J179614 DOI: 10.
2118/179614-PA Date: 21-March-17 Stage: Page: 438
Polymer Flooding: Establishing
Specifications for Dissolved Oxygen
and Iron in Injection Water
S. Jouenne, A. Klimenko, and D. Levitt, Total E&P
Summary
It is now common knowledge among enhanced-oil-recovery
(EOR) practitioners that the combination of ferrous iron (Fe2þ)
and dissolved oxygen (O2) causes severe oxidative degradation
to EOR polymers, resulting in a lowering of molecular weight
(MW) and hence, a loss of viscosity. During the design of
polymer-flooding projects, an important question is thus the
acceptable levels of Fe2þ and O2 that can be tolerated in injec-
tion-water specifications. Furthermore, we would like to be able
to predict the extent of degradation in the case of excess Fe2þor
oxygen ingress.
However, despite more than 50 years of research and a general
understanding of the degradation mechanism involved, quantita-
tive prediction of the extent of degradation has proved elusive and
dependent on the measurement protocol. This is likely because of
the fastidious experimental protocols required to work under an-
aerobic or limited-oxygen conditions.
We examine existing protocols and demonstrate that experi-
ments in which either Fe2þ or O2 is the limiting reagent yield
equivalent results when the stoichiometry of the Fe2þ autoxida-
tion reaction with oxygen is taken into account. On the basis
of these findings, a novel, easy approach is proposed to quantify
polymer-oxidative degradation as a function of either O2 or
Fe2þ content.
The limits of 225 ppb Fe2þ and 32 ppb of O2 are fixed for Flo-
paam 3630S in 6 g/L brine in the concentration range
500–1,500 ppm to ensure that degradation of low-shear plateau
viscosity does not exceed 10%. Higher levels will lead to severe
polymer degradation. The influence of polymer concentration,
temperature, and salinity is also investigated. At last, evolution of
redox potential and pH during Fe2þ oxidation is discussed along
with the injectivity risk associated with the formation of Fe3þ.
There is a direct practical application of these findings for the
design of surface facilities for polymer dissolution and transport
and for the prediction of degradation in case of oxygen ingress.
Moreover, a simple and easily performed protocol is proposed for
the evaluation of polymer oxidative degradation for any given
field conditions.
Introduction
Chemical, thermal, and oxidative degradation of hydrolyzed poly-
acrylamides (HPAMs) and biopolymers such as xanthan has been
extensively studied over the years (studies are reviewed in Sorbie
1991; Tolstikh et al. 1992; Levitt and Pope 2008; Seright et al.
2010; Levitt et al. 2011; Seright and Skjevrak 2015). Early, it was
well-known that oxidation of iron II (Fe2þ) in the presence of O2
leads to a severe and rapid viscosity loss corresponding to a
decrease of the polymer MW. In the presence of O2, polymer-
chain scission would result from the attack of the polymer back-
bone (hydrogen abstraction) by hydroxyl radical HO (Gröllmann
and Schnabel 1982; Ramsden and McKay 1986a, b) and a subse-
quent b scission (Al-Malaika 2003; Billingham 2008). In their
Copyright V
C 2017 Society of Petroleum Engineers
This paper (SPE 179614) was accepted for presentation at the SPE Improved Oil Recovery
Conference, Tulsa, 11–13 April 2016, and revised for publication. Original manuscript
received for review 4 May 2016. Revised manuscript received for review 29 June 2016.
Paper peer approved 11 July 2016.
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experiences, Gröllmann and Schnabel found that only a small
fraction (1%) of the attacking HO initiated chain scission.
Fe2þ autoxidation by O2 is known as an important route to
free-radical oxidation of biological systems. In the biology and
medicine community, the exact nature of the initiator that triggers
oxidative reaction is debated; Fe-O complexes have been pro-
posed as alternating species to HO (Halliwell and Gutteridge
1992; Qian and Buettner 1999). Oxidative degradation of HPAM
by Fe2þ/O2 is at the crossroad of two very complex domains—
iron chemistry and polymer oxidation. The detailed mechanisms
at the origin of chain scission are beyond the scope of this paper.
In studies on Fe2þ autoxidation, the rate and the stoichiometry of
Fe2þ autoxidation were found to be dependent on the pH and the
presence of iron chelatants (Ramsden and McKay 1986b; Welch
et al. 2002). What about the influence of the polymer on this stoi-
chiometry? In a recent paper, Seright and Skjevrak (2015) pre-
sented a detailed study about the kinetics and the stability of
HPAM in the presence of controlled levels of O2 and Fe2þ. They
observed that degradation can depend on the ratio [O2]/[Fe2þ].
This result would imply that polymer degradation does not follow
the stoichiometry of the Fe2þ autoxidation reaction (1 mole O2
reacts with 4 moles Fe2þ).
In the presence of only one of the two components, O2 or
Fe2þ, results were debated. It is indeed necessary to have one oxi-
dant and one reducer for the oxydo-reduction reaction to occur. In
the absence of Fe2þ, degradation of solutions containing O2 is
attributed to the presence of metallic impurities and/or reducing
substances in the polymer that react with oxygen. Elimination of
these impurities by purification through polymer precipitation in
methanol resulted in the absence of degradation (Muller 1981;
Kheradmand et al. 1988). In the absence of oxygen, Kheradmand
(1988) reported degradation in the presence of dissolved Fe2þ.
This result was quite contradictory with former results that were
not showing any degradation (Shupe 1981; Yang and Treiber
1985; Ramsden and McKay 1986a). Degradation was attributed
to the presence of hydroperoxides on the polymer chains that
would behave as oxidant. However, some oxygen leaks during
these experiments or the specificity of the studied polymer
(obtained by photopolymerization) could also reunify them.
Indeed, recent studies indicate that degradation does not occur in
the presence of Fe2þ (Levitt et al. 2011; Seright and Skjevrak
2015) provided that O2 stays at a very low level (ppb).
Working with very-low oxygen levels or dealing with Fe2þ
salt that immediately oxidizes in Fe3þ at the contact of oxygen is
very tedious and time-consuming. For all the studies on oxidative
degradation, different experimental protocols were tested to
remove the oxygen during preparation of the solution and to pre-
vent it from subsequent oxygen ingress. Initial deoxygenation was
generally fulfilled with sealed-glass ampoules following succes-
sive nitrogen bubbling/vacuum cycles or by preparing the solution
in a glove box with controlled anaerobic atmosphere.
In a case in which a control of the O2 level is targeted, the
number of nitrogen bubbling/vacuum cycles can be adjusted, bub-
bling can be performed with a mix of gases (Gaillard et al. 2010),
and the deoxygenated solution can be mixed with a completely
aerated solution (Seright and Skjevrak 2015). For these experi-
