Author’s Accepted Manuscript

Water Tracers in Oilfield Applications: Guidelines

C. Serres-Piole, H. Preud’homme, N. Moradi-
Tehrani, C. Allanic, Hugo Jullia, R. Lobinski

www.elsevier.com/locate/petrol

PII: S0920-4105(12)00197-0
DOI: http://dx.doi.org/10.1016/j.petrol.2012.08.009
Reference: PETROL2295

To appear in: Journal of Petroleum Science and Engineering

Received date: 23 May 2011

Revised date: 9 July 2012
Accepted date: 13 August 2012

Cite this article as: C. Serres-Piole, H. Preud’homme, N. Moradi-Tehrani, C. Allanic,

Hugo Jullia and R. Lobinski, Water Tracers in Oilfield Applications: Guidelines, Journal
of Petroleum Science and Engineering, http://dx.doi.org/10.1016/j.petrol.2012.08.009

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 Water Tracers in Oilfield Applications:
Guidelines
C. Serres-Piole a,b, H. Preud’homme b, *, N. Moradi-Tehrani a, C. Allanic a, Hugo Jullia a and R. Lobinski b:
a
TOTAL, CSTJF, Avenue Larribau, 64018 Pau cedex, France
b
CNRS/UPPA, Laboratory of Analytical Bio-Inorganic and Environmental Chemistry (LCABIE), UMR 5254 -
IPREM, 2 avenue Angot, 64053 Pau cedex9, France

* Corresponding author:
E-mail address: hugues.preudhomme@univ-pau.fr
Full postal address: LCABIE - UMR5254 CNRS – IPREM, 2 avenue Angot, 64053 PAU cedex9
Telephone and fax numbers: +33(0)559407738 - +33(0)559407781

Abstract
A key parameter in tracing tests is the selection of the molecules used as water tracers. Many previous tests have failed
because of improper selection of these molecules. To address this issue, the first part of this paper provides guidelines,
offering data and advice for choosing the best possible tracers for a tracing campaign. This part of the paper presents the
different types of water tracers proposed and used in oilfield applications, from the first qualitative tracer study in the 1960s
to tracer studies in the 2000s, with their respective advantages and drawbacks. The oil industry began to conduct interwell
tracer tests with molecules already successfully used in hydrology. These compounds included radioactive species and
stable isotopes, chemicals such as fluorescent dyes, and inorganic ions. Some of the early chemical tracers have been
rejected because of issues with adsorption onto the rock. Radioactive species, with a low detection limit, a low reactivity,
and a low presence in the environment, have been widely used. However, their use has become more restricted throughout
the world in response to the radioactive hazards associated with their use. Therefore, new types of non-radioactive tracers
were developed and tested in the 1990s. Currently, however, few chemical molecules possess characteristics matching the
selection criteria of an effective water tracer (with regard to environmental and economic aspects, etc.). The most effective
molecules currently used as water tracers are the fluorinated benzoic acids (FBA); these molecules can be detected with
very low limits of detection (LOD) using analytical techniques such as gas chromatography or ultra-high-performance
liquid chromatography coupled with mass spectrometers (GC/MS and UHPLC/MS-MS, respectively).
The second part of the paper deals with the analytical aspect of a tracing test. An alternative technique to the
fluorescence methods currently used for the naphthalene sulfonic acids (NSA) is proposed: UHPLC/MS-MS. With this
original tool, FBA and NSA could be simultaneously detected in water samples in only one 5-min analysis. Other
molecules, halogenated boronic acids, were also tested analytically for their potential application as tracers. However, these
molecules were not retained because of their overly high LOD, requiring the injection of large quantities into oil reservoirs.

Keywords
Water tracers, oil reservoir, passive, partitioning, detection

Abbreviations
EDTA: ethylene diamine tetra acetic acid
FBA: fluorinated benzoic acid
FID: flame ionization detector
FLD: fluorescence detector
GC: gas chromatography
HPLC: high-performance liquid chromatography
HTO: tritiated water
IC: ionic chromatography
ICP-MS: inductively coupled plasma – mass spectrometry
IR-MS: isotopic ratio – mass spectrometry
IWTT: interwell tracer test
MS: mass spectrometer
MS-MS: tandem mass spectrometry
NMR: nuclear magnetic resonance
NSA: naphthalene sulfonic acid
PITT: partitioning interwell tracer test
SWTT: single-well tracer test
UHPLC: ultra-high-performance liquid chromatography
UV: UV detector

1. Introduction
 Tracer techniques are a powerful diagnostic tool in numerous scientific disciplines (Bjornstad et al., 1990; Divine and
McDonnell, 2005) and for technologies in many industrial sectors. Tracer tests were first used in the early 1900s in
hydrology (Du and Guan, 2005; Guan et al., 2005). Today, these tests are used with increasing frequency in oilfield
applications (Bingyu et al., 2002; Bjornstad, 1991; Jin et al., 1997) when no other investigation technique is applicable.
Tracer tests provide a better understanding of the studied oil reservoir (including interwell connections, connections
between layers and heterogeneities) (Coronado and Ramirez-Sabag, 2008; Coronado et al., 2009; Guan and Du, 2004;
Manichand et al., 2010; Nugroho and Ardianto, 2010; Sinha et al., 2004).
Petroleum companies began to conduct interwell tracer tests in the 1960s (Asadi and Shook, 2010; Du and Guan, 2005;
Guan and Du, 2004; Shook et al., 2009) by selecting molecules already successfully used in hydrology (Ahmad et al.,
2003). Although several methods exist to obtain precise information for reservoir description purposes, such as production
rates of reservoir fluids and 4D seismic and pressure testing (Barree et al., 2010; Bjornstad, 1998; Bjornstad et al., 1997;
Bragg et al., 1978; Myal and Wesson, 1981; Huseby et al., 2008, 2010; Hutchins et al., 1991; Prakash Das et al., 2009;
Sathyamoorthy et al., 2009), tracers have proven a very useful and efficient experimental tool in complex reservoirs where
data are difficult to obtain with other techniques (Asadi and Shook, 2010; Bennion et al., 1995; Cubillos et al., 2006; Shook
et al., 2009). With the development of chemical tracers in the 1990s, the water tracer test has become increasingly
important for the petroleum industry (Guan et al., 2005). These tests are increasingly used in the design of enhanced oil
recovery methods to follow the flow though the reservoir, control breakthroughs (Manichand et al., 2010; Manrique et al.,
2010), and select the most appropriate wells for enhanced oil recovery projects (Nugroho and Ardianto, 2010).
According to Du and Guan, 2005 (Shook et al., 2009), of 43 tracer tests reported in the literature in the 2000s, 60%
were aqueous phase tracers and 70% were interpreted qualitatively (Nava et al., 2009).
A key parameter in tracer tests is the appropriate selection of the molecules used as water tracers. The success of a
tracer test depends on this parameter. One of the objectives of the present paper is to provide guidance for the appropriate
selection of tracers according to the study and the desired objectives.

2. Water tracers and tracing tests

The selection of the tracer type and tracing test (Gardien et al., 1996) for use in a tracing campaign design depends on
the application, the specific conditions of the reservoir, the study objectives, and the nature of the data under investigation.
Two main types of water tracers are referenced in the literature: natural and artificial, with either passive or partitioning
properties. Three types of tracer tests are referenced: non-partitioning and partitioning interwell tracer tests and the single-
well tracer test (Anisimov et al., 2009).

