SCIENCE
Effects of a Corrosion Inhibitor on Bacteria
and Microbiologically Influenced Corrosion
E.R. Freiter*
ABSTRACT
The effect of a corrosion inhibitor (CI) formulation on the
population of sessile and planktonic field bacteria was
measured and related to coupon pitting and general corro-
sion using controlled laboratory flow-through loops.
Coupons were periodically removed from the flow loops, vi-
sually examined, scraped, and enumerated and subjected
to epifluorescent microscopy and, in some instances, to
scanning electron microscopy (SEM) before being cleaned
and reweighed. For the most part, the presence of CI had
no detectable effects on the populations of several types of
sessile and planktonic bacteria. In one set of experiments,
the populations of sulfate-reducing bacteria were more
than one order of magnitude greater in the presence of the
CI. In another instance, there was a generally higher popu-
lation of planktonic anaerobic bacteria in the absence of CI.
A lower Eh tended to coincide with higher populations of all
types of bacteria. The presence of CI resulted in less cou-
pon corrosion. There was only minor pitting corrosion. SEM
scans of pit surfaces indicated varying concentrations of
sulfur across the pits. There were many small tubercles
present on the surface of the coupons. The tubercles ap-
peared to be hollow, and SEM micrographs showed
depressions in the coupons directly under the tubercles, in-
dicating the possible beginning of microscopic pits.
KEY WORDS: microbiologically influenced corrosion, oxy-
gen, pit changes and effects, redox potential, scanning
electron, weight loss
Submitted for publication May 1991; in revised form, October 1991.
Presented as paper no. 584 at CORROSION/91 in Cincinnati, OH.
* Exxon Chemical Company, 8230 Stedman St., Houston, TX 77029.
0010-9312/92/000061/$3.00/0
266 1992, National Association of Corrosion Engineers
INTRODUCTION
The possible effects of corrosion inhibitors on bacte-
ria is of considerable interest to people involved in oil
and gas production and transmission. It is possible
that corrosion inhibitors will have biocidal effects on
bacteria. This has already been the subject of investi-
gation.1 Bacteria are also well-known for their ability
to oxidize a wide variety of chemicals and use them
as nutrients (sources of carbon and nitrogen) under a
variety of conditions.2,3 Therefore, corrosion inhibitors
could act as a nutrient source and enhance popula-
tions of bacteria. In oil fields and water floods that are
treated with corrosion inhibitors, these effects are ob-
viously important because bacteria are sometimes
present and can influence corrosion. Thus, in many
instances, it is necessary to treat with both biocides
and corrosion inhibitors. Under these conditions, it
would be an advantage to know if the corrosion in-
hibitor is acting as a nutrient source, as a biocide, or,
indeed, if there is any effect at all. For these reasons,
a laboratory experiment was designed to test a pro-
prietary corrosion inhibitor formulation that contained
tallow trimethylene diamine as the main active ingre-
dient. The purpose was to determine if the corrosion
inhibitor would act as a biocide or a nutrient source or
have any other significant effect on bacteria or micro-
biologically influenced corrosion.
APPARATUS AND GENERAL DISCUSSION
OF PROCEDURES
The laboratory test loops consisted of four
opaque polyethylene carboys that were connected
through a peristaltic pump with lines connecting the
CORROSIONAPRIL 1992