ments, measurement of the O2 level can be problematic along
with the choice of the aging container (Shupe 1981; Audibert and
April 2017 SPE Journal
 J179614 DOI: 10.2118/179614-PA Date: 21-March-17
Lecourtier 1992). Indeed, one must ensure that the container is
not very permeable to oxygen or does not contain initially some
adsorbed oxygen on the walls. Moreover, when aged in tempera-
ture, sealing problems and leaks frequently occur. In addition,
when a gas cap exists on top of the solution, O2 is always in equi-
librium with the gas cap following Henry’s law. Thus, when oxy-
gen is consumed in solution, there is an intake caused by the
exchange with the gas cap (Seright and Skjevrak 2015). In such
experiments, O2 concentration is thus varying with time, and
kinetics is modified.
In addition, dealing with Fe2þ complicates the protocol
because the Fe2þ salt (e.g., FeCl2) must be added in a deoxygen-
ated polymer solution without bringing any oxygen that would
contaminate the solution and oxidize immediately one part of
the added Fe2þ. For experiments at controlled oxygen levels, a
deoxygenated polymer/Fe2þ solution is first prepared. The oxygen
level is then adjusted by bubbling with air or adding
aerated water. We can anticipate an oxidation of Fe2þ during this
adjustment if the oxidation rate is high.
Scope of This Study
Most of the previous studies on HPAM or biopolymer oxidative
degradation were performed at controlled oxygen levels and gave
rise to numerous experimental problems and challenges.
On the basis of the observations that polymer degradation
stops when O2 is completely consumed and Fe2þ does not play
the role of a catalyst in Fe2þ autoxidation (Fe2þ is consumed and
not regenerated), we search for a stoichiometric relation between
the quantities of Fe2þ oxidized and O2 consumed during polymer
degradation. If such a relation exists and is not dependent on the
ratio [Fe2þ]/[O2], performing degradation experiments at con-
trolled O2 or Fe2þ levels should give the same results. In this pa-
per, we present an easy and fast protocol to measure oxidative
degradation of polymers. With this protocol, which is based on
the stoichiometry of Fe2þ autoxidation reaction, the curves degra-
dation vs. [O2]ini and degradation vs. [Fe2þ]ini are easily obtained.
These results have a direct practical application for:
• Defining the maximum allowable level of O2 at the injec-
tion. Indeed, in a case in which injection water contains
some Fe2þ or because of the rusting process of the injection
pipe or well, oxidative degradation will be experienced
quickly by the polymer.
• Predicting polymer degradation in case of oxygen ingress
during polymer-solution transportation.
• Predicting the maximal polymer degradation during a core-
flood with a reduced core containing iron oxides.
In a second time, an attempt is made to follow the consump-
tion of Fe2þ during its oxidation by manipulating Nernst equa-
tions related to iron-species equilibriums and pH.
At last, the injectivity risk associated with the formation of
Fe3þ is briefly evaluated and discussed.
Experimental
Flopaam 3630S (SNF Floerger, Andrezieux, France), an HPAM
with 30% hydrolysis, MW ¼ 18 MDa in powder form, was used
for all the experiments. It was dissolved in anaerobic synthetic
brine at 6 g/L (4.7 g/L NaCl, 0.75 g/L CaCl2, 2H2O, 0.56 g/L
MgCl2, 6H2O). A source polymer solution at 5,000 ppm was first
prepared by stirring the solution for 2 hours with a mechanical
stirrer. This solution was then diluted in a beaker by gentle stir-
ring with a magnetic stirrer.
Dissolution was performed in a glove box (Jacomex) with a
controlled atmosphere exempted from oxygen traces. Water-based
polymer solutions in equilibrium with the glove-box atmosphere
were presenting a O2 content lesser than 1 ppb (detection limit of
the more-sensitive oxygen probe). Two oxygen probes were used
inside the glove box: a polarographic probe Inpro 6950i from
Mettler Toledo (detection limit ¼ 6 ppb) and an optical probe
(Fibox 3 LCD trace v7/Minisensor Trace Oxygen Meter) based on
fluorescence decay from Presens (detection limit ¼ 1 ppb). In
such an environment, Fe2þ salts such as FeCl2 can be easily
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handled and dissolved in water without the instantaneous oxida-
tion experienced when contacting the atmosphere out of the
glove box.
O2 concentration in solution during Fe2þ oxidation was meas-
ured with noninvasive optical oxygen sensors from Presens. A
sensor spot was stuck on the inner surface of the flask. O2 concen-
tration was then measured from outside, through the transparent
glass wall of the flask.
Viscosity measurements were performed on a ProRheo low-
shear LS300 rheometer in the shear-rate range 0.03–94 s1. With
this very-sensitive rheometer, it was possible to determine accu-
rately the low-shear Newtonian viscosity.
The pH and redox potential measurements were performed
with a probe 4800i/SG/120 from Mettler Toledo.
Iron titrations ([Fe2þ], [Fe3þ], Fetot]) were performed with
Hach Lange reactive test kits LCK 320 on a Hach Lange DR2800
UV spectrophotometer. In this method, a red-orange complex is
formed between Fe2þ and 1,10-phenantroline. Fe3þ is then
reduced as Fe2þ.
Two different protocols were tested to evaluate the polymer
degradation with various levels of O2 and Fe2þ.
Protocol 1: Very Fastidious.
• Preparation of a polymer solution at the desired polymer
concentration in the glove box in complete anaerobic condi-
tion ([O2] ¼ 0 ppb).
• Viscosity measurement g0 on one part of the solution at am-
bient temperature (25 C) with a low-shear rheometer out of
the glove box.
• For the solution still in the glove box, bubbling of the solu-
tion with air to adjust the initial O2 level ([O2]ini). O2 con-
centration measurement ([O2]) is made through the wall of
the flask with a sensor spot.
• Addition of a small volume of FeCl2 source solution to
reach the desired Fe2þconcentration ([Fe2þ]ini).
• Closure of the flask without letting any gas cap. Caps were
in polytetrafluoroethylene-coated with silicone seal.
• Follow-up with time of the O2 content ([O2]t) by noninva-
sive measurement with the sensor spot.
• After some days, concentration measurement of O2 ([O2]t)
and Fe2þ ([Fe2þ]t).
• Viscosity measurement gdeg out of the glove box on the low-
shear rheometer under nitrogen blanketing to prevent the so-
lution from additional oxidative degradation.
Protocol 2: Very Easy.
• Preparation of a polymer solution at the desired polymer
concentration in the glove box in complete anaerobic condi-
tion ([O2] ¼ 0 ppb).
• Viscosity measurement g0 on one part of the solution at am-
bient temperature (25 C) with a low-shear rheometer out of
the glove box.
• For the solution still in the glove box, addition of a small
volume of FeCl2 source solution to reach the desired
Fe2þconcentration ([Fe2þ]ini).
• Complete oxidation of the solution in a beaker at the exterior
of the glove box by letting the flask be opened to the
atmosphere.
• After 7 days, measurement of viscosity gdeg at ambient tem-