2.1. Tracer types

Natural and artificial tracers have been used for many years (Chrysikopoulos, 1993). Natural tracers are defined as
elements already naturally present in the studied environment (Asakawa, 2005). Artificial tracers are defined as non-
naturally existing compounds that are introduced into the reservoir.
A natural tracer is used for information about the distribution of the production in time, the water origin with the
identification of the source of the water produced and the contribution of the injected water to the producing well (Huseby
et al., 2009; Khan et al., 2006; Nava et al., 2009). An artificial tracer is used for both qualitative (interwell connections,
flow direction, the pathway of the water, heterogeneity) and quantitative information (velocities of the fluids, permeability,
residual oil saturation (SOR)) (Bjornstad, 1991; Du and Guan, 2005).
The differences between a passive and partitioning tracer result from their chemical natures and their particular physico-
chemical behaviors in the oil reservoir (Devegowda et al., 2009; Oyerinde, 2004).
The passive tracer has the same physico-chemical properties as the fluid in which it is injected (water). Also called a
“non partitioning” or “aqueous” tracer, it moves at the approximate velocity of the water phase without chemical reaction
or interaction (sorption, ion-exchange) with reservoir phases (formation water, oil) or with the rock as it moves through the
oil reservoir (Asadi and Shook, 2010; Guan and Du, 2004; Huseby et al., 2009; Oyerinde, 2004; Shook et al., 2009). In fact,
a tracer classified as passive will never be totally passive because of the small amount of adsorption and desorption that
occurs.
The partitioning tracer is soluble in both the oil and water phases (Knaepen et al., 1990). This partitioning phenomenon
with the oil phase (physical and chemical interactions with the rock or the fluids) causes a “chromatographic delay” in the
response of the partitioning tracer in comparison with the passive tracer (Jin et al., 1997; Oyerinde, 2004; Tang, 1995).
Four mechanisms can affect this delay: a partitioning effect with the other fluids (oil), adsorption to the rock, ion exchange,
and size exclusion. The first mechanism is the most recognized (Tang, 2005).
A passive tracer can be selected in a tracing campaign when the reservoir engineer requires both qualitative (a better
understanding of the water pathway, interwell connections, etc.) and quantitative information (sweep volumes, flow
velocities, permeability estimates, etc.) (Gardien et al., 1996; Huseby et al., 2009; Khan et al., 2006; Lliassov et al., 2001;
Meza et al., 2007; Nava et al., 2009; Somaruga et al., 2001).
When the reservoir engineer requires quantitative information about the oil in place (SOR), the simultaneous injection of a
passive tracer (used as reference tracer) and a partitioning tracer is required (Devegowda et al., 2009; Lliassov et al., 2002;
Tang, 1995; Tang and Zhang, 2001).

2.2. Types of tracing tests

 To obtain qualitative and quantitative information, interwell tracer tests (IWTTs) with passive tracers are used.
To estimate the residual oil in place, two types of tests, using both passive and partitioning tracers, are possible
(Oyerinde, 2004): the partitioning interwell tracer test (PITT) (Asakawa, 2005; Jin et al., 1997), described by Cooke in
1971 (Cooke, 1971; Deans and Mut, 1997; Tang, 2002, 2003a; Tang and Zhang, 2000), and the single-well tracer test
(SWTT), patented by Exxon in 1971 (Deans, 1971; Deans and Mut, 1997). These two tests represent useful tools for
evaluating the efficiency of enhanced oil recovery methods (Buijse et al., 2010; Deans, 1978; McGuire et al., 2005).
In the SWTT test, a partitioning tracer is injected and reacts with the reservoir water to form a second tracer in situ
(Anisimov et al., 2009). The difference between the relative breakthrough times of the partitioning and non-partitioning
tracers is relative to the SOR (Tang and Harker, 1991).
Since 1971, this SWTT technique has been used in more than 200 sandstone and carbonate reservoirs. When the oil
fractional flow is negligible, the SOR can be estimated by the following formula, proposed by Deans (Chatzichristos et al.
2000):
SOR = (Δt / t0) / [ (Δt / t0) + Kow],
where t0 is the breakthrough time of the passive tracer, Δt is the time delay on the arrival between the partitioning and
ideal tracers, and Kow is the partitioning coefficient, defined as the ratio of the concentration of the partitioning tracer of the
immobile phase to its concentration of the mobile phase (Kow = Ctraceroil / Ctracerwater).
Whereas the PITT is used to quantify the volume of both mobile and residual oil over the entire reservoir volume swept by
the tracers, the SWTT is used to quantify oil near the well region only (Deans and Carlisle, 1986; Sinha et al. 2004;
Valestrand et al., 2010). However, the SWTT generally yields more rapid results. Thus, the SWTT was the most frequently
used application of partitioning tracers for measuring the SOR in the 1990s (O’Brien et al., 1978; Tang, 1995) and is still
considered more practical than the PITT by the oil industry (because of difficulties in interpreting PITT results) (Somaruga
et al., 2001).

2.3. The selection criteria for water tracers

2.3.1 Artificial tracers
Before the 1990s, many IWTT tests using artificial tracers were unsuccessful in hydrological and oilfield applications
(Davis et al., 1980; Reeves et al., 1996). One of the reasons for this failure was improper selection of the artificial tracers.
Some compounds were used without sufficient knowledge of their behavior under reservoir conditions. Some chemical
compounds were adsorbed to the rock, were broken down (Bjornstad et al., 2001) or progressed too slowly (Reeves et al.,
1996). These problems led to an incorrect interpretation of the data.
One of the most important parameters in a tracing test is the appropriate selection of tracers (Hutchins et al., 1991).
Many parameters (temperature, pressure, pH, rock type and properties, ionic force, water salinity, biological activity) have
an influence on tracer behavior (Bjornstad et al., 1994). Thus, the examination of an artificial tracer before injection,
including its physicochemical properties, is a required step in the tracer test (Bjornstad et al., 2001).
To correctly use artificial tracers and to conduct a quantitative analysis of tracer data, the selection criteria are as
follows (Becker and Coplen, 2001; Behrens et al., 2001; Bjornstad, 1991, 1998; Carr et al., 1997; Cubillos et al., 2006;
Dombrowski and Stetzenbach, 1993; Gozalpour et al., 2005; Jin et al., 1997; Shook et al., 2009; Wood et al., 1990):
• a tracer must be inert under injection, reservoir and production conditions; it must be highly stable thermally,
chemically, physically, and biologically for several years;
• a passive tracer must passively follow the phase in which it is injected (water), i.e., not be adsorbed to the rock or
partitioned with oil and be water soluble;
• a partitioning tracer must have a constant and reversible partitioning (Shook et al., 2009) with oil;
• a tracer must not influence the physical properties of the reservoir fluids;
• a tracer must not be present in the fluids of the reservoir to avoid background noise;
• a tracer must be detectable in very low concentrations with simple and fast analytical methods to reduce the costs and
the environmental impact via small injected quantities,
• a tracer must be at an acceptably low level of toxicity for the population and the environment;
• a tracer must not be capable of bio-accumulation;
• a tracer must be commercially available in large quantities at an acceptable cost.

2.3.2. Natural tracers

To apply natural tracers in oilfield applications, three conditions must be met. First, a careful characterization (chemical
and isotopic analysis) of the fluids is required before, during and after the water breakthrough (containing the natural
tracer). Second, the production water and the injection water must differ significantly in composition (sea water or aquifer
water) (Manichand et al., 2010; Webb and Kuhn, 1994). Third, the passive natural tracer must be inert (no chemical
reactions or ion exchanges).
If these conditions are met, the breakthrough of injected water can be naturally detected due to a significant change of
the composition of the produced water from the formation water in relation to the composition of the injected water
(Bjornstad et al., 1990; Huseby et al., 2009).

