluding dissolved oxygen concentration, presence of salts, pH values,
redox potential and conductivity, among others. These parameters can
be influenced by microorganisms growing on the interior or exterior
surface of a pipeline system. The organisms can attach to surfaces,
embed themselves in slime known as extracellular polymeric substance
(EPS), and subsequently form biofilms [4]. These biofilms are com-
posed primarily of microbial cells and EPS [5]. EPS may account for the
majority of the total organic carbon of biofilms, and can be considered
the primary matrix material of the biofilm. EPS may vary in chemical
and physical properties, but it is primarily composed of polysaccharides
[6]. Biofilms can vary in thickness from microns to centimeters, and are
quite heterogeneous in composition. Biofilms are characterized by a
clusters of organisms can change the local pH value by more than 3
units [4]. This means that directly at the interface between the biofilm
and the metallic surface where the corrosion process is actually taking
place, the local pH values can differ significantly from that in the bulk
fluid. Thus, biofilms can promote interfacial physicochemical reactions
not favored under abiotic conditions [7].
Although risk based inspection (RBI) models can provide insight
into the likelihood of MIC, their ability to predict MIC progression ac-
curately is limited [8]. Gu et al. [8] suggested that mechanistic models
can reliably predict MIC pitting progression if the factors that influence
MIC are taken into account, such as microbial growth kinetics, mass
transfer phenomena; and chemical, biochemical and electrochemical
reactions.
This paper presents a comprehensive literature review of MIC me-
chanistic models available in the public domain, and is intended to be a
reference for both researchers and practitioners in corrosion science
and engineering.
2. Mechanistic MIC predictive models
It is imperative to understand the mechanisms of MIC in order to
develop a comprehensive predictive model. Key factors that need to be
taken to account include:
• Biofilm development kinetics: microbial cell transport from bulk
fluid to the metal surface, and their attachment, accumulation
(biofilm growth) and detachment,

⁎
Corresponding author.
E-mail address: Tesfa.Haile@innotechalberta.ca (T. Haile).

https://doi.org/10.1016/j.corsci.2018.10.004
Received 22 May 2018; Received in revised form 30 August 2018; Accepted 1 October 2018
Available online 09 October 2018
0010-938X/ Crown Copyright © 2018 Published by Elsevier Ltd. All rights reserved.
A. Marciales et al. Corrosion Science 146 (2019) 99–111

Nomenclature in a plane sheet

MWS Molecular weight of sulphide (kg/mol)
Symbol MWFe Molecular weight of iron (kg/mol)
NS Sessile bacteria (cell numbers/m2), in biofilm
a Coupon surface area (m2) Ni Inoculum (cell numbers/m2)
A Inner surface area of the pit (m2) Np Number of planktonic cells in the inlet fluids (cell num-
Β Biocide concentration bers/m3)
C Corrosion rate constant (m/s) Np Number of planktonic cells in wash out phase (cell num-
c Constant for attachment (-) bers/m3)
CRFe Corrosion rate of iron (mm/yr) NS Biofilm growth rate after biocide addition (cell numbers/
Ci Concentration of species (kg/m3) m3)
C SO4 2 Bulk concentration of sulphate (mol/m3) NS , o Bacterial numbers before biocide (cell numbers/m3)
*
C SO 2 Sulphate concentration in the biocorroded pit (kg/m3) NS , i Number of cells (cells/m2)
Planktonic cells (cells/m3)
4
C SO4 2, lim Concentration limiting substrate (kg/m3) Ni, p
D SO4 2 Diffusion coefficient of sulphate (m2/s) Ni, S Number of sessile bacteria (cell numbers/kg solid)
Deff Effective diffusivity in the biofilm (m2/s) Nk Proportionality between iron and sulphate consumption
D SO4 2, Ac, bfl Diffusion coefficient for sulphate or acetate in the bio- rate (mol Fe/mol SO4 2 )
film (m2/s) Empirical constants (-)
Di Diffusion coefficient of specie i (m2/s) n Number of electrons involved in reaction (-)
δ Detachment constant (-) qs Utilization rate of sulphate by SRB in the biofilm (kg S/kg
Change in variable (-) SRB s)
E Corrosion potential (V/SHE) qmax Maximum utilization rate of sulphate (kgS/kgSRB s)
Eeq Equilibrium potential (V/SHE) Ri Reaction rate of i species (mol/m3 s)
F Faraday constant (C/V) Rs Rate of precipitation
fi Factors in corrosion model (-) R Universal gas constant (J/mol K)
ia (Fe) Cathodic reduction current density (A/m2) Rde Biofilm detachment rate (kg SRB/m2 s)
ic (H )
+ Cathodic reduction hydrogen reduction current density RS / P Ratio between sessile and planktonic microorganisms
(A/m2) (cells/kg per cells/m3)
ic (H2 CO3) Acetic acid reduction current density (A/m2)
*
R SO 2 Sulphate consumption rate by SRB (mol/m3*s)
4
ic (SO4 2) Sulphate current density (A/m2) Fe Iron density (kg/m3)
ja (Fe) Anodic current density for iron oxidation (A/m2) bfl Biofilm density (kg/m3)
jc (H +) Cathodic current density for H+ reduction (A/m2) Si Cell-specific activities (mol S−2/cell*s)
jc (SO4 2) Cathodic current density for sulphate reduction (A/m2) t Time (s)
jc (SO4 2) Cathodic current density (A/m2) T Absolute temperature (K)
jlim (SO4 2) Mass transfer limiting current density for sulphate reduc- 1 Thiele module (-)
tion (A/m2) Porosity of the biofilm (-)
Km Monod half-velocity coefficient constant of substrate s Solid phase (-)
(mol/m3) b Biofilm phase (-)
K SO4 , blf Monod half-velocity coefficient constant for sulphate in
2 w Mobile water phase (-)
biofilm (mol/m3) µ Monod average population growth (s−1)
KAc, bfl Monod half-velocity coefficient constant for acetate in µs, bfl Monod specific growth rate (s−1)
biofilm (mol/m3) µmax Monod maximum specific growth rate (s−1)
K dl Non-growth associated detachment (-) V Volume of total fluids per day (m3)
k Empirical constants (-) v Mass average volumetric velocity of the system (m/s)
Lf Biofilm thickness (m) Integration constant for numerical solution (-)
L Characteristic pith length (m) X* Biofilm density times the biofilm thickness (kg/m2)
Dimensionless symmetry factor (-) Xs SRB concentration inside the pit (kg/m3)
m Element of series for Crank numerical solution to diffusion Ys True yield (kg SRB/ kg SO4−2cell numbers*s)

• Mass transfer phenomena: diffusion of chemical species (e.g., sub- limitations. The order of presentation of the different models was ac-
strate, metabolites, buffering species), from bulk fluid through the cording to their complexity, i.e. number of parameters considered and
bulk-biofilm interface to the biofilm-metal interface, and numerical solution employed to solve the equations and calculate the
• Chemical, biochemical, and electrochemical reactions: within the corrosion rate.
biofilm, biofilm- metal interface, and on the surface of the metal.
2.1. S. Maxwell model (2006)
Although there are considerable literature in the public domain
reporting on the effect of biofilm formation on corrosion rate [9–14]; to
In 2006, Maxwell [15] developed a qualitative model capable of
date there are very few models that take into consideration the afore-
predicting MIC occurrence. The authors stated the model would be
mentioned factors for the development of mechanistic MIC predictive
quantitative once a constant for pitting rate is included. The relevance
models. Furthermore, information regarding validation and/or cali-
of this model to mechanistic modeling relies in its inclusion of sulphidic
bration of the models, either in lab or field environment, is often
biofilm formation prior to MIC, including bacterial kinetics in sea water
missing. Each of the following sections summarizes a number of MIC
systems. In addition, it predicts MIC using the various corrosion control
mechanistic models available in the public domain. Model development
measures often implemented in industry: biocide, oxygen scavenger,
and assumptions are provided, along with relative strengths and
pigging, among others. Maxwell recommended the inclusion of sessile