bottom of each carboy to the bottom of a coupon
chamber. Each carboy was set up so that the pump
would pump fluid from the bottom of the carboy
through the coupon chamber, from the bottom to the
top then back into the top of the carboy. The coupons
were composed of AISI 1008-1010 (UNS G10080-
G10100) mild steel (polished with 180 grit cloth). They
were 1 in.2 and 1/32-in. thick with a 3/18-in. hole near
one end. They were fastened with plastic bolts to a
long plastic bar that was placed loosely into the cou-
pon chamber. Each carboy was equipped with a
stirring motor and stirring bar. The top of each carboy
was further equipped with lines that made it possible
to withdraw and add field water or condensate. The
line at the top of the coupon chamber could be discon-
nected to provide access to the coupons. During the
course of the experiment, the coupons were removed
by starting from the top of the bar. In this way, the re-
maining coupons were not exposed to the air during
the removal procedure. Lines were also available so
that the systems could be individually purged with car-
bon dioxide, argon, or nitrogen. All carboys were
placed in large containers so that leaks would be con-
tained. The flow rates could be adjusted with the
peristaltic pump.
At the beginning of the experiment, the carboys
were loaded with 8 L of condensate and 8 L of field
water that had been previously checked (serial dilution
into sulfate-reducing media, aerobic media, and
anaerobic media) and found to contain 106 microbes/
mL of planktonic bacteria. In two of the carboys (car-
boys A and C), enough corrosion inhibitor was added
to give concentrations of approximately 50 ppm in the
aqueous phase. In the remaining two carboys (car-
boys B and D), no corrosion inhibitor was added.
Sixteen coupons were placed into each chamber.
Oxygen concentrations, corrosion inhibitor con-
centrations, pH, and redox potential (Eh) were
periodically checked during the course of the 135-day
experiment. The pH of the system was regulated by
bubbling CO2 into the aqueous fluid. In these experi-
ments, large partial pressures of CO2 were never
present in the fluids because it only took small
amounts of CO2 to adjust the pH. The oxygen concen-
tration was kept as low as practically possible by
bubbling argon or nitrogen into the aqueous layer. The
oxygen concentration was measured using a colori-
metric oxygen test kit (see Experimental Procedures)
and was held below 1 ppm throughout most of the ex-
periment.
At the outset of the experiment, it was hoped that
a pH of 6 or slightly lower would be possible with a
corresponding Eh less than 100 mV. This would
closely mimic the condition of the water in the field.
However, this proved difficult to accomplish. The water
obtained from the field was oxygenated during the
CORROSIONVol. 48, No. 4
SCIENCE
sampling procedure and thus had a positive Eh. It was
difficult to lower the Eh of the field water even after de-
oxygenating for a long period of time. It was possible
to obtain the desired low Eh originally present in the
field only by raising the pH to around 7.5.
In spite of the difficulties mentioned, it was de-
cided to run the first portion of the experiment without
supplementation by poising agents (chemicals that ad-
just Eh). The flow rate was kept low at approximately
15 mL/min. Portions of the field water and condensate
were exchanged approximately once per week with
fresh liquids from the field. It was thought that with
time, the low Eh and low pH would develop as the
bacteria grew. Accordingly, the first 49 days were run
under these natural conditions. In most cases, two
coupons were pulled from each chamber at days 20,
35, 42, and 49. Concentrations of sessile bacteria
were obtained by scraping the coupons on one side,
transferring the scrapings to liquid phase, and carrying
out serial dilutions. The other side was prepared for
epifluorescence spectroscopy or for scanning electron
microscopy (SEM). All coupons were cleaned and re-
weighed. Planktonic populations were obtained by
sampling the water in each of the carboys and carry-
ing out serial dilutions in the appropriate media.
Similar procedures were followed for days 73, 86,
115, and 135 in the second portion of the experiment.
However, at these times, a small amount (approxi-
mately 50 ppm, based on the amount of water present
in each carboy) of sodium sulfide was periodically
added as a poising agent.
EXPERIMENTAL PROCEDURES
Oxygen concentrations were measured by obtain-
ing under an argon atmosphere approximately 20 mL
of the water to be tested. An ampoule from a colori-
metric oxygen test kit was inserted under the surface
of the water, and the tip was broken off. This allowed a
small portion of water to be sucked into the ampoule.
The ampoule was removed, the broken tip was cov-
ered, and the contents were mixed by shaking. The
resulting color of the liquid in the ampoule was com-
pared with color standards to determine oxygen
concentration. Ampoules contain a liquid analytical re-
agent under a partial vacuum. The liquid containing
the analytical reagent develops a color, the intensity of
which is proportional to the oxygen concentration in
the fluid being measured.
Redox potentials (Eh) were determined using a
pH/ion meter. Prior to carrying out Eh determinations,
the meter and electrode were standardized on the mil-
livolt scale using excess quinhydrone in buffered
water. The meter was set at +86 mV at pH = 7.0 or at