perature and Fe2þconcentration ([Fe2þ]t).
The retention of viscosity is calculated according to the
formula
gdeg  gH2 O
Viscosity retention ð%Þ ¼  100; . . . . . . . . ð1Þ
g0  gH2 O
where g0 is the viscosity of the nondegraded solution, gdeg is the
viscosity of the degraded solution, and gH2 O is the water viscosity
(0.9 cp at 23 C). Because polymer solutions are non-Newtonian,
the value of the viscosity retention depends on the shear rate at
which viscosity is measured.
439
 J179614 DOI: 10.2118/179614-PA Date: 21-March-17
10000
O2 in excess
Initial O2 Concentration (ppb) Fe2+ in excess
Stoechiometry
O2 Concentration (ppb)
1000
100
10
1 1
1 10 100 1000 10000 100000
Initial Fe2+ Concentration (ppb)
Fig. 1—Protocol 1 results. Initial O2 vs. initial Fe21 concentrations of 800 ppm polymer solutions prepared in a glove box according
to Protocol 1 (left). Evolution of O2 concentration vs. time in closed flasks at rest in the anaerobic atmosphere of the glove box.
Results: Comparison of Protocols 1 and 2
Protocol 1: Investigation of O2 and Fe21 Consumptions
During Oxidative Degradation of HPAM. Reviewing radical-
degradation mechanisms of HPAM, Levitt et al. (2011) described
the mechanism of redox cycling that could promote the formation
of additional hydroxyl radicals HO by reducing oxidized Fe3þ.
This redox cycling is well-known in microbial and metabolic
reactions and photo-oxidation of dissolved organic matter
(Voelker et al. 1997). However, the development of our new pro-
tocol is based on the assumption that oxidation of Fe2þ by O2 is
total (Fe2þ is totally oxidized when O2 is in excess or inversely,
O2 is totally consumed when Fe2þ is in excess) and not cycled (no
reduction of Fe3þ during the oxidation). Recent results of Seright
and Skjevrak (2015) along with former results of Ramsden and
McKay (1986b) and Shupe (1981) are in-line with this assump-
tion. Indeed, for samples that did not gel, they did not observe any
viscosity loss when preparing polymer solutions with Fe3þ only
in the presence of oxygen. The absence of degradation is the indi-
cation that Fe3þ is not reduced to Fe2þ because degradation would
be observed if Fe2þ was present with oxygen.
The idea behind our protocol is to consider that polymer deg-
radation is a function of the limiting-reactant quantity in the oxi-
dation of Fe2þ by O2. The limiting reactant is determined
according to the stoichiometry of the oxidation reaction:
Fe2þ þ [1/4] O2 þ Hþ ! Fe3þ þ [1/2] H2O. It gives the following
stoichiometry: 1 mole dissolved O2 reacts with 4 moles Fe2þ
equivalent to 1 ppm O2 reacts with 7 ppm Fe2þ (7 is coming
from 4  MFe/MO2 ¼ 4  55.85/32 ¼ 7). From then on, degrada-
tion results should be the same when performing tests at con-
trolled levels of oxygen or, inversely, when performing tests at
controlled levels of Fe2þ.
As a first step to demonstrate the validity of these assumptions,
polymer solutions at 800 ppm containing various levels of Fe2þ
and dissolved oxygen (10 < [Fe2þ]ini < 46,000 ppb and
5 < [O2]ini < 940 ppb) were prepared with one of the two reactants
in excess. Oxidation was proceeding in closed flasks at rest in the
glove box. After some days (between 5 and 56 days), remaining
Fe2þ and O2 concentrations ([Fe2þ]t and [O2]t) along with solu-
tion viscosity were measured. This test is called Protocol 1.
All measuring conditions are summarized in Fig. 1, left. The
black straight line corresponds to stoichiometric conditions, 1 ppb
O2 reacts with 7 ppb Fe2þ. Evolution of O2 concentration with
time for some experiments is plotted in Fig. 1, right.
Two methods are used to evaluate the quantity of Fe2þ oxi-
dized in the closed flask:
• From the O2 measurement with the sensor spot and stoichi-
ometry of the oxidation reaction,
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1000
100 [Fe2+]ini = 0 ppb,
[O2]ini = 940 ppb,
[Fe2+]ini = 1700 ppb,
[O2]ini = 920 ppb,
[Fe2+]ini = 1370 ppb,
10 [O2]ini = 470 ppb"
[Fe2+]ini = 765 ppb,
[O2]ini = 100 ppb
[Fe2+]ini = 175 ppb,
[O2]ini = 30 ppb
1 10 100
Time (days)
[Fe2þ oxidized] ¼ [O2 consumed]  7 ¼ ([O2]ini  [O2]t)  7.
• From Fe2þ titration [Fe2þ oxidized] ¼ [[Fe2þ]ini  [[Fe2þ]t.
Alternatively, the quantity of O2 consumed can be evaluated
as {[O2]ini  [O2]t or ([Fe2þ]ini  [Fe2þ]t)/7}.
The quantity of Fe2þ oxidized evaluated by these two methods
is plotted in Fig. 2, left.
If oxidation follows stoichiometry, all the experimental points
should be on the bissectrice. Only points for which Fe2þ was ini-
tially in excess follow the bissectrice, whereas points for which
O2 was in excess are below. It means that incomplete oxidation of
Fe2þ occurred for the experiments with O2 in excess. When plot-
ting viscosity retention vs. Fe2þ oxidized evaluated from O2 mea-
surement (Fig. 2, right), viscosity retention decreases with the
quantity of Fe2þ oxidized. However, experiments with O2 in
excess are shifted to higher quantities of Fe2þ oxidized. This ob-
servation agrees with our previous conclusion, O2 consumption is
abnormally high for the experiments with O2 in excess (it results
in a overestimation of the quantity of Fe2þ oxidized if calculated
through {[O2]ini  [O2]t)  7}.
When plotting viscosity retention vs. quantity of Fe2þ oxidized
evaluated from Fe2þ titration (left, Fig. 3), the two sets of experi-
ments are on the same curve. Whatever, the limiting reactant, vis-
cosity retention is only a function of the quantity of Fe2þ oxidized.
If these results are compared with previous ones for which the quan-
tity of Fe2þ oxidized was evaluated from O2 measurement, all data
are superimposed except those with O2 in excess. An unclear expla-
nation would consist in arguing that O2 consumption for the oxida-
tion of a given quantity of Fe2þ is a function of the ratio O2/Fe2þ.
A more-convincing explanation comes from the black curve of Fig.
1, right. This black curve represents the evolution of the O2 concen-
tration of an 800-ppm solution in a closed flask with an initial O2
quantity of 940 ppb without Fe2þ. O2 concentration is continuously
decreasing with time, whereas the flask is closed. Seright et al.
(2010) made a similar observation, and presumed this loss occurred
during opening of the flask at the end of the experiment. It could
also be attributed to polymer oxidation, although no degradation
was observed. Because this decrease was also observed on pure
water, we can conclude that oxygen was diffusing through the cap
of the flask into the anaerobic chamber of the glove box. Apparent
consumption of O2 in experiments with O2 in excess was thus not
caused by oxidation of Fe2þ but rather to a leak that depleted the so-
lution in O2. For the experiments with Fe2þ in excess, the leak did
not lead to erroneous results. Fe2þ oxidation is very fast. We can
think that most of the O2 initially present in the tube was initially
consumed by the oxidation reaction. Although these explanations
are plausible, it would have been better and easier to work with caps
that do not leak.
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10000 100

