This work investigated the microbiologically influenced corrosion (MIC)
threat in pipeline hydrotesting; usingoffshore seawater samples
for coupon tests in anaerobic vials. Longer-term sulfatereducing bacteria
pitting Was predicted using a MIC prediction software program Calibrated With
short-term pitting data from the tests.
Hydrotesting is a common practice to assess pipeline integrity before
service. Different from pneumatic testing that is used only for leak testing,
hydrotesting is applied to test for both leaks and strength. During
hydrotesting, a pipeline is filled with a liquid and pressurized
to a pressure (usually 10%) greater than the anticipated future operating
pressure.
Background
In general, hydrotesting itself lasts only eight to 10 h. In the oil and
gas industry, however, it is often the case that water is left in the system afterward
for many months before the system is actually commissioned. During this holding
time or when the pipeline is first exposed to an aqueous
environment like wet lay-up, corrosion due to microbiologically influenced
corrosion (MIC) can commence.
When the system makes contact with the ground or is even exposed to air, there are further possibilities for microbial contamination. Reuse of water
also increases chances for MIC. Improper hydrotesting practices can cause MIC
Pittin attacks and also black powder problems. MIC pitting during hydrotest itself may not
be a big problem because of the limited hydrotest time frame. The
biofilms left behind during hydrotest, however, may present
a serious threat once the pipelines become
operational, because fluids transported in pipelinesmay contain sufficient
nutrients for biofflms to "and apipf ne is ofte" expected to be
operational tor several decades.
Seawater in Pipelines
Seawater is routinely used in the hydrotesting of subsea pipelines. Occasionally, other
water sources may be used and they mainly come from aquifer water and/or
produced water. Any water source for hydrotesting can contain microorganisms.
Natural seawater contains viruses, prokaryotes, protists (mainly flagellates),
and algae. Water used in hydrotesting is sometimes treated with biocides. Even
treated water can be a source of sulfate-reducing bacteria (SRB) inoculum. Two
other methods to treat the hydrotest water are
adjusting pH and using water sources without sulfate. The pH adjustment
(within a basic range), however, could increase the possibility of mineral
scale formation on the pipe surface, and using a large amount of
water without sulfate is usually costly and inconvenient when hydrotesting
takes place offshore. Furthermore, the method ofpipeline laying or water
filling makes water treatment very difficult, if possible at all.
Sulfate-Reducing Bacteria Metabolism
It has been known that some SRB are able to utilize hydrocarbons or even
live on carbon dioxide-hydrogen (CO,-H") autotrophically,"
which means they can live without organic carbon intakes. Rossmoore" found
that a variety of bacteria have the capability to reduce in size, decreasing
energy consumption during starvation and residing in smaller pores. These bacteria
can then wait to thrive when the appropriate environmental conditions are met.
This unique feature of bacteria makes predicting and preventing the MIC in
hydrotesting difficult. Steel corrosion in seawater sometimes has been
misdiagnosed as attack induced only by conventional chloride corrosion.
Borenstein1 found that microorganisms contained in a stagnant chloride-bearing
medium can cause steel failure much faster than in conventional chloride
crevice corrosion alone. This increased corrosion rate may come from sulfate
and other nutrients in the seawater, which cause souring and pipelinecorrosion due to SRB
activities.
Use of Oxygen Scavengers
In the field, oxygen scavengers are usually added to the hydrotesting water
to prevent oxygen-caused corrosion. This provides an anaerobic environment for
anaerobic bacteria such as SRB. MIC occurs when several favorable factors are
present simultaneously, such as suitable water chemistry, temperature,
nutrients (organic and inorganic), microorganisms, and pressure. The majority
of SRB can thrive at pH ranges from 5 to 9, and except for thermophiles, are
unable to thrive at temperatures >45 °C. Availability of a carbon source is
usually considered to be the most important factor for SRB growth; SRB growth
will be severely restricted if utilizable carbon in organic nutrients in the
form of volatile fatty acids such as formate, acetate, and propionate, is
<20 ppm.1" Pots, et al.10 also indicated that SRB growth would be the
most prominent if the ratio of carbon to utilizable nitrogen was 1 0: 1 .
