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The Biocidal Efficacy of Chlorine

Dioxide (ClO2) in the Control of Oil Field
Reservoir Souring and Bio-corrosion in
the Oil and Gas Industries
a
C. C. Okoro
a
Petroleum Microbiology Research Unit, Department of Biology,
Microbiology and Biotechnology, Federal University, Ndufu Alike-
Ikwo, Ebonyi State, Nigeria
Published online: 20 Dec 2014.

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To cite this article: C. C. Okoro (2015) The Biocidal Efficacy of Chlorine Dioxide (ClO2) in the Control
of Oil Field Reservoir Souring and Bio-corrosion in the Oil and Gas Industries, Petroleum Science and
Technology, 33:2, 170-177, DOI: 10.1080/10916466.2014.908913

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 Petroleum Science and Technology, 33:170177, 2015
Copyright 
C Taylor & Francis Group, LLC
ISSN: 1091-6466 print / 1532-2459 online
DOI: 10.1080/10916466.2014.908913

The Biocidal Efficacy of Chlorine Dioxide (ClO2 ) in the

Control of Oil Field Reservoir Souring and Bio-corrosion in
the Oil and Gas Industries
C. C. Okoro1
1
Petroleum Microbiology Research Unit, Department of Biology, Microbiology and Biotechnology,
Downloaded by [Chuma Okoro] at 22:03 23 December 2014

Federal University, Ndufu Alike-Ikwo, Ebonyi State, Nigeria

The efficacy of chlorine dioxide (ClO2 ) as an oil field biocide was determined by direct MPN counts
of SRB and APB after incubation at various concentrations of ClO2 for 14 days in produced and
injection water samples and also by monitoring its inhibitory effects on functional group activities of
some microorganisms. ClO2 was effective in inhibiting the ability of SRB to reduce sulfate to sulfide at
relatively high concentrations (0.7 and 1.0 mg/L). It was also observed that ClO2 did not considerably
inhibit the activities of so-NRB as was the case with SRBs and hNRBs but rather facilitated sulfide
oxidation.

Keywords: APB, ClO2 , soNRB, SRB, Sulfide oxidation

1. INTRODUCTION

Chlorine dioxide is a gas produced by activating sodium chlorite with an oxidizing agent or acid
source (Nelson, 1982). Sodium chlorite is converted to chlorine dioxide through a chlorine dioxide
generator and applied as dilute solutions in liquefied form (Nelson, 1982; Simson et al., 1993).
Chlorine dioxide is an efficient biocide and can be applied either continuously or intermittently
depending on the degree of contamination (GlobalEX, 2010). The range is usually 0.11.0 mg/L
for continuous doses and 0.15 mg/L for intermittent doses and the minimum acceptable residual
concentration is 0.1 mg/L (Simson et al., 1993; GlobeEX, 2010).
Chlorine dioxide is a very efficient biocide and can be used to remove organic materials, biomass,
and iron sulfide deposits from a system (Romaire et al., 1996). Its advantages over other oxidizing
agents such as chlorine, bromine, and ozone are that it is effective at a wider pH range, does not
react with organic matter and ammonia, and is effective at relatively lower concentrations (Nelson,
1982; Mayack et al., 1984; Sadip et al., 2004).
Oil field reservoir souring is the undesirable production of hydrogen sulfide (H2 S) in oil reservoirs
by sulfate reducing bacteria (SRB; Voordouw, 2008). This is a common problem during secondary
oil recovery when sea water is injected to produce the remaining oil in the reservoir. SRB reduce
sulfate in the injection water to sulfide, while oxidizing degradable organic electron donors present
in the oil reservoir (Voordouw, 2008, 2011). The production of sulfide by SRB in the oil and gas
fields causes other problems like corrosion, reservoir plugging, deterioration of product quality and

Address correspondence to C. C. Okoro, Petroleum Microbiology Research Unit, Department of Biology, Microbiology
and Biotechnology, Federal University, Ndufu Alike-Ikwo, Ebonyi State, Nigeria. E-mail: Chuma2k2001@yahoo.com

