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New Developments on the Analysis of Scale Inhibitors

Article  in  SPE production & operations · November 2010

DOI: 10.2118/130401-MS

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 New Developments in the Analysis
of Scale Inhibitors
L.S. Boak, SPE, and K.S. Sorbie, SPE, Heriot Watt University, Edinburgh, UK
Summary
Scale inhibitors (SIs) are used to control oilfield scale formation,
and the ability to analyze these species is very important such
that SI concentrations as low as 0.5-ppm active need to be mea-
sured accurately. If phosphorus is present in the SI molecule, then
inductively-coupled-plasma (ICP) -based methods may be used
for analysis. However, the oil industry’s increasing requirement to
be environmentally friendly means that polymeric “green” SIs are
now being used more, which raises issues concerning detection
techniques (i.e., ICP vs. wet-chemical techniques). ICP detec-
tion for SIs is generally easier, but if it cannot be used, then at
least time-saving improvements to wet-chemical techniques are
extremely beneficial.
In this paper, analytical approaches are described that have
been used recently to improve chemical SI assay, especially at low
near-threshold levels (a few ppm active of SI). Progress is reported
in five areas of SI analysis:
1. Assay of sulfonated copolymer (VS-Co) was not possible
by straightforward analysis without extensive dialysis and sample
preparation. However, calibrations and repeats of accuracy similar
to that of the C18 were found for VS-Co using amino-propyl (NH2)
cartridges and the Hyamine method.
2. The Oasis® 2×4 method has been applied to SI analysis, and
this is able to assay all types of polymeric SIs in principle. This
method has been used to detect a VS-Co SI in a wide variety of
different brine salinities from distilled water (DW) to high-salin-
ity formation waters (FW) (e.g., a Heron-type FW). Although
achievable under these different conditions, there was a signifi-
cant decrease in the absorbance signals recorded with increasing
salinity that was not significantly improved by a higher-capacity
sorbent cartridge.
3. Various elements have been assayed in the oil phase using
the ICP method. Calibrations and accurate repeats within 5 to 10%
error were achieved. After solving compatibility issues, the con-
centration of an oil-tolerant SI was determined successfully using
calibrations and accurate repeats over a range of 0 to 10 ppm and
0 to 2,500 ppm active SI.
4. A matrix-matching Hyamine technique has been developed
that allows any chloride-ion effects on the chelating process
between the Hyamine and SI to be negated, allowing accurate
analysis of low-polymeric SI concentrations.
5. ICP and wet-chemical techniques have been able to accu-
rately detect a P-tagged (phosphorus-tagged) copolymer-type SI.
The ability to apply two independent analytical methods to a given
species offers some important advantages when more than one SI
is deployed in a field system. In this work, excellent correlation
is observed between the wet-chemical and ICP assay methods for
this P-tagged SI.
This study updates and adds to the set of analytical methods and
procedures reported for SI analysis almost 20 years ago (Graham et
al. 1993, 1995a, 1995b, 1996; Sorbie et al. 1992) and are described
in our Flow Assurance and Scale Team (FAST) laboratory proce-
dures manual (Sorbie and Boak 2006).
Copyright © 2010 Society of Petroleum Engineers
This paper (SPE 130401) was accepted for presentation at the SPE International
Conference on Oilfield Scale, Aberdeen, UK, 26–27 May 2010, and revised for publication.
Original manuscript received 8 March 2010. Revised manuscript received 22 June 10.
Paper peer approved 26 July 10.
November 2010 SPE Production & Operations
Introduction
Squeeze treatments using large volumes of SIs remain one of the
most widely used techniques to protect the entire oil-production
system against scale formation. This is especially significant for
barium sulfate scale because once it is formed, much lost time
and production may incurre while removing the deposit mechani-
cally or by chemical means. In squeeze treatments, the injected
inhibitor must return to the production tubing at levels above the
threshold concentration Ct over long periods of time (typically, 3
to 12 months). After a squeeze treatment, the produced brine must
be monitored to determine the SI concentrations so that the timing
for a resqueeze can be correctly identified. Because threshold con-
centrations are often in the region of 5 ppm or less, it is important
to accurately monitor the returning inhibitor at these low levels in
order to determine the approach of the end of the squeeze lifetime.
This monitoring allows preparation time for a new squeeze treat-
ment to be deployed. In addition, the monitoring and collating
of these low SI concentrations allows modeling of the SI-return
profile from which predictions of the future squeeze lifetimes can
be obtained. The optimization of these squeeze lifetimes can sig-
nificantly reduce financial expenditure in terms of both chemical
cost and deferred oil production.
Previous work on SI assay has been reported by this group
(Sorbie et al. 1992; Graham et al. 1993, 1995a, 1995b, 1996) on
the basis of earlier developments (Christian 1993; Murphy and
Riley 1962; Walters 1989; McTeir et al. 1993; Pennington 1988;
Kan et al. 1991; Bedford et al. 1994). The group’s earlier work
has examined many problems associated with SI analysis in both
synthetic brines and in field-produced waters. The problems faced
by oilfield analysts ranged from interferences with the analytical
procedure by other constituents within the produced brines, pre-
cipitation, particulates, and limitations of the analytical techniques.
However, despite these difficulties, a number of successful proce-
dures were obtained for the analysis of many generically different
SIs such as phosphonates (PH), polyphosphino carboxylic acids
(PPCAs), polyacrylic acids (PAAs), polyvinyl sulfonates (PVSs),
and many others. A range of techniques were established, from
wet-chemical to the use of ICP, because no single technique can
be used for all the generically different SI species. A summary
of the various SI assay methods with estimates of their analytical
accuracy is shown in Table 1. The detailed techniques developed
previously for oilfield SI application along with the structures of
most common SIs can be found in the FAST Laboratory Manual
(Sorbie and Boak 2006).
Since these early years, these techniques have not only been
used widely throughout the oil industry, but they have also been
adapted and developed to allow more-accurate results for the con-
ventional SIs of that time.
However for more than 15 years now, the oil industry is
much more environmentally aware. One of the consequences is
that more-environmentally-friendly SIs have been developed and
applied. These are known as green scale inhibitors (GSIs), and they
do not pollute the waters around platforms and the pipeline sys-
tems through bioaccumulation and nondegradation (Inches et al.
2006). GSIs are also being applied in chemical squeeze treatments.
Although these GSIs are more environmentally friendly, they bring
their own set of problems to the analysis world because they do
not contain phosphorus, making analysis by ICP nonapplicable. In
some cases, it may be possible that a P-tag can be attached to the
GSI, which for now appears to be in limited concentration, making
low-level SI analysis by ICP potentially possible but extremely
533
 TABLE 1—PRACTICALLY ACHIEVABLE ASSAY LIMITS FOR VARIOUS SIs AT 2 AND 5 ppm (ACTIVE) LEVEL*
Synthetic Brine Produced Brine
Detection (Acc. +/- ppm) (Acc. +/- ppm)
Inhibitor Method 2ppm 5ppm 2ppm 5ppm Comments

Phosphonate (PH) ICP 0.1 0.1 < 0.2 < 0.2 Very accurate detection in various brines.
Possibly matrix independent.
Phosphino poly- Hyamine 0.1 0.1 0.2 0.4 Accurate detection in various brines.
carboxylate (PPCA) Errors larger in very contaminated brines.
Phosphino poly- ICP 0.1 0.1 0.1 0.1 Very accurate detection in various brines.
carboxylate (PPCA) Possibly matrix independent
Poly acrylate (PAA) Hyamine 0.1 0.1 0.2 0.4 Accurate detection in various brines.
Errors larger in very contaminated brines.
Poly vinyl sulphonate Pinacyanol 0.2 0.5 0.8 1.0 Detection in low-salinity brines.
(PVS)** Blue Repeat analysis essential for accuracy.
Pretreatment to isolate inhibitor assists
detection in high-salinity brines.
Background response very variable—daily
calibration and repeat analysis essential.
Poly vinyl sulphonate Hyamine 0.2 0.3 0.2 0.5 Accurate detection in many brines.
(PVS)** Pretreatment essential to isolate inhibitor.
PVS/PAA copolymer** Hyamine 0.2 0.3 0.3 0.5 Accurate detection in many brines.
Pretreatment essential to isolate inhibitor.
PVS/PAA copolymer** Pinacyanol 0.2 0.5 0.8 1.0 Detection in low-salinity brines.
Blue Repeat analysis essential for accuracy.
Pretreatment to isolate inhibitor assists
detection in high-salinity brines.
Background response very variable—daily
calibration and repeat analysis essential.
* Graham et al. (1995b)
** Graham et al. (1993)