Fe2+ Oxidized From Fe2+ Titration (ppb)

Protocol 1: Fe2+ in excess 90

Viscosity Retention at 8 s–1 (%)

Protocol 1: O2 in excess
80
1000
70 O2 in excess
60 Fe2+ in excess
100 50
40
30
10
20
10
1 0
1 10 100 1000 10000 1 10 100 1000 10000
Fe2+ Oxidized From O2 Measurement (ppb) Fe2+ Oxidized From O2 Measurement (ppb)

Fig. 2—Protocol 1 results. Quantity of Fe21 oxidized evaluated through Fe21 titration vs. that evaluated through O2 measurement
(left). Viscosity retention at 8 s21 of 800 ppm polymer solutions vs. quantity of Fe21 oxidized evaluated through O2-consumption
measurement (right).

From the results obtained with Protocol 1, the following con-
clusions can be drawn:
• Whatever the limiting reactant between O2 and Fe2þ, poly-
mer degradation depends on the quantity of Fe2þ oxidized
or the real O2 consumption. The consumption of both reac-
tants follows the stoichiometry of the oxidation reaction: 1
ppb O2 reacts with 7 ppb Fe2þ.
• Degradation is concomitant with oxidation of Fe2þ. It con-
tinues until the complete consumption of one of the two
reactants.
• In these preliminary experiments, we investigated the con-
centration ranges 10–39,500 ppb for [Fe2þ]ini and 5–940
ppb for [O2]ini. The absolute concentration of both reactants
does not have any influence on the degradation level, neither
does the ratio [O2]ini/[Fe2þ]ini.
Protocol 2: Development of a Simple Protocol To Evaluate
Oxidative Degradation in the Presence of Controlled Levels of
Fe21 and O2. For decades, oxidative degradation has been inves-
tigated through oxygen-controlled experiments and their associ-
ated problems of leaks. On the basis of previous results, it seems
that degradation does not depend on the ratio [Fe2þ]ini/[O2]ini. As
a consequence, similar results should be obtained through Fe2þ-
controlled experiments that are far easier to perform when a glove
box with inert atmosphere is used. To check this assumption, a sec-
ond protocol was tested (Protocol 2). It comprises preparing poly-
mer solution in anaerobic conditions in the glove box, adjusting the
Fe2þ concentration and letting the solution at the atmosphere for
complete oxidation of Fe2þ. Experiments were performed with
Fe2þ concentrations between 5 and 46,000 ppb.
The quantity of Fe2þ oxidized was evaluated through Fe2þ ti-
tration: Fe2þ oxidized ¼ [Fe2þ]ini  [Fe2þ]t. According to the
results of Protocol 1, with the stoichiometry of the oxidation reac-
tion, the quantity of oxidized Fe2þ can be converted into the quan-
tity of O2 consumed: O2 consumed ¼ ([Fe2þ]ini  [Fe2þ]t)/7.
Viscosity retentions obtained with this protocol are plotted on
Fig. 4 as a function of either the Fe2þ oxidized or the O2 consumed.
Results obtained with Protocol 1 are also plotted for comparison.
Results of both protocols superimpose very well, reinforcing
the conclusions drawn from Protocol 1. Moreover, Fe2þ titrations
of experiments performed with Protocol 2 revealed that Fe2þ
oxidation is nearly total after 10 days f([Fe2þ]ini  [Fe2þ]t)/
[Fe2þ]ini > 95%g. Fe2þ titration after oxidation is thus no longer
necessary. We can assume that all Fe2þ is oxidized when the solu-
tion is letting in contact with the atmosphere.
Discussion
Prediction of the Extent of Oxidative Degradation. Curves of
Fig. 4 can be directly applied to predict the level of oxidative deg-
radation on a field or during a coreflood in the laboratory. The