+263 mV at pH = 4.0. Eh values were obtained by
allowing the electrode to equilibrate in the water for
267
SCIENCE
approximately 5 min and reading directly from the mil-
livolt scale.
Corrosion inhibitor concentrations in the aqueous
portions of the carboys were determined on small
aliquots of liquid. The procedure used was an adapta-
tion of some commonly used procedures for
determining amines and quaternary ammonium com-
pounds.4 Six mL of sample to be tested were added to
a 1/2-oz (20 mL) bottle containing 0.25 mL of a methyl
orange solution. The methyl orange solution was
made by dissolving 0.05 g of the solid dye in 100 mL
of deionized water and adding 0.25 mL of a buffer
composed of 125 g of potassium chloride, 70 g of so-
dium acetate, and 300 mL of acetic acid in 500 mL of
deionized water (pH adjusted to 3.75 with hydrochloric
acid or sodium hydroxide). Four mL of chloroform
were added to this solution, the contents were shaken
vigorously, and the two layers were allowed to sepa-
rate. The bottom chloroform layer was transferred to a
UV cuvette, and the absorbance was read at 430 nm
on a spectrophotometer. Unknowns were compared to
a standard curve.
Sessile bacteria were enumerated by rapidly
scraping the surface with a sterile scalpel. The
scrapings were put into a 1/2-oz (20 mL) bottle con-
taining 1 g of glass beads (diameter = 2 mm) and 10
mL of a specially prepared fluid (composition: dibasic
potassium phosphate, 6.06 g; monobasic potassium
phosphate, 0.4 g; cysteine hydrochloride, 0.5 g;
polysorbate 80, 1.0 mL; NaCl, 80 g; and water added
to a total volume of 1 L). After the scraping was com-
plete, the cap was screwed on tightly, and the
contents were shaken 500 times. Using 1 mL aliquots
from the bottle, serial dilutions were then made into
the appropriate media in the standard manner. Popu-
lations of bacteria were reported as the number of
organisms per square inch.
The table below shows the results of corrosion
wheel tests performed using the corrosion inhibitor
formulation used in this study. Under the given condi-
tions, 95%+ corrosion protection was obtained.
Corrosion Inhibitor
Concentration Average
(ppm) Coupon Wt. Loss C.R. (mpy)
0 26.6, 36.2, 39.3, 31.1 83.3
50 2.10, 0.60 3.38
100 0.40, 0.20 0.50
200 1.40, 1.20 3.25
Conditions: Continuous test (24 h), 100 mL of field water and 100
mL of hydrocarbon, CO2 saturated, 49C (120F).
Coupons were prepared for epifluorescence spec-
troscopy by immersing them for 10 min in an aqueous
solution containing 5% glutaraldehyde and 1.3% so-
dium cacodylate (ph adjusted to 7.0 with HCl, filtered
through a 0.2-m filter). The coupon was then
removed and immersed for 10 min in a solution
268
containing fresh, buffered acridine orange (AO). The
coupon was removed and rinsed by being dipped
three times into an isopropyl alcohol (IPA) solution and
allowed to air dry. The AO solution was prepared by
adding 10 mL of an IPA solution containing 10 mg of
AO to 84 mL of dibasic potassium phosphate (5.35 g/
500 mL of deionized water) and 16 mL of monobasic
potassium phosphate (3.4 g/500 mL of deionized wa-
ter). The solution was stirred for several minutes then
filtered through a 0.2-m filter.
Coupons for SEM were prepared by immersing
the coupon in a solution containing 5% glutaraldehyde
and 1.3% sodium cacodylate with the pH adjusted to
7.0 with HCl. The coupon was removed and dehyrated
by sequentially soaking in serial solvents in a manner
quite similar to literature procedures.5
The medium used for sulfate-reducing bacteria
(SRB) was the standard API RP38 broth that con-
tained a nail and to which was added 7.0% by weight
of sodium chloride.6 The medium used for anaerobic
bacteria was similar to the TSB3 broth used by Bragg
et al.7 The only differences were that 0.004 g/L of fer-
ric chloride was substituted for 0.004 g/L of ferrous
sulfate, and no sodium sulfate or resazurin was
added. Also, this medium had 7% sodium chloride
added. The medium used for aerobic bacteria was
similar to bactophenol red broth base.8 In this medium,
5 g/L of dextrose was substituted for 1 g/L of beef ex-
tract, and 7% by weight of sodium chloride was added.
All broth bottles were incubated at 36C (98F).
Final readings were taken after no further growth took
place, which was usually after two weeks of incuba-
tion.
Coupons were washed by placing them into 200
mL of inhibited 15% HCl for 5 min. The coupons were
then rinsed with water and cleaned by scrubbing with
a mildly abrasive soap solution. They were then rinsed
three times with acetone, air dried, and weighed.
Calculation of Standard Deviation
Percent Protection with Corrosion Inhibitor
X = 52.8 (Average of values given in Figure 16);
% 2
Protection
S =
(X X) = 14.6
0 n1
96
99 Two-Way Analysis of Variance for Sessile SRB in the
96 Absence of a Poising Agent 9
Experiment #1
Days Carboy A(1)(2) Carboy B(1)
20 6.0 4.0
35 6.0 3.5
42 6.0 5.5
49 5.5 4.0
(1)
Numbers given are, in most cases, averages of the two values given in
Table 2 for sessile SRB.
(2)
Contained corrosion inhibitor.
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Experiment #2 Experiment #2
Days Carboy C(1)(2) Carboy D(1) Days Carboy C(1)(2) Carboy D(1)
20 6.0 5.0 20 2.0 4.0
35 6.5 4.5 35 4.0 5.0
42 6.5 4.5 42 3.0 6.0
49 6.0 4.5 49 6.0 6.0
2 2
(Correction Factor) C = T = 441.00 (Correction Factor) C = T = 361.00
rmn rmn
n n
(Row Effects) SSR = 1 T2i C = 0.8750 (Row Effects) SSR = 1 T2i C = 8.00
rm i = 1 rm i = 1