170
 BIOCIDAL EFFICACY OF CLO2 171

decrease in the permeability of fine pores of underground petroleum reservoirs which impedes the
secondary recovery of petroleum by water injection (Vance and Trasher, 2005; Voordouw, 2008).
Apart from souring, SRB are also the primary cause of microbially influenced corrosion (MIC).
Chlorine dioxide effectively kills SRB and oxidizes the H2 S they produce, reducing the sour in the
formation water, which further reduces corrosion rates (Mayack et al., 1984).
A clear understanding of the activities of the three main microbial functional groups that play
active roles in oil fields such as the ability to reduce sulfate by SRB, reduce nitrate by heterotrophic
nitrate reducing bacteria (hNRB), and oxidize sulfide and reduce nitrate by sulfide oxidizing, nitrate
reducing bacteria (so-NRB) is important in the control of microbial induced problems in oil fields
such as corrosion, souring and fouling. SRB for instance can initiate an incomplete oxidation of oil
organics to acetate and carbon dioxide or complete oxidation of acetate to carbon dioxide and the
reduction of sulfate to sulfide. hNRB can initiate the incomplete oxidation of oil organics to acetate
or carbon dioxide and reduction of nitrate to nitrite and then to either nitrogen or ammonia while
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so-NRB oxidizes sulfide to sulfate or sulfur with nitrate being reduced to nitrite and then to either
nitrogen (with NO and N2 O) as intermediates or ammonia without intermediates (Voordouw, 2008).
The implication of this is that while SRB is problem causing, hNRB and so-NRB are beneficial to
the environment.
Nitrite, which is a product of nitrate reduction by hNRB and the so-NRB, is a powerful SRB
inhibitor and nitrite has worked efficiently with some biocides to inhibit SRB (Voordouw, 2008).
Nitrate can also inhibit SRB activities by stimulation of hNRB (competitive exclusion). Recently,
it has been discovered that so-NRB can be used to control souring by its ability to oxidize sulfide
(lowering sulfide levels) and reduce nitrate to nitrite which further inhibit SRB (Greene et al., 2006;
Voordouw, 2008).
The main objective of the present contribution therefore is to determine the biocidal efficacy of
chlorine dioxide in the control of souring and bio-corrosion using its inhibitory actions on some
microbial functional group activities as an index for efficiency.

2. MATERIALS AND METHODS

2.1 Sample Collection

Sample of chlorine dioxide in liquid form was obtained from Microcheck Nigeria Limited while the
injection and produced water samples were collected from Chevrons Escravos facility, Nigeria.

2.2 Most Probable Number Measurement

To quantify the presence of SRB and acid producing bacteria in the samples, the API RP-38 broth
medium (SRB) and ZPRA-5 medium (APB) were used as previously described (Okoro et al., 2013).

2.3 Physicochemical Analysis of Samples

Sulfate ion (SO4 2) was analyzed with high-performance liquid chromatography (HPLC) as de-
scribed by Eaton et al. (1995). Dissolved sulfide was determined using the diamine method (Truper
and Schlegel, 1964). NH4 + measurement was done using the indole-phenol method while NO3 ,
NO2 , and organic acids such as acetate, propionate and butyrate were analyzed using HPLC as
described in the Standard Methods of Eaton et al. (1995). Salinity was measured as Chloride as
 172 C. C. OKORO

TABLE 1
Composition of Biocide Activity Test Protocol

UPW UIW

Sample Volume in 80 mL serum 25 25

bottle (mL)
SRB LS
Lactate (mM) 40 40
SO4 2(mM) 20 20
SRB VS
VFA (mM) 3 3
SO4 2 (mM) 20 20
hNRB
VFA (mM) 3 3
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NO3 (mM) 10 10
So-NRB
HS (mM) 5 5
NO3 (mM) 10 10
Biocide
Conc., mg/L 0, 0.3, 0.5, 0.7, 1 0, 0.3, 0.5, 0.7,1
Days monitored 0, 1, 4, 7, 10, 14 0, 1, 4, 7, 10, 14

UPW = untreated produced water; UIW = untreated injection water; VFA = volatile fatty acids.

described in the Standard Methods of Eaton et al. (1995), while temperature, pH, and conductivity
were measured with Orion Temp, pH, and conductivity meters, respectively.