difficult. Therefore, the industry may have to resort to wet-chemi-
cal techniques or other instrumentation such as high-pressure
liquid chromatography (HPLC) (Dionex). In either case, major
improvements are needed to allow low-level SI assay in produced
brine to be acheived, at less than 0.5 ppm active in some cases.
Some of the current techniques, such as membrane or car-
tridge dialysis, to remove the interfering brine salts before using
Hyamine 1622 for generic species such as PVS and VS-Co need
to be made less laborious, or an alternative technique needs to be
found. Recently, an alternative method for the detection of sul-
fonated SI products using amino-propyl cartridges was reported by
researchers (Jones et al. 2007), and this method has been applied
here. Following this approach, a number of other solid-phase-
extraction (SPE) methods for polymeric-SI analysis were studied,
allowing the development of the OASIS® 2×4 method described
in this paper.
Experimental Procedures
The final SI assay experimental procedures developed in the course
of this work are presented in detail at the end of this paper in
Appendix A, some of which are also detailed in the FAST labora-
tory manual (Sorbie and Boak 2006). The various brine composi-
tions used thoughout the following studies are also detailed in
Appendix A.
Presentation of Data and Results
C18 and NH2 (Amino-Propyl) Cartridges and Hyamine. C18
cartridges have been used routinely for many years for Hyamine
analysis of PPCA and other SIs containing the carboxylic acid
functional group. Fig. 1 and Table 2 illustrate the calibrations and
repeats that can be obtained for PPCA, polymaleic acid (PMA),
and polyaspartate using C18 cartridges. Note that the calibration
and repeats for PMA had to be performed simultaneously for the
results to be successful.
However, C18 cartridges have never been successful with sul-
fonated products. This relates to the bonding that occurs between
the SI and the silica sorbent within these cartridges. The SI is
applied at pH = 2 with C18 cartridges. This ensures that the SI
is fully nondissociated, allowing the SI to be retained on the C18
cartridge through H-bonding or weak interactions. This allows
separation of the SI from the brine salts that flow through the
cartridges and are discarded. This cannot be achieved for sul-
fonated products because they remain extensively dissociated at
pH = 2 because they possess such low pKa values. Therefore,
the sulfonated SI cannot be retained on the C18 by reverse phase
hydrogen bonding. Hence, in late 2006, investigations into alter-
native cartridges, such as the amino-propyl (NH2) cartridges, for
sulfonated products commenced. This work coincided with other
researchers’ examinations (Jones et al. 2007) presented at the
National Association of Corrosion Engineers (NACE) 2007 con-
ference describing their techniques for sulfonated products using
these same NH2 cartridges.
FAST’s investigations examined these cartridges using the
normal C18 procedure. As stated previously, these NH2 cartridges
are more polar and basic in nature. Hence, ionic interactions could
occur between the sulfonated SI and the NH2 cartridge at low pH
allowing the sulfonated SI to be retained on the cartridge, separat-
ing it from the salt ions (mainly the Cl– ions) that interfere with
the ionization of the Hyamine—quaternary ammonium chloride—
reducing the turbidity signal. The normal 5% sodium citrate wash,
however, did not appear strong enough to release the sulfonated SI
from the cartridge to allow its detection. After trying a number of
different solutions, 0.1N NaOH was found to be of a sufficiently
high pH value (pH 10–12) to release the sulfonated product from
the NH2 cartridge to allow its detection. An initial calibration (and
repeats) in DW was achieved for VS-Co. This led to trials of both
VS-Co and PVS in seawater (SW) where successful calibrations
and repeats were also achieved, as shown in Fig. 2 and Table 3.

534 November 2010 SPE Production & Operations

 (a) C18 Hyamine for PPCA /SW (b) C18 Hyamine for PMA /SW (c) C18 Hyamine for Aspartate
in SW
12 10 10
y = 2.9348x 3 –5.6514x 2 + 5.7912x + y = 576.72x 3 –235.48x2 + 47.38x + y = 466.34x 3 –179.75x 2 + 46.026x +
[SI], active ppm 10

[SI], active ppm

[SI], Active ppm

0.0194 8 8
0.2273 0.081
8 R 2 = 0.9995 6 R 2 = 0.9979
R 2 = 0.9973 6
6
4 4
4
2 2
2
0 0 0
0 0.5 1 1.5 2 0.000 0.100 0.200 0.300 0.000 0.100 0.200 0.300
Absorbance at 500nm Absorbance (500nm) Absorbance (500nm)

Fig. 1—Examples of calibration graphs that can be obtained following the C18 Hyamine procedure for (a) PPCA, (b) PMA, and
(c) polyaspartate.

TABLE 3—A SUMMARY OF THE R COEFFICIENTS AND

2
TABLE 2—A SUMMARY OF THE R COEFFICIENTS AND
2

STANDARD REPEATS FOR PPCA, PMA, AND STANDARD REPEATS FOR VS-Co in DW/SW and PVS/SW
POLYASPARTATE USING C18 HYAMINE USING NH2 HYAMINE

Poly-Phosphino VS-Co/DW VS-Co/SW PVS/SW

Carboxylic Acid Poly Maleic Poly
Calibration R
2
(PPCA) Acid (PMA) Aspartate 0.9981 0.9991 0.9996
Repeats
Calibration R
2
0.9995 0.9973 0.9979
0ppm –0.159 –0.103 0.081
Repeats
1ppm 0.804 0.897 0.965
0ppm 0.409 –0.081 0.227
3ppm 3.04
1ppm 1.04 1.01
4ppm 4.02 3.81 4.94
2ppm
5ppm
4ppm 4.15 4.06
6ppm 5.98
5ppm 4.759
Note: The absorbance for the 0ppm repeat was similar to the absorbance of
Note: The absorbance for the 0ppm repeat was similar to the absorbance of the 0ppm in the calibration. However, depending on the curve fit the determined
the 0ppm in the calibration. However, depending on the curve fit the determined 0ppm concentration could be higher/lower than expected.
0ppm concentration could be higher/lower than expected.

OASIS® 2×4 Method. Oasis cartridges are not thought to have Therefore, all further experiments were performed on the WAX
been used previously for polymeric-SI assay within the oil indus- cartridge. Since there is great flexibility with these cartridges,
try despite having been featured very prominently throughout due to of the high stability of the sorbent material, a number of
the pharmaceutical industry for many years. As a result, a major variables were examined:
method development was undertaken to establish a method that • Effect of pH on the SI being retained on the cartridge
could detect both conventional SIs and GSIs because these car- • Volume of reagents (i.e., of acid, alkali, DW wash, sodium
tridges have two main advantages: (1) the robustness of the citrate, Hyamine)
sorbent material to aid separation from interferences and (2) the • Volume of SI sample to achieve greatest signal, which in
high throughput of 20 tests simultaneously that can be achieved. turn should provide better repeatability, eventually requiring an
A brief explanation of how this SPE method works using the vari- introduction vessel for larger sample volumes to avoid errors from
ous types of cartridge (MCX, MAX, WCX, and WAX) is presented pipetting
in Appendix A, Section A2. • Type of acid used to pretreat sorbent before SI wash step to
An initial screening of all the cartridges (MCX, MAX, WCX, lock SI onto cartridge
and WAX) was performed on the basis of the C18 Hyamine • Type/concentration of alkali used to release SI from sorbent
method. This showed that the main cartridge of interest for oilfield before its detection by Hyamine method
SIs appeared to be WAX, although under certain circumstances, By optimizing these factors to allow the greatest and clean-
a signal was detected for PPCA and PCA on the MCX cartridge. est separation of the SI from the interfering SW salts, a method

(a) NH2 Hyamine for VS-Co/DW (b) NH2 Hyamine for VS-Co/SW (c) NH2 Hyamine for PVS/SW
10 8 8
y = 173.17x 3 –101.69x 2 + 35.969x– y = 984.51x 3 –308.76x2 + 56.556x– y = 109x 3 –48.577x 2 + 30.434x–0.1
[SI], active ppm
[SI], active ppm

8
[SI], active ppm

0.4402 6 0.3248 6 R 2 = 0.9996

6 R 2 = 0.9981 R 2 = 0.9991
4 4
4

2 2 2

0 0 0
0.000 0.100 0.200 0.300 0.400 0 0.05 0.1 0.15 0.2 0 0.1 0.2 0.3
Absorbance (500nm) Absorbance (500nm) Absorbance (500nm)

Fig. 2—Calibration graphs obtained following the NH2 Hyamine procedure for (a) VS-Co in DW, (b) VS-Co in SW, and (c) PVS in SW.