m m
(Column Effects) SSC = 1 T2j C = 10.563 (Column Effects) SSC = 1 T2j C = 9.0
rn j = 1 rn j = 1

r r
(Replicate Effects) SSr = 1 T2k C = 0.5625 (Replicate Effects) SSr = 1 T2k C = 1.0
mn k = 1 mn k = 1

n m r n m r
(Total) SST = y2ik C + 14.00 (Total) SST = y2ijk C = 23.00
i=1 j=1 k=1 i=1 j=1 k=1

Analysis of Variants Analysis of Variants

Source Degrees Sum Source Degrees Sum
of of of Mean % Distribution of of of Mean % Distribution
Variation Freedom Squares Squares F of Variants Variation Freedom Squares Squares F of Variants

(Time) (Time)
Columns 3 0.8750 0.2917 1.46 2.5 Columns 3 8.0 2.6666 5.30 20.2
(CI)Rows 1 10.5630 10.5630 52.82 90.9 (CI)Rows 1 9.0 9.0000 18.00 68.4
Replicates 1 0.5625 0.5625 2.81 4.9 Replicates 1 1.0 1.0000 2.00 7.6
Error 10 1.9995 0.2000 1.7 Error 10 5.0 0.5000 3.8
Total 15 14.000 11.6172 100.0 Total 15 2.3 13.1666 100.0

Values of F Values of F

F3, 10, 0.15 = 3.71; F1, 10, 0.05 = 4.96; F1, 10, 0.01 = 10.00 F3, 10, 0.05 = 3.71: F3, 10, 0.01 = 6.55; F1, 10, 0.05 = 4.96;
10 < 52.82: Effect of corrosion inhibitor is significant F1, 10, 0.02 = 10.00
at the 99% level of confidence. 10 < 18.00: Effect of corrosion inhibitor is significant
3.71 > 1.46: Effect of time is not significant at the at the 99% level of confidence.
95% level of confidence. 3.71 < 5.3 < 6.55: Effect of time is significant at the
3.71 > 2.81: Effect of replicates is not significant at 95% level of confidence but not at the
the 95% level of confidence. 99% level.
3.71 > 2.00: Effect of replicates is not significant at
Two-Way Analysis of Variance for Planktonic the 95% level of confidence.
Anaerobic Bacteria in the Absence of a Poising
Agent9 DISCUSSION OF RESULTS