Synergistic microorganisms can enrich the nutrients (such as organic carbons)
in the local environment and thus promote SRB growth and accelerate the MIC
process even though the initial environmental conditions are not suitable for
SRB growth. Fermentative acid-producing bacteria (APB) should be considered in
MIC forensics, especially in zero-sulfate and low-sulfate environments.
Laboratory Testing
Performing MIC tests in a laboratory setting for hydrotest has always been
a challenge. Pipeline fluids (especially those in
subsea pipelines) can be at very high local pressures.
Barophilic SRB are adapted to this kind of pressure.8 In a laboratory, however,
it is difficult and cost prohibitive to perform many tests in high-pressure
reservoir simulators. It is possible that laboratory tests at one atmosphere
may be able to simulate SRB growth at a high pressure because it has been
reported that barophilic SRB isolated from a high-pressure oil reservoir grew
well at one atmosphere and 30,000 kPa in a laboratory.
Experimental Methods
Anaerobic 125-mL vials filled with 1 00-mL liquid were used in the tests. A
glovebox deoxygenated with N,, gas provided an anaerobic environment. X65
carbon steel coupons were used. These coupons had typical dimensions of 47.6 by
10.9 by 1.6 mm. Prior to use, the coupon surfaces were polished successively
with 200 and 400 grit SiC abrasive papers, rinsed with alcohol, and then
sonicated in a beaker filled with alcohol. The ratio of coupon surface to
liquid volume was close to that in 0.30-m ( 1 2-in) inside diameter (ID) pipes.
All liquids in the tests were deoxygenated using sparging for at least 30
min before use to reflect oxygen scavenger use in the field. Planktonic SRB
bacterial count was determined by manual counting under an optical microscope
at 400X using a hemacytometer. Only motile SRB were counted. If needed, a
Rodine hydrochloric acid (HCl) solution was applied to remove any films on the coupon
surfaces. Scanning electron microscopy (SEM) and energy dispersive spectrometry
(EDS) were employed to perform surface analyses. A CHEMetsf test kit was used
to test the oxygen concentration in the experimental vials.
Desulfovibrio alaskensis (ATCC 14563) was used in this work as a laboratory
strain of SRB. Some experimental results as indicated were obtained by
enriching artificial seawater and natural seawater samples with 1 g/L yeast
extract, 3.5 g/L sodium lactate, and 200 ppm Fe2+.
For biofilm observations under SEM, unless mentioned specifically, coupons
were pretreated according to the following procedures: coupons were removed
from vials and were immediately treated with 4% w/w glutaraldehyde for around 1
h (to immobilize the biofilm), and dien were dehydrated with 30% (v/v), 50, 75,
and 100% alcohol in sequence. Before observing the biofilm, the coupons were
first treated using a Bal-Tec CPD 030t critical point dryer and then coated
with a gold film.
Gulf of Mexico Seawater
Gulf of Mexico (GoM) seawater had a similar chemical
composition to that of typical natural seawater. The total organic carbon (TOC)
in the first GoM sample was < 1 ppm compared to < 1 to 2 ppm TOC for
typical seawater while the TOC of a second GoM sample was 4.6 ppm. The GoM
seawater sample analyzed using polymerase chain reaction (PCR) was actually
very clean. It had a total bacterial concentration of only 1 3.3 cells/mL, and
its SRB cell count was below the detection limit of 1 to 3 SRB cells/L. The
sample was taken from an offshore platform.
When Hardy" measured seven seawater samples from two similar locations
of the North Sea, he obtained SRB numbers from 0 to 90 cells/mL, the average
being 22 SRB/mL. Lee, et al.,12 using the most probable number enumeration
method, detected ~ 1 0 and 1 00 SRB/mL in Persian Gulf and Florida Key West
seawaters, respectively. These two water samples came from 1 .2 to 1.5 m deep
and near-shore (within 100 m) locations that could be contaminated by sewage,
agricultural run-off, or other waste streams. Table 2 shows Na+, S042 , and TOC
in a comparison between typical natural seawater and Qurrayah seawater in Saudi
Arabia. It is clear that Na+ and S042 concentrations in Qurrayah seawater are
~1.6 times higher than in typical seawater, and the TOC concentration, which is
very important for microbial growth, can be 500 times higher.