November 2010 SPE Production & Operations 535

 (b) 0–2 ppm Calibration (c) Calibration for VS-Co in SW (d) 0-2 ppm Calibration
(a) Calibration for VS-Co in DW
for VS-Co in DW at initial pH2 using WAX for VS-Co in DW
at initial pH2 using WAX
2.5
12 2.5 10
2
y= -150.57x + 35.893x - y= 72.769x3 - 64.702x2 +
10 30.726x - 0.0795 2
2 0.0357 8

[SI] active ppm

R2 = 0.9999
[SI] active ppm

[SI] active ppm

[SI] active ppm

R2 = 1
8 1.5
1.5 6
6
1
1 4
4 3 2 y= -427.79x2 - 61.028x -
y= 19.598x -28.225x + 0.5 0.1584
2 22.015x + 0.087 0.5 2
R2 = 0.9989
R2 = 0.9995
0 0 0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.00 0.02 0.04 0.06 0.08 0.10 0.0 0.2 0.4 0.6 0.00 0.02 0.04 0.06 0.08 0.10
Absorbance (500 nm) Absorbance (500 nm) Absorbance (500 nm) Absorbance (500 nm)

(e) Calibration for VS-Co in (f) 0–2 ppm Calibration (g) Calibration for VS-Co in (h) 0–2ppm Calibration
Forties FW at initial pH2, WAX for VS-Co in Forties FW Heron FW at initial pH2, WAX for VS-Co in Heron FW
2.5 2.5
10 12 y= -31768x2 + 624.31x -
3 2
y= -2091.5x2 + 134.12x -
y= 2435.5x -680.18x + 0.132 10 2 0.6008
8 87.924x + 0.0176 2 R2 = 0.9997
R2 = 1

[SI] active ppm

[SI] active ppm
[SI] active ppm

[SI] active ppm

R2 = 0.9992 8
6 1.5 1.5
6
1 1
4
4
y= 24842x3 - 4114.1x2 -
2 0.5 2 289.36x + 0.0174 0.5
R2 = 0.9963
0 0 0
0
0.00 0.05 0.10 0.15 0.20 0.000 0.010 0.020 0.030 0.040 0.00 0.02 0.04 0.06 0.08 0.10 0.000 0.002 0.004 0.006 0.008

Absorbance (500 nm) Absorbance (500 nm) Absorbance (500 nm) Absorbance (500 nm)

Fig. 3—Calibration graphs obtained for VS-Co initially in various salinity brines: DW, NSSW, Forties FW, and Heron FW; (a, c,
e, g) Full 0–8 or 0–10 ppm active range achieved and (b, d, f, h) 0–2 ppm active calibration using the same absorbance values
improves accuracy at low concentrations, mainly 1 ppm active.

was developed that has the potential to detect both conventional an FW-type brine system (i.e., containing a high quantity of salts),
SIs and GSIs, although the major focus after initial examinations an increase in the absorbance signals of SIs, especially at the high-
was on the polymeric VS-Co-type inhibitor. This VS-Co inhibitor end of the calibration range, would be observed. However, this
was initially examined in DW and SW, but this analysis was later was not the case. A slight increase was observed for the low end
extended to include higher-salinity FWs such as a medium-scaling of the calibration range but no significant increases for the high
Forties-type FW and an even-higher-salinity Heron-type FW. The end, implying that all the SI was “sticking” to the previously used
calibrations and repeats for the VS-Co SI in a variety of different lower-capacity sorbent, and there was no competition between the
salinity brines—DW, North Sea seawater (NSSW), Forties FW, and salts and SI.
Heron FW—are shown in Fig. 3 and Table 4. It was observed that
if the calibration range was decreased, then more-accurate repeats ICP Analysis in the Oil Phase. Aqueous ICP methods have
were recorded for the lower concentrations. been used routinely for many years. However, with nonaqueous
It was also observed that as the salinity of the brine system SI treatments now being widely applied for scale protection, the
increased, the absorbance signal decreased. This was thought to detection of various elements within an oil matrix needs to be
relate to sorbent site competition on the cartridge between the brine examined. The main difference between ICP aqueous and oil anal-
salts and the SI during the SI lock-on in Step 3 of the procedure. ysis is the range of settings required in order to light the plasma,
It was hoped that by using a higher-sorbent-capacity cartridge for as highlighted in Appendix A. Once this has been achieved, then

TABLE 4—EXAMPLE OF THE R COEFFICIENT AND STANDARD REPEATS FOR THE 10 -mL
2

ANALYSIS OF THE SIs, VS-Co IN THE VARIOUS SALINITY BRINES: DW, NSSW, FORTIES
FW, AND HERON FW; (a) FULL CALIBRATION REPEATS, (b) 0–2ppm CALIBRATION
REPEATS

(a) Full Calibration DW NSSW Forties FW Heron FW

Calibration R
2
0.9995 0.9999 0.9992 0.9963
Repeats
0ppm 0.109 –0.049 0.105 0.303
0.5ppm 0.336 0.147 0.400 0.303
1ppm 0.661 0.538 0.906 0.849
4ppm 3.15 3.92 4.02 4.20
6ppm 5.77 5.90 5.17 5.85
(b) 0–2 Calibration DW NSSW Forties FW Heron FW

Calibration R
2
1.0000 0.9989 0.9972 0.9997
Repeats
0ppm 0.109 –0.098 –0.024 –0.008
0.5ppm 0.357 0.274 0.397 –0.008
1ppm 0.823 0.934 1.049 0.986
Note: The absorbance for the 0ppm repeat was similar to the absorbance of the 0ppm in the calibration however
depending on the curve fit the determined 0ppm concentration could be higher/lower than expected.

536 November 2010 SPE Production & Operations

 TABLE 5—ACCURACY AND REPEATABILITY FOR SEVERAL IONS DURING ICP OIL ANALYSIS IN WHITE SPIRIT
317.933nm 213.618nm

Sample Name Ca Corrected Ca Mean Sample Name P Corrected P Mean

0ppm 0.002 0.002 0.001 0ppm 0.000 0.00 0.00

0ppm 0.000 0.000 0ppm 0.000 0.00
5ppm 4.93 4.97 4.96 5ppm 5.14 5.02 5.00
5ppm 4.91 4.95 5ppm 5.10 4.98
10ppm 9.67 9.84 9.90 10ppm 10.01 9.79 9.82
10ppm 9.78 9.96 10ppm 10.06 9.84
259.940nm 181.978nm

Sample Name Fe Corrected Fe Mean Sample Name S Corrected S Mean

0ppm 0.000 0.000 0.000 0ppm –0.120 0.012 0.001

0ppm 0.000 0.000 0ppm –0.145 –0.010
5ppm 5.02 4.97 4.97 5ppm 5.52 4.99 4.66
5ppm 5.03 4.98 5ppm 4.79 4.34
10ppm 9.95 9.84 9.86 10ppm 9.75 10.03 10.08
10ppm 10.00 9.89 10ppm 9.84 10.12
279.553nm 371.029nm

Sample Name Mg Corrected Mg Mean Sample Name Y Corrected Y Mean

0ppm 0.000 0.000 0.000 0ppm 0.001 0.000 0.000

0ppm 0.000 0.000 0ppm 0.001 0.000
5ppm 5.05 5.07 5.06 5ppm 4.97 5.03 5.05
5ppm 5.03 5.05 5ppm 5.02 5.08
10ppm 9.85 9.98 10.02 10ppm 10.00 10.15 10.16
10ppm 9.92 10.05 10ppm 10.03 10.18
178.229nm 670.784nm

