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Corrosion Science xxx (xxxx) xxx–xxx

Contents lists available at ScienceDirect

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

Short Communication

An enhanced oil recovery polymer promoted microbial growth and


accelerated microbiologically influenced corrosion against carbon steel

Ru Jiaa, Dongqing Yanga, Hasrizal Bin Abd Rahmanb, Tingyue Gua,
a
Department of Chemical and Biomolecular Engineering, Institute for Corrosion and Multiphase Technology, Ohio University, Athens, OH, 45701, USA
b
Hydrocarbon Recovery Technology, Group Research & Technology, Project Delivery & Technology, Petronas, Kuala Lumpur, 50088, Malaysia

A R T I C LE I N FO A B S T R A C T

Keywords: Enhanced oil recovery typically relies on injection of seawater mixed with chemicals to increase reservoir
A. Carbon steel pressure. A polymer such as partially hydrolyzed polyacrylamide (HPAM) is often added to increase viscosity. In
B. SEM this work, an oilfield biofilm consortium was found to utilize a commercial HPAM-based polymer. The polymer
B. Weight loss at 1000 ppm (w/w) promoted the growth of planktonic cells and sulfate reducing bacteria sessile cells in an
B. XRD
artificial seawater medium during a 30-day incubation period in anaerobic vials. The polymer utilization led to
C. Microbiological corrosion
34.5% viscosity loss and more severe microbiologically influenced corrosion weight loss and pitting against
C. Pitting corrosion
C1018 carbon steel.

1. Introduction viscous crude oil for better oil recovery [21]. Xanthan gum is a poly-
saccharide [22]. It was a popular EOR polymer in the past, but this
After many years in operation, a reservoir’s pressure dwindles. polymer is more readily utilized by downhole microbes [23], which is
Enhanced oil recovery (EOR) is needed to continue oil production [1]. not surprising because it is widely used as a food additive. Partially
Seawater is typically injected along with other oilfield chemicals [2]. hydrolyzed polyacrylamide (HPAM) is gaining popularity in EOR be-
Water flooding brings microbes, nutrients and oxidants (e.g., sulfate) to cause it can tolerate high mechanical forces during water flooding
the downhole environment, causing microbes to flourish [3]. In nature, [24,25]. In addition, HPAM is inexpensive [25]. However, HPAM also
microbes often live in communities and form biofilms to protect has a potential to be utilized by downhole microbes as nitrogen and
themselves against harmful environmental factors [4]. They can cause carbon sources, which is a major concern to field operators [24]. Ma
corrosion or accelerate the corrosion caused by other corrosive agents et al. found that a sulfate reducing bacterium utilized HPAM as a carbon
in the oil and gas industry and many other industries [5–10]. This is source by hydrolyzing the amide group to carboxyl group, leading to
known as microbiologically influenced corrosion (MIC) [11–15]. There loss of viscosity [26]. Bao et al. found that Bacillus spp. degraded
is a growing awareness of MIC after the 2006 Trans-Alaska Pipeline leak HPAM. Their results showed that bacteria such as Bacillus cereus can
[16]. Without contamination, an oil reservoir is strictly anaerobic be- utilize the amide group of HPAM as their nitrogen source, and the
cause the organic matters downhole consumed all the oxygen since HPAM carbon backbone can be metabolized as an organic carbon
geological times [17]. Oxygen is typically removed in the injection fluid source [27]. It is expected that a biofilm consortium can degrade HPAM
to avoid oxygen corrosion of downhole tubing and downstream trans- more easily than pure-strain microbes because there are multiple mi-
port pipelines. In such an anaerobic environment, anaerobic microbes, crobial species in a consortium [28]. Li et al. found that HPAM was
such as sulfate reducing bacteria (SRB) flourish because seawater con- degraded to lower molecular weight fragments by a biofilm consortium
tains sulfate [18]. Other microbes such as fermentative microbes can containing diverse bacterial groups [24]. So far, there is a lack of lit-
also grow [19]. SRB generate biogenic H2S, which causes reservoir erature data discussing the impact of the utilization of HPAM on MIC
souring [20]. Since EOR uses polymers which are organic molecules, it due to enhanced microbial growth.
is necessary to investigate whether they can be utilized by downhole In this work, a commercial HPAM-based polymer was tested to see
microbes and thus contribute to increased MIC. whether it could be biodegraded by an oilfield biofilm consortium
Polymer flooding is one of the most efficient EOR technologies that during a 30-day incubation period. Corrosion analyses and electro-
started as early as the late 1950 s [21]. Adding polymers increases the chemical measurements were performed to check its effects on the MIC
viscosity of the injected fluid downhole, which helps to push out of C1018 carbon steel. This is the first systematic study on the impact of