Experiment #1 The effects of pH and oxygen concentration on

Days Carboy A(3)(4) Carboy B(3) Eh are well documented.10 The presence of trace
20 4.0 5.0 amounts of oxygen will usually result in a positive Eh.
35 4.0 6.0 It has been shown that lowering the pH value by one
42 4.0 6.0 unit (i.e., from 7 to 6) will cause the Eh to become
49 5.0 6.0 more positive by 57.7 mV.
(3)
These numbers are taken from Table 2. Eh values are of importance when bacteria are
(4)
Contained corrosion inhibitor. cultured because SRB and other anaerobic bacteria

CORROSIONVol. 48, No. 4 269

SCIENCE

require a negative Eh of 100 mV or lower to survive

FIGURE 1. Sulfate-reducing bacteria.
FIGURE 2. Anaerobic bacteria.
and/or multiply. To ensure low Eh values, poising
agents are often added to bacteria cultures. There are
several poising agents that are routinely used. Sodium
sulfide is quoted by one source as being the agent of
choice in many instances.11
Diamines and other related corrosion inhibitors
have been discussed in the literature.12 An example of
the corrosion protection that can be obtained with this
type of inhibitor is given in the experimental.
First portion of experiment (no sodium sulfide
added)The values for the Eh, pH, oxygen concen-
tration, and corrosion inhibitor concentration obtained
during this portion of the experiment are shown in
Table 1. No poising agent was added for the first 49
days. Under these conditions, Eh values below 50
mV could only be obtained at pH values above 7.0.
This may have been due to the presence of small
amounts of oxygen in the field brine. The effect of pH
on Eh can be seen with the data shown on day 41 in
Table 1. On this day, the Eh was measured at two dif-
ferent pH values and showed a concomitant increase
in Eh with a decrease in pH. This was similar to the lit-
erature results mentioned above. The corrosion
inhibitor concentration varied between 40 and 85 ppm
most of the time.
The populations of SRB, other anaerobic bacteria,
and aerobic bacteria are given at days 20, 35, 42, and
49 in Table 2 and Figures 1, 2, and 3, respectively.
These results indicate that in most instances, there
were 104 sessile organisms present/in.2 of coupon
surface and that there were 104 planktonic organisms
present/mL. The effect of the corrosion inhibitor on
populations of bacteria can be ascertained by examin-
ing the differences in populations obtained in carboys
A and C that contained corrosion inhibitor vs carboys
B and D, which contained no corrosion inhibitor. In
most cases, there were no remarkable differences in
the populations of bacteria. One relatively small differ-
ence that was observed was in the case of the sessile
SRB population where there was more than one order
of magnitude higher populations with the bacteria
growing in the presence of corrosion inhibitor for days
20 through 49 (Figure 1). If one assumes that the data
were normally distributed, a two-way analysis of vari-
ance can be calculated. This indicates that the
corrosion inhibitor exerted a positive effect on the
population of sessile SRB at the 99% level of confi-
dence. In the case of anaerobic planktonic populations
(days 20 through 49 in the lower graph in Figure 2),
there was a generally higher population of bacteria in
the carboys that did not contain corrosion inhibitor. A
two-way analysis of variance in this instance indicates
that the corrosion inhibitor exerted a negative effect on
the population of anaerobic planktonic bacteria at the
99% level of confidence.

270 CORROSIONAPRIL 1992

 TABLE 1
Measurements Carried out on Water in Carboys(1)
(First Portion of Experiment)
Days

CORROSIONVol. 48, No. 4

* After large water loss due to overnight leak.
(1)
No sodium sulfide added.
SCIENCE

271
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Second portion of experiment (approximately 50

ppm of sodium sulfide added)The values obtained
for Eh, pH, oxygen concentration, and corrosion inhibi-
tor concentration are shown in Table 3. The values for
Eh and pH are different from Table 1 and show the ef-
fects of adding a small amount of sodium sulfide to the
carboys. The Eh was generally lower at lower pHs
than those given in Table 1. The oxygen concentration
remained well below 1.0 ppm.
Data for days 73 through 135 (Figures 1 through
3 and Table 4) show the bacterial populations ob-
tained after adding sodium sulfide. Under these
conditions, no remarkable differences in the bacterial
populations between field water containing corrosion
inhibitor and that containing no corrosion inhibitor
were observed. Interestingly, the population of bacte-
ria growing in all three media increased slightly during
the last three to five sampling periods. Whether this
was due to the different conditions or to a population
of bacteria that had adapted to the conditions of the
experiment is not clear at this time.
On day 73, sessile SRB and anaerobic popula-
tions of 102 microbes/in.2 were obtained (Figure 1,
carboys B, C, and D and Figure 2, carboys C and D).
These populations were very much lower than those
FIGURE 3. Aerobic bacteria.