2.4 Microbiological Assay

The medium that was used for the microbiological assay was Coleville synthetic brine (CSB-K)
with composition in (g/L); NaCl (1.50), CaCl2 2H2 O (0.21), MgCl2 5H2 O (0.54), NH4 Cl (0.30),
KCl (0.10), KH2 PO4 (0.05), and resazurin (1%) 23 drops as previously described (Hubert and
Voordouw, 2007).

2.5 Components Added to CSB-K for Specific Microbiological Tests

The following electron donors and acceptors were added to the CSB-K medium in serum bottles to
determine the functional group activity of major bacterial groups as indicated in Table 1.

3. RESULTS

3.1 Microbiological and Chemical Constituents of Untreated Produced and Injection

Water Samples Used in the Study

Both samples (untreated injection and produced water) recorded relatively high concentrations of
SRB (106 and 105 cells/mL, respectively) and APB (107 and 105 cells/mL, respectively). There were
also considerable presence of hNRB and so-NRB in both samples. Comparatively, sulfate was higher
 BIOCIDAL EFFICACY OF CLO2 173

TABLE 2
Microbiological and Chemical Constituents of Untreated Produced and Injection
Water Used in the Study

Parameters measured Untreated Produced Water (UPW) Untreated Injection Water (UIW)

SRB (per mL) 106 105

APB (per mL) 107 105
hNRB + +
so-NRB + +
pH 7.1 6.2
HS (mM) 0 0
SO4 2 (mM) 11.50 28.50
NH4 + (mM) 1.40 0.56
NO3 (mM) 0 0
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NO2 (mM) 0 0
Acetate (mM) 4.50 0
Propionate (mM) 1.40 0
Butyrate (mM) 0 0
Salinity (mg/L) 5408 16025
Electrical conductivity, Ohms 18.70 26.50

in injection water (28.50 mM) than in produced water (11.50 mM), while ammonia was higher in
produced water (1.40 mM) than in injection water (0.56 mM) as shown in Table 2.

3.2 MPN Counts of SRB and APB in Untreated Produced and Injection Water Samples
After 2 Weeks of Incubation With Different Concentrations of Chlorine Dioxide

Injection and produced water samples used in the study recorded relatively high concentrations of
SRB and APB which ranged between 105 and 106 cells/mL (SRB) and 107108 cells/mL (APB). A
total inhibition of SRB growth was observed at 0.7 mg/L (ClO2 ) in produced water while injection
water recorded total SRB inhibition at 0.5 mg/L (ClO2 ). APB concentrations were totally inhibited
at 1.0 mg/L (ClO2 ) in produced water and 0.7 mg/L (ClO2 ) in injection water as shown in Table 3.

3.3 Microbial Activities in Untreated Produced and Injection Water Samples Incubated
With Various Concentrations of Chlorine Dioxide

Chlorine dioxide recorded considerable inhibition of sulfate reduction in both lactate and VFA media
at higher biocide concentrations (0.5, 0.7, and 1.0 mg/L). Similar results were obtained with nitrate
reduction but the reverse was the case with sulfide oxidation. The higher the biocide concentration
is, the higher the rate of sulfide oxidation is. It was also observed that chlorine dioxide did not
considerably inhibit the growth of so-NRBs but rather facilitated the rate of sulfide oxidation.
Similarly, the rate of nitrate reduction by the so-NRBs was not considerably affected as shown in
Figure 1.
As with produced water, chlorine dioxide was only effective in the inhibition of sulfate reduction
rate at higher concentrations (0.5, 0.7, and 1.0 mg/L) in both lactate and VFA media but the rate of
inhibition was higher in the injection seawater. Similar trend was observed with nitrate reduction
by the hNRB. It was also observed as in produced water that chlorine dioxide did not considerably
inhibit the growth of so-NRB but rather facilitated the rate of sulfide oxidation as shown in Figure 2.
 174 C. C. OKORO
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FIGURE 1 Microbial activities in untreated produced water incubated with various concentrations of chlorine
dioxide (mg/L).
 BIOCIDAL EFFICACY OF CLO2 175
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FIGURE 2 Microbial activities in untreated injection water incubated with various concentrations of chlorine
dioxide (mg/L).
 176 C. C. OKORO