Corresponding author.
E-mail address: gu@ohio.edu (T. Gu).

https://doi.org/10.1016/j.corsci.2018.05.015
Received 21 August 2017; Received in revised form 30 April 2018; Accepted 12 May 2018
0010-938X/ © 2018 Elsevier Ltd. All rights reserved.

Please cite this article as: Jia, R., Corrosion Science (2018), https://doi.org/10.1016/j.corsci.2018.05.015
R. Jia et al. Corrosion Science xxx (xxxx) xxx–xxx

microbial utilization of an EOR polymer on MIC.

2. Materials and methods

2.1. Microbes, culture medium, metal and chemicals

A corrosive oilfield biofilm consortium labeled as Consortium II was


tested in this work. Its metagenomics data were disclosed previously,
which indicated that the consortium contained SRB, biodegradation
microbes and fermentative microbes [19]. The consortium was cultured
anaerobically in 125 mL anaerobic vials (Wheaton Industries Inc.,
Millville, NJ, USA). An artificial seawater medium was used as the
culture medium to grow the consortium [29]. Its composition (g/L)
was: Na2SO4 3.917, NaCl 23.476, Na2SO4 3.917, KCl 0.664, NaHCO3
0.192, KBr 0.096, MgCl2·6H2O 10.61, H3BO3 0.026, SrCl2·6H2O 0.040,
MgSO4·H2O 0.4, CaCl2·2H2O 1.469, tri-sodium citrate 0.5, CaSO4 0.1,
K2HPO4 0.050, NH4Cl 0.1, Fe(NH4)2(SO4)2 0.1. Square coupons used in
this work were cut from a C1018 carbon steel (AISI G10180) rod. The
mass percentage composition of the carbon steel was: P 0.017, C 0.200,
S 0.012, Mn 0.900, Si 0.044, Cr 0.061, Ni 0.044, Mo 0.018, and Fe
balance [30]. Only the top surface area of 1 cm2 was exposed on each
coupon. The other surfaces were coated with an inert Teflon paint.
Coupons were polished and cleaned before use according to previously
reported procedures [31]. A commercial HPAM-based polymer (la-
belled as cHPAM in this work) was provided by Petronas. Other che-
micals were purchased from Fisher Scientific (Pittsburgh, PA, USA) or
Sigma-Aldrich (St Louis, MO, USA).