Temperature Effect
how temperature affected planktonic SRB growth, where 37 °C
is the optimum growth temperature for the lab strain SRB. Compared to the full
nutrient medium (ATCC 1 250 modified Baar's medium), the enriched artificial
seawater with limited nutrients is an acceptable environment for SRB growth,
especially at 37 °C, and those added chemicals provided adequate nutrients for
SRB growth. In general, mesophilic SRB grow well at 37 °C. Thermophilic SRB
prefer even a higher temperature, but 37 °C is likely sufficiently high forpipelines in a shallow
seabed in a hot climate. This means increased SRB growth with increasing
temperature is generally expected in practical situations. It should be pointed
out that planktonic cell counts may be used to help indicate the sessile cell
health in laboratory tests, but the planktonic cell counts should not be used
to correlate with sessile cell counts.
Microbial Growth
No microbial growth was detected after one month and six months in vials
containing untreated GoM seawater. After cleaning with Clark's solution, SEM
images showed roughness on the entire surface of a coupon
with one-month exposure to the seawater in a vial at 37 °C, and also of a
coupon with six-month exposure at 25 °C. Due to lack of microbial activities
and a hydrogen sulfide (H,S) smell at the end of the test, the roughness was
likely not caused by SRB. Similar roughness was also observed in tests using
heat-sterilized GoM seawater.
Quarrayah Seawater
The Qurrayah seawater from the Persian Gulf is much saltier than the GoM
seawater. Inhouse quantitative PCR analysis did not detect
SRB in the Qurrayah seawater. a mineral
layer covered the coupon surface after a three-month exposure at 37 °C. scattered pits after the coupon surfaces were cleaned. They
were likely due to factors such as a trace amount of oxygen leaking through the
capped rubber septum rather than microbial activities. Oxygen leakage was not a
problem, however, in the tests for vials that were a few weeks long. Some
threemonth vials were discarded in tests because of visible oxygen rust. A wax
seal around the aluminum cap was subsequently used but it did not completely
eliminate oxygen egress. An anaerobic chamber would be the last solution other
than using an oxygen scavenger to prevent oxygen egress in long-term tests.
The EDS analysis of the surface indicates the absence of the
sulfur element, which means that SRB activity was likely absent.
Due to the lack of native viable microbes and the lack of nutrients, no MIC
pitting was observed in untreated seawater samples. To simulate a
contaminated hydrotest fluid and to speed up laboratory
testing, worst-case scenario tests were carried out by enriching seawater
samples and spiking them with the laboratory SRB strain. SEM image of the biofilm on a one-week old coupon. Kidney
bean-shaped SRB cells are clearly visible. Pits characteristic of MIC attack
were revealed after acid cleaning of the coupon surface.
Kinetics-Based Mechanistic Model
Recently, Gu, et al.'3 introduced an electrochemical kinetics-based
mechanistic model for MIC using a new biocatalytic cathodic sulfate reduction
(BCSR) theory. It assumes that a corrosive SRB biofilm is present on an iron surface,
causing the following reactions to go forward due to biocatalysis:
Anodic: 4Fe -» 4Fe2* + 8e (iron oxidation) (1)
(ProQuest: ... denotes formulae omitted.)(2)
By using charge transfer and mass transfer theories and electrochemical
kinetics, a mechanistic model was developed and solved numerically.14 The
software based on the model is known as MICORP. It incorporates
BCSR, proton reduction, and organic acid reduction to account for low pH at a
pit bottom due to organic acids. Figure 4 shows the model prediction and
experimental data obtained in this work. The model was calibrated with a single
pit depth data to predict long-term pitting.
Tetrakis hydroxymetliyl
phosphonium sulfate (THPS) is a biodegradable biocide that is most often
proposed forhydrotest fluid treatment. A minimum dosage is needed to prevent biofilm
establishment. Tests were carried out in anaerobic vials to evaluate the THPS
degradation profiles in artificial seawater, GoM seawater, and Qurrayah
seawater. A mechanistic model of THPS degradation under alkaline pH was
obtained and reported elsewhere.
Sumber : Zhao, Kaili; Gu, Tingyue; Cruz, Ivan; Kopliku, Ardjan. "Investigation of Microbiologically Influenced Corrosion in Pipeline Hydrotesting Using Seawater". 27 Januari 2014. http://search.proquest.com/docview/1355867605?accountid=31562
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