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A. Marciales et al.
SRB monitoring as part of the corrosion management strategy. The
author considered 4 factors to determine SRB induced corrosion:
• Presence of sulphide,
• Oxygen ingress,
• Pigging frequency, and
• Age of pipeline,
The MIC rate (CRFe , mm/yr) was calculated as per the following
equation:
CRFe = C × F P
where C (m/s) is a corrosion rate constant,
F = fsulphide × foxygen × fpigging × fage (-), with p as the power law index.
This model was developed after Pots [16], who considered a total of
15 factors to determine sulphide induced corrosion rate. Each factor
was assessed using a multilevel factorial design against the other ones
with regards to increased corrosivity. It was assumed that the longer the
age of the system ( fage ), the more susceptible the system will be influ-
enced by MIC corrosion rate. The time it takes for a steady state biofilm
development was calculated through Eq. (2):
t = 10/(Ys × MWS × NS )
where t (s) is the time it takes to achieve a sulphide concentration of
10−5 kg per m2 in an existing MIC pit, Ys is sulphide production (kg
Sulphate/cell numbers*s), MWS (kg/mol) the molecular weight of sul-
phide, and Ns the cell numbers/m2 (biofilm). The mass balance of the
sessile SRB cells within the biofilm can be determined using Eq. (3):
Biofilm = Inoculum + Growth – Death − Wash Out
2
The Inoculum Ni (cell numbers/m ) was calculated according to the
following Eq. (4):
Np × V
Ni = c
a (4)
where c (-) is a constant for attachment, Np (cell numbers/m ) the 3 determined by qPCR analysis of solid samples obtained from pigging
number of planktonic cells in the inlet fluids, V (m3) the volume of total
fluids per day, and a (m2) is the surface area.
Biofilm growth (NS , cell numbers/m3) is calculated by Monod ki-
netics for average population growth ( µ , s−1) as per Eq. (5):
(t t o )
NS = Ni × 10 µ
2.303
and the growth kinetics ( µ , s−1) is modeled by Eq. (6) using the max-
imum specific growth rate ( µmax , s−1), the half saturation constant of
substrate, Km (mol/m3), and the concentration limiting substrate
(C SO4 2, lim , mol/m3).
µmax × C SO4 2, lim
µ=
C SO4 2, lim + Km
The death phase (bacteria left after biocide application) was related
to biofilm growth rate after biocide addition (NS ), and the bacterial
numbers before biocide (NS , o , cell numbers/m3), as described in Eq. (7):
ln
NS
= k t
NS , o
where, k and (-) are empirical constants, t(s) is biocide treatment
time, and β is the concentration of biocide.
Finally, wash out phase (Np ) (planktonic cell numbers/m3) was re-
lated to the sessile SRB (Ns ), surface area (a , m2), detachment constant
( ,-) and volume of total fluids per day (V, m3) as follows in Eq. (8):
× Ns × a
Np = V (8)
While this was the first attempt in the literature to relate biofilm
phenomena (inoculation, growth, detachment, and death,) to the effect
Corrosion Science 146 (2019) 99–111
of biocides, this model does not take into account electrochemical
variables.
2.2. Bernt, Thomsen, Juhler and Larsen model (2012)
Brent et al. [17] developed a model which calculates MIC risk factor
and worst-case pitting corrosion rates caused by Sulphate Reducing
Bacteria (SRB), Sulphate Reducing Archaea (SRA) and methanogens
(MET) through three different steps. The sulphate reducing micro-
organisms and methanogens contribute to iron dissolution according to
(1) Eqs. (9) and (10), respectively:
4Fe 0 + 3H2 S + SO4 2 + 2H+ 4FeS + 4H2 O (9)
4Fe 0 + 4H2 S + CO2 4FeS + 2H2 O + CH4 (10)
The authors recommend if both the MIC risk factor and Potential Pit
Generation Rate (PPGR) values are high, intelligent pigging along with
reverse transcription of quantitative Polymerase Chain Reaction (qPCR)
analysis are performed on sludge samples, and mitigation actions are
taken to control microbial growth. qPCR will confirm whether micro-
bial cells are growing exponentially or not.
The first step of this model evaluates an Integrated MIC Risk Factor
(2)
(IMRF) which takes into account the activities of SRA, SRB and MET
based on: a) the time required to achieve sufficient biogenic sulfide
concentration for corrosion to commence (MRF), and b) the time
needed to develop a layer of corrosion products and biofilm that may
promote cathode and anode reactions (MRF’). The IMRF, time (s), is
determined Eq. (11), as follows:
(3) IMRF = MRF + MRF’ (11)
The values for MRF and MRF’ are based on sessile SRA, SRB and
MET cell numbers, and their cell-specific activities (Si, mol S−2/cell*s).
The calculation of IMRF is based on the model developed by Maxwell
[15] with values for Si found experimentally for a range of temperatures
in situ (i: SRA, SRB, MET). The number of cells (Ns,i, cells/m2) was
debris or water samples retrieved from the system and was calculated as
follows:
NS , i = Ni, S bfl Lf (12)
where, Ni, s is the number of sessile bacteria (cells/kg solid), and
(5)
( ) and L (m) are the density and thickness of the biofilm, re-
Kg
bfl m3 f
spectively. The number of cells (NS,i) can also be calculated from the
number of planktonic cells according to Eq. (13) below:
NS , i = Ni, p, (Rs/ p) bfl Lf (13)
3
The planktonic cells (Ni, p, cells/m ) can be measured from field
samples, and the values of the ratio between sessile and planktonic
(6) microorganisms (Rs/ p , cells/kg per cells/m3) can be calculated empiri-
cally from solid and water samples retrieved from different locations in
the field.
According to this model, low IMRF values pose high MIC risk
(meaning the time it takes for MIC to initiate is short). The model also
calculates Potential Pit Generation Rate (m/s) for different pipe seg-
(7) ments (14):
Rate of Fe dissolution = 4[(NSRA × SSRA) + (NSRB × SSRB) + (NMET ×
SMET)] (14)
where NSRA, NSRB and NMET represent the sessile population of sulphate
reducing archaea, bacteria and methanogens, respectively.
The authors recommend that when the IMRF and PPGR parameters
are high, qPCR testing should be performed to identify the different
phases of microbial growth, and appropriate mitigation strategies
should be implemented accordingly. The model and its parameters can
be calibrated with field data and/or laboratory tests. One limitation of
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A. Marciales et al. Corrosion Science 146 (2019) 99–111