2.2. The impact of cHPAM on microbial growth

The culture medium and lab tools were sterilized in an autoclave at


121 °C for 20 min. The culture medium and stock solutions of other
chemicals were sparged with filter-sterilized nitrogen (N2) for at least
1 h to remove dissolved oxygen. The culture medium was supplemented
with 100 ppm (w/w) L-cysteine as an oxygen scavenger to mitigate any
possible oxygen ingress. cHPAM was added to the culture medium to
reach a concentration of 1000 ppm as requested by Petronas. Five re-
plicate coupons, 100 mL culture medium, and 1 mL seed culture were
added to each 125 mL anaerobic vial in an anaerobic chamber. The
initial pH of the culture medium was adjusted to 7.0 before inoculation.
The biofilm seed culture was grown in the artificial seawater medium
enriched with 3.5 g/L sodium lactate and 1 g/L yeast extract. It should
be noted that a very small amount of organic carbon was introduced to
each vial by the 1 mL seed culture upon inoculation. After inoculation,
the initial planktonic cell amount in each vial was 106 cells/mL. The
anaerobic vials were sealed and incubated at 37 °C without shaking.
During the 30-day incubation period, a 0.3 mL broth was withdrawn
each time from each vial to measure the planktonic cell count with a
hemocytometer under an optical microscope at 400X magnification
[32]. After 7, 14, 21 and 30 days of incubation, coupons were taken out
for SRB sessile cell count using most probable number (MPN) method.
Once a vial was opened, its incubation was terminated. The MPN
method used the modified Postgate's B medium (Biotechnology Solu-
tions, Houston, TX, USA) for SRB. The detailed procedure for the sessile
cell enumeration was described before [4]. The viscosity was measured
using a falling ball viscometer at 23 °C according to the reference [33].
After the 30-day incubation, scanning electron microscopy (SEM)
(Model JSM-6390, JEOL, Tokyo, Japan) was used to observe biofilm
morphology [31]. Confocal laser scanning microscopy (CLSM) (Model Fig. 1. Planktonic cell counts (A) and SRB sessile cell counts (B) in inoculated
LSM 510, Carl Zeiss, Jena, Germany) was used to visualize live and artificial seawater medium with and without cHPAM. (Error bars represent
dead cells in the biofilm on a coupon surface [34]. standard deviations from 4 independent samples.) Viscosities of the abiotic
artificial seawater medium and inoculated artificial seawater medium, both
with 1000 ppm cHPAM (C). (Error bars represent standard deviations from 3
2.3. Corrosion analyses
independent samples.).

Weight loss was measured using at least 6 coupons for every data
point. The corrosion products and biofilms on coupons were removed

2
R. Jia et al. Corrosion Science xxx (xxxx) xxx–xxx

Fig. 2. Biofilm SEM and CLSM images on the surfaces of coupons after the 30-day incubation in inoculated artificial seawater medium with 0 ppm cHPAM (A, A′),
and with 1000 ppm cHPAM (B, B′). (For interpretation of the references to colour in the figure text, the reader is referred to the web version of this article.)

using Clarke’s solution according to ASTM G1–03 [35,36]. MIC pit electrochemical impedance spectroscopy (EIS) data were measured
morphology was observed under SEM. The maximum pit depth on each during a 30-day incubation period. LPR was scanned between −10 mV
coupon was examined using an infinite focus microscope (IFM) (Model and + 10 mV at a rate of 0.167 mV/s. EIS was measured in the fre-
ALC13, Alicona Imaging GmbH, Graz, Austria). X-ray diffraction (XRD) quency range of 10−2 to 105 Hz with a 10 mV sinusoidal voltage signal
with a Co K-alpha X-ray tube (D8 Discovery, Bruker AXS GmbH, at the stable OCP. EIS data were fitted using the ZSimDemo software
Karlsruhe, Germany) was used to identify the corrosion products [37]. (Version 3.30d, EChem Software, Ann Arbor, MI, USA).
Samples used for the XRD analysis were first dehydrated sequentially
using 25% (v/v), 50%, 75% and 100% isopropanol for 5 min at each
concentration. They were then dried with supercritical CO2 in a critical 3. Results and discussion
point dryer (Model CPD 020, Balzers Union, Liechtenstein). After that,
they were stored in a vacuumed desiccator before the XRD analysis. 3.1. Microbial growth and culture medium viscosity

Fig. 1A shows planktonic cell counts during the 30-day incubation


2.4. Electrochemical tests with and without cHPAM in the inoculated culture medium. The
planktonic cell count in the artificial seawater medium with 0 ppm
Electrochemical measurements were used to corroborate anaerobic cHPAM decreased continuously during the 30 days. With 1000 ppm
vial corrosion data. The measurements were performed in 450 mL glass cHPAM added to the medium, the planktonic cell amount decreased in
cells filled with 350 mL culture medium using a potentiostat the first 5 days, but then it started to increase. This suggests that
(VersaSTAT 3, Princeton Applied Research, Oak Ridge, TN, USA) with Consortium II adapted to the new organic carbon source after a lag
VersaStudio version 2.44.4 software. In each glass cell, the working phage and started to utilize the polymer for growth. The SRB sessile cell
electrode was a C1018 coupon with an exposed surface of counts on C1018 coupons in Fig. 1B show that SRB sessile cells also
10 mm × 10 mm. The counter electrode was a platinum mesh plate and benefited from cHPAM utilization. The SRB sessile cell count con-
the reference electrode was a saturated calomel electrode (SCE) fitted tinuously increased with 1000 ppm cHPAM in the medium while it
with a Vycor tip. Each glass cell was sealed with a 6.2 cm-diameter continuously decreased in the medium without cHPAM. Here, only SRB
rubber stopper in the anaerobic chamber and incubated at 37 °C. Open sessile cell count was monitored in this work because SRB dominated in
circuit potential (OCP), linear polarization resistance (LPR), and the biofilm consortium [19] and SRB MIC was the primary concern in