3. An overview of water tracers

 Few publications about the use of tracers in the oil industry provide details about the choice of tracers or the design of
the interwell tracer tests (Du and Guan, 2005; Guan et al., 2005). Prior to the 1990s, the oil industry literature contained
fewer documents accessible to the public on tracer technology than did the hydrological industry literature. This lack of
public literature slowed the development of analytical methods for tracers. However, this situation changed substantially in
the 1990s (Kleven, 2008). Field studies with water tracers are available in Dugstad et al. (1999), de Melo et al. (2001),
Gieles and Beuthan (2004), and Meza et al. (2007).
Researchers have proposed different tracer classifications. Three tracer types are referenced by Zemel (1995): natural,
radioactive, and chemical tracers. Other authors describe four main types of tracers: radioisotopes, fluorescent dyes, water-
soluble alcohols, and water-soluble salts (Jaripatke and Dalrymple, 2010) or chemical tracers (applied in the 1950s),
radioactive isotopes (applied in the 1970s), stable isotopes (applied in the 1980s), and microelement tracers (applied after
the 1990s) (Bingyu et al., 2002).
Because the passive water tracers must be in a form that follows the water pathway, they are often anionic or neutral
atoms or molecules; indeed, the anions tend to be more conservative than the cations in natural systems (Chrysikopoulos,
1993).

3.1. Passive tracers

3.1.1. Natural tracers
Every compound present in a given environment, such as reservoir water, can be a natural tracer (Huseby et al., 2009).
The main advantage of the natural tracers is their presence in the reservoir water, resulting in a lower cost than artificial
tracers, which must be bought and injected into the reservoir (Manichand et al., 2010; Wei, 2010). The use of natural
tracers prevents possible problems associated with the addition of a foreign substance (Raheim and Smalley, 1986). In
addition, natural tracers are more environmentally friendly than chemical or radioactive tracers (Asakawa, 2005). The
efficiency of natural tracers, described by Huseby et al. (2005, 2009), is also explained by the fact that every water body is
characterized by unique isotopic ratios (Skilbrei et al., 1990; Smalley et al., 1988).
Several elements and molecules have been proposed as tracers in oilfield applications: Cl-, Br-, SO42-, Ca2+, Mg2+, Na+,
K , Sr2+, Ba2+, HCO3- (Bjornstad, 1991; Huseby et al., 2005, 2009; Manichand et al., 2010; Munz et al., 2010; Wei, 2010;
+

Ziegler et al., 2001). However, some of these elements can be affected by chemical reactions (ion exchange) with the rock
matrix or the water of the reservoir formation. Only SO42-, Cl-, K+, and Mg2+ can be considered passive seawater tracers.
Stable isotopic elements, such as 18O, 2H, and 13C (Ahmad et al., 2003; Birkle et al., 2006; Khan et al., 2006) have also
been used as natural tracers, as have the following ratios (Bjornstad, 1991; Huseby et al., 2005; Zemel, 1995; Ziegler et al.,
2001): δ18O (18O/16O,) δD (2H/1H), δ13C, δ37Cl, 87Sr/86Sr (Birkle et al., 2006; Bjornstad et al., 1990; Munz et al., 2010;
Raheim and Smalley, 1986), Cl/Br (Alcala and Custodio, 2008), and 34S/32S (Huseby et al., 2005).
Among these isotopic elements, 18O and 2H are considered excellent passive water tracers because these elements
belong to the water molecules themselves. These elements have often been used to determine the origin of water or to
characterize the efficiency of injected water (Ahmad et al., 2003; Huseby et al., 2005, 2009). The strontium ratio (87Sr/86Sr),
proposed by Raheim and Smalley (1986), has been widely and successfully applied as a natural tracer for the injection of
seawater into reservoirs (Huseby et al., 2009). The stable isotopic ratio of chloride is also useful in tracing the origin and
transport mechanisms of water (Ziegler et al., 2001).
Some ratios, such as 2H/1H and 87Sr/86Sr, are only appropriate for sandstone and limestone reservoirs (Ziegler et al.,
2001). These ratios can be modified by water-rock interactions. Other elements are not always appropriate for use as water
tracers; for instance, Ba2+ can be neutralized by precipitation or by the formation of undissociated molecules of the form
BaS04 (Bjornstad, 1991), and SO42- can precipitate with barium or strontium ions (Huseby et al., 2005).
The natural elements, such as δD, δ18O, and 87Sr/86Sr, can be detected by mass spectroscopy (MS) techniques (Birkle et
al., 2006; Bjornstad, 1991; Khan et al., 2006; Zemel, 1995), such as ICP-MS (Birkle et al., 2006). In the case of a reservoir
in the North Sea, the sensitivity limit was of 0.5-1% content of injection water into formation water.
Several studies have confirmed the utility of natural elements for IWTT tests by providing information about the
breakthrough of the injected water containing a natural element as a tracer (Ahmad et al., 2003). However, the use of these
tracers has not been frequently reported in the literature, likely because of the need for sophisticated and expensive
analytical equipment for very sensitive mass spectrometry techniques (Ahmad et al., 2003; Bjornstad, 1991). In addition,
the accuracy and the sensitivity of a tracer test using natural tracers depends on the degree to which the three conditions
described in Section 2.3.2. are fulfilled (Bjornstad, 1991; Zemel, 1995). A significant difference in composition between
production water and injection water is not always detected. The analytical techniques and the data provided by this type of
test are respectively more complex and difficult to interpret than those of a tracer test with artificial tracers. As a result,
artificial tracers are often preferred in many cases of interwell tracer tests because they allow for a higher degree of
accuracy of the breakthrough detection, and their ease of interpretation provides a better characterization and understanding
of the reservoir (Ahmad et al., 2003; Manichand et al., 2010).

3.1.2. Artificial tracers

3.1.2.1. Radioactive elements
For oilfield applications between the 1960s and the 1990s, tracer tests were generally conducted with radioactive
elements (Bingyu et al., 2002; de Melo et al., 2001; Du and Guan, 2005; Fjerstad et al., 1993).