this model is the fact that sessile microbial counts used in the IMRF The model assumes the following: 1) sulphate concentration is the
calculation are estimated based on a ratio between sessile and plank- only growth-limiting substrate, and is constant within the bulk solution
tonic cell numbers. If the measured planktonic cell numbers are low, (Co); 2) the SRB pit is axisymmetric with respect to its radius and ro-
the assumed sessile microbial cell numbers might be underestimated. tation plane (r,θ) and the pit grows in axial (z) direction; 3) only mo-
lecular diffusion is considered, and as sulphate diffuses from bulk to the
2.3. Larsen, Bernt, Juhler, and Pedersen model (2013) pit, a sulphate concentration profile is established along the axial di-
rection, at a slow rate of motion in the steel-biofilm interface; 4) the
Larsen et al. [18] proposed evaluating MIC risk by analysing the biofilm thickness is much less than the thickness of the diffusion zone.
presence of Sulphate Reducing Prokaryotes (SRP), i.e., sulphate redu- In addition, the sulphate utilization rate is assumed to occur only on the
cing bacteria and archaea; and determining the activity of methano- corroding surface, i.e., corrosion reaction zone, and in steady state, the
gens. This was done using molecular microbiological methods (MMM), sulphate flux equals the rate of sulphate utilization.
i.e., qPCR and reverse transcription qPCR (RT-qPCR). With these tech- The mass balance of species in the pit region with limiting biofilm
niques, cell specific activities, designated as RNA gen units (GU) per surface is expressed as follows:
cell, are calculated by measuring the amount of rRNA detected by RT- Ci
+ (v Ci ) = Di 2C + Ri
qPCR divided by the number of microbes detected by qPCR. These re- t
i
(23)
sults differentiate the total number of cells from the number of active 3
cells present in the system. Ci (mol/m ) is the concentration of species, v (m/s) the mass average
This RT-qPCR technique was compared to conventional qPCR velocity, Di (m2/s) the diffusion coefficient and Ri (mol/m3*s) the re-
methods using a risk analysis case study previously performed by the action rate of i species.
authors on four pipelines operating in the North Sea [17]. When con- The authors neglected the second term in both sides of Eq. (23) due
ventional qPCR methods were used in the analysis, three of four pipe- to the assumption considered above; i.e. stagnant condition inside the
lines assessed were considered to have a high potential risk of MIC. pit, and sulphate consumed by SRB is a boundary condition (Eq. (23)).
When the MMM technique (RT-qPCR) was used, only two of the four Therefore, in steady state and cylindrical coordinates, Eq. (23) be-
pipelines were subsequently found to have a high MIC risk potential. comes:
The authors concluded that the MMM method was the preferred choice 2C
SO4 2 1 C SO4 2
2C
SO4 2
2C = + + =0
in evaluating IMRF risk factors, and should be used in future assess- SO4 2
r2 r r z2 (24)
ments of systems susceptible to MIC.
Eq. (24) and its boundary conditions are transformed to dimensionless
2.4. Peng, Suen and Park model (1994) groups by dividing dimension variables ( r and z ) by a characteristic
length L, and C SO4 2 by the bulk concentration as follows:
Peng et al. [19] developed a mathematical model based on SRB C SO4 2
*
C SO =
depolarization theory described in Eqs. (15) through (21) below. Note 4
2
Co (25)
in Eq. (18), cathode SRB mediated depolarization considers Had instead
of H2, a correction to the approach initially proposed by Wolgozen Kuhr r
r¯ =
and Van der Vlugt where they assumed biological sulfate reduction L (26)
consumes dihydrogen (H2) [20]. The authors validated their theory in z
z¯ =
lab at SRB and sulphate concentrations of 0.1 and 0.5 mol/m3, re- L (27)
spectively. n
n¯ =
Anodicreaction: 4Fe 4Fe+2 + 8e (15) L (28)
As a result, Eq. (24) is transformed to following Eq. (29), and the
Waterdissociation: 8H2 O 8H+ + 8OH (16)
model is defined below as:
Cathodicreaction: 8H+ + 8e 8H (17) 2C * 2C * 2C *
2 * SO4 2 1 SO4 2 SO4 2
C SO = + + =0
r¯2 z¯2 (29)
2
CathodicSRBdepolarization: SO4 2 + 8Had S 2 + 4H2 O (18) 4 r¯ r¯
*
D SO4 2 Co C SO4 2 qmax X *C SO
*
Corrosionproductsreactions: Fe+2 + S 2 FeS . (19) 4
2
= Km
L n¯ + *
C SO
3Fe+2 + 6OH 3Fe (OH ) 2 (20) Co 4
2
(30)
Assumption #4 is mathematically expressed by Eq. (30) where Km
Balancedoverallreaction: 4Fe + SO4 2 + 4H2 O FeS + 3Fe (OH )2 (mol/m3) is the Monod half-velocity coefficient; X * (kg/m2) is the
+ 2OH biofilm density ( bfl , kg/m3) multiplied by the biofilm thickness (Lf , m),
(21) and qmax (kg S/kg SRB s) is the maximum utilization rate of sulphate.
In addition, assumption 1) and 2) are expressed as follows:
The corrosion rate at any time is related to the change in distance, or
pit depth (ΔL) in a small time increment of time ( t ): C*SO
4
2 = 1 inbulksolution
(31)
D SO4 2 Co C¯SO24 MWFe C*
L = ( t) (Nk ) SO4 2
L n¯ = 0 (axisymmetric )
Fe (22) r̄ (32)

where 3
(mol/m ) is the sulphate concentration in the pit, D SO4 2
CSO24
(m2/s) is the diffusion coefficient of sulphate, n is a unit outward
normal to the surface, Nk (mol Fe/mol SO4 2 ) is the ratio between total
corroded iron to sulphate, MWFe (kg/mol) is the molecular weight of
iron, and Fe (kg/m3) is the density of iron. This expression considers
the corroded iron influenced by the local reaction rate of biogenic
sulphate reduction.
Eqs. (29)–(32) were solved numerically using the Boundary Integral
Equation Method (BIEM), and solved by the bisection and the inter-
polative method. Once the authors determined the fundamental solu-
tion and its normal derivative, the integration was carried out by di-
viding the boundary path into a number of segments of elements. The
boundary values and sulphate gradient for sulphate concentration were
then computed for all points within the pit domain. Next, the time

102
A. Marciales et al. Corrosion Science 146 (2019) 99–111

evolution of the moving boundary was obtained applying the bisection 2.5. Al-Darbi, Agha and Islam model (2005)
method and Eq. (21), followed by the interpolative method to estimate
concentration at new points. These last set of concentration values were Al-Darbi et al. [22,23], developed a numerical model for anaerobic
used as new input data for the calculation at t + t . MIC in SRB environments (marine, landfill and fresh water) with MIC
The authors found that the model predicts three phases for the mechanism based on the cathodic depolarization theory proposed by
evolution of the pitting corrosion rate: increasing, transitional and Wolgozen Kuhr and van der Vlugt [20] however note in Eq. (39), sul-
stationary phases. All of these phases can be approximated by com- fate reduction considers Had instead of H2, a correction to the approach
bining Eqs. (21) and (29), depending on the relative magnitude be- initially proposed by Wolgozen Kuhr and Van der Vlugt where they
tween Km and C SO4 2 : assumed biological sulfate reduction consumes dihydrogen (H2) [20].
The following sets of reactions, (36) to (40), represent the corrosive
qmax X *C SO
*
2 qmax X *C SO4 2 attack:
4
L Km
( t) = t
Co
*
+ C SO 2
Km + C SO4 2
(33) 4Fe 4Fe+2 + 8e (36)
4

8H2 O 8H+ + 8OH (37)

During the increasing phase, there is a constant slope and
*
C SO Km/ Co , resulting in Eq. (34):
4
2
8H+ + 8e 8Had (38)
L qmax X * t (34)
SO4 2 + 8Had S 2 + 4H2 O (39)
They also describe the start of the transitional phase when the pit
4Fe+2 + S 2 + 6OH FeS + 3Fe (OH )2 (40)
increases beyond a certain point, after which C SO or C SO4 2 Km ,
* Km
2 Co
4 −2
and pitting rate is approximated by Eq. (33). Lastly, the stationary The corrosion rate (CRFe ) is Nk (mol S /cell*s) times proportional
3
phase occurs when C SO4 2 is small, i.e., C SO4 2 Km or Km *
C SO 2 * Co : (Eq. (40)) to the consumption of sulphate (R SO
*
2 , mol/m* s) by SRB as
4 4
described in the following equation:
qmax X *C SO
*
2 qmax X *C SO4 2
L 4
( t) = t CRFe
Km
Km Nk =
Co (35) *
R SO 2
(41)
4

The model was found most sensitive to D SO4 2 , followed by and the corrosion rate, (CRFe , mm/yr), as expressed in Eq. (41), is re-
qmax and X * after a sensitivity analysis was performed through simula- lated to the pit length according to Eqs. (43) and (44):
tion by changing each of the values previously described by ± 20%. V Fe
Higher values for D SO4 2 produced higher corrosion rates during the CRFe =
(MWFe ) t A (42)
transitional and stationary phases, while lower values for either or both
qmax and X * increased pitting rate during the initial stage. V
Furthermore, the MIC pitting rate prediction was in agreement with L=
(43)
A
results from laboratory experiments, with major discrepancies during
the initial stage, mainly due to lack of representation of the initial lag Fe
CRFe = L
phase of MIC development, uncertainty of parameters and mechanisms, (MWFe ) t (44)
as well as human errors during the experimentation.
Later on, Hao [21], discussed this model and its results suggesting where V (m3) is the volume of oxidized iron, MWFe (kg/mol) is the
several variables should be included or modified for reflecting real- molecular weight of iron, Fe (kg/m3) is the density of iron, t (s) is time,
world scenarios. First, they recommended that sulphate reduction A (m2) is the inner surface area of the pit, and L is the change in the
should be considered in the bulk solution, not only at the biofilm-metal pit depth.
interface; second, they propose the use of values lower than 4 for Nk The authors then found the direct relationship CRFe = f ( L , RSO *
2)
4
(Nk 4 mol Fe/mol SO4 2 ); third, they also express the necessity for by carrying out a mass balance for sulphate concentration (SO4 2 ) with a
inclusion of a sink term in Eq. (21) described previously to account for cylindrical pit as a control volume, as follows:
other metal-sulfide reaction, decreasing available sulphate for SRB;
*
C SO 2C * *
1 C SO 2C *
fourth, Hao et al. [21] also imply that using variability of the film 4
2
SO4 2 4
2
SO4 2 *
= D SO4 2 + + + R SO
density ( X *) should be considered to avoid over predictions of pitting t r*2 r* r* z *2 4
2
(45)
depth at the different times of MIC; and finally, the authors also advise
further investigation for the effect of extracellular polysaccharides where C SO
*
2 (mol/m3) is the concentration of sulphate inside the pit,
(EPS) produced by SRB on anaerobic corrosion besides cathodic depo- 2
4
D SO4 2 (m /s) is the sulphate diffusion coefficient in water systems, and
larization. 3
2 (mol/m* s) is the consumption rate of sulphate inside the pit. This
*
R SO
The original authors [19] addressed these opinions in the same 4
last term, depends on the Monod expression used for SRB:
discussion by Hao [21]. Their response to the first observation was that
SRB accumulates at the reaction zone and the consumption of sulphate qmax Xs C *
SO4 2
by diffusion is limited and negligible. Regarding the second suggestion, *
R SO 2 = *
Km + C SO
(46)
4
he [19] mentions [21] that oxidation of cathodic hydrogen by SRB is 4
2