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R. Jia et al. Corrosion Science xxx (xxxx) xxx–xxx

Fig. 3. Pit images for coupons after 30 days of incubation in artificial seawater medium with and without cHPAM: 1000 ppm cHPAM (abiotic control) (A), 0 ppm
cHPAM (inoculated) (B), and 1000 ppm cHPAM (inoculated) (C).

this work [31]. It is interesting to note that the sessile cell count for Consortium II inoculation, the viscosity decreased by 34.5% after the
week 1 was lower for 1000 ppm cHPAM than for 0 ppm cHPAM. 30-day incubation. The results further proved that microbes in the
However Fig. 1A did not show any planktonic cell count difference culture medium degraded cHPAM.
before the cHPAM utilization impact kicked in on Day 6. This was
consistent with some findings in the literature [38,39] suggesting that 3.2. Biofilm observation
some polymer molecules hindered sessile cell attachment.
Fig. 1C shows the viscosity decline with time due to cHPAM con- Biofilm SEM and CLSM images of the coupon surfaces after the 30-
sumption in the inoculated culture medium. In the abiotic control day incubation in inoculated vials with and without cHPAM are shown
medium with 1000 ppm cHPAM, the viscosity remained nearly constant in Fig. 2. Fig. 2A and B show SEM images of sessile cells on the coupons
as expected during the 30-day incubation period. However, with in the media with 0 ppm cHPAM and 1000 ppm cHPAM. The images

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R. Jia et al. Corrosion Science xxx (xxxx) xxx–xxx

1000 ppm cHPAM. Fig. 2B′ shows that the sessile cells were mostly live
cells (green dots) on the coupon incubated in the medium with
1000 ppm cHPAM. It should be noted that CLSM images do not show
cell morphology, unlike SEM.