Sample Name P Corrected Pa Mean Sample Name Li Corrected Li Mean

0ppm –0.011 0.011 0.014 0ppm 0.008 –0.020 –0.020

0ppm –0.004 0.018 0ppm 0.007 –0.021
5ppm 4.88 5.00 4.97 5ppm 5.26 4.94 4.99
5ppm 4.82 4.94 5ppm 4.37 5.04
10ppm 9.72 9.51 9.47 10ppm 11.53 10.71 10.84
10ppm 9.63 9.42 10ppm 10.94 10.97

methods can be set up for the ions of interest. The oil methods
are very similar to the aqueous methods, with any differences
mainly relating to an element’s wavelength and background cor-
rection points. The analysis can then be performed, and successful
calibrations were achieved. The accuracy and repeatability of the
results obtained for the ions Ca2+, Mg2+, Fe3+, S–, P–, Y+, and Li+
are shown in Table 5.
The first column of results for each ion shows the original raw
ICP data and the next shows the determined drift-corrected ion
concentration. Because these two sets of concentrations are very
close in value (both to themselves and the known concentration),
the analysis was deemed successful. Therefore, having achieved
both accurate and repeatable analysis for several ions, it was of
great importance to be able to determine SI concentrations within
an oil sample.
Initially, incompatibility issues were observed for an oil-toler-
ant SI in white spirit. However, after a number of investigations
examining different solvent packages and different ways of dilut-
ing the oil-tolerant SI, it was decided to look at different ratios of
ethylene glycol monobutyl ether (EGMBE) (or 2-butoxyethanol),
containing the SI to white spirit. It was found that ratios of 10 to
50% EGMBE/SI to white spirit gave clear solutions, while 60%
EGMBE/SI and upward gave cloudy or precipitated solutions,
which could not be used. Because the 10 to 50% EGMBE/SI to
white spirit solutions were clear, these ratios could be used for
testing the analysis method. No major differences in accuracy or
repeatability were noted between the 0- to 2,500-ppm active cali-
brations and repeats, performed for all the 10 to 50% EGMBE to
white spirit ratios. Hence, in order to choose one ratio, the deterio-
ration in the signal of the solutions was examined after 1 week. It
was observed that as long as a new 50 ppm standard was prepared
in a manner similar to that of the previous one (from the original
500 ppm diluted standard and not from the very high original
stock), the repeatability of the 50 ppm standard was acceptable.
However, no major differences were recorded for the calibration
intensity values from the original or the 1-week-later analysis,
although both the 10 and 50% EGMBE/SI solutions were observed
to have the least variation. These two ratios of EGMBE/SI to white
spirit were then carried forward to a low-calibration range of 0 to
10 ppm active SI, which were successful.
The ICP raw data recorded for the 10% EGMBE/SI: 90% white
spirit ratio was initially more accurate. However, once the data had
been drift corrected, then data from either EGBME/SI to white
spirit ratio were acceptable to use. However, it was decided that
the 10% EGMBE/SI: 90% white spirit was the most suitable ratio
to be used for this oil-tolerant SI, as shown in Table 6.
This work shows that it is possible to analyze for ions of interest
in an oil matrix, such as white spirit. This includes an oil-tolerant
SI, although it required a constant matrix of 10% EGMBE/SI:
90% white spirit and for all the standards to be made fresh at the

November 2010 SPE Production & Operations 537

 TABLE 6—DATA RECORDED FOR STANDARD REPEATS DURING THE 0–10ppm ACTIVE SI IN 10% EGMBE/SI: 90% WHITE
SPIRIT AND 50% EGMBE/SI: 50% WHITE SPIRIT MATRIX RATIOS *

10% E : 90% WS 178.229nm 50% E : 50% WS 178.229nm

Sample Name P Corrected P Sample Name P Corrected P

0ppm 0.036 0.000 0ppm –0.053 –0.038

0.5ppm 0.459 0.490 0.5ppm 0.375 0.508
1ppm 1.007 0.999 1ppm 0.941 1.05
2.5ppm 2.33 2.51 2.5ppm 2.37 2.48
5ppm 4.96 4.96 5ppm 4.69 4.87
10ppm 9.91 9.97 10ppm 9.78 9.93
* The first column contains the raw ICP data and the second the Drift Corrected Data.

same time or for any to be made by exactly the same procedure
as when made for the first time. This oil-phase analytical method
will be applied to a nonaqueous phase coreflood during the oil-
flowback period.
Easy Hyamine: Matrix-Matching Technique. This method
development was carried out because of the difficulties of deter-
mining low polymeric-SI concentration from a restricted sample
volume. The procedure for the actual detection is exactly the
same as the normal easy Hyamine in Appendix A, Section A4 of
this paper. However, it is the steps taken before the analysis that
require some thought. The final procedure developed avoids the
negative effects of the remaining chloride ion on the chelating
process between the Hyamine and SI. For example, an SI stock
would be prepared in SW, as would happen for any experimental
procedure, which would then be diluted to give a 25 ppm active
SI/DW stock in order to create an easy Hyamine calibration
range of 0 to 10 ppm active SI/DW (i.e., easy Hyamine relies
on the diluting out of any salts that may interfere with the SI
detection).
However, it was found that as the SI/SW concentration became
lower in the samples, requiring a smaller dilution in DW (e.g., a ×2
dilution—2,500 d and 2,500 s on the diluter for a 5-mL DW test
solution), then a greater chloride ion concentration is present with
respect to the target 0- to 10-ppm active SI DW calibration stan-
dards. The greater concentration of chloride ions present interfere
more significantly with the chelating process between the Hyamine
and the SI. Therefore, the turbidity absorbance recorded for that
concentration of SI is incorrect. Matrix matching the sample and
calibration standards, for example using the same dilution factor
from an SW background to a DW background for both, gives
equivalent chloride-ion concentration within both. This means
that any chloride-ion effects on the chelating process between the
Hyamine and SI can be negated, allowing accurate analysis to be
performed for the low-SI-concentration samples. For example, if a
sample was thought to require a ×10 dilution to give an SI within
a 0-to-10 ppm active SI DW calibration range, then initially 0-to-
100 ppm SW calibration standards would be prepared. These SW
calibration standards would then require the same ×10 DW dilution
as the samples (i.e., 500 s and 4,500 d for 5 mL), and hence both
the sample and calibration standards will have equivalent chloride-
ion concentration. Thus, the sample and calibration standards will
undergo similar interferences from these ions, allowing accurate
analysis to be performed (i.e., matrix matching).
Fig. 4 shows the successful calibration graph achieved for this
×10 dilution matrix-matching technique.
This process was also successfully performed for ×5, ×2.5,
and ×2 dilution factors for the matrix-matching technique from
SW to DW. With no dilution at all in DW (i.e., at full SW chlo-
ride-ion composition, approximately 19,700 ppm), a calibration
cannot be achieved. No dilutions in DW between 0 and 2 have
been performed.
If all the calibration graphs for both easy Hyamine and matrix-
matching Hyamine at various dilutions are plotted together, it is
obvious that the presence of chloride ions can have a significant
effect on the absorbance recorded, as shown in Fig. 5.
For example, if a sample gave an absorbance value of approxi-
mately 0.24, then depending on which calibration had been used
during the analysis, the determined ppm value of the sample could
range between approximately 2.7 and 6 ppm active SI. Therefore,
it is very important to matrix match the background of the sample
and calibration.
Validation of the Matrix-Matching Technique. Having achieved
successful calibrations using the matrix-matching technique for
×10, ×5, ×2.5, and ×2 dilutions, the procedure was validated by
examining the repeatability and robustness of the process. Table 7
presents the average SI concentration of three repeats at each of
these known concentrations using the matrix-matching technique
for different dilutions.
Using this matrix-matching technique allowed samples to be
analyzed down to 2 to 3 ppm with confidence (approximately 0.022
absorbance units ≈ 1 ppm on calibration).

Hyamine for SI in x10 DW from

SW calibration stks Comparison of Calibration Graphs:
12 3 2 Easy, matrix x10, 5, 2.5 and 2 DW
y = 4.7788x – 5.4539x +
12
[SI], active ppm

10 12.823x + 0.1223 Easy

[SI], active ppm

8 2 10
R = 0.999 x10 DW
6 8 x5 DW
6 x2.5 DW
4
4 x2 DW
2
2
0
0
0.0 0.2 0.4 0.6 0.8 1.0
Absorbance (500nm) 0.000 0.200 0.400 0.600 0.800 1.000
Absorbance (500nm)
Fig. 4—The successful matrix-matching calibration from 0- to
100-ppm SW standards to give a 0 to 10 ppm active DW range Fig. 5—Comparison of all calibration types—Easy Hyamine and
for a ×10 DW dilution. Matrix-Matching Hyamine at ×10, ×5, ×2.5 and ×2 dilutions.