TABLE 3
Most Probable Number (MPN) Counts of Sulfate Reducing Bacteria (SRB) and Acid
Producing Bacteria in Produced and Injection Water Samples After Two Weeks of Incubation
With Different Concentrations Chlorine Dioxide

ClO2 Conc. (mg/L) SRB, mL APB, mL

Produced water
0 105 107
0.3 104 105
0.5 101 102
0.7 100 101
1 100 100
Injection water
0 106 108
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0.3 102 104

0.5 100 101
0.7 100 100
1 100 100

4. DISCUSSION

Direct MPN counts on samples showed that total inhibition of SRB with chlorine dioxide in injection
water was possible at a concentration of 0.5 mg/L while that of produced water was at a concentration
of 0.7 mg/L. APB on the contrary, required a much higher concentration of the biocide for its total
inhibition (0.7 mg/L in injection water and 1 mg/L in produced water). With this observation, the
universal application of chlorine dioxide at a continuous concentration dose range of 0.11.0 mg/L
or intermittent dose range of 0.15.0 mg/L will still be effective in controlling SRBs and APBs in
oil field environments. GlobeEX (2010) demonstrated that chlorine dioxide was very effective at a
continuous application of 0.5 mg/L in the control of sulfide plugging in the near-wellbore area by
completely dissolving iron sulfide and converting it to water soluble iron sulfate. Chlorine dioxide
according to GlobalEX (2010) also inactivated the SRBs present in the near-wellbore area thereby
preventing the formation of iron sulfide deposits that impede well performance.
Chlorine dioxide has also been reported to be effective at a concentration of 0.5 mg/L (continuous
application) in the control of biofouling in an electron donor delivery well over a period of six
months (Geosynthetic, 2003). It has also been shown to remove biofilm in very difficult systems
when applied intermittently at 0.61.0 mg/L based on the recirculation rate (Mayack et al., 1984).
GlobalEX has successfully used chlorine dioxide to treat offshore oil producing well that generated
160 ppm of hydrogen sulfide in gas phase and 5 ppm of soluble sulfide in water phase with active
SRB growth throughout the field. After 6 months of continuous application of 0.6 mg/L of chlorine
dioxide, sulfide levels were considerably oxidized to less than 2 ppm in gas phase.
In the present study, the ability of SRB to reduce sulfate to sulfide was considerably inhibited by
chlorine dioxide at higher concentrations. At 0.7 mg/L, about 5% of the original sulfate concentration
was reduced while 1.0 mg/L concentration recorded 2% reduction. Similar trend followed with nitrate
reduction but the reverse was the case with sulfide oxidation by the so-NRB. It was observed that the
higher the biocide concentration, the higher the rate of sulfide oxidation. It was also observed that
chlorine dioxide did not considerably inhibit the growth of so-NRBs but rather facilitated sulfide
oxidation. Generally, biocide inhibition rate was higher in injection than in produced water. From
these findings, I observed that since chlorine dioxide oxidizes sulfide and so-NRB also oxidizes
sulfide, the rate of sulfide oxidation is expected to be higher when both chlorine dioxide and so-NRB
are present. Recently, it has been discovered that so-NRB can be used to control souring by its
 BIOCIDAL EFFICACY OF CLO2 177

ability to oxidize sulfide (lowering sulfide levels) and reduce nitrate to nitrite which further inhibit
SRB (Greene et al., 2003; Voordouw, 2008). Naturally, so-NRB and hNRB are very useful for the
control of souring and corrosion and any biocide that does not inhibit their activities considerably
in a selective pattern will be the ideal biocide for the future.

5. CONCLUSION

The findings shows that chlorine dioxide is effective in inhibiting the ability of SRB to reduce
sulfate to sulfide at higher concentrations (0.7 and 1.0 mg/L), but with the presence of so-NRB,
sulfide concentration was considerably reduced and nitrate was reduced to nitrite which further
inhibits SRB growth. Further research is required to see how chlorine dioxide can be effective at
lower concentrations and work in synergy with some metabolic inhibitors such as nitrite to make its
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application cost effective.

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