• Neutral species
 The neutral element with the best characteristics for a use as a passive tracer is tritium (3H) in the form of tritiated water
(HTO) (Wheelet et al., 1985). This element is an optimal water tracer because it has the same physico-chemical properties
as water molecules (Samuelsen et al., 2010).
HTO is a powerful tool in hydrology (Bouchaou et al., 2008) and geothermal applications (Dennis et al., 1981). It is
even considered the best passive water tracer available for vapor-dominated geothermal fields. In addition, HTO has been
largely used in oil reservoirs, as reported in the literature (Abernathy et al., 1994; Agca et al., 1990; Ahmad et al., 2003; Ali
et al., 2000; Allison et al., 1991; Anisimov et al., 2009; Bennion et al., 1995; Bingyu et al., 2002; Bjornstad, 1991;
Bjornstad et al. 1990; Cheng et al., 2005; Coronado et al., 2009; de Melo et al., 2001, 2005; Du and Guan, 2005; Huseby et
al., 2009; Khan et al., 2006; Khisamov et al., 2009; Lliassov et al., 2002; Maure et al., 2001; Nitzberg and Broman, 1992;
Oyerinde, 2004; Quang and Loder, 2006; Riedel, 1975; Samulesen et al., 2010; Skilbrei et al., 1990; Tang, 1995, 2003a;
Tang et al., 1992; Valestrand et al., 2010; Vilela et al., 1999; Zemel, 1995).
HTO has a low reactivity with the fluids and the reservoir rock (Bjornstad et al., 1990). It has been successfully tested
in the laboratory and under various field conditions (sandstone, limestone, and carbonate reservoirs with a recovery
percentage of 85.2%) (Khisamov et al., 2009). However, HTO is not applicable in some cases because of interference
caused by a high presence of natural tritium (Adams et al., 1992; Chrysikopoulos, 1993).
HTO guarantees an easy and safe manipulation because of its low radiation emissions, and the cost is relatively low (de
Melo et al., 2001; Hutchins et al., 1991).
HTO can be analyzed on site, and it is easily detectable at low concentrations by the liquid scintillation counting
method (Chatzichristos et al., 2000; de Melo et al., 2001; Khan et al., 2006). Different limits of detection (LODs) are
referenced in the literature, from 2-4 Bq/L (Bjornstad, 1991; Wheelet et al., 1985; Zemel, 1995) to 37-74 Bq/L
(Lichtenberger, 1991; Tyler, 2010). These LODs could be enhanced by an order of magnitude using specialized sample-
enrichment techniques (Birkle et al., 2006). However, when hundreds of samples must be analyzed, these methods are
economically unattractive (Lichtenberger, 1991).
HTO is still largely used as a reference tracer (Huseby et al., 2010; Valestrand et al., 2010) in many oilfield tests to
evaluate other compounds as tracers (Bjornstad et al., 2001) or as a material balance tracer in SWTT methods (Sheely and
Baldwin, 1982).
Other neutral radioactive molecules were also proposed as tracers, including benzoic acids and light alcohols (methanol,
ethanol, isopropanol), ketones and aldehydes, labeled with 3H and 14C (Bingyu et al., 2002; Bjornstad et al., 1994; Quang
and Loder, 2006; Tang, 1995). The advantages of these molecules are their reasonable cost (with the exception of 14C) and
low hazard levels. The labeled benzoic acids and light alcohols were tested successfully in reservoirs at 150°C in Vietnam.
These compounds showed the same behavior as HTO, having similar breakthrough curves (Quang and Loder, 2006). With
half-lives of 12.4 (Khan et al., 2006) and 5730 years for 3H and 14C, respectively, they are considered useful for long-term
tracer tests. Among these molecules, tritiated methanol is an effective water tracer with high stability in the reservoir
(Wood et al., 1990) and minimal losses by adsorption or chemical, radiochemical or biological degradation. However,
some alcohols exhibited a partitioning behavior at high temperature (100°C) or a biodegradation below 70-80°C in oil
reservoirs, in the case of tritiated ethanol. Tritiated alcohols can also be analyzed by liquid scintillation counting (Bingyu et
al., 2002) at the ng/mL level.

• Anionic and cationic species

Several anionic and cationic elements have been tested as passive water tracers (Abernathy et al. 1994; Allison et al.,
1991; Bjornstad, 1991; Bjornstad et al., 1994; Tester et al., 1979; Wheelet et al., 1985; Zemel, 1995), including 36Cl-
(Na+,36Cl-), 129I- (Birkle et al., 2006), 125I- (Skilbrei et al., 1990), 131I-, 35SCN-, S14CN- (Ali et al., 2000; Huseby et al. 2008),
(K+,SCN-, NH4+,SCN-), 35SO42-, 82Br- (NH4+,Br-), H14CO3-, 57, 58, 59, 60Co3+ ([Co(CN)6]3-) (Bennion et al., 1995; Cayias et al.,
1990; Cheng et al., 2005; Hutchins et al., 1991; Lichtenberger, 1991; Lliassov et al., 2002; Nitzberg and Broman, 1992;
Oyerinde, 2004; Tang, 1995), and 60Co2+ ([60Co2+-EDTA], denoted [60CoY]2- (ethylene diamine tetraacetic acid or YH4)).
These elements present a low reactivity with the fluids and with the rock. They are stable at high temperatures
(Bjornstad et al., 1994): up to 200°C for 131I- and 82Br- and up to 90-100°C for 35SCN-, S14CN- and 60Co2+ (Tester et al.,
1979). Among them, 36Cl-, 125I-, 131I- and Co2+ have been successfully used in sandstone and limestone reservoirs, with a
similar passive behavior as HTO. In addition, 36Cl-, 57, 60Co2+, and 129I- are suitable for long-term tracer tests, as opposed to
125 - 131 - 35
I , I , SCN-, 35SO42-, 82Br-, 58Co2+, which have short half-lives, on the order of days (Wheelet et al., 1985).
However, some ions have drawbacks. For example, 36Cl- and [57,58CO(CN)6]3- are costly. In addition, some tests have
shown that 36Cl-, 125I-, 131I-, 35SO42- could be affected by the negative surface of the rock (ion exclusion) and by possible
chemical reactions (131I-, 35SO42-) (Bjornstad, 1991; Bjornstad et al., 1994). H14CO3- may have a strong interaction with the
matrix in limestone or carbonate reservoirs (sorption or precipitation as CaCO3). [57CO(CN)6]3- and [57,60CoY]2- exhibit low
recoveries as a result of adsorption in the reservoir (Bjornstad et al., 1994). 35SCN- and 35SO42- have a proven application
only in sandstone (and limestone for 35SCN-) reservoirs. Finally, during a field test, S14CN- exhibited a restitution curve
that differed from HTO but was similar to the other anionic passive tracers. Since the 1990s, radioactive cobalts have not
been used widely as a result of safety concerns (absorption or complexation on the well tubing) (Lichtenberger, 1991).
They are easily detectable at low concentrations using an accelerator mass spectrometer for 36Cl- and 129I- (Bjornstad,
1991) or liquid scintillation counting for S14CN-, 35SCN- (LOD ~ 0.005 Bq/L) and 35SO42- (LOD < 0.05 Bq/L) (Bjornstad,
1991; Zemel, 1995). The liquid scintillation counting and gamma spectroscopy methods are also used for 125I- (LOD < 0.05
Bq/L) and [56;57;58;60Co(CN)6]3- (LOD ~ 0.01 Bq/L) (Bjornstad, 1991).
 Radioactive cationic molecules have rarely been used in IWTT tests because of adsorption issues. In addition to cobalt,
other elements have been tested (Bennion et al., 1995; Bjornstad, 1991; Bjornstad et al., 1994; Hutchins et al., 1991;
Wheelet et al., 1985), including 22Na+ (Na+, Cl-) (Bjornstad, 1998; Vilela et al., 1999; Zemel, 1995), 134,137Cs+ (Du and
Guan, 2005; Wood et al., 1993), 63Ni2+, 59Fe3+, 85,90Sr2+ ([90SrY]2-), Zn2+ ([65ZnY]2-), and Ir3+ ([192IrY]- or [192Ir(Cl)6]3-).
Other radioactive molecules, such as radon, have also been proposed to follow the injected fluids (Nava et al., 2009).
Among these radioactive cationic molecules, only 22Na+, 134,137Cs+, 63Ni2+ (Bennion et al., 1995) and [65ZnY]2- are used
in long-term tracer tests because of their half-lives of several years (2.6 years for 22Na+). 22Na+ (LOD between 0.06 and
0.10 Bq/L using liquid scintillation counting (Bjornstad, 1991; Zemel, 1995)) has been described as a useful tracer in
sandstone reservoirs at high temperatures in saline waters (according to laboratory tests). 134,137Cs+ yielded excellent results
during tests (Bjornstad et al., 1994 a) in a carbonate reservoir. 90Sr2+ and [90SrY]2- have shown an acceptable recovery
during a field test (Bjornstad et al., 1994).
However, 22Na+ and 134, 137Cs+ can also be affected by the negative surface of the rock (low reversible sorption) and are
delayed in comparison with HTO. 63Ni2+ showed a strong sorption in a sandstone reservoir (Bjornstad, 1991) during field
tests. 85Sr2+ has never been detected in a production well during a field test.
In 2000, 22Na+ was successfully used as passive water tracer in the development of a low-cost, two-dimensional
positron emission tomography system. This tool, commonly used in nuclear medicine, is an imaging technique that can
measure two- or three-dimensional tracer distributions and, thus, can visualize tracer flow inside porous media (Haugan,
2000).
Radioactive species such as scandium, iridium, and antimony, analyzed by gamma ray spectrometry (Scott et al., 2010),
were recently proposed as tracer tools (Sanford et al., 2010; Scott et al., 2010) to better understand fracture geometry or to
evaluate the distribution of fluid across a long perforated interval.