538 November 2010 SPE Production & Operations

 TABLE 7—REPEATS FOR KNOWN SI CONCENTRATIONS
USING THE MATRIX-MATCHING CALIBRATIONS*

SI Repeats
Active ppm x10 x5 x2.5 x2

0 0.144 0.077 0.124 0.132

3 3.24 2.99 3.54 2.91
5 5.44 4.98 5.00 4.90
8 8.11 7.89 8.78 –
* 8ppm missing for the x2 calibration as it was out of range

TABLE 8—COMPARISONS OF A 5ppm ACTIVE SI SW SOLUTION ANALYZED BY BOTH

2.5 AND 2 DW MATRIX-MATCHED CALIBRATIONS

5ppm Active Comparison Analysis 1 Analysis 2 Analysis 3 Average

x2.5 calibration 5.33 5.25 5.25 5.28

x2 calibration 5.32 5.62 5.68 5.54

To ensure that repeatable results could be achieved for the same
sample but using different matrix-matching calibrations, a 5 ppm
active SI SW solution was prepared and analyzed by both ×2.5 and
×2 DW calibrations. The results are shown in Table 8.
By analysing the same 5-ppm active SI SW solution by both
×2.5 and ×2 matrix-matched DW calibrations, the achieved con-
centration was reasonably accurate taking into consideration that
fairly low absorbance numbers (approximately 0.060 equivalent
to 2.5 or 2 ppm on the ×2 or ×2.5 DW calibration) were being
recorded. Hence, this work provides an initial evaluation and vali-
dation of a technique that will be very useful for future analysis.
ICP and Wet-Chemical Analysis of a New P-Tagged Copolymer.
Recently, one of the FAST sponsors supplied the research group
with a new P-tagged polymer that they claimed had sufficient P-tag-
ging to be easily detectable with ICP but was low enough for it to
be classed as environmentally friendly. In terms of inhibitor assay,
FAST’s interest in this material was that it may be one of only a
few polymeric products (e.g., PPCA, other P-tagged polymers) that
could be detectable by both wet-chemical and ICP techniques.
ICP Detection: Initial examinations in this study investigated
the ICP detection of this new P-tagged copolymer in NSSW along-
side more commonly used SIs such as di-ethylene triamine penta
methylene phosphonic acide (DETPMP), poly-phosphino methyl-
ated poly-amine (PMPA), and PPCA that can also be detected by
ICP. Two ICP methods were employed—the PHOS method and
the P POLYMER method. The major differences between the two
methods are the wavelengths used and the fact that the PHOS
method uses a peak height measurement where as the P POLY-
MER uses a Gaussian peak area. In each method, there are two
lines, one which examines the lower end of the calibration range (0,
5, 50 ppm active) and the other the high end (0, 50, 500, 2,500 ppm
active). The results observed show that all the SI species examined
can be detected by ICP, including the new P-tagged copolymer,
over a range of 0 to 2,500 ppm. The same set of standard solutions
was used for both method types.
This ICP process was repeated for a low-end calibration of 0, 5,
and 10 ppm active to compare the level of quantification between
the P-tagged copolymer and the PPCA. This is important because
very-low-level polymer analysis is now required for returning
squeeze-treatment samples in the field as more-environmentally-
friendly-polymer-type species are being used.
The results in Table 9 highlight that the detection of the P-tagged
copolymer is very similar to the PPCA by ICP at these low concen-
trations. Again, both inhibitors can be detected by each ICP method
equally well, with the level of quantification being around 0.5 ppm
active for both SIs, although lower concentrations may be achievable.
The signal intensities for both methods indicate that the P-
tagged copolymer contains more P content within its structure than
PPCA. Although this does not make a significant difference in the
actual levels recorded here for each SI in NSSW (Table 9), it may
make a difference in detecting the P-tagged copolymer compared
to the PPCA at lower concentrations or in more-severe brines—for
instance, if the samples were in more-severely-scaling brine or there
were interferences in the produced water that contained the SI. This
higher signal may also be helpful if ICP detection cannot be used for
some reason and wet-chemical techniques need to be adopted.
Wet-Chemical Techniques and Analysis of ICP Solutions.
In addition to using ICP, a number of wet-chemical techniques
were investigated to see if they could not only detect the P-tagged

TABLE 9—RESULTS FOR LOW-END CALIBRATIONS, 0–10ppm ACTIVE, FOR THE SIs P-TAGGED COPOLYMER AND PPCA

PHOS Method (peak height)

Determined Concentrations for Known Active Concentrations

177.440nm line 0 0.5 1 2.5 5 10

P-tagged copolymer –0.035 0.472 1.00 2.38 5.04 10.53
PPCA –0.021 0.489 0.929 2.63 4.84 10.51
P Polymer Method (Gaussian peak area)

Determined Concentrations for Known Active Concentrations

177.440nm low line 0 0.5 1 2.5 5 10

P-tagged copolymer 0.017 0.488 0.957 2.40 4.91 10.15
PPCA 0.005 0.519 1.002 2.44 4.90 9.85
177.440nm high line 0 0.5 1 2.5 5 10
P-tagged copolymer –0.035 0.482 1.02 2.46 4.90 10.10

November 2010 SPE Production & Operations 539

 TABLE 10—SUMMARY TABLE FOR THE DETERMINED CONCENTRATIONS OF THE P-
TAGGED COPOLYMER ICP STANDARDS BY WET-CHEMICAL ANALYSIS

Known Active Concentrations For

Amino Propyl Oasis -

P-tagged Copolymer Cartridge/Hyamine WAX/Hyamine Easy Hyamine

0 0.244 0.205 0.466

5 – – –
50 53.56 52.49 109.94
500 510.22 502.81 597.85
1000 1023.7 981.73 1149.04
2500 2635.6 2394.31 2565.72
5000 5181.63 4770.08 5405.46

copolymer but, by using the same ICP standard solutions, could determined concentrations are of the correct magnitude, except at
determine corresponding values for these standards by each wet- 50 and 500 ppm active for the Easy Hyamine. This Easy Hyamine
chemical technique. result at the lower concentrations was expected because the dilu-
Successful calibrations and repeats were achieved for amino- tions required from these concentrations to within the calibration
propyl cartridge Hyamine, Oasis Hyamine, and Easy Hyamine. range mean that there is still an influence of the salt ions, mainly
Again a lower range of calibration improves the low-end accuracy chloride ions, in the solution on the Hyamine process, although
of the repeats approximately 0.5 and 1 ppm. All the procedures for they are being diluted out in DW. This observation relates to the
each wet-chemical technique and any brine compositions used are matrix-matching technique.
detailed in Appendix A. If the wet-chemical analysis for the P-tagged copolymer is then
To verify that the range of wet-chemical techniques will give compared with the corresponding ICP determined values (Fig. 6), it
concentrations similar to those of the ICP analysis, the previously can be said that the PHOS ICP methods are a slightly better match
used ICP solutions and additional independent 1,000 and 5,000 (shown by the linear relationships) with the wet-chemical analysis,
ppm active solutions were analyzed by each of the wet-chemi- while the Oasis technique appears to be rather low in its determina-
cal techniques. The corresponding values determined for these tions at the high values of 2,500 and 5,000 ppm active SI.
P-tagged copolymer ICP solutions by wet-chemical analysis are
highlighted in Table 10. Summary and Conclusions
Between the wet-chemical techniques, there is variation in the A survey of some recent developments in the analysis of SI species
measured concentrations of these ICP solutions, although all of the has been presented with an emphasis on their assay at threshold

PHOS 177.440nm Determined [SI]: PHOS 214.914nm Determined [SI]:

ICP v.s. Wet Chemical Analysis ICP v.s. Wet Chemical Analysis
Wet Chemical Analysis [SI],