100 100
90 90
Viscosity Retention at 8 s–1 (%)

Viscosity Retention at 8 s–1 (%)

80 80
70 70 O2 in excess, from
O2 in excess Fe2+ titration
60 60
Fe2+ in excess, from
50 Fe2+ in excess 50 Fe2+ titration
40 40 O2 in excess, from
O2 measurement
30 30
Fe2+ in excess, from
20 20 O2 measurement
10 10
0 0
1 10 100 1000 10000 1 10 100 1000 10000
Fe2+ Oxidized From Fe2+ Titration (ppb) Fe2+ Oxidized (ppb)

Fig. 3—Protocol 1 results. Viscosity retention at 8 s21 vs. quantity of Fe21 oxidized when polymer solutions at 800 ppm are oxi-
dized in the presence of varying quantities of Fe21 and O2 according to Protocol 1. Quantity of Fe21 oxidized evaluated through ei-
ther Fe21 titration (left) or both methods (i.e., Fe21 titration and O2-consumption measurements) (right).

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 J179614 DOI: 10.2118/179614-PA Date: 21-March-17
100
Viscosity Retention at 8 s–1 (%)
90
80
70
60
Protocol 1: O2 in
50 excess
40 Protocol 1: Fe2+ in
excess
30
Protocol 2: Oxidation
20
at the atmosphere
10
0 0
1 10 100
Fe2+ Oxidized From Fe2+ Titration (ppb)
Fig. 4—Comparison of results obtained with Protocols 1 and 2. Viscosity retention at 8 s21 quantity of Fe21 oxidized (left) or quan-
tity of O2 consumed (right). Quantity of Fe21 oxidized is evaluated through Fe21 titration (left) and converted in O2 consumption
(right).
concentration of the limiting reactant will determine the extent of
polymer degradation. Levels of Fe2þ and O2 that lead to 90 and
75% viscosity retention are summarized in Table 1. Whatever the
level of Fe2þ, degradation at 8 s1 will be minor (<10%) if the O2
content is inferior to approximately 46 ppb (this value is conserva-
tive because oxygen can be consumed by sources other than Fe2þ
oxidation). The limits of 650 ppb Fe3þ and 93 ppb O2 are fixed for
Flopaam 3630S in 6 g/L brine at 800 ppm to ensure that degrada-
tion of low-shear plateau viscosity (0.2 s1) does not exceed 25%.
In a case in which oxygen ingress occurs in the surface process,
degradation will depend on the relative concentration of Fe2þ and
O2. According to the stoichiometry of Fe2þ autoxidation reaction:
• If [Fe2þ]/[O2]<7 (concentrations in ppm), Fe2þ is the limit-
ing reactant and viscosity loss will be predicted from the
graph on the left of Fig. 4.
• If [Fe2þ]/[O2]>7, O2 is the limiting reactant and viscosity
loss will be predicted from the graph on the right in Fig. 4.
Remark 1. In a case in which a chelatant is present, the curves
of Fig. 4 are no longer valid. It was shown by Ramsden and
McKay (1986b) that iron chelation (EDTA, DTPA) will increase
the rate of Fe2þ oxidation, and will be accompanied by an
increase of the polymer degradation. Moreover, the stoichiometry
is varying from 4:1 to 2:1 (Welch et al. 2002). Hence, the shape
of the curves will vary along with the way to convert the quantity
of Fe2þ oxidized into the quantity of O2 consumed (passage from
left to right graph on Fig. 4). Comments are similar in a case in
which a reducer is present. Ramsden and McKay (1986b) showed
the cyclic process in which ascorbic acid reduces Fe3þ to Fe2þ
that, in turn, oxidizes with O2 to give Fe3þ. In that case, if reducer
is in excess, degradation is controlled by the amount of reducer
and not Fe2þ, which plays the role of catalyst.
Remark 2. Does one radical lead to numerous chain ruptures
through a chain-propagation cycle in which one scission produces
a new radical that will initiate new scissions? For a given quantity
of O2 and Fe2þ, degradation is limited. It tends to prove that deg-
radation is not associated with a propagation process in which one
at 8 s–1
Viscosity retention Fe2+ O2
(%) (ppb) (ppb)
90 320 46
75 1300 186
Table 1—Viscosity retention at 0.2 and 8 s vs. quantities of Fe21
and dissolved O2 that will be consumed through the oxidation
reaction.
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100
Viscosity Retention at 8 s–1 (%)
90
80
70
60
Protocol 1: O2 in
50 excess
40 Protocol 1: Fe2+ in
excess
30
Protocol 2: Oxidation
20
at the atmosphere
10
1000 10000 100000 0.1 1 10 100 1000 10000
O2 Consumed During Fe2+ Oxidation (ppb)
radical would lead to numerous chain ruptures. From our degrada-
tion measurements, the number of O2 molecules consumed for 1
bond scission can be roughly estimated. If we consider a 800-ppm
solution (MW ¼ 20 MDa), a viscosity loss of 50% corresponds
approximately to MW divided by two (MW ¼ 10 MDa) which is
equivalent to 1 scission per chain. This viscosity loss occurs when
500 ppb O2 is consumed. The number of O2 moles consumed per
mole of polymer chain is: (500  109/32) / [1000  106/
(20  106)] ¼ 312. In their experiences, Gröllmann and Schnabel
(1982) found that only a small fraction (1%) of the attacking
HO initiated chain scission. If we consider that each O2 molecule
leads to the formation of one HO radical, 100 O2 molecules
would be necessary to initiate one chain scission. Both figures are
of the same order.
Oxidative Degradation: Sensitivity to Temperature, Salinity,
and Polymer Concentration. The influence of physical-chemistry
parameters such as temperature, salinity, and polymer concentra-
tions was investigated with Protocol 2. Results are plotted in Fig. 5.
Salinity. According to Wellington (1983), a salinity increase
is beneficial to reduce degradation. From our results, degradation
is similar in the range 0.4–35 g/L. We had anticipated some differ-
ences because of the variation of solution viscosity and chain con-
formation that would affect the degradation process by radicals.
More work is needed to draw more-detailed conclusion because
trend is not clear (degradation is slightly higher at 0.4 and 35 g/L
than at 6 g/L), and results are in the uncertainty of the method.
Temperature. Oxidation was proceeding at 50 C at the atmos-
phere, but viscosity measurements were performed at 25 C.
Degradation curves are similar at 25 and 50 C. In general, degra-
dation increases a lot at temperature higher than 90 C. It would
be valuable to perform the oxidation at this temperature to check
if the degradation curve and mechanisms are still similar.
Polymer Concentration. In the concentration range 500–
1,500 ppm, degradation curves are superimposed. We had antici-
pated a higher degradation at lower polymer concentration think-
ing that the number of chain-breaking events would depend on the
quantity of Fe2þ oxidized. In that case, a chain would undergo
at 0.2 s–1 more scission events at decreasing polymer concentration. In light
of our results, viscosity loss is not sensitive to polymer concentra-
Fe2+ O2
tion. This might be explained by the fact that viscosity-loss evolu-
(ppb) (ppb)
tion does not represent the evolution of the number of bond
225 32 scissions. A more-detailed analysis of the evolution of MW distri-
650 93 bution for each concentration, and thus, the number of bond scis-
sions per chain, is needed.
21
From our experiments, neither salinity nor temperature nor
polymer concentration has a significant effect on polymer degra-
dation. However, degradations measured on Fig. 5 are at
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100 100
90 90