• Conclusion
Despite their potential radiation hazards, toxicity (radioactive halides), and short half-lives (with the exception of HTO),
radioactive tracers have advantages that motivated their use until the 1990s (de Melo et al., 2001; Du and Guan, 2005;
Fjerstad et al., 1993): ease of measurement (Bingyu et al., 2002); detection at very low concentrations (Adams et al., 1992;
Bjornstad, 1991; Bjornstad et al. 1990, Zemel, 1995), requiring very small injection quantities (Bennion et al., 1995); a
very low natural background in the environment (Du and Guan, 2005); and few reactions with the fluids and with the rock.
Radioactive tracers were long considered more reliable than chemical tracers (Bennion et al., 1995). However, because
the 1990s, chemical species have been preferred to radioactive species as a result of radiation hazards (Adams et al., 1992;
Bjornstad et al., 2001).

3.1.2.2. Chemicals
Prior to the 1980s, only a few chemical tracers had proven their efficiency or reliability (Adams et al., 1986, 1992;
Hutchins and Saunders, 1992): the orthophosphate anion (H2PO4-, HPO42-, PO43-), detected by colorimetry (µg/mL
detection level) (Brown, 1959); various water-soluble iodide salts (NaI, KI) (Sandiford, 1967) (µg/mL level) and water-
soluble thiocyanates and salicylates patented by Sandiford (1967) (µg/mL level); water-soluble salicylate and thiocyanate
ions (Sandiford, 1967); and PBTS (polyhydroxyalkyl-bis-triazinylamino-stilbene), detected by UV (Saniford and Knight,
1973). Salicylic acid and EDTA were also proposed by Riedel (1975), but their efficiency was not proven. Finally, these
molecules were largely abandoned as a result of problems such as adsorption onto the rock; destruction (oxidization,
precipitation, etc.); natural interference and contamination, which make analysis difficult (fluorescent compounds); large
required volumes and expense required for accurate detection, contrary to radioactive elements (for example, an alcohol
requires several thousand liters compared to only 5 mL of HTO) (Bennion et al., 1995).
Since the 1990s, interest in chemical tracers has greatly increased (Adams et al., 1992; Bjornstad et al., 2001) because
they present advantages over radioactive tracers: a lack of radiation hazards and easier detection as a result of simpler
analytical techniques (gas chromatography (GC), high performance liquid chromatography (HPLC), nuclear magnetic
resonance (NMR), ionic chromatography (IC), fluorimetry, colorimetry, UV spectroscopy, etc.) (Bennion et al., 1995;
Bjornstad, 1991; Zemel, 1995), reaching the pg/mL level (Bennion et al., 1995).

• Inorganic elements
Inorganic elements are interesting because they are cheap to purchase in large quantities (with the exception of I-)
(Hutchins et al., 1991) and to analyze (Cheung et al., 1999; Dalla Costa and Gaudet, 2006). They are also easier to use than
water isotopes (Dalla Costa and Gaudet, 2006) and are typically available in water-soluble sodium or ammonium salts
(Lichtenberger, 1991).
Among the inorganic elements, halides, Cl- (Carter and Sides, 1979; Ohno et al., 1987), Br- (Hetterschijt et al. 2000),
and I- (Axellson et al., 2001; Bjornstad et al., 1990; Riedel, 1975; Wagner, 1976) have often been applied as conservative
tracers in the oil industry (Bingyu et al., 2002; Shook et al., 2009) and geothermal applications (Axelsson et al., 2001;
Kumagai et al., 2004; Yanagisawa et al., 2002). These applications are well documented (Hutchins et al., 1991).
Cl- and Br- have proven their conservative behavior (Benson and Bowman, 1994; Dalla Costa and Gaudet, 2006; Munz
et al., 2010; Wienhöfer et al., 2009) with low adsorption and low thermal, chemical, and biological reactivity at low
temperatures. However, a weak delay in porous systems (anion exchange) has been observed for Cl- (Carter and Sides,
1979) and Br-. In addition, these elements can only be used in cases of low aquifer salinity or where their concentration in
the injected water is higher than in the formation water (to avoid the need to inject large quantities) (Wagner, 1976). I- is
not recommended in oil reservoirs because of its natural presence in formation waters (Wagner, 1976) and its less
conservative behavior than Cl- and Br- (Bjornstad et al., 1990; Chrysikopoulos, 1993).
Other molecules have also been proposed as tracers (Bjornstad, 1991; Bjornstad et al., 1997; Cheung et al., 1999; de
Melo et al., 2001; Hutchins et al., 1991; Zemel, 1995), including NO3- (NaNO3, LiNO3, NH4N03, KNO3) (Bjornstad et al.,
1994; Carter and Sides, 1979; Song et al., 1995; Yang et al., 2000) and NO2- (KNO2) (Ohno et al., 1987), SCN-(NaSCN,
NH4SCN, KSCN) (Agca et al., 1990; Ali et al., 2000; Allison et al., 1991; Cayias et al., 1990; Cheng et al., 2005; Gregory
and Kocsis, 1984; Hutchins et al., 1991; Lichtenberger, 1991; Lliassov et al., 2002; Oyerinde, 2004; Quang and Loder,
2006; Shook et al., 2009; Song et al., 1995; Tang, 2003a; Vilela et al., 1999; Yang et al., 2000), [CO(CN) 6]3- (Quang and
Loder, 2006), SO42-, BO33-, HBO32-, and B4072- (Bjornstad, 1991 and 1998).
Among these molecules, KNO2 was successfully tested in a 56-day laboratory test (Ohno et al., 1987). Li+ (LiCl) and I- also
demonstrated their usefulness as tracers able to follow the fluids during core tests in the laboratory (Shields et al., 2008).
The thiocyanate ion SCN- and the nitrate ion NO3- have often been used as tracers in the oil industry to study fluid
distribution (Song et al., 1995). However, researchers have found mixed results concerning their stability. SCN-,
characterized by a very low adsorption and presence in oil reservoirs, has been used with good results in a sandstone
reservoir (with a recovery of 90%) (Agca et al., 1990; Lichtenberger, 1991; Stetzenbach and Farnhalm, ). However, it has
also been shown that SCN- is not biologically and chemically stable, with possible degradation at temperatures above
100°C (Quang and Loder, 2006) and adsorption to rock (laboratory test for NH4SCN over 56 days, with C/C0 = 0.4 after 56
days) (Ohno et al., 1987).
Nitrate salts (NO3-) are not always applicable because they are subject to chemical and bacterial degradation in aerobic
and anaerobic conditions in oilfield brines (Bjornstad et al., 1990; Carter and Sides, 1979; Cheung et al., 1999; de Melo et
al., 2001).
Among the other tested elements, [Co(CN)6]3- has been decomposed after three months in a reservoir at 150°C
(biological reactions) (Quang and Loder, 2006), and BO33- (lost by adsorption (Bjornstad et al., 1994)), HBO32-, B4O72-
(Bjornstad, 1991, 1998) were not detected in produced sampled waters of the tested field (Zemel, 1995).
These anions are generally detectable by IC or HPLC (Lichtenberger, 1991; Yanagisawa et al., 2002). The IC LOD is
approximately 1 μg/mL for I- and Br- and approximately 0.1 μg/mL for NO3- and SCN- (Hutchins et al., 1991). SCN- was
also analyzed by spectrophotometry, with an LOD of approximately 1 µg/mL (Gregory and Kocsis, 1984). I- is also
detectable by UV adsorption and Li+ by ICP-AES (Shields et al., 2008), but the sensitivity depends on the water salinity
and overall composition.