3.3. Corrosion analyses

The specific weight loss data of coupons incubated in the abiotic


control with 1000 ppm cHPAM, inoculated medium with 0 ppm
cHPAM, and inoculated medium with 1000 ppm cHPAM after the 30-
day incubation were 0.3 ± 0.1 mg/cm2, 3.3 ± 0.3 mg/cm2 and
4.1 ± 0.2 mg/cm2, respectively. The abiotic control had a very small
weight loss, indicating negligible corrosion by the chemicals under
anaerobic abiotic condition. The weight loss data here show that
cHPAM utilization by microbes resulted in more severe corrosion. The
pH value for the abiotic control with 1000 ppm cHPAM was 7.0 after
the 30-day incubation. The pH values in the inoculated medium with
Fig. 4. XRD patterns of corrosion products on coupons after 30-day incubation 0 ppm cHPAM and inoculated medium with 1000 ppm cHPAM were
in inoculated artificial seawater medium with and without 1000 ppm cHPAM. 7.5 ± 0.4 and 7.1 ± 0.3, respectively after the 30-day incubation.
With this kind of pH, the organic acid attack was unlikely a contributing
factor to corrosion.
Fig. 3 shows pit morphologies for the abiotic control with 1000 ppm
cHPAM, inoculated medium with 0 ppm cHPAM, and inoculated
medium with 1000 ppm cHPAM after the 30-day incubation. Fig. 3(A,
A′) confirms that the chemicals in the abiotic medium with 1000 ppm
cHPAM caused negligible corrosion under anaerobic condition. Al-
though the abiotic medium contained an oxidant (sulfate), its reduction
reaction rate was very small without biocatalysis of SRB. Numerous pits
were found on the coupon surface from the inoculated medium with
0 ppm cHPAM as shown in Fig. 3(B, B′). Larger pits were found on the
coupon surface that incubated with 1000 ppm cHPAM as shown in
Fig. 3(C, C′). The pit images here prove that biocatalysis was needed for
MIC due to sulfate reduction [32]. The pit images in Fig. 3 are con-
sistent with the weight loss data.
Maximum pit depth is an important parameter in MIC analysis be-
cause MIC failures are often caused by pinhole leaks [16]. The max-
imum pit depth of coupons incubated in the inoculated medium with
0 ppm cHPAM after 30 days was 20.4 μm as shown in Fig. S1 in the
Supporting information. The coupons incubated in the inoculated
medium with 1000 ppm cHPAM after 30 days led to a maximum pit
depth of 32.5 μm. The maximum pit depth data corroborate the SEM pit
morphologies in Fig. 3 and the weight loss data. The data here indicate
an increase of maximum pit depth of 59% when cHPAM was utilized. It
should be pointed out that IFM identification of maximum pit depth is
not foolproof. Nonetheless, in this work, the maximum pit depth data
are supported by weight loss data.
The corrosion products on the coupons from inoculated vials with
and without cHPAM were identified by XRD as iron sulfides in Fig. 4.
Mackinawite (FeS) and pyrite (FeS2) were found among the iron sul-
fides from the coupon incubated in the inoculated medium with 0 ppm
cHPAM. Mackinawite, pyrite and pyrrhotite (Fe1−xS, 0 ≤ x ≤ 0.17)
were detected among the iron sulfides on the biotic coupons incubated
with 1000 ppm cHPAM. The XRD patterns in Fig. 4 indicate that
mackinawite was the main corrosion product with and without cHPAM.
Fig. 5. Variations of OCP (A) and LPR (B) with time for coupons incubated in There are two distinct types of anaerobic MIC mechanisms [40,41].
inoculated artificial seawater medium with and without 1000 ppm cHPAM. In Type I MIC, biofilms work as biocatalysts and their sessile cells
(Error bars represent standard deviations from 3 independent samples.). transfer extracellular electrons from iron oxidation to the cytoplasm for
the reduction of non-oxygen oxidants such as sulfate and nitrate to
produce energy [42]. Thus, this type of MIC is also called EET-MIC
show that there were different cell shapes, confirming that Consortium
(extracellular electron transfer-MIC) [40]. In evolutionary micro-
II was a mixed-culture biofilm consortium. The SEM images show that
biology, elemental iron has already been proven to be an electron donor
sessile cells were abundant on both coupons, but SEM cannot distin-
(energy source) for microbial growth [43]. Type II MIC is caused by
guish live and dead cells. CLSM images in Fig. 2A′ and B′ indicate that
corrosive metabolites such as organic acids secreted by microbes [30].
the sessile cells on the coupon incubated in the medium with 0 ppm
Thus, it is also called M-MIC (metabolite-MIC) [40]. These secreted
cHPAM were mostly dead cells (red dots) and the biofilm thickness was
corrosive metabolites are far more concentrated underneath an APB
smaller than that on the coupon incubated in the medium with
(acid producing bacteria) biofilm. In this work, the contribution of acid

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R. Jia et al. Corrosion Science xxx (xxxx) xxx–xxx

Fig. 6. Nyquist and Bode plots for the coupons during the 30-day incubation in inoculated artificial seawater: (A, A′) with 0 ppm cHPAM, and (B, B′) with 1000 ppm
cHPAM. (The frequency value at the top of each fitted semi-circle in (A, B) is marked.).

Table 1
EIS parameters of coupons during the 30 days of incubation in artificial seawater medium.
Duration (day) Rs Yb nb Rb Ydl ndl Rct
(Ω cm2) (Ω−1 cm−2 sn) (Ω cm2) (Ω−1 cm−2 sn) (Ω cm2)

With 0 ppm cHPAM (inoculated)