Viscosity Retention at 8 s–1 (%)

Viscosity Retention at 8 s–1 (%)

80 80
70 70
60 60
50 50
40 40
Protocol 2: 0.4 g/L, 800 ppm
30 30
Protocol 2: 6 g/L, 800 ppm
20 Protocol 2: 35 g/L, 800 ppm 20 Protocol 2: 23°C, 800 ppm
10 10 Protocol 2: 50°C, 800 ppm

0 0
1 10 100 1000 10000 100000 1 10 100 1000 10000 100000
Fe2+ Oxidized (ppb) Fe2+ Oxidized (ppb)

100
90
Viscosity Retention at 8 s–1 (%)

80
70
60
50
40 Protocol 2: 500ppm, 6g/L
30 Protocol 2: 800ppm, 6g/L
20 Protocol 2: 1500ppm, 6g/L
10
0
1 10 100 1000 10000 100000
Fe2+ Oxidized (ppb)

Fig. 5—Viscosity retention at 8 s21 vs. quantity of Fe21 oxidized. Influence of salinity, temperature, and polymer concentration.

thermodynamic equilibrium. We guess that degradation kinetics oxidized at the atmosphere. The pH, redox potential, and Fe2þ
is different because of concentration were followed during the course of the oxidation, as
• The test protocol. For the experiments at varying salinity plotted in Fig. 6.
and polymer concentration, diffusion of oxygen and, thus, The pH is rapidly falling to approximately 4.9 for the brine,
concentration of O2 will be functions of solution viscosity. whereas it stayed at 6 for the solution-containing polymer. Fe2þ
• The radical reaction rates that might depend on temperature, concentration stays close to the initial concentration for the brine
solution viscosity, and polymer concentration. without polymer, whereas it rapidly falls down to 0 ppm for the
solution containing polymer. Presence of polymer is thus promot-
ing rapid Fe2þ oxidation because of its pH-buffering capacity
Evolution of Redox Potential and pH During Fe21 Autoxi- compared with water.
dation. A brine at 6 g/L and a polymer solution at 1,000 ppm in Thermodynamically, it was calculated (with a geochemistry
the same brine, both containing 20 ppm Fe2þ, were prepared in simulator or by solving the system of redox reactions) that Fe2þ
the glove box in anaerobic conditions. Both solutions were then should be completely consumed for both solutions to produce

20 0.4 20 0.4

15 0.3 15 0.3
[Fe2+] (ppm), pH
[Fe2+] (ppm), pH

[Fe2+] [Fe2+]
Eh (V)

Eh (V)

10 pH 0.2 10 pH 0.2
Eh Eh
5 0.1 5 0.1

0 0 0 0
0 5 10 15 20 25 0 10 20 30 40 50 60 70
Time (hours) Time (hours)

Fig. 6—Evolution of pH, redox potential, and Fe21 concentration vs. time during exposure and stirring at atmosphere (left). Brine at
6 g/L containing initially 20 ppm Fe21 (right). Polymer solution at 1,000 ppm in brine at 6 g/L containing initially 20 ppm Fe21.