• Alcohols
The alcohols and ketones are chemical products with a low cost (Cheung et al., 1999). As a result, these compounds
have greatly interested the oil industry for more than 50 years for use as tracers.
Only ketones and alcohols from C1 to C3 with Kow near zero are applicable as passive water tracers, including methanol
(Kow = 0.0001), ethanol (Kow = 0.0004) (Cockin et al., 2000), propanol (n-propanol or NPA for normal propyl alcohol),
isopropanol (IPA for isopropyl alcohol) (Kow = 0.03) (Bingyu et al., 2002; Bjornstad, 1991; Bjornstad et al., 1997; Carter et
al., 1979; Cayias et al., 1990; Cheung et al., 1999; Du and Guan, 2005; Gregory and Kocsis, 1984; Hutchins et al., 1991;
Jin et al., 1997; Lichtenberger, 1991; Shook et al., 2009; Vilela et al., 1999; Zemel, 1995) and acetone (Cayias et al., 1990).
However, despite their stability at very high temperatures (above 300°C for methanol) (Adams et al., 2004), these
products have drawbacks. For example, CH3OH is toxic (Cheung et al., 1999). In addition, these compounds can be subject
to bacterial degradation (Carter and Sides, 1979; Hutchins et al., 1991; Zemel, 1995) at low temperatures. Thus, they are
only suitable for moderate temperatures, according to Lichtenberger (1991). Finally, an initial high background noise for
alcohols is possible in oil reservoirs because of the presence of chemical reagents containing many alcohols, leading to a
false interpretation of the tracer test results.
Among these alcohols, a field test of propanol showed adsorption on the rock, with a recovery of 50% (Hutchins et al.,
1991). Isopropanol is less susceptible to biological attack than either methanol or ethanol (Zemel, 1995). Acetone, also less
affected by bacteria, was considered an effective tracer in 1990 (Cayias et al., 1990).
Alcohols, such as methanol, ethanol, isopropanol, and acetone, can be analyzed by GC/FID (µg/mL LOD for alcohols)
(Cayias et al., 1990; Lichtenberger, 1991) or spectrophotometry (µg/mL LOD) (Bingyu et al. 2002). LODs of 100 ng/mL
were also reached (Adams et al., 2004).
Methanol can also be analyzed by a GC coupled with a thermal conductivity detector (Wood et al., 1990). After 2004,
ethanol analyzed by GC (with a solid-phase microextraction) could be detected with an LOD of 1 ng/mL (Adams et al.,
2004; Mella et al., 2006).

• Fluorescent molecules
Fluorescent dyes have several advantages: they are easy to use (Cheung et al., 1999; de Melo et al., 2001) and
inexpensive to buy and analyze. The molecules tested in oilfield applications include fluorescein (Coronado et al., 2009; de
Melo et al., 2001, 2005; Khalil and Oliveira, 1999; Ohms et al., 2009; Stray et al., 2005), eosin, rhodamine, (Du and Guan,
2005; Lichtenberger, 1991; Ohms et al., 2009), and rhodamine-B (Bjornstad, 1991, 1998; Bjornstad et al., 1997; Cheung et
al., 1999; Hutchins et al., 1991; Riedel, 1975; Zemel, 1995).
Fluorescein is thermally stable and is generally not adsorbed to the geothermal reservoir rock (Axellson et al., 2001;
Rose et al., 2001b). With a highly stable fluorescence, fluorescein has been successfully used in a carbonate reservoir with
an 82.1% recovery percentage (Khisamov et al., 2009). However, according to these authors, fluorescein, eosin, and
rhodamine may sometimes adsorb onto the reservoir rock, partition with the oil phase (Cheung et al., 1999; de Melo et al.,
2001; Lichtenberger, 1991; Wienhöfer et al., 2009) and be biologically degraded (Stetzenbach and Farnhalm, ).
Rhodamine-B has been lost during field tests, according to Bjornstad (1991). Laboratory tests showed that fluorescein was
quickly degraded above 260°C (Adams et al., 1992) and was unstable at 200°C in the presence of oxygen.
As a result of these shortcomings, the application of such dyes (fluorescein, rhodamine) is limited to fractured
reservoirs with quick breakthroughs (up to five days) (Cheung et al., 1999; Lichtenberger, 1991).
These chemicals are relatively non-toxic at low concentrations (ultra-traces) (Becker and Coplen, 2001, Behrens et al.,
2001), with the exception of rhodamine-B, which exhibits genotoxic properties and is not recommended for water tracing
(Behrens et al., 2001).
These dyes are detectable on site by fluorimetry (LOD at low ng/mL levels (0.3 ng/mL for fluorescein) assuming a
negligible background fluorescence) (Chrysikopoulos, 1993; Hutchins et al., 1991; Kleimeyer et al., 2001; Wienhöfer et al.,
2009; Yanagisawa et al., 2002;). However, interference is possible during analysis as a result of the natural fluorescence in
the reservoir (oil and water) (Bennion et al., 1995; Cheung et al., 1999). Another method, spectrofluorimetry, enables the
achievement of an LOD of 10 pg/mL for fluorescein.
The dyes are also easily detectable by colorimetry (µg/mL level) (Khalil and Oliveira, 1999) and UV (fluorescein
detected at 0.1-10 µg/mL) (Khalil and Oliveira, 1999).
As an alternative to these techniques and to reach LOD at the sub-pg/mL level, Kleimeyer et al. (2001) proposed, for
hydrological applications, high-performance liquid chromatography (HPLC) coupled with a high-sensitivity laser-induced,
multi-wavelength fluorescence detector. A fluorescein concentration of 40 fg/mL could be detected.
A fiber optic probe can also be coupled to a light source, and both the fluorescence and reflectance signal can be
detected (Ramos and Stephenson, 1999).
Other commercially available fluorescent molecules, including naphthalene sulfonic acid (NSA), naphthalene disulfonic
acid (NdSA) and naphthalene trisulfonic acid (NtSA), have also been proposed as conservative water tracers in oil
reservoirs (Hutchins and Saunders, 1992; Stray et al., 2005), but their use in oil reservoirs has occasionally been
controversial in the 2000s (Hirtz et al., 2001).
Polycyclic aromatic sulfonic acids were first evaluated for geothermal applications. Among them, the un-substituted
NSA were the most promising based on the selection criteria (thermal stability up to 300°C, good detectability) (Rose and
McPherson, 1997).
NSA, NdSA, and NtSA were successfully tested in lab and in geothermal applications (Adams et al., 1992; Hirtz et al.,
2001; Mella et al.,, 2006; Rose et al., 2001b, 2003; Sanjuan et al., 2006; Stray, 2006; Stray et al., 2005; Yanagisawa et al.,
2002, 2009). These compounds have a conservative behavior, are very thermally stable (until 250°C-330°C) in liquid-
dominated geothermal reservoirs and are resistant to adsorption to the rock (strong electronic charge in the sulfonic acid
group) and do not pose hazards to the environment for long times (up to 4 years for 1,5-NdSA (Sanjuan et al., 2006))
according to Rose et al. (2001a).
2-NSA and 2,7-NdSA are the most stable compounds among the tested polyaromatic sulfonic acids (Rose et al., 2001
a). However, 2-NSA is not always recommended in oilfield applications because of its possible presence in the wells as an
additive (Stray, 2006).
The polyaromatic sulfonic acids substituted with hydroxy and amino groups were also successfully tested up to 250°C
(Rose et al., 2001b). However, their thermal stability is lower than NSA, and the compounds substituted with amino groups
can react to form stable and fluorescent compounds.
The biphenyl, p-terphenyl and fluorene sulfonic acids, proposed by Stray (2006), have a high thermal stability similar to
FBA. Among them, 4,4’-biphényl-disulfonic acid has a very low adsorption to the rock (tested at 195°C over 60 days).
NSA are detectable by HPLC/FLD, with an LOD of 200 pg/mL (Rose et al., 2001a, 2001b, 2003), or at the ng/mL level
by HPLC/UV using a pre-concentration procedure (Hutchins and Saunders, 1992). The choice of fluorescence detector can
be determined by the compounds’ fluorescence properties and financial considerations.
The biphenyl, p-terphenyl and fluorene sulfonic acids are also detectable by HPLC/FLD (10-100 pg/mL) (Stray, 2006).
The polyaromatic sulfonic acids substituted with hydroxy and amino groups present a better detectability (pg/mL level) by
fluorimetry than NSA (Rose and McPherson, 1997; Stray, 2006).