the main mechanism and, although Nk 4 does not count for the cor-
where Xs (kg/m3) is the SRB concentration inside the pit, Km (mol/m3)
rosive nature of hydrogen sulfide and ferrous sulfide corrosion pro-
is the Monod half velocity coefficient for SRB in the biofilm, and qmax
ducts, this value varies in practice from 0.9 to 50, therefore, there is a
(kg S/kgSRB s) is the maximum utilization rate of sulphate.
need for further studies to account for this parameters. In addition, the
To simplify the solution, the authors transformed Eq. (45) to a di-
original author state in the discussion [21] that X * practical effect was
mensionless equation by introducing L (m) as the characteristic length,
analyzed in the discussed work [19] and that any iron oxide and hy-
and C SO4 2 (mol/m3) as the sulphate concentration in the bulk solution.
droxide effect is beyond the discussion of the paper. However, they also
Using Eqs. (47) thru (51), Eq. (45) can be re-written as Eq. (52), as
suggest addressing those observations in a future work.
follows:

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A. Marciales et al. Corrosion Science 146 (2019) 99–111

*
C SO *
C= 4
2
MWFe qmax Xs Lf C SO4 2
L = NK t
C SO4 2 (47) Km + C SO *
Fe 2
4 (59)
r*
r=
L (48) MWFe D SO4 2 C SO4 2 C
L= NK t
Fe L np (60)
z*
z=
L (49) The model can be solved numerically using central differentiation of
terms in Eq. (51) along with the boundary conditions in (55). Al-Darbi
np * et al. [22,23] employed the Alternating Direction Implicit (ADI) method
np =
L (50) of numerical solution with two time steps for this model. During the
first half time step (n+(1/2)), the partial derivatives in r are solved,
t D SO4 2
= and during the second half time step, the partial differences in z are
L2 (51) solved.
2C 2C From their numerical results, the authors concluded that for small
C 1 C
= + + +R pit depths, the concentration of the sulphate is similar to the bulk so-
r2 r r z2 (52)
lution leading to a reaction-controlled process in the pit. Initially, there
The boundary conditions required to solve this system of equations is rapid pit growth but the rate eventually decreases to a low steady
was prescribed as follows: a) sulphate concentration at t = 0 (or = 0) state value. After this point, it becomes more difficult for sulphate to
for any given z and r (z * and r * ) in Eq. (53); b) sulphate concentration reach the bottom of the pit and the process becomes diffusion con-
for z (z * = 0) in Eq. (54), and c) r = 0 (or r * = 0, axisymmetric geo- trolled. This results in a slowdown of the bacterial growth and, conse-
metry effect) in Eq. (55). These set of conditions are described as fol- quently, a decrease in the MIC rate. In addition, lower Km Monod
lows: parameter values result in deeper pits up to a critical value. After that,
low sulphate concentration in the environment is most influential in
C* (r , z , = 0) decreasing MIC rates [23].
SO4 2
C (r , z , = 0) =
CO

=
(e z *
0.367879 ) cos ( ) cos ( )
r*
2
z*
2
2.6. Melchers and Wells model (2006)

0.632121
Melchers and Wells [24] developed a phenomenological model for
(53) the anaerobic corrosion in the presence of SRB for offshore oilfield pi-
pelines after oxygen is depleted in the rust layer of an aerated pipeline
z * = 0, z = 0, C = 1 (C SO
* = C SO4 2 )
4
2
(54) surface. Their approach consisted of modeling MIC corrosion in two
stages: a transient corrosion behavior and a longer-term quasi-steady-
C* C state corrosion response.
SO4 2
At r* = 0, = 0 orat r = 0, =0 The transient phase is modeled by the Fickian diffusion of sulphate
r* r (55)
described by Eq. (61):
Although the authors did not give any details on the derivation of
Eq. (53), a brief analysis shows that the initial concentration profile C SO4 2 2C
SO4 2
assumes the existence of an initial micro pit with maximum con- =D
t x2 (61)
centration of sulphate at the pit surface (r * = 0, z * = 0 ) equal to the
concentration of sulphate in the bulk solution (or C SO*
2 = C SO4 2 ), and In the model, the control volume consists of an aerobically formed
4
with a minimum sulphate concentration value (C SO
*
2 = 0 ) at the center rust layer of thickness 0 < x < Lf on the metal surface. At the corroding
4
rust-steel interface, the nutrients are consumed immediately upon ar-
bottom of the pit (r * = 0, z * = 1).
rival. Thus, at x = Lf (m), Ci x = L = 0 for all t (s). In addition, after any
Finally, this model considers the partial change in sulphate con-
centration at any outward point (np*) on the biofilm surface which is time passes, i.e., t > 0 any preexisting nutrient in the rust layer would
proportional to the rate of sulphate utilization by the biofilm: be additionally supplied by nutrients from the sea water, resulting in a
constant concentration of nutrients at the rust surface, or Ci = 0.
x x=0
*
C SO 2 Before anaerobic SRB corrosion starts, it is also assumed that there is a
D SO4 2 4
= RB*
np* (56) uniform concentration of nutrients through the rust layer, or
C SO4 2 (x , t )t = 0 = Ci (kg/m3) for 0 < x < Lf . Melchers and Wells [24]
qmax Xs Lf C * solved Eq. (61) assuming constant diffusivity Di (m2/s) to and diffusion
SO4 2
RB* ( C * = in a plane sheet with uniform initial distribution and equal surface
2) *
SO4 Km + C SO concentration as described by Crank [25]:
4
2
(57)

where, Xs (kg/m3) in Eq. (57) represents the SRB concentration in the *

C SO 2 (x , t )
biofilm, and Lf (m) is the biofilm thickness (both considered constant 4

during the numerical simulation). As a result, the relationship between 4Ci ( 1)m (2m + 1) x (2m + 1) 2 2Di t
cos exp
the corrosion rate and the model parameters is developed after Eqs. m =0 (2m + 1) 2L f 4Lf 2 (62)
(42) and (57) are related as follows:
Next, the authors assumed that the SRB rate of metabolite produc-
qmax Xs Lf C *
SO4 2 tion was nearly proportional to the nutrient flux and therefore the
CRFe = NK * RB* = NK *
Km + C SO 2
(58) corrosion on the steel-rust interface. As a result, the instantaneous
4
corrosion rate is calculated by evaluating Eq. (62) as the nutrient flux
By combining Eqs. (44) and (58), the pit depth can be calculated using (Fick’s) on the steel surface (x = Lf ) by integration over any 0 < t < t
the following equations: as follows:

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A. Marciales et al. Corrosion Science 146 (2019) 99–111

t C corrosion rate and nutrient concentration, the experimental data fitted

C* (t ) = A D SO4 2 dt
SO4 2 0 x x= L properly Eqs. (64) and (69) accordingly. They found that corrosion in
these phases is directly proportional to the concentration of environ-
2D SO4 2 Ci t (2m + 1) 2 2D SO4 2 t
exp dt mental nutrients and the diffusivity of rust layers.
Lf 0
m =0 4Lf 2 (63)
2.7. Afanasyev, van Paassen and Heimovaara model (2013)
Eq. (63) was integrated and evaluated for a time t = t to and
3
2 = C SO4 2 C SO4 2, o (mol/m ) resulting in Eq. (65) below:
*
C SO
4 Afanasyev et al. [26] developed a numerical model of controlled bio
8Ci Lf 1 (2m + 1) 2 2D SO4 2 t induced mineralization in a porous medium as a possible corrosion
*
C SO 2 (t ) = 2
1 exp protection mechanism. Considering the net SRB reaction in Eq. (71)
4
m=0 (2m + 1) 2 4Lf 2
below:
+ C SO4 2, o (64) 4Fe + SO4 2 + 3HCO3 + 5H+ FeS + 3FeCO3 + 4H2 O (71)
1
With =
(2m + 1)2 2DSO 2 to
( ) This model includes 3 phases: solid ( s , -), biofilm ( b , -) and mobile
exp 4 ( w , -) water. The reactive elements are dissolved in the mobile water
4L2
f (65) phase, and their content in the control volume are related as follows:
The constants in Eq. (64) were determined by fitting the equation to w + b + s =1 (72)
field data.
Where the mass balance of the reactive transport of solutes for each i
The second steady state phase of the model was approximated by a
species are described by Eq. (73) as follows:
quasi-steady-state scenario. During this phase, the approximations for
the model assumes: a) the nutrients are consumed immediately upon w Ci
= (Di Ci ) Ri
arrival at the corrosion interface, therefore, at the metal surface their t (73)
value is minimum, i.e., C SO*
2 = 0; b) There is a bulk nutrient con- 3 2
4 Ci (kg/m ) is the concentration of specie i, Di (m /s) the diffusion
centration (C SO4 2 ) in the bulk sea water and a bulk nutrient con- coefficient for i and Ri (mol/m3 s) the sink-source term. The substrate
centration on the rust surface (C SO
*
2 ); c) Due to a and b, at any given (SO4 2 ) consumption in the biofilm is described by Monod equation in
4
point and suitable conditions, C SO
*
2 will dominate both nutrient con- (74):
4
sumption (also, metabolites production), and in consequence, corrosion C*
SO4 2
rate; and d) when nutrient flux is small, C SO
*
2 ≈ C SO4 2 . The proposed Rb = q b Xs
4 *
Km + C SO
Eq. (66) [24] is an expression for the corrosion rate as a direct result of 4
2
(74)
the Fickian diffusion based on the transport of nutrients from then With q (kg S/kg SRB s) as the substrate utilization rate, Xs (kg/m ) the 3
environment to the SRB at the corroding surface: bacteria concentration, C SO 3
2 (kg/m ) sulphate concentration and K m
*
4
dC SO4 2 (t ) C SO4 2 D SO4 2 (y ) (mol/m3) the Monod constant. The porosity changes as a result of solid
= K0
dt y (t ) (66) precipitation such as FeS in (74), according to Eq. (75) as:

With K 0 as a constant and D SO4 2 the diffusivity of nutrients through s Ms

(y ) = Rs
rust layer, this is a function of the thickness y (t) of the rust layer. t s (75)
Therefore, for this quasi-steady-state phase at t = tb , c = C SO4 2, b , With MWs (kg/mol) as the molecular mass, s (kg/m3) as density and Rs
D SO4 2 (yb ) and y = yb = C SO4 2, b with as a constant volumetric con- (mol/m3*s) as rate of precipitation.
version, the diffusivity is approximated by a linear relationship as Although the report does not show boundary conditions or para-
D SO4 2 (y ) D SO4 2, b (y yb ) with constant , and C SO*
2 ≈ C SO4 2 as meters used in Eqs. (73)–(75), Afanasyev et al. [26] mentioned that
4
constant, Eq. (66) derives in Eq. (67) as follows: after solving the model with simple analytical solutions, the results
D SO4 2, b (y yb ) were successfully validated with experimental data.
1dy (t )
= K0
dt y (t ) (67)
2.8. Gu, Zhao, and Nessic model (2009)
This equation is solved analytically leading to Eqs. (67) and (68):
Gu et al [8], developed a mechanistic model for MIC based on
y B A1 y A12 y 2
+… K2 t + K1 biocatalytic cathodic sulphate reduction theory (BCSR), considering
A1 A12 B 2B 2 (68) mass and charge transfer resistance on sessile SRB cells at the biofilm-
With constants K2 = (B /A12 ) lnB , A1 = K0 3
(m /mol) and metal surface interface. The process is conceptualized on a set of che-
B = K 0 (A1 + yb ) and finally, mical reactions, in Eqs. (76)–(78), that combined with the Butler-
Volmer equation and mass balance calculates the pitting corrosion rate
c (t ) = M1 (1 + M2 t )1/2 + M3 (69) and largest pit depth without passivation (Eqs. (79)–(83)).
With Mi (i = 1, …, n) constants. The transition of phases is defined by After biofilm is formed, SRB reduces sulphate at the cathode using
C SO4 2, transtient (tb) = C SO4 2, quasi ss (tb ) at time tb . After equalizing Eqs. (64) the electrons released by iron dissolution at the anode (Eqs. (76) and
and (69) and evaluated it for the first term of the resulting series, Eq. (77)), resulting in corrosion. In addition, some hydrogen sulfide ion
(70) is obtained as: (HS ) will convert to hydrogen sulfide at acidic pH (Eq. (78)). There-
fore, the authors [8] indicated that only areas covered by SRB biofilm
(M4 M5) + M5 (1 exp ( M6 t )) = M1 [1 + M2 t ]1/2 + M3 at t = tb present a sulfide film underneath on top of the metal surface.
(70)
Fe Fe 2+ + 2e (76)
The models expressed in (64) and (69) were fitted to corrosion loss
‘at sea’ data for phases with corrosion loss values between 0.02 during SO4 2 + 8H+ + 8e HS + OH + 3H2 O (77)
the transient phase to up to 0.14 mm/year (4.44 × 10−12 m/s) during
HS + H+ H2 S (78)
the quasi steady state phase in low polluted water. The authors con-
clude that although they did not include a relationship between The corrosion rate, (CRFe , mm/yr), calculated by the model uses the

105
A. Marciales et al. Corrosion Science 146 (2019) 99–111

anodic current density expressed by Eqs. (79), and (80) after sub- Fe Fe+2 + 2e (E 0 = 447mV / SHE ) (84)
stituting molecular weight (MWFe , kg/mol) and density ( Fe , kg/m3 ) for
iron: SO4 2 + 9H+ + 8e HS + 4H2 O (E 0 = 217mV / SHE ) (85)
MWFe According to Gu [27], both of these reactions are thermo-
CRFe = ia (Fe)
2F Fe (79) dynamically favorable since iron oxidation can donate electrons for
sulphate reduction with concomitant energy production, establishing
mm A sulphate as the terminal electron acceptor. In addition, the author
CRFe = 1.55 ia (Fe) ( 2 ) proposes to consider Nitrate Reducing Bacteria (NRB) when significant
yr m (80)
nitrate is injected to simulate nitrate reduction or when there is high
Thus, the model considers iron dissolution as the only anodic cur- NRB count in the systems, because nitrate reduction is thermo-
rent density, which equals the combined effect of any possible cathodic dynamically favorable over sulphate reduction in systems containing
reduction, e.g., H+ reduction, sulphate reduction, acetic acid reduction both groups of bacteria according to Eq. (86):
(Eq. (81)):
2NO3 + 12H+ + 10e N2 + 6H2 O (E 0 = +0.76V / SHE ) (86)
ia (Fe) = ic (H +) + ic (H2 CO3) + ic (org acid) + ic (SO4 2) (81)
Acid Producing Bacteria (APB) are considered also in the model
Where each cathodic reduction (ic , A/m2) is the sum of charge transfer because APB can secrete corrosive organic acids (mainly acetic acid,
resistance and mass transfer resistance. The charge transfer resistance is HAc), that would be in free acid form when present in aqueous media.
calculated by the Tafel equation, while the mass transfer resistance is Furthermore, besides proton reduction (Eq. 87), HAc reduction is
calculated through mass transfer resistance equations including diffu- thermodynamically favorable (Eq. 88) and kinetically propagated when
sivity (Eq. (82)): combined with iron oxidation [27].