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 J179614 DOI: 10.2118/179614-PA Date: 21-March-17
0 ppm
Viscosity (cP)
10 1 ppm
5 ppm
20 ppm
1 0
0.01 0.1 1 10
Shear Rate (s–1)
Fig. 7—(left) Flow curves of polymer solutions at 800 ppm in 6 g/L brine containing different levels of Fe21 (0, 1, 5, and 20 ppm) after
complete oxidation at the atmosphere (right). Filter ratio test on 3-lm Nucleopore filter under 1 bar. Insert is a picture of the film
left on the filter after filtration of the solution containing initially 20 ppm Fe21.
precipitated iron hydroxide Fe(OH)3 following the reaction
Fe2þ þ [1/4] O2 þ 5/2 H2O ! Fe(OH)3 þ 2 Hþ. However, accord-
ing to the literature (Ramsden and McKay 1986a, b; Morgan and
Lahav 2007), the rate of Fe2þ oxidation rapidly falls down when
pH decreases from 7 to 4. Hence, because of the polymer-buffer-
ing effect, oxidation of Fe2þ is much faster in the solution-con-
taining polymer. After one month, it was checked that all Fe2þ
was consumed in the brine with no polymer.
The idea of this experiment was initially to use the evolution
of pH and Eh to follow directly the consumption of Fe2þ without
having recourse to a titration. Indeed, by considering the two reac-
tions Fe2þ þ [1/4] O2 þ Hþ ! Fe3þ þ H2O and Fe2þ þ [1/4]
O2 þ 5/2 H2O ! Fe(OH)3 þ 2 Hþ, it should be possible to calcu-
late Fe2þ, Fe3þ, and Fe(OH)3 concentrations and, from then on, to
convert the pH evolution in Fe2þ consumption [assuming that oxi-
dation of Fe2þ in Fe3þ consumes one Hþ and that oxidation of
Fe2þ in Fe(OH)3 produces 3 Hþ]. This approach was revealed to
be valid only on the final pH. Polymer solution was first titrated
with HCl to evaluate the quantity of Hþ necessary to drop the pH.
By comparing initial and final pH of the polymer solution contain-
ing initially 20 ppm Fe2þ, the production of Hþ was calculated.
Assuming a production of two Hþ moles for one mole of Fe2þ
oxidized [all the oxidized Fe2þ is considered to be on Fe(OH)3
form], it was found that 18.5 ppm Fe2þ had been oxidized. As
a comparison, Fe2þ titration gave a concentration of 1 ppm, mean-
ing that 19 ppm had been consumed ([Fe2þ]ini  [Fe2þ]final ¼
20-1 ¼ 19 ppm). Calculation from pH measurements is thus in
agreement with Fe2þ titration, but only on the final pH.
For both solutions with and without polymer, the evolution of
Eh and pH during the course of the oxidation does not follow the-
oretical calculations. It is attributed to the fact that Fe2þ is not the
only Iron II-soluble species. Indeed, there is a distribution
between Fe2þ, Fe(OH)þ, and Fe(OH)2 that is pH-dependent (Mor-
gan and Lahav 2007). These three species are simultaneously oxi-
dized (Fe2þ is the less readily oxidized species) to produce
different kinds of iron oxides, with surface reactivity that is
neglected. Moreover, redox potential is possibly not at the equi-
librium with redox species.
Form and Injectability of Fe21 Oxidation Products. Seright
and Skjevrak (2015) observed the appearance of a yellow-orange
gel/precipitate after the addition of Fe3þ (as FeCl3) to HPAM
polymer solutions without any loss of viscosity. Gels result from
the formation of aggregates of crosslinked HPAM chains through
ion-pair formation between negative charges of HPAM and Fe3þ.
These gels did not appear during the oxidation of polymer solu-
tions containing up to 30 ppm Fe2þ. Fletcher et al. (1992) eval-
uated the potential injectivity decline resulting from crosslinking
of xanthan with Fe3þ (xanthan is also negatively charged through
its pyruvate groups). They observed a severe face plugging on
cores for Fe3þ concentration as low as 1 ppm. At higher concen-
tration, a gel of rigid consistency was observed at the inlet face,
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5 ppm 1 ppm
200
0 ppm 20 ppm
180
Cumulated Weight (g)
160
140
120
100
80
60
40
20
100 0 10 20 30 40 50
Time (minutes)
with an impairment effect that was function of the pressure gradi-
ent. On a field, in a case in which part of Fe2þ present in injection
water is oxidized in the presence of polymer, the question is still
pending about the associated injectivity risk.
Compared with water for which a red precipitate rapidly
appears, oxidation of Fe2þ in the presence of polymer does not
lead to any visible precipitate even if the color of the solution
turns yellowish. A parallel can be performed with the application
of sodium polyacrylates as antiscaling agents (Reddy and Hoch
2001; Kelland 2014). At very-low concentration (10 ppm), they
would block the formation of precipitate, such as calcium carbon-
ate, by inhibiting nucleation. Similarly, during the oxidation of
Fe2þ, the presence of polymer would inhibit the formation of iron
precipitate by an association of carboxylate groups with formed
iron hydroxide or oxide nuclei. A second explanation would be
that Fe2þ autoxidation leads to a homogeneous dispersion at the
molecular level of Fe3þ. This state of dispersion would prevent
the formation of big Fe3þ/polymer/Fe(OH)3 aggregates.
The risk of impairment associated with the formation of Fe3þ
in the presence of negatively charged HPAM was briefly in-
vestigated through filterability tests. Filter-ratio tests (200 cm3 of
solution on 3-mm NucleoporeTM filters at 1-bar differential pres-
sure) were performed on polymer solutions at 800 ppm containing
different levels of Fe2þ (1, 5, and 20 ppm) and exposed to the
atmosphere for complete oxidation. As seen on Fig. 7, graph on
the left, solution viscosity is decreasing when the quantity of oxi-
dized Fe2þ increases. As a consequence, filtration is faster (graph
on the right) for solution at 1 and 5 ppm compared with 0 ppm.
Moreover, for 0, 1, and 5 ppm, the cumulated weight passing
through the filter is proportional to the time, which indicates the
absence of filter plugging. On the contrary, at 20 ppm, the curva-