• Substituted benzoic acids and fluorinated benzoic acids

In the 1990s, other types of tracers were developed for hydrothermal, geothermal and oilfield applications (Hutchins
and Saunders (1992), including sodium benzoate (Sanjuan et al., 2006) and variously substituted benzoic acids
(Chrysikopoulos, 1993; Hirtz et al., 2001; Hutchins and Saunders, 1992; Rose and McPherson, 1997; Rose et al., 2001b),
such as trifluoro-p-toluic acid (Ghaddhab et al., 2010) and fluorinated benzoic acids (FBA) (Ali et al., 2000; Bjornstad,
1994b, 1998; Du and Guan, 2005; Dugstad et al., 1999; Galdiga, 1998; Galdiga and Greibrokk, 1998a, 1998b, 1998c;
Gieles and Beuthan, 2004; Hampton et al., 2001; Hernandez et al., 2002a; Huseby et al., 2009; Meza et al., 2007; Quang
and Loder, 2006;Stray et al., 2005).
These aromatic compounds are not adsorbed to negatively charged reservoir rocks because of electrostatic repulsion
forces (Rose and McPherson, 1997). The substituted carboxylic and benzoic acids are take an anionic form in the basic pH
of natural groundwater and, as a result, are highly soluble in water.
Initial laboratory tests showed conservative behavior for these compounds (150°C, 172 h, in nitrogen and oxygen
atmospheres) (Adams et al., 1986).
 Some of these compounds, such as tetra benzenic carboxylic acids and methyled benzoic acids (Adams et al., 1992;
Hutchins and Saunders, 1992; Rose et al., 2001b), are characterized by a high thermal stability (250°C-300°C) and a low
presence in the fluids in the reservoir.
However, the methyled benzoic acids can be subject to biodegradation. However, in geothermal studies, bacteria are not
active at temperatures over 100°C (the use of a preservative (NaN3) between sampling and analysis avoids this problem
(Adams, 1992)).
According to laboratory tests, fluorinated phenyl acetic acids are less stable than the FBA, and perfluorinated benzoic
acids are the least stable compounds, being subject to chemically decomposition (Adams, 1992).
The use of sodium benzoate in geothermal applications showed that the tracer behaved conservatively over a long
period (up to 4 years) (Sanjuan et al., 2006), but its use in oil reservoirs was not advised according to Hirtz et al. (2001).
Commercially available, these acids can be detected at very low concentrations (ng/mL level) by HPLC/UV methods
(Adams et al., 1992; Hutchins, 1992; Rose and McPherson, 1997).
Finally, of all these aromatic acids, the oil industry has preferred to focus on fluorinated organic compounds with a high
level of stability and detectability (Adams et al., 2004): FBA compounds (19 molecules are commercially available). Even
if they are less thermally stable than their methyled analogs (Adams et al., 1992), several studies, conducted in both
laboratories and oilfields, have shown that FBA exhibit conservative behavior (low adsorption on rock), high thermal
stability (up to 150-175°C), and chemical and biological stability (Bjornstad, 1994b, 1997, 1998; Galdiga, 1998; Gieles and
Beuthan, 2004; Hernandez et al., 2002a). Similar restitution curves to those for HTO and SCN- (Bjornstad, 1994 b; Dugstad
et al., 1999) or Br- (Benson and Bowman, 1994; Dahan and Ronen, 2001) were observed.
According to different experimental tests (Bjornstad, 1994 b, 1997; Seaman et al., 1997), the thermal stability of FBA is
very satisfying up to 120°C (2-fluorinatedbenzoic acid; 2,6-difluorobenzoic acid; 2,3,4-trifluorobenzoic acid; 2,4,5-
trifluorobenzoic acid; 3,4,5-trifluorobenzoic acid). The thermal stability is judged as acceptable up to 150°C for 3-
fluorobenzoic acid and even up to 175°C for some other FBA molecules (4-fluorobenzoic acid).
The stability of FBA can be explained by the carbon-fluor bond, which is the shortest, and thus strongest and most
stable, carbon-halide bond (Stetzenbach and Farnhalm). In addition, FBA has a very low presence in the reservoir fluids
and a low toxicity (Stetzenbach and Farnhalm).
All of these characteristics explain the common use of FBA in the oil industry since the 2000s (Huseby et al., 2009;
Malone et al., 2003; Meza et al., 2007; Pritchett et al., 2010; Seccombe et al., 2010; Valestrand et al., 2010).
However, a comparison study between some FBA and HTO molecules showed a weak delay in the restitution curves
for 3-trifluoromethylbenzoic acid, 2,4-difluorobenzoic acid and 2,6-difluorobenzoic acid (Seaman et al., 2007). In contrast,
2-fluorobenzoic acid had a higher velocity than HTO in field tests because of ion exclusion.
To date, several analytical methods have been proposed (Malone et al., 2003), including LC and GC methods with
LODs of approximately 10 ng/mL by HPLC/UV, 0.1-1 ng/mL by LC/MS-MS and 0.1-0.01 ng/mL by GC/MS (Galdiga and
Greibrokk, 1998a, 1998c; Hernandez et al., 2002; Tyler, 2010). Recently, a simpler, faster and more robust method, with a
similar LOD to GC/MS, has been developed: UHPLC/MS-MS (ultra-high-performance liquid chromatography coupled
with tandem mass spectrometry) (Preud’homme et al., 2010 ; Serres-Piole et al., 2011).