0.43 0.92 2H+ + 2e H2 (87)

Deff bfl
=1
D SO4 2 11.19 + 0.27 bfl
0.99
(82) 2HAc + 2e 2Ac + H2 (88)

Deff Effective diffusivity in the biofilm (m2/s) Eq. (88) refers to the classic theory of dissociation of weak acids
D SO4 2 Diffusivity in aqueous liquid without the biofilm (m2/s) [29]. In this case, HAc is considered a proton reservoir that releases
3 protons on demand, causing more severe iron oxidation than proton
bfl Biofilm density (kg/m )
In addition, the concentration of each species across the biofilm reduction.
layer can be calculated from the mass balance equation applied to the The model calculates the corrosion rate (CRFe , mm/yr) proportional
system (Eq. (83)), and the numerical solution of Eqs. (79)–(83) provides to iron anodic current density, according to Eqs. (89) and (90) for ty-
corrosion potential and current density at different times. pical iron and carbon steel:
MWFe
Ci C CRFe = ia (Fe)
= Di i + Ri 2F Fe (89)
t x x (83)

Ci Concentration of chemical species j in biofilm (mol/m3)

CRFe = 1.55ia (Fe) (90)
Di Diffusion coefficient for species j (m2/s) With ia (Fe) (A/m2) as the iron anodic current density in (90). The author
Ri Rate of consumption or production of species j by sessile cells in states it should be equal to the cathodic current densities for: proton
biofilm (mol/m3*s) ic (H +) , acetic acid ic (HAc ) and sulphate ic (SO4 2) reduction, as shown in Eq.
For this model, the contribution to corrosion by other corrosive (91):
metabolites produced by existent planktonic cells, e.g. SRB and APB, is
ia (Fe) = ic (H +) + ic (HAc ) + ic (SO4 2) (91)
neglected because the amount of such corrosive species are small when
compared to the amount produced by sessile cells, and their con- Next, the cathodic current density is related to mass transfer lim-
centration is constant in the bulk of the fluid. iting (ilim ) and charge transfer limiting (ict ) current density in Eq. (92).
The analysis of results concluded that charge transfer resistance is This approach followed electrochemical kinetics as in mechanistic CO2
important at initial stages of biofilm formation (small thickness), and corrosion modeling [27]:
mass transfer resistance, known as concentration polarization, controls
1 1 1
pit growth after they grow to a sizable depth. In addition, this model = +
ic ilim ict (92)
predicts the corrosion rate in a worst case scenario where biofilm is
already formed ignoring pH, temperature effect, and sulphate con- Therefore, the charge transfer limiting (ict ) used in Eq. (92) is ob-
sumption by SRB inside the biofilm. Although this model is useful to tained from the Butler-Volmer Eq. (93) with as a dimensionless
predict MIC pit growth rate over time, it is necessary to estimate the symmetry factor, n the number of electrons involved in reaction, F (C/
likelihood of biofilm formation in the pipe. As a result, the authors V) the Faraday constant, R (J/molK) the universal gas constant, E (V)
propose to solve this uncertainty through MIC risk based models. the corrosion potential, Eeq (V) the equilibrium potential and T (K) as
the absolute temperature. The remaining term, i 0 represents the sessile
2.9. Gu model (2014) bacteria aggressiveness. Gu [27] explains i 0 as an electrochemical
parameter equivalent to the rate constant in conventional chemical
Gu [27] states that reported MIC pitting corrosion rates as high as reaction kinetics; and its value depend on several variables as: the re-
9.6 mm/yr (3.044 × 10−10 m/s) [28] in water-wet and no oxygen action activation energy, temperature, sessile cell density directly on
conditioned pipes are not the result of exclusively SRB activity, but the the iron surface, their enzyme activities, type of steel and type of iron
effect of the presence of acid producing bacteria (APB) besides SRB sulfide on iron surface.
under these conditions. This work was built on his previously developed (1 )n F F
biocatalytic Sulphate Reduction theory (BCSR) based model [8]. The ict = i 0 exp (E Eeq) exp (E Eeq)
R T R T (93)
theory is based on Eqs. (84) and (85) below; with elemental iron oxi-
dation happening outside the SRB cells in (84) and sulphate reduction The following step in Gu [27] model involves the calculation of the
inside SRB cytoplasm cells (85): mass transfer current density from Eq. (92) in terms of the sulphate

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A. Marciales et al. Corrosion Science 146 (2019) 99–111

concentration gradient ( C ) on the iron surface as shown in Eq. (94). express in terms of charge transfer limiting and mass transfer limiting,
x
Here n = 8 since there are consumed 8 electrons for each sulphate following classic CO2 corrosion modeling technique (Eqs. (100) and
molecule reduced (as in Eq. (85)) and D SO4 2 the sulphate diffusion (101)). The authors assuming there is not mass transfer resistance; as a
coefficient: result, this term (1/ jct (H +) ) is set to zero in Eq. (101).
C SO4 2 1 1 1
ilim = nFD SO4 2 = +
x (94) jc (SO4 2) jct (SO4 2) jlim (SO4 2) (100)
Finally, the relationship between Eq. (94) and concentration 1 1 1
= +
changes within the biofilm occurs through a mass transfer across the jc (H +) jct (H +) jlim (H +) (101)
biofilm as in Eq. (95):
The charge transfer limit in Eqs. (100) and (101) ( jct ) are calculated by
C SO4 2 C SO4 2 Butler-Volmer equation using the equilibrium potential calculated by
= D SO4 2 + Ri
t x x (95) the Nerst equation, described by Eqs. (102) and (103) for the SO4 2 / HS
3
and H2/ H pair respectively.
With Ri (mol/m s) as the negative value representing the consump-
tion of sulphate by sessile SRB cells in the bulk of the biofilm. Gu [27] V 2.591RT RT SO4 2
Ee = 0.249 pH + ln
affirms that electrons from iron oxidation can only reach the sessile SHE F 8F HS (102)
cells near the iron surface (or a monolayer cell region) and that for deep
pits, mass transfer resistance dominates because sulphate should be V 2.303RT RT p H2
Ee = pH + ln
diffuse through the biofilm pits. SHE F 2F p0 (103)
Therefore, Gu [27] establishes that in order to solve the model, the
Eq. (102) is simplified assuming the pit bottom has a fixed pH value at a
elements at the right side of Eq. (91) should be calculated after applying
certain time, p0 = 1 bar, and p H2 = 1 bar due to lack of data on hy-
Eqs. (93)–(95) for sulphate and only Eq. (93) for the HAc and proton
drogen partial pressure at equilibrium with CO2, disappearing the last
case; i.e., mass transfer resistance is not considered due to the lack of
term of Eq. (103)
data to calculate pH and HAc concentration underneath the biofilm. In
Finally, the mass transfer limiting sulphate reduction current den-
addition, the hydrogen partial pressure on the iron surface is assumed
sity ( jlim (SO4 2) , A/m2) is calculated from Fick’s law according to Eq.
as 1 bar for the Nerst equation needed to calculate the proton reduction
(104); i.e., the mass transfer limiting current density is a function of the
potential (E° in Eqs. (87) and (88)), as a consequence of absence of this
sulphate diffusivity (D SO4 2 , m2/ s ) in the biofilm and the variation of
value on literature.
The numerical solution of the model predicted a corrosion rate SO4 2 within the biofilm. This last term is expressed in Eq. (105) as a
around 3.3 mm/year with 400 ppm (w/w) sulphate in the bulk-fluid function of diffusivity inside the biofilm and consumption of sulphate
phase, even with an aggressive biofilm, i.e., log10 scale between -12 and by SRB, which is simplified as zero by the authors, expecting to com-
-6 for this model. In addition, sulphate consumption by bulk sessile SRB pensate the error effect by experimental calibration.
cells (Ri ) was not considered in the simulation. When same sulphate C SO4 2
concentration combined with constant pH = 3.6, 226.3 ppm free HAc jlim (SO4 2) = nFD SO4 2
x (104)
and a biofilm aggressiveness of -10 were considered, the predicted
2C
corrosion rate was above 10 mm/yr. Therefore, this results suggested C SO4 2 SO4 2
= D SO4 2 + Ri
HAc contributed to 94.5% of the total cathodic current density (and t x2 (105)
total corrosion rate), concluding that HAc is far more corrosive than
The computational results provided by the set of Eqs. (98)–(105)
proton and sulphate in MIC phenomena [27]-.
described in this model conclude that pitting rate decreases over time
when biofilm thickness is increased, because the sulphate has to travel a
2.10. Xu, Li and Gu model (2016)
longer distance through the biofilm during the diffusion process, low-
ering rate of sulphate consumption by SRB. Also, higher temperatures
Later on, Xu et al [30] developed a mechanistic model for micro-
favor higher corrosion rates because diffusivity is enhanced at higher
biologically inflicted corrosion by SRB and Acid Producing Bacteria
temperatures. On the other hand, the effect of temperature on the
(APB). Their model is based on biocatalytic sulphate reduction theory
metabolism of microbes depends on the type of bacteria and/or strain.
previously established by Gu et al. [8]. In this approach, sulphate is the
For example, there are thermophilic SRB that can grow at 50 °C opti-
terminal acceptor for SRB, inflecting corrosion directly, according to
mally. In this paper the assumption was based on SRB commonly found
Eq. (96) and APB contributes indirectly to MIC by dissociating abiotic
in conventional transmission lines and their optimal temperature is
acetic acid (HAc), acting as a proton reservoir as displayed by Eq. (97)
30 °C [31].
[29].
In addition, the simulation results showed that the combined cor-
SO4 2 + 9H+ + 8e HS + 4H2 O (96) rosion current density is lower than that of individual ones for SRB and
APB respectively, indicating an anty-syntergistic effect between sul-
2HAc + 2e 2Ac + H2 (97) phate reduction and proton reduction in the system. This model pre-
The MIC corrosion rate, used directly to calculate pit depth, is cal- dicts MIC pitting under worst case scenario, assuming the presence of
culated using the anodic current density for iron oxidation, ja (Fe) (A/m2) aggressive biofilm, and simplified representation of SRB consumption
(Eq. (98)): by biofilm.
MWFe ja (Fe )
CRFe = Or CRFe (mm /yr ) = 1.16ja (Fe) 2.11. Haile, Teevens, and Zhu model (2015)
2F Fe (98)
This anodic current density (Eq. 99) is the result of the combined Haile et al. [32] developed a mechanistic model that predicts sessile
effects of cathodic SRB reduction ( jc (SO4 2) ), and proton reduction by APB SRB concentration, SRB growth-induced pitting corrosion rate, biofilm
( jc (H +) ): thickness and density, and biomass detachment rate. The model is
ja (Fe) = jc (SO4 2) + jc (H +) based on dual Monod kinetics where sulphate is the terminal electron
(99)
acceptor (TEA), and acetate is the electron donor. The overall electro-
−2 +
For both cases, SO4 and H , the cathodic current density can be chemical equation for the model can be represented as follows:

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A. Marciales et al. Corrosion Science 146 (2019) 99–111

4Fe + SO4 2 + 4H2 O FeS + 3Fe (OH ) 2 + 2OH (106) decay rate, SRBd:

The corrosion rate, or SRB-induced pitting corrosion rate (CRFe) is SRBP

Lf =
calculated below by Eq. (107). This equation, depends on the ratio of bfl SRBd (114)
the corrosion rate of iron to the consumption rate of sulphate (NK, mol
Fe/mol SO4 2 ), iron density ( Fe , kg/m3), iron molecular weight (MWFe, Moreover, the biofilm thickness and density are also related in Eq.
kg/mol), concentration of sulphate in the biofilm (C SO4 2, blf , kg/m3), (115) to the rate of biofilm production rate by the Monod maximum
SRB sessile concentration ( XS , kg/m3), utilization rate of sulphate by specific utilization rate of sulphate by SRB ( µmax , s−1) and the Thiele
SRB in the biofilm (qs , kg S/kg SRB s) and Monod half velocity coef- module ( 1). This last one is the relation between reaction and diffusion
ficient for sulphate (K SO4 2, blf , mol/m3): rates [33]. In addition, Haile et al. [32] also includes in Eq. (116), the
expression for the Thiele module with all terms as described previously:
NK MWFe qs XS C SO4 2, bfl
CRFe = tanh 1
Km + C SO4 SRBP = µmax bfl Lf
Fe 2
, blf (107) 1 (115)
From Eq. (107), XS ( kg/m3) value varies over time. This change is 2
2µ bfl Lf
described as the difference between Monod equation for the rate-lim- 1 =
iting substrate, µs, bfl and the first order maintenance or decay coeffi- K SO4 2, bfl Ys Deff (116)
cient (SRBd), as detailed below:
As a result, after replacing Eqs. (115) in (116) and combining it with
dXS
= {µs, bfl SRBd } XS Eqs. (114), (117) is obtained and should be solved for Lf :
dt (108)
2µ bfl Lf 2
The decay coefficient (SRBd), is a function of Monod first order tanh
K SO 2, bfl Ys Deff
4
maintenance coefficient, in which the limited substrate (C SO4 2, min , kg/ Lf bfl SRBd µmax bfl Lf =0
2µ bfl Lf 2
m3) corresponds to zero biomass growth rate, i.e., dtS = 0 ; while the
dX
K SO 2, bfl Ys Deff
(117)
Monod specific growth rate, µs, bfl (s−1) is expressed by a dual substrate
4

Monod kinetics. SRBd and µs, bfl are calculated by Eqs. (109) and (110), Finally, this model includes an empirical equation to predict the
respectively: biofilm detachment rate Rde (mgSRB/m2s), as described by Eq. (118):
YS µmax C SO4 2, min Rde = K dl v (C SO4 2, bfl C SO4 2 ) Ys Lf (118)
SRBd =
Km + C SO4 2
(109)
, min
In Eq. (118), new terms are introduced. K dl (-), represents a non-growth
µmax CAc, bfl associated detachment rate, v (m/s) the volumetric velocity of the
µs, bfl = system and (C SO4 2, bfl C SO4 2, kg/m3) the change in substrate con-
(KAc, bfl + CAc,bfl)(K SO4 2,bfl + C SO4 2, bfl) (110) centration.
−1
On one hand, µmax (s ) represents the Monod maximum specific The model was simulated numerically and tuned with selected oil
growth rate, YS the true yield coefficient for SRB utilizing sulphate (kg pipelines from different fields. The results concluded the proportion-
SRB/kg SO4-2), and C SO4 2, min (kg/m3) is the minimum concentration of ality of sessile SRB and the high influence of flow velocity to pitting
sulphate require for SRB growth (109). On the other hand, CAc, bfl (kg/ corrosion rates. Moreover, the higher the flow velocity, the higher the
m3), and C SO4 2, bfl (kg/m3) are the concentrations of sulphate and acetate detachment rate and therefore, the lower the sessile SRB and the lower
in the biofilm, respectively; while K SO4 2, bfl and KAc, bfl (mol/m3) are the the pitting corrosion rate.
Monod half-velocity coefficients of sulphate and acetate in the biofilm, Table 1 summarized the main findings of the papers reviewed, in-
respectively. Sulphate utilization rate, qs (kg S/kg SRB s) in the biofilm cluding the factors considered in the models, microorganisms modeled,
is calculated as follows (111): parameters predicted, and advantages and limitations.
q max CAc, bfl C SO4 2, bfl
qs = 3. Conclusions
(KAc, bfl + CAc,bfl)(K SO4 2,bfl + C SO4 2, bfl) (111)
MIC is not satisfactory assessed by the models currently available in
Where, q max (kg S/kg SRB s) is the maximum sulphate utilization rate.
the public domain; and the models do not take into account the various
Sulphate concentration in the biofilm changes with time depending
factors implicated in MIC. Summary of the literature review findings
on its diffusivity into the biofilm and its consumption by SRB. Hence,
are presented as follows:
the authors proposed sulphate mass balance within the biofilm as a
control volume as follows (112):
• Most of the mechanistic MIC models reviewed base their prediction
C SO4 2, bfl 2C
SO4 2, bfl Xs bm Xs C SO4 2, bfl on SRB as the main player; and only few models adopted a sulphate
= Deff µ mass balance concept across the biofilm.
t z2 Ys s, bfl Ys K SO4 2, bfl + C SO4 2, bfl
(112)
• Few models considered Monod growth kinetics of corrosive bacteria
as a basis of microbiologically influenced corrosion mechanistic
With Deff (m2/s) as the effective diffusion coefficient and bm (s−1) as the models; i.e. microbial growth within a biofilm for specific environ-
first order maintenance coefficient in (112). mental conditions; chemistry, temperature, pipeline flow velocity,
The effective diffusion coefficient (Deff , m2/s) takes into account the pH, among others.
porosity of the biofilm ( ) and the diffusion coefficient for sulphate or • Several authors reported the importance of measuring sessile po-
acetate in the bulk fluid (D SO4 2, Ac, bfl , m2/s) according to the following pulation as the basis for MIC mitigation and management. However,
Eq. (113): no model was found to accurately predict sessile microbial com-
munities.
•
Deff = 2D
SO4 2, Ac, bfl (113)
Most of the models predict worst case scenario for localized MIC
In addition, this model considers the biofilm production rate and the pitting rate; for example sulphate sink was assumed to be biological
detachment process (114) to (116). In Eq. (114), the biofilm thickness, sulphate reduction; i.e. no chemical reaction that can use sulphate
Lf (m), is proportional to the amount of biomass production rate, SRBP was taken into consideration.
(kg/m2.s) and inverse to the biofilm density, bfl (kg/m3), and SRB • Most models were not validated in lab or field conditions simulating