4 9±1 0.00041 ± 0.00011 0.91 ± 0.08 81 ± 6 0.00052 ± 0.00013 0.71 ± 0.08 1494 ± 212
7 7±2 0.00052 ± 0.00008 0.93 ± 0.05 69 ± 8 0.00061 ± 0.00015 0.76 ± 0.05 1580 ± 161
14 5±1 0.00048 ± 0.00011 0.92 ± 0.06 48 ± 7 0.00066 ± 0.00014 0.67 ± 0.07 1098 ± 108
21 6±1 0.00071 ± 0.00022 0.94 ± 0.03 33 ± 6 0.00069 ± 0.00019 0.63 ± 0.04 1012 ± 85
30 6±1 0.00162 ± 0.00043 0.91 ± 0.07 21 ± 5 0.00151 ± 0.00051 0.53 ± 0.07 1161 ± 67

With 1000 ppm cHPAM (inoculated)


4 6±1 0.00025 ± 0.00007 0.94 ± 0.05 41 ± 7 0.00101 ± 0.00039 0.51 ± 0.06 1862 ± 241
7 7±2 0.00048 ± 0.00011 0.95 ± 0.04 38 ± 7 0.00151 ± 0.00041 0.56 ± 0.12 1322 ±
151
14 6±1 0.00159 ± 0.00056 0.91 ± 0.06 28 ± 6 0.00216 ± 0.00055 0.71 ± 0.09 782 ±
81
21 6±1 0.00629 ± 0.00148 0.85 ± 0.08 22 ± 5 0.00221 ± 0.00061 0.91 ± 0.07 746 ±
68
30 6±1 0.00769 ± 0.00216 0.89 ± 0.09 14 ± 3 0.13976 ± 0.04395 0.92 ± 0.06 762 ±
79

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attack to corrosion was not significant because the culture medium pH of cHPAM by microbes decreased charge transfer resistance, thus in-
was not low (7.5 for the medium with 0 ppm cHPAM and 7.1 for the creasing the corrosion rate.
medium with 1000 ppm cHPAM). The main corrosive mechanism was
the reduction of sulfate to HS− using the electrons from iron oxidation 4. Conclusion
as indicated by Reactions 1 and 2 and the black color of the broth which
was caused by FeS precipitation [40]. In this work, an EOR polymer (cHPAM) was found to be utilized by
− an oilfield biofilm consortium grown in an artificial seawater medium
Fe → Fe 2+
+ 2e (1)
for 30 days in anaerobic vials with C1018 carbon steel coupons. The
− −
SO4 2−
+ 9H +
+ 8e → HS + 4H2O (2) polymer utilization promoted the planktonic cell growth and SRB ses-
sile cell growth. Furthermore, the utilization of cHPAM resulted in re-
Ferrous ions in the presence of sulfides form various iron sulfides duced viscosity. It also led to higher weight loss and more severe pitting
such as mackinawite and pyrite in reversible reactions [44]. The XRD corrosion. Electrochemical measurements in electrochemical cells
results in Fig. 4 confirm that the corrosion products were mainly iron confirmed these corrosion data from the anaerobic vials. For the first
sulfides. There was also a possibility that the reduction of a biode- time, a systematic corrosion study was presented on the impact of EOR
gradation product could contribute to MIC. Thus, it is desirable to polymer utilization on MIC. The results here will be helpful to field
identify biodegradation products in a further investigation. operators in the selection of EOR polymers and in the evaluation of the
need for biocide treatment.
3.4. Electrochemical measurements
Acknowledgement
Fig. 5A shows the variation of OCP vs. time for coupons incubated in
the inoculated artificial seawater medium with and without cHPAM. It We acknowledge the financial support from Petronas Research Sdn.
can be seen that the OCP of the coupon incubated without cHPAM Bhd., Malaysia.
generally shifted to the positive direction and then kept steady after day
20 during the 30-day incubation. With 1000 ppm cHPAM in the in- Appendix A. Supplementary data
oculated medium, the OCP shifted to the positive direction from the
start of the incubation period and then shifted slightly to the negative Supplementary material related to this article can be found, in the
direction from day 15 till the end of incubation period. It was suggested online version, at doi:https://doi.org/10.1016/j.corsci.2018.05.015.
that the positive shift of OCP could be the results of sessile cell growth
and corrosion product formation [45,46]. The slight OCP shift to the References
negative direction in the presence of cHPAM could be due to the in-
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7
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