3000
Wet Chemical Analysis [SI],

3000 y = 1.0636x– 4.907

y = 1.0781x–6.5428 2
2 2500 R = 0.9999
2500 R = 0.9999
Active ppm

y = 0.9648x + 5.0102
Active ppm

2000 y = 0.9781x + 3.5093 2000

2
2 R = 0.9999
R = 0.9999
1500 1500
y = 1.0259x + 32.804
y = 1.04x + 31.185 2
1000 2 1000 R = 0.9987
R = 0.9988
500 500
NH2 NH2
0 0
Oasis Oasis
0 1000 2000 3000 0 1000 2000 3000
Easy Easy
ICP [SI], Active ppm ICP [SI], Active ppm
(a) (b)

P POLYMER 177.440nm Low determined P POLYMER 177.440nm high Determined

[SI]: ICP v.s. Wet Chemical Analysis [SI]: ICP v.s. Wet Chemical Analysis
3000
Wet Chemical Analysis [SI],

3000
Wet Chemical Analysis [SI],

y = 0.9784x + 2.435 y = 0.9706x + 12.692

2 2
2500 R =1 2500 R = 0.9999
y = 0.8833x + 13.91
Active ppm

y = 0.8874x + 11.787
Active ppm

2000 2000 2
2
R = 0.9995 R = 0.9994
1500 1500 y = 0.9389x + 42.454
y = 0.9434x + 40.156
2
2
R = 0.9979 R = 0.9976
1000 1000

500 NH2 500 NH2

0 Oasis Oasis
0
0 1000 2000 3000 Easy 0 1000 2000 3000 Easy
ICP [SI], Active ppm ICP [SI], Active ppm
(c) (d)

Fig. 6—A Comparison of the ICP-determined values with the wet-chemical determination for the P-tagged copolymer in NSSW,
(a) PHOS 177.440 nm, (b) PHOS 214.914 nm, (c) P POLYMER 177.440 nm low, and (d) P POLYMER 177.440 nm high.