ture is the signature of a progressive plugging of the filter. After
filtration, a gel deposit was clearly visible on the filter. It indicates
that, even in the absence of visible gel, the solution contains big
aggregates of crosslinked polymer that plug 3-lm pores. For solu-
tions at lower Fe3þ concentration, we anticipate a more-progres-
sive plugging function of both the cumulated weight and the
concentration of polymer/Fe3þ aggregates. The question is still
open if these gels can deform and become injectable at high pres-
sure in the near-wellbore region.
Conclusions
For decades, oxidative degradation of polymers used in EOR has
been investigated through oxygen-controlled experiments and
their associated problems of leaks. In this study, a simple and
easy-to-run protocol is proposed for the evaluation of polymer
oxidative degradation. It consists in preparing polymer solutions
in anaerobic conditions with controlled levels of Fe2þ. Solutions
are then oxidized at the atmosphere. Degradation is measured
at the end of the oxidation. This protocol is based on the assump-
tion that polymer degradation is function of the limiting-reactant
quantity in the oxidation of Fe2þ by O2. The limiting reactant
April 2017 SPE Journal
 J179614 DOI: 10.2118/179614-PA Date: 21-March-17
is determined according to the stoichiometry of the oxidation
reaction: Fe2þ þ [1/4] O2 þ H þ ! Fe3þ þ [1/2] H2O. It gives the
following stoichiometry: 1 ppm O2 reacts with 7 ppm Fe2þ. This
protocol was validated through a comparison with another proto-
col in which initial levels of O2 and Fe2þ were controlled. It was
found that polymer degradation does not depend on the absolute
concentration, nor the ratio of both reactants, and that reaction is
total (the limiting reactant is totally consumed).
With our new protocol, for a given set of conditions (polymer
concentration, salinity, temperature), a curve describing the level
of polymer degradation as a function of the O2 consumed or the
oxidized Fe2þ is obtained. This curve enables one to predict the
level of oxidative degradation on a field in case of incomplete
water deoxygenation or oxygen ingress in polymer-dissolution
surface facilities. Whatever the level of Fe2þ, degradation will be
minor (<10% at 8 s1) if the O2 content is inferior to approxi-
mately 46 ppb. Higher levels can lead to severe and rapid
degradation (25% degradation at 8 s1 if [O2] ¼ 186 ppb, 25%
degradation at 0.2 s1 if [O2] ¼ 93 ppb). In a case in which
oxygen ingress occurs in the surface process, the concentration
of the limiting reactant (Fe2þ or O2) will determine the extent
of polymer degradation. According to the stoichiometry of the
Fe2þ autoxidation reaction, if [Fe2þ]/[O2] < 7 (concentrations in
ppm), Fe2þ is the limiting reactant; if [Fe2þ]/[O2] > 7, O2 is the
limiting reactant. Influences of polymer concentration, tempera-
ture, and salinity were investigated. Degradation was found simi-
lar in the concentration range 500–1,500 ppm, in the temperature
range 25–50 C, and in the salinity range 0.4–35 g/L. In a case in
which iron chelatants or a reducer is present, the stoichiometric
relation is no longer valid along with degradation values.
It was not possible to predict Fe2þ consumption by following
pH and Eh evolutions. However, it was observed that Fe2þ oxida-
tion is faster in the presence of polymer compared with water
because of the pH-buffering effect of the polymer.
At last, oxidation of Fe2þ in the presence of polymer does not
lead to the formation of visible gel. However, big aggregates of
crosslinked polymer are present because a solution containing
20 ppm oxidized Fe2þ did not pass the filter ratio test on 3-mm
NucleoporeTM filter. A film with a gel consistency was deposited
on the filter. This result indicates that, in addition to polymer deg-
radation, improper control of the O2 level could lead to wellbore
damage because of the plugging effect of polymer/Fe3þ cross-
linked gels.
Acknowledgments
We gratefully acknowledge Michele Joly who performed all the
experiments of this study. We thank Total E&P management for
the permission to publish this work. We thank Randy Seright for
suggesting to estimate the number of O2 molecules consumed per
polymer bond scission.
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Stephane Jouenne is a research engineer at Total, leading
since 2005 a team dedicated to surface and subsurface
topics for polymer flooding. His research interests include oil-
recovery mechanisms with polymers, physical chemistry, rheol-
ogy, and process engineering. Jouenne has authored or
coauthored more than 20 technical papers and holds three
patents. He holds an MS degree in chemical and process en-
gineering from Nancy Process Engineering School, France,
and a PhD degree in physical chemistry of materials from Paris
6 University, France.
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Alexandra Klimenko is a research engineer at Total, leading a
team dedicated to subsurface research topics for chemical
EOR (polymer and alkaline/surfactant/polymer). Her research
interests include physical chemistry, hydrodynamics, geo-
chemistry, and rheology. Klimenko holds an MS degree in res-
ervoir evaluation and management from Heriot-Watt
University and an MS degree in physical chemistry from Ural
State University, Russia.
David Levitt is currently seconded to ADMA-OPCO. He was for-
merly the manager of Total’s Surfactant Laboratory, focusing
on EOR applications. His research interests include instability
phenomena and subsurface redox gradients and their effect
on surface chemistry. Levitt has authored or coauthored more
than 20 technical papers and holds four patents. He holds a
BS degree in engineering from Harvey Mudd College and MS
and PhD degrees in petroleum engineering from the University
of Texas at Austin.
April 2017 SPE Journal