TABLE 2
Log of Population of Sessile Bacteria/in.2 and Planktonic Bacteria/mL
(First Portion of Experiment; No Sodium Sulfide Added)
20 days 35 days 42 days 49 days
Organism Carboy Sessile Planktonic Sessile Planktonic Sessile Planktonic Sessile Planktonic

SRB A 6 5 7 5 6 6 6 6
5 6 5
B 4 6 3 5 6 5 4 4
4 5 1 or 0
C 6 6 7 5 7 5 6 5
6 6 6 6
D 4 5 5 4 4 5 4 4
6 4 5 5
Other
Anaerobes A 5 4 5 4 5 4 6 5
5 6 5
B 5 5 4 6 6 6 6 6
5 5 2
C 4 2 4 4 5 3 5 6
3 5 4 5
D 4 4 5 5 5 6 6 6
4 4 5 5
Aerobes A 5 5 6 4 7 3 7 7
6 5 8
B 3 4 5 3 5 3 8 7
4 5 4
C 3 6 4 3 4 6 7 5
3 3 5 6
D 3 5 3 3 4 4 6 6
3 3 4 6

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TABLE 3
Measurements Carried out on Water in Carboys(1)
(Second Portion of Experiment)
Days
Carboy 61 62 63 66 67 76 77 77 89 97 102 117 127

Eh (mv)
A -135 -53 -68 -10 -120 -180 -40 -100 -140 -104 -210 -86
B -90 -38 -60 -8 -126 -200 -15 -90 -134 -106 -220 -100
C -140 -66 -52 10 -110 -210 +10 -62 -114 -80 -230 -100
D -80 -48 -54 10 -96 -260 -25 -75 -130 -104 -240 -120

pH
A 6.8 5.8 5.9 5.9 5.3 7.3 5.9 6.0 7.0 6.5 7.4 5.8
B 5.4 5.9 6.0 5.9 5.8 7.3 5.8 5.9 6.8 6.6 7.4 5.8
C 6.1 6.4 6.0 5.8 5.4 7.4 5.8 5.7 6.8 6.4 7.5 5.8
D 5.5 5.9 6.0 5.8 5.4 7.8 5.9 5.9 6.8 6.4 7.5 5.8

O2 (ppm)
A 0.4 0.4 0.4 0.4 0.2 0.2 0.3 <.1 0.2
B 0.4 0.4 0.4 0.4 0.2 0.1 0.3 <.1 0.2
C 0.4 0.4 0.4 0.4 0.2 0.2 0.3 <.1 0.2
D 0.4 0.4 0.4 0.4 0.2 0.05 0.3 <.1 0.2

C.I. (ppm)
A 50 30 35 20
B
C 35 25 77 67
D
(1)
Sodium sulfide (50 ppm) added.

TABLE 4
Log of Population of Sessile Bacteria/in.2 and Planktonic Bacteria/mL
(Second Portion of Experiment; Sodium Sulfide Added)
73 days 86 days 115 days 134 days
Organism Carboy Sessile Planktonic Sessile Planktonic Sessile Planktonic Sessile Planktonic

SRB A 5 7+ 6 7+ 8+ 6 6 6
4 7 6 6
B 4 7+ 7 7+ 7 6 5 6
3 6 6 7
C 4 6 6 7+ 6 7+ 7 7
3 6 6 7
D 1 or 0 7+ 6 7+ 6 7+ 6 7
4 4 6 5
Anaerobes A 6 7+ 6 5 6 7+ 7 6
6 6 6 6
B 6 7+ 5 6 6 6 6 9+
6 6 6 7
C 5 6 6 5 6 7+ 6 6
1 or 0 5 7 6
D 1 or 0 7+ 7 6 6 7+ 7 9+
4 4 6 7
Aerobes A 6 7+ 7 7+ 7 5 6 6
7 7 7 6
B 5 7+ 6 7+ 4 6 8 8
6 6 6 5
C 5 7+ 6 5 6 5 5 5
4 6 6 6
D 3 7+ 6 7+ 6 5 7 8
5 5 7 7