540 November 2010 SPE Production & Operations

levels (a few ppm active). This work updates earlier work on SI
analytical methods and procedures reported by this group almost
20 years ago (Graham et al. 1993, 1995a, 1995b, 1996; Sorbie
et al. 1992). Detailed procedures are presented in Appendix A
of this paper and they are also described in the FAST laboratory
procedures manual (Sorbie and Boak 2006). Under each topic
presented here, some comments are made on the field or laboratory
significance of these analytical developments.
C18 and NH2 Cartridges and Hyamine. Through the use of
amino-propyl (NH2) cartridges, sulfonated polymeric species have
been detected to the same accuracy as with the previously used
C18 cartridges for nonsulfonated polymers such as PPCA and
PCA. This means that the normally laborious separation step for
sulfonated polymers from interfering salts by dialysis cartridges
can now be avoided. Similar work has been investigated (Jones
et al. 2007). Wet-chemical analysis required for field samples of
sulfonated polymerics should now be a quicker and more accurate
process, using this new technique of amino-propyl cartridges and
Hyamine.
Oasis® 2×4 Method. This generalized SPE method was used to
detect a VS-Co SI, and again highlighted calibrations and repeats
were of a similar accuracy (less than 10%) to normal C18 or NH2
Hyamine methods. This statement holds when the method is used
for a range of different-salinity brines: DW, NSSW, Forties type
FW, and a high-salinity Heron-type FW. Although achievable
under these different conditions, there was a significant decrease
in the absorbance signals recorded with an increase in salinity.
Using a more-expensive, higher-capacity sorbent cartridge did not
significantly improve the results recorded.
Although of similar accuracy and repeatability to C18 and
NH2 cartridge Hyamine, the Oasis® 2×4 method still has a number
of advantages over these methods. For instance less sample is
required; it is less time consuming as 20 samples can be processed
simultaneously as compared to 10; and this one method can poten-
tially be used for a variety of different generic types of polymeric
SIs. In addition, the methods using the Oasis® 2x4 method are not
fully optimized and would probably benefit from further study for
SI analysis.
ICP Analysis in the Oil Phase. For a range of different ions such
as Ca2+, Mg2+, Fe3+, S–, P–, Y+, and Li+, calibrations and accurate
repeats within 5 to 10% error were achievable for ICP analysis
in an oil matrix such as white spirit. After solving a number of
compatibility issues, the concentration of an oil-tolerant SI was
determined successfully through the use of a calibration and
accurate repeats over a range of 0-to-10 and 0-to-2,500 ppm active
SI by using a matrix of 10% EGMBE/SI:90% white spirit. This
method allows direct analysis of ions of interest and SI concentra-
tions in the oil phase without the need for a partitioning step into
water from a nonaqueous SI treatment. This reduces the potential
problems of loss of ions/SI, giving a more-accurate picture of what
is present in each produced phase. This will be particularly useful
for analyzing coreflood returns and closing the mass balance on
the oil-soluble (or oil-dispersed) SI.
Easy Hyamine: Matrix-Matching Technique. A matrix-match-
ing Hyamine technique has been developed that allows any chlo-
ride-ion effects on the chelating process between the Hyamine and
SI to be negated, allowing accurate analysis to be performed for
low polymeric-SI concentrations. This matrix-matching technique
would be advantageous to analysts working in a field environment
where there was no additional equipment or apparatus (normally
required for removing/isolating the inhibitor from the brine system)
available other than an ultraviolet spectrometer and pipettes.
ICP and Wet-Chemical Analysis of a New P-Tagged Copolymer.
This polymer can be determined by both ICP and wet-chemical-
analysis techniques. Equivalent analysis was performed by both
routes, and similar determined concentrations for the same test
solutions were observed. The signal intensities from the ICP 0 to
November 2010 SPE Production & Operations
10 ppm active analysis indicate that this P-tagged copolymer gives
a greater P signal (especially at lower concentrations) than PPCA,
which helps with low-end concentration determination, such as
0.5 and 1 ppm. The additional P content within the P-tagged
copolymer would be useful under field conditions or in a harsher
brine system than NSSW where interferences could be present in
the produced water, making analysis of the SI more difficult (i.e.,
it would be easier to identify the SI content from the background
response). Because a number of comparable techniques are avail-
able to detect this P-tagged copolymer SI, greater flexibility is
offered to the analyst. In addition, measurements can be performed
by different techniques and the results compared to ensure that
each analysis is consistent, if difficulties are experienced. There
may also be potential for deploying such species with other P-con-
taining phosphonates in subsea wells. For example, a combination
of total P and polymer wet-chemical detection may allow the assay
of two species to be performed.
Nomenclature
d = diluent volume on diluter
MAX = mixed-mode anion exchange
MCX = mixed-mode cation exchange
NH2 = amino-propyl (solid-phase-extraction cartridges)
s = sample volume on diluter
VS-Co = vinyl Sulfonated copolymer
WAX = mixed-mode weak anion exchange
WCX = mixed-mode weak cation exchange
Acknowledgments
The authors would like to thank the following sponsors of the FAST
group at Heriot-Watt University for their support: Baker Hughes, BP,
BWA Water additives, Champion Technologies, Chevron, Clariant,
ConocoPhillips, Halliburton, MI-Swaco, Nalco, Petrobras, Petronas,
REP, Rhodia, Saudi Aramco, Shell, Statoil, and Total.
References
Bedford, C.T., Burns, P., Fallah, A., Garnham, P.J., and Barbour, W.J. 1994.
A New Aassay for Phosphinocarboxylate Scale Inhibitors at the 5ppm
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Symposium on Chemistry in the Oil Industry, Ambleside, Cumbria,
UK, 12–14 April.
Christian, G.D. 1993. Analytical Chemistry, fifth edition. New York: John
Wiley & Sons.
Graham, G.M., Sorbie, K.S., and Littlehales, I. 1993. The Detection
and Assay of Oilfield Scale Inhibitors in Real Field Brines. Paper
presented at the Water Management Offshore Conference, Aberdeen,
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Graham, G.M., Sorbie, K.S., Boak, L.S. 1995a. Development of Accurate
Assay Techniques for Poly Vinyl Sulphonate (PVS) and Sulphonated
Co-Polymer (VS-Co) Oilfield Scale Inhibitors. Paper presented at the
6th NIF International Oil Field Chemicals Symposium, Geilo, Norway,
19–22 March.
Graham, G.M., Sorbie, K.S., Boak, L.S., Taylor, K., and Blilie, L.A.
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Graham, G.M., Sorbie, K.S., Johnston, A., and Boak, L.S. 1996. Com-
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International Oil Field Chemicals Symposium, Geilo, Norway, 17–20
March.
Inches, C.E., Sorbie, K.S., and El Doueiri, K. 2006. Green Inhibitors:
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Jones, C.R., Hails, M.J., and Downward, B.L. 2007. New Convenient Ana-
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Appendix A: Experimental Procedures
A1: C18- and NH2-Cartridge Hyamine. These cartridges represent
an SPE technique where the C18 and NH2 cartridges have varying
sorbent properties and applications. The C18 is a silica-bonded phase
with strong hydrophobicity that can be used to absorb analytes of
weak hydrophobicity from aqueous solutions, similar to reversed-
phase HPLC columns. The NH2 cartridge however, although similarly
silica-based, is a polar bonded phase with a basic character. This allows
selectivity for acidic/basic analytes or as a weak anion exchanger in
aqueous medium. It therefore works through both reversed or normal
phase methodology. Having slightly different functions at retaining
analytes does not affect the visible appearance of these cartridges
because both types look exactly the same (Fig. A-1).
Sample preparation time can be reduced by using Waters Sep-
Pak® cartridges. These cartridges can be used to aid an analytical
technique by
1. Enhancing purification of the sample by retaining the main
species (i.e., SI and allowing interferences such as brine salts to
flow through the system)
2. Concentrate up an SI if it is below detection level. Once the
SI has been retained on the cartridge, then
3. A solvent-exchange process can be performed to allow the
retained SI to be eluted into a desirable solvent for the analytical
procedure that is to follow.
C18-Cartridge Hyamine.
1. Dilute the inhibitor stock solution to make 50-mL standards
at concentrations of 0 to 10 ppm active in the appropriate brine
(i.e., SW, FW).
Fig. A-1—The visible appearance of a C18 and NH2 cartridge is
exactly the same.
542
2. Adjust 50 mL of each standard solution to pH 1.5 to 2.0 by
dropwise addition of hydrochloric acid 10% v/v.
3. Attach a 5-mL syringe of methanol to the long end of a
Sep-Pak C18 cartridge. Pass the methanol through the cartridge
dropwise and discard the expelled solution.
4. Using a syringe, pass 10 mL of DW slowly through the
cartridge and discard the expelled solution.
5. Using a 60-mL syringe and the Razel syringe pumps, pass
inhibitor solution through the cartridge (7 to 8 minutes of flow).
Collect the fluid in a cup.
6. Wash the cartridge from the same end with 10 mL of DW
from a syringe, again using the Razel syringe pumps. The com-
bined collected fluids from Steps 5 and 6 for each of the standard
solutions can now be discarded, because the inhibitor should be
adsorbed onto the cartridge.
7. Invert the cartridge and attach to the short end a syringe
containing 10 mL of a 5% solution of sodium citrate in DW.
8. Elute the inhibitor slowly from the C18 cartridge using the
10 mL of sodium citrate solution on the syringe pumps and collect
each eluent in a 50-mL volumetric flask.
9. Using the same 10-mL syringe, pass 10 mL of DW through
the C18 cartridge, again collecting the eluent in the 50-mL volu-
metric flask.
10. Pipette 10 mL of a 5,000 ppm (as supplied) aqueous solu-
tion of Hyamine 1622 into the flask and dilute to the mark (50
mL) with DW. A time interval of 1 minute is suggested for the
addition of Hyamine to each flask to allow for analysis time on
the spectrophotometer.
11. Shake the volumetric flask rapidly to ensure that the solu-
tions are mixed, and leave to stand for 40 minutes.
12. After 40 minutes, measure the absorbance of each of the
standard solutions at 500 nm using a spectrophotometer.
13. Construct a calibration graph from the recorded standard
solution absorbance values. It is normally a third-order curve.
14. Perform repeat analysis at known concentrations (i.e., 2 and
5 ppm) to determine the method repeatability using the previously
constructed calibration graph.
15. Repeat the procedure for samples and determine the concen-
tration of chemical in the solution using their recorded absorbance
values and the previously constructed calibration graph. Remember
to include blanks and repeat standards within the analysis run.
NH2-Cartridge Hyamine. The procedure for the NH2-cartridge
Hyamine is similar to that of the C18-cartridge procedure detailed
except
1. Use NH2, amino-propyl cartridges and substitute 0.1N NaOH
for the 5% sodium citrate, in Steps 7 and 8.
2. Include Step 9a. Pipette 10 mL of 5% sodium citrate into a
50-mL flask after the NaOH and DW, but before the addition of
10 mL Hyamine.
A2: OASIS® 2×4 Method. This family of extraction products—
MCX, MAX, WCX, and WAX—combine the right absorbent
chemistry with robustness and sensitive/selectivite SPE methods.
MCX and MAX are two mixed-mode strong-ion-exchange chem-
istries to address weak basic and acidic compounds, respectively,
while WCX and WAX selectively extract strongly basic and
strongly acidic compounds, respectively. By using all four car-
tridges in the Oasis® 2×4 Method alongside the Oasis® hydrophilic-
lipophilic-balanced (HLB) cartridge, the reversed phase sorbent,
they provide a simplified strategy for method development by
selecting the correct SPE sorbent and protocol.
In summary,
Oasis® HLB—hydrophilic-lipophilic-balanced reversed phase
sorbent for acids, bases, and neutrals
Oasis® MCX—nixed-mode cation-exchange reversed phase
sorbent for bases
Oasis® MAX—mixed-mode anion-exchange reversed phase
sorbent for acids
Oasis® WCX—mixed-mode weak cation-exchange reversed
phase sorbent for strong bases (e.g., quaternary amines)
Oasis® WAX—mixed-mode weak anion-exchange reversed
phase sorbent for strong acids (e.g., sulfonates)
November 2010 SPE Production & Operations
 Although there are four different sorbent types and the HLB
cartridge, only two protocols for detection are required. The
MCX and WAX cartridges can be paired together and follow one
protocol, while MAX and WCX follow another to extract acids,
bases, and neutrals with high SPE recoveries while removing
matrix components that may interfere with analysis. The main
advantage of this Oasis® 2×4 Method is the key features of the
sorbent material. It has stability at all pH values from pH = 0
to pH > 14, allowing great flexibility for retaining the SI and in
a wide range of solvents (i.e., different types of acids/alkalis),
allowing significant retention of polar compounds while having
a hydrophobic retention capacity that is three times that of the
traditional C18. The sorbent capacity/performance is not affected
by drying out as in the C18 because the sorbent is polymeric and
has hydrophilic portions that “hang on” to the water in contrast to
the C18/NH2 silica, which actively tries to expel the water from
its pores, causing a drying-out effect and loss of retention. These
mixed-mode cartridges operate through both reversed phase and
ion-exchange, enabling much stronger washes, resulting in very
clean extracts. There is no analyte breakthrough or loss of recov-
ery because of dissolving silica particles at high pH or cleaving
the bonded phase at low pH. One major overriding advantage of
the Oasis® 2×4 Method is that large batches of 20 samples can be
prepared simultaneously as opposed to 10 using the C18 or NH2
cartridges, making the whole process more efficient.
To address any source of pipetting error, a larger introduction
vessel was attached to an adaptor that consequently fitted into the
top of the previously used cartridge, as shown in Fig. A-2.
For more information on these cartridges or the Oasis® 2×4
Method and protocols, visit www.waters.com and www.waters.
com/oasis.
The Oasis® cartridges—MAX, MCX, WAX, WCX, and HLB—
being used have a 3-mL volume capacity and contain 60 mg sor-
bent (higher sorbent capacity is 150 mg), which has a particle size
of 30 µm. The main cartridge used by FAST for their analysis has
been the WAX cartridge. The following procedure will be based
on the WAX protocol.
1. Dilute the inhibitor stock solution (normally 100 ppm active)
to make 10-mL standards at concentrations of 0 to 10 ppm active
in the appropriate brine (i.e., SW).
2. Adjust 10 mL of each standard/repeat solution to pH 1.5 to
2.0 by drop-wise addition of hydrochloric acid 10% v/v.
3. Set up the Oasis tank with no test-tube rack inside and the
vacuum pump apparatus with waste flask in line between the tank
and pump.
4. Put holders into tank top plate before attaching a cartridge to
each holder. Block off any free openings not being used, although cali-
bration and method repeats can be performed simultaneously, which
potentially uses up all holders. Remember to label cartridges.
5. To the top of each cartridge, attach an adaptor and then a
large introduction vessel ensuring that all the pieces are securely
together to avoid leaks and loss of fluids, which would introduce
errors.
Fig. A-2—A photo of the Oasis® 2×4 Method apparatus including
the larger introduction vessels, the adaptors, cartridges, and a
vacuum pump to draw the fluids through the system.
6. To prepare the cartridges, pipette 5 mL of methanol into each
cartridge by the large introduction vessel.
7. Turn on the pump, then adjust the valve on the tank so that
the solution is being pulled through the cartridge in a drop-wise
fashion. This should allow adequate contact time for each solution
with the sorbent. After passing through the cartridge, the methanol
goes to waste into the flask between the tank and pump. Watch
the level in the flask and empty before the fluid level reaches the
outlet.
8. Wait for the methanol to be fully through the cartridge before
switching the pump off.
9. Add 5 mL of 1.76% formic acid while following Steps 6
through 8.
10. Add 10 mL of each standard repeat (at pH = 2) to its cor-
responding cartridge through its large introduction vessel while
following Steps 6 through 8.
11. Add 5 mL of 1.76% formic acid while following Steps 6
through 8.
12. Add 5 mL of DW while following Steps 6 through 8.
13. Dry off the inside of the tank and place the test-tube rack
containing labelled test tubes into the tank. Replace the tank top
plate.
14. Add 3 mL 10% ammonium hydroxide and allow it to be
pulled through the cartridges into the test tubes. Turn off pump.
Release pressure in tank using relief valve on top plate and remove
test-tube rack of calibration standards/repeats.
15. Add 1 mL of 5% sodium citrate solution to each standard/
repeat solution.
16. Add 1 mL of 5,000 ppm (as supplied) Hyamine 1622 solu-
tion to each standard/repeat solution. Stopper the test tube, shake,
and then leave for 40 minutes. A time interval of 1 minute is sug-
gested for the addition of Hyamine to each test tube to allow for
analysis time on the spectrophotometer.
17. After 40 minutes, measure the absorbance of each of the
standard/repeat solutions at 500 nm using a spectrophotometer.
18. Construct a calibration graph from the recorded standard
solution absorbance values. It is normally a third-order curve.