108
 Table 1
Summary the main parameters considered in the development of the mechanistic models reviewed.
Factors considered in model Microbe Predicts Author Advantages Limitations
A. Marciales et al.

• Sulfide presence, • SRB • MIC Risk S. Maxwell [15] • The model is based on field experience, and • Corrosion rate prediction was based on SRB only,
• Oxygen ingress, • Corrosion rate considered parameters that can be monitored and no other microorganism was taken into
• pigging frequency, routinely. account.
• System age, • Mass transfer and/or hydrodynamic phenomena were
• Monod growth kinetics, not accounted.
• biocides application,
• Biofilm washout.
• Sessile number (MMM), • SRB • Integrated MIC risk factor, Brent, Thomsen, Juhler • Three types of microorganisms were considered in • Mass transfer and/or hydrodynamic phenomena
• Cell specific activities. • SRA • Pitting corrosion rates and Larsen [17] the model. were not accounted.
• MET • MMM were used for microbial enumeration.
• Sessile number (MMM), • SRB • Integrated MIC risk factor, Larsen, Brent, Juhler and • Three types of microorganisms were considered in • Mass transfer and/or hydrodynamic phenomena
• Cell specific activities. • SRA measured in days to develop Skou [18] the model. were not accounted.
• MET MIC pitting corrosion
• MMM provides an early warning of MIC
• Worst-case
rates
• Sulfate mass balance over biofilm, • SRB • Corrosion rate Peng, Suen and Park • Corrosion rate prediction was based on SRB • Corrosion rate prediction was based on SRB only,
• Monod equation, [19] growth kinetics in a biofilm in existing pit and no other microorganism was taken into
• Sulfate diffusivity, • The model was validated based on data obtained account.
• Biofilm density (constant), from laboratory corrosion testing.
• Biofilm thickness(constant) • Mass transfer and/or hydrodynamic phenomena
were accounted.
• Sulfate mass balance over biofilm, • SRB • Corrosion rate Al-Darbi, Agha and Islam • Corrosion rate prediction was based on SRB • Corrosion rate prediction was based on SRB only,
• Monod equation, Sulfate diffusivity, [23,22] growth kinetics in a biofilm in existing pit. and no other microorganism was taken into
• Biofilm density (constant), • The model was validated using data obtained from account.
laboratory corrosion testing.

109
• Biofilm thickness(constant) transfer and/or hydrodynamic phenomena
• Mass
were accounted.
• Sulfate diffusion • SRB • Corrosion rate Melchers and Wells [24] • The model considers nutrient availability and • The application of the model is limited to
• SRB reduction metabolites diffusivity. conditions where a metal substrate is previously
• Mass transfer and/or hydrodynamic phenomena exposed to oxygenated environment.
were accounted. • Corrosion rate prediction was based on SRB only, and
no other microorganism was taken into account.
• Solid, biofilm and mobile water, • SRB • Corrosion rate Afanasyev, van Paassen • The model considers biochemical reaction in • The model does not consider sessile bacteria growth
• Mass balance of the reactive transport of and Heimovaara [26] metal, biofilm and bulk aqueous phases. kinetics in a biofilm environment.
solutes, • The model was validated using corrosion testing • Corrosion rate prediction was based on SRB only, and
• Monod equation, data. no other microorganism was taken into account.
• Sulfate concentration • Mass transfer and/or hydrodynamic phenomena
were accounted.
• Butler-Volmer equation, • SRB • Corrosion rate Gu, Zhao, and Nessic [8] • The model considers mass and charge transfer • Does not consider sessile bacteria growth kinetics in
• Mass balance across the biofilm layer, resistance on at the biofilm- metal interface. a biofilm environment.
• Sulfate diffusivity • Mass transfer and/or hydrodynamic phenomena • Corrosion rate prediction was based on SRB only, and
were accounted. no other microorganism was taken into account.
• Anodic and cathodic current densities of the • APB • Corrosion rate Gu [27] • The model considers mass and charge transfer • Does not consider sessile bacteria growth kinetics in
system, • SRB resistance on at the biofilm- metal interface. a biofilm environment.
• The Butler-Volmer equation, • Mass transfer and/or hydrodynamic phenomena • Corrosion rate prediction was based on SRB, and no
• Anodic and cathodic Tafel slopes, were accounted. other microorganisms were taken into account.
• Nerst equation,
• Sulfate concentration and diffusivity through
a biofilm,
• Anodic and cathodic current densities of the • APB • Corrosion rate Xu, Li and Gu [30] • The model considers mass and charge transfer • Model was calibrated with SRB short term pit depth
system, • SRB resistance on at the biofilm- metal interface. data to predict long term pitting depths
• The Butler-Volmer equation, • The influence of two types of microorganisms in
• Anodic and cathodic Tafel slopes, corrosion prediction was considered.
• Nerst equation,
(continued on next page)
Corrosion Science 146 (2019) 99–111
A. Marciales et al. Corrosion Science 146 (2019) 99–111

rate prediction was based on SRB only, and

actual environmental conditions (chemistry and operating condi-

no other microorganisms were taken into account.

was not validated with either laboratory or
tions); and those validated were based on short-term lab testing.

4. Recommendations

Taking into consideration the factors believed to be essential but not

considered by the authors reviewed in this paper, the following re-
commendations are forwarded to develop a reliable MIC predictive
model:

• A comprehensive mechanistic model should include the interaction

of various microorganisms in a biofilm environment including SRB,
field data.
• Corrosion

SRA, methanogen, acetogens, fermenters, IRB, IRA, IOB, MOB, APB,

Limitations

• Model

and slime formers, among others.

• Development of predictive models should account both chemical
and electrochemical phenomena on the surface of the metal, in the
biofilm, and in the interface; i.e. metal-biofilm interface.
•
transfer and/or hydrodynamic phenomena

transfer and/or hydrodynamic phenomena

Laboratory validation of predictive models should be designed to

bacteria growth kinetics within the

reflect the environmental conditions (chemistry and operating

biofilm matrix; including, growth, decay,

conditions) seen in field.

attachment, and detachment rates.

Acknowledgments

This work is part of a multi-national project on MIC entitled

“Managing Microbial Corrosion in Canadian Offshore & Onshore Oil
Production Operations.” The authors would like to acknowledge the
were accounted.

were accounted.

funding contributions from Genome Canada, the Government of

Alberta, Alberta Innovates, Newfoundland and Labrador’s Department
• Considers
Advantages

of Tourism, Culture, Industry and Innovation (TCII) and Mitacs, along

• Mass

• Mass

with in-kind support from a number of industry partners.

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