CORROSIONVol. 48, No. 4 273

SCIENCE
FIGURE 4. Epifluorescence micrograph of coupon from car-
boy A (day no. 135)(contained 50 ppm corrosion inhibitor).
Bacteria are visible as white, elongated rods in vertical stria-
tions. Bare spots show the metal.
FIGURE 5. Epifluorescence micrograph of coupon from car-
boy B (day no. 135)(contained no corrosion inhibitor). A
massive thick bacterial buildup. The bacteria in the left lower
corner are in focus and show up as white rods and kidney
bean-shaped cells.
FIGURE 6. EDXA analysis of a coupon from carboy C (day no.
135)(contained 50 ppm of corrosion inhibitor).
274
obtained at any other time and were probably due to
an anomaly in the scraping procedure. In this in-
stance, the scraping procedure was inadvertently
carried out more slowly, and the coupons were al-
lowed to partially dry before scraping. It is likely that
the bacteria present on the surface of the partially air-
dried coupons were exposed to relatively large
amounts of oxygen. This could be toxic to the SRB
and anaerobic bacteria and might well result in a large
decrease in these populations. There was no de-
crease observed in the aerobic bacterial population
for day 73 (Figure 3).
Epifluorescence Studies
Many of the coupons were stained and subjected
to epifluorescence spectroscopy (1500X magnifica-
tion) during the course of the experiment. Only two
examples of micrographs from carboys A and B from
the last day (no.135) are shown and given in Figures 4
and 5. Micrographs from carboys C and D were simi-
lar and are not shown. There did not appear to be any
qualitative correlations that could be made between
the number or appearance of bacteria and the pres-
ence or absence of corrosion inhibitor.
Scanning Electron Microscopy (SEM) Data
SEM data obtained from the early parts of the ex-
periment showed little or no corrosion. A coupon from
carboy C (contained 50 ppm corrosion inhibitor) ex-
posed for 135 days was examined by SEM. The
coupon surface was found to contain sulfur and iron
as the main components (Figure 6) by energy disper-
sive x-ray analysis (EDXA).
An SEM line scan micrograph across a small pit
on the coupon surface and an accompanying line
graph is shown in Figure 7. This scan indicated that
there were varying amounts of sulfur present on the pit
surface (the middle line on the graph, which indicates
how the sulfur concentration varies as one follows the
white line across the pit [Figure 7]). There were also
varying amounts of silicon present in the pit (the bot-
tom line in the graph [Figure 7]). The presence of
varying amounts of sulfur across the pit surface could
have significant implications regarding possible
mechanisms of corrosion. SEM scans across other pit
surfaces did not show any readily discernible patterns
regarding varying sulfur concentrations.
Figures 8(a) and (b) show SEM scans at 1000X
magnification and at 5400X magnification of large nod-
ules that were present on the surface of the coupon.
These nodules appeared to be hollow, and from the
micrographs, it appeared that some small pits were
forming underneath them. SEM scans across these
nodules indicated that they were composed mainly of
iron and oxygen, some silicon, and a small amount of
carbon. These findings suggest that more significant
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FIGURE 7. Micrograph of SEM line scan of pit on coupon

surface from carboy C (day no. 135)(containing 50 ppm
corrosion inhibitor). The accompanying line graph shows
concentrations of sulfur (middle line) and silicon (bottom line)
as the line proceeds through the pit.

corrosion might have occurred if the experiment had

been run for a longer time.