TABLE A-1—THE WAX PROTOCOL

Volume of Solution Collecting
Step Why? Type and Concentration Process Test-Tubes

1 Cartridge preparation 5 mL methanol Equilibration No

pH treatment to allow
2 pH adjusting sorbent 5 mL 1.76% formic acid No
better SI ‘lock on’
3 SI solution 10 mL sample at pH2 SI onto cartridge No
pH treatment to ensure
4 Ensure SI is ‘locked on’ 5 mL 1.76% formic acid No
SI is ‘locked on’
5 Wash 5 mL DW Clean up of salts No
6 To release SI 3 mL 10% ammonium hydroxide Elution of SI Yes
7 Involved in analysis 1 mL 5% sodium citrate / /
8 Reagent 1 mL 5000ppm ‘as supplied’ Hyamine Determination of [SI] /

November 2010 SPE Production & Operations 543

 TABLE A-2—OIL ANALYSIS BY ICP

Settings on Ultima 2 Aqueous Oil

Argon humidifier Use Do not use—tubing in its place

Power (watts) 1250 1200
Pump speed 20 20 ok for yellow tubing, 10 for black tubing
PL1 -> PL2 15 15
AUX 0.8 0.8 adjust on front of machine if required
G1 -> G2 0.2 0.3
Pneb 2.70 2.40 adjusted by flow through metal nebulizer
Cref 193.026 at 700V 247.856 at 400V
Global rinse X5 Y-20 Z75- 500 tray Tray 4 position 1—Oils tray 070509

TABLE A-3—BRINE COMPOSITIONS

Forties ‘type’ FW (ppm) Heron ‘test’ FW (ppm)
Ion NSSW (ppm) (Original [Ca2+] = 5038ppm) SPE 49197
+
Na 10,890 31,275 75,000
Ca2+ 428 2,000 42,000
Mg2+ 1,368 739 1,930
K+ 460 654 11,400
Ba2+ 0 269 1,360
Sr2+ 0 771 1,340
SO42- 2,960 0 0
-
Cl 19,773 55,279 207,712

19. Calculate the concentration of the repeat tests at their
known concentrations (i.e., 0, 0.5, 1, 4, and 6 ppm) to determine
the method repeatability using the previously constructed calibra-
tion graph.
20. Repeat the procedure for samples, and determine the concen-
tration of chemical in the solution using their recorded absorbance
values and the previously constructed calibration graph. Remember
to include blanks and repeat standards within the analysis run.
In summary, the WAX protocol is in Table A-1.
A3: Oil Analysis by Inductively Coupled Plasma. Table A-2
displays the gas settings required to achieve a lit plasma for aque-
ous and oil ICP analysis.
A4: Easy Hyamine. In this procedure, the interferences from brine
salts are diluted out. The initial stock has to be of a high enough
value that when a dilution in DW is performed from the experiment
SW stock, little interference is observed from the brine salts on
the addition of the sodium citrate and Hyamine for the detection
of the SI concentration present. This is checked by ensuring that
a calibration and good repeatability can be achieved for each SI
species being evaluated. The advantage of this method is that little
pretreatment of the sample, other than a dilution in DW, is required.
Therefore, it is a quick method to use.
If the inhibitor samples to be analyzed are low-salinity brines
(e.g., SW) or if the SI stock/samples are of a sufficiently high
concentration, then dialysis is not required and a large dilution in
DW is sufficient to reduce the salinity.
The analytical procedure is therefore as follows:
1. Dilute the inhibitor stock/sample that is in SW or FW brine
to a concentration that is appropriate for the test type and the fol-
lowing analysis (i.e., 25 ppm or 100 ppm active, in DW).
2. From this lower DW stock, make 5-mL standards at con-
centrations 0, 0.5, 1, 2, 3, 4, 5, 6, 8, and 10 ppm active in DW, in
order to obtain a calibration curve.
3. Add 1 mL of 5% sodium citrate solution to each standard
solution.
4. Add 1 mL of 5,000 ppm (as supplied) Hyamine 1622 solution
to each standard solution. Stopper the test tube, shake, and then
leave for 40 minutes. A time interval of 1 minute is suggested for
the addition of Hyamine to each test tube to allow for analysis time
on the spectrophotometer.
5. After 40 minutes, pour the solution into a 2-cm cell and
measure the absorbance at 500 nm using a spectrophotometer.
6. Construct a calibration graph from the recorded standard
solution absorbance values.
7. Perform repeats at known concentrations (i.e., 2, 5, and 10
ppm) to determine the method repeatability using the previously
constructed calibration graph.
8. Repeat the procedure for samples and determine the con-
centration of chemical in the solution using their recorded
absorbance values and the previously constructed calibration
graph. Remember to include blanks and repeat standards within
the analysis run.
A5: Brine Compositions. The brine compositions used throughout
this study are given in Table A-3.
Ken Sorbie is a professor of petroleum engineering at Heriot-Watt
University, Edinburgh, Scotland, UK. His research interests include
the modeling of multiphase flow in porous media, particularly
on the fundamentals of two- and three-phase flow at the pore
level and on the effects of wettability. He is also active in the
study of chemical and porous media transport aspects of min-
eral-scale formation and prevention in oil fields. Sorbie holds a BS
degree in chemistry from Strathclyde University, Scotland, and a
PhD degree in theoretical chemistry/applied mathematics from
Sussex University. Sorbie received the SCA 2004 Distinguished
Achievement Award and the SPE IOR Pioneer Award in 2008.
Lorraine Boak is a research fellow and also laboratory manager
with the Flow Assurance and Scale Team (FAST) at The Institute
of Petroleum Engineering, Heriot-Watt University, Edinburgh,
Scotland. She joined the FAST group in 1993 as a research tech-
nician. Her research examines the mechanisms/kinetics of sur-
face nucleation and growth of barium sulphate, the effects of
desulphation, and analytical techniques. Boak has presented a
number of papers/posters at both international and national
conferences. She holds a BSc degree in chemistry and a MPhil
degree by research from Heriot-Watt University.

544 November 2010 SPE Production & Operations

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