Corrosion Rates
Figure 9 and Table 5 show the corrosion rates
that were obtained during the loop tests and the per-
cent protection that was obtained in the presence of
the corrosion inhibitor. The data indicate that under
the conditions of the test, relatively low rates of corro-
sion were observed when the corrosion inhibitor was
present. The coupons from carboys A and C contain- FIGURE 8. SEM scans at 1000X (a) and at 5400X (b) of large
ing the corrosion inhibitor had overall average corrosion nodules on the surface of the coupon from carboy C (day no.
rates of 0.58 mpy, while the coupons from carboys B 135)(contained 50 ppm corrosion inhibitor).
and D without corrosion inhibitor gave overall average
corrosion rates of 1.06 mpy. Figure 9 shows a plot of
the averaged corrosion rates on coupons in mpy ob-
tained at each of the days measured. The corrosion
rate in the two carboys containing corrosion inhibitor is
compared with that in the two carboys containing no
corrosion inhibitor. In all instances, the fluids contain-
ing corrosion inhibitor gave less corrosion. The
percentage of corrosion protection is also plotted in
Figure 9 and ranges from just over 20% on day 86 to
67% on day 42. At this time, there is no explanation
available for low corrosion rate on day 86. The overall
percentage protection, which includes the data at all
days, is 52.8 (+14.6%). This indicates that the pres-
ence of corrosion inhibitor gave significant corrosion
protection under the conditions of this experiment. Vi-
sual inspection showed that the coupons treated with
corrosion inhibitor looked cleaner than the untreated
coupons. It is particularly interesting that very low cor-
rosion rates were observed in all cases in spite of the
FIGURE 9. Corrosion data.
rather high populations of bacteria that were present.

CORROSIONVol. 48, No. 4 275

SCIENCE

TABLE 5
Corrosion Weight Loss Data*

Carboy A Carboy B Carboy C Carboy D

Days
Wt. Loss Avg. C.R. Wt. Loss Avg. C. R. Wt. Loss Avg. C. R. Wt. Loss Avg. C. R.

20 11.4 0.8 14.5 (13.3) 29.2 19.2 (20.8) 1.5

12.1 1.0 2.1 22.3
35 14.8 (14.4) 0.6 13.8 (13.4) 0.6 25.4 (28.3) 1.2 26.7 (26.2) 1.1
14.0 13.0 31.3 25.6
42 16.2 (15.1) 0.5 14.4 (13.8) 0.5 40.6 (40.6) 1.9 33.5 (32.9) 1.1
14.0 13.2 40.6 32.3
49 16.4 (17.4) 0.5 13.3 (13.5) 0.4 36.8 (38.5) 1.1 30.0 (29.6) 0.9
18.4 13.6 40.3 29.3
73 19.3 (19.2) 0.4 20.9 (22.8) 0.4 48.0 (49.1) 0.9 46.7 (42.9) 0.8
19.1 24.7 50.1 39.0
86 48.8 (55.8) 0.9 77.4 (57.5) 0.9 73.6 84.5 1.4 63.0 (57.2) 0.9
62.8 37.5 95.3 51.4
115 19.4 0.2 17.9 (18.8) 0.2 51.1 (59.6) 0.7 43.1 (41.0) 0.5
19.6 68.0 38.8
135 16.8 (17.8) 0.2 14.6 0.15 52.2 (52.0) 0.5 41.1 (43.9) 0.4
18.7 51.7 46.7
Overall average C.R. 0.58 1.06

*For washing procedure see Experimental Procedures

CONCLUSIONS
The presence of corrosion inhibitor did not result
in any large increases in the numbers of bacteria that
were present under the conditions used.
The corrosion inhibitor formulation did not exhibit
any major biocidal activity under the conditions and
concentrations used.
High concentrations of sessile and planktonic bac-
teria did not give high corrosion rates.
There were some small differences in populations
of bacteria. The population of sessile SRBs may
have been slightly enhanced in the presence of cor-
rosion inhibitor in one series of experiments. The
population of planktonic anaerobic bacteria may have
been slightly inhibited in the presence of corrosion in-
hibitor in another series of experiments.
ACKNOWLEDGMENTS
The author would like to thank Exxon Chemical
for allowing the publication of these investigations.
Thanks are also due to Dennis Manual and Robert
Botto and their associates for the SEM work that ap-
pears in this paper. Isaac Ho calculated the two-way
analysis of variance.
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276 CORROSIONAPRIL 1992