3.1.3. Other types of tracers

3.1.3.1. Deuterated compounds
Deuterium oxide (D2O) (Bennion et al., 1995; Fjerstad et al., 1993; Zemel, 1995) and deuterated water (HDO)
(Anderson, 2006) have been successfully used as passive water tracers in the oil industry and hydrology because of their
similar properties and structure to water (Anderson, 2006).
A comparative hydrological study between HDO and Br- (Becker and Coplen, 2001) showed that HDO had
passive properties. HDO, which is non-toxic, has a low natural abundance in the environment compared with water
enriched with 18O. It is commercially available, easy to use and sample, and has an acceptable cost. HDO can be
distinguished from other waters by its low levels of deuterium or deuterium oxide. However, isotopic exchange (H) can
occur and cause a delay compared to the other tracers because of the presence of minerals.
HDO can be analyzed by isotope ratio mass spectrometry (IR-MS) with an LOD of 0.1 mg/L (field tests) (Becker and
Coplen, 2001). However, the analysis cost is high because of the need for specialized equipment.
Finally, despite its high cost, this type of deuterium-labeled tracer was widely used during the early 1990s, especially
for SWTT operations (Bjornstad, 1991).
D2O is not highly recommended. It is expensive (Anderson, 2006) because of the ratio of water necessary to form
the product (approximately 10 tons of water to prepare 1 kg of oxide of deuterium) and for analysis (Rossi, 1994). D2O
requires knowledge of the natural abundance of deuterium in the formation water to conduct a quantitative analysis. In
addition, it can be present in the environment (150 µg/mL), which limits its use.
D2O can be detected by GC or HPLC coupled with mass spectrophotometry, nuclear magnetic resonance (NMR)
imaging (Anderson, 2006), or mass spectrometry (pg/mL LOD) (Bennion et al., 1995).
Deuterated short-chained fatty acids, which are also analyzed by GC/MS, have also been considered as possible tracers
(Galdiga et al.,). These short-chained acids, water soluble and stable under reservoir conditions, are naturally present in the
reservoirs. These compounds are tagged with deuterium content above the natural level to allow detection (ethanoic acid,
propionic acid, butanoic acid, etc.). Thus, they have the same properties as the natural short-chained acids. They are stable
under reservoir conditions (tested at 150°C over 8 weeks), with similar behavior to HTO. Among these compounds, pivalic
acid is unstable under reservoir conditions. In addition, the costs are high, and the low number of suppliers indicates low
available quantities.

3.1.3.2. Stable activable tracers

The stable activable tracers (stable transition metals 51V, 59Co, 115In, etc.) are stable isotope tracers. Their properties
were first used in hydrological and geothermal applications (Behrens et al., 2001). These tracers have the same advantages
as the radioactive isotope tracers (Bingyu et al., 2002). As a result, they are used as an alternative to radioactive species
(3H, 14C, 82Br, 131I, etc.). However, as with the radioactive species, special equipment is needed (Bingyu et al., 2002).
Among the stable activable tracers, non-radioactive gadolinium was proposed as a tracer, but the technique (pulsed
neutron tool) used for its detection has disadvantages (Ramos and Stephenson, 1999).
Indium (In) (Chrysikopoulos and Kruger, 1987) has been considered as an excellent activable tracer for geothermal
applications because of its high detectability and low presence in the subsurface formation (less 100 ng/mL). It is a
conservative tracer at low temperatures, with very low sorption in natural materials, and is applicable for short-term tracer
tests (20 days) at temperatures below 200°C. Stable activable tracers cannot be used as cationic tracers because of the risk
of hydrolysis at the basic pH of geothermal fluids. Thus, they are used with organic ligands (EDTA) to form chelated
species. This complex form ensures geochemical stability, mobility, and solubility in water and prevents precipitation
(Chrysikopoulos, 1993). However, the complex [InY]- is not applicable at high temperature owing to its degradation at 150-
200°C.
For oilfield applications, Green and Stubbs (2006) proposed a new type of non-radioactive tracer, particularly for the
determination of the flow of fluid from a well (SWTT test). These new tracers are composed of one metal (cesium,
niobium, tantalum, tellurium, iridium, osmium, iron, platinum, palladium, rhenium, ruthenium, rhodium, hafnium, indium)
or a lanthanide metal (lanthanum, cerium, terbium).
The stable activable tracers are detectable at very low concentrations (Adams et al., 1992) using analytical techniques
such as inductively coupled plasma – mass spectrometry (ICP-MS). This technique provides an LOD and LOQ of
lanthanum of 35 pg/mL and 117 pg/mL, respectively (Green and Stubbs, 2006). These tracers can also be analyzed by
neutron activation at the pg/mL level (Bingyu et al., 2002).

3.1.3.3. Microelements
Microelements that are very rare or absent in the reservoir water could be used as tracers (the types of elements that fit
this description are not available). These elements have the advantages of stable tracers, including low cost, higher
measurement precision with fg/mL detection, and stability at high temperatures, but special equipment is also required
(Bingyu et al., 2002).

3.1.3.4. Polymers
In enhanced oil recovery methods using a polymer (polyacrylamides), the use of the polymer itself as potential tracer
has been proposed by Manichand et al. (2010). The advantage is that the polymer is not present in the studied reservoir.
However, it has a high LOD (50 µg/mL). In addition, the travel time of the polymer was too slow because of retention in
porous media. Thus, polymers are not suitable as tracers to establish interwell connections.

3.2. The partitioning tracers

3.2.1. For SWTT
The primary partitioning tracers used in SWTT are reactive compounds such as esters. The injected ester in the well-
bore zone partitions into the immobile oil phase, which slows the tracer penetration (Buijse et al., 2010). The ester reacts,
by a hydrolysis reaction, with the reservoir water to form an alcohol tracer, which does not partition with oil. After a shut-in
of several days, the two tracers, ester and alcohol, are back produced. The interpretation of this test requires the knowledge
of the partition coefficient Kow and the hydrolysis rate of the ester in the reservoir conditions (determined in lab) (O’Brien
et al., 1978). The difference in time between the alcohol (which travels faster than the ester) and ester peaks is a direct
measure of the SOR, for a homogeneous system (Buijse et al., 2010; O’Brien et al., 1978 ; Deans, 1978).
The most commonly used tracers are esters of formic and acetic acids (Garnes, 1992; Keller, 1972;): methyl acetate
(Kow = 0.869; Kow = 1.92 (Deans, 1978; Dijk et al., 2010; Sheely, 1982; Tang and Zhang, 2001), ethyl acetate (Kow = 2.786
(Keller, 1972); Kow = 4.65 (Buijse et al., 2010; Chang, 1988; Cockin et al., 2000; Deans, 1978; Hernandez, 2002b; Jerauld
et al., 2010; Knaepen et al., 1990; Othman et al., 2007; Sheely, 1978; Sheely and Baldwin, 1982; Shook et al., 2009;
Skretinggland et al., 2010; Tomish et al., 1973; Wellington and Richardson, 1994)), isopropyl acetate (Kow = 8.478;
Kow=8.20 (Deans, 1978; Sheely and Baldwin, 1982)), ethyl formate (Bragg, 1978; Gardien, 1996; Oyemade at al., 2010;
Shook et al., 2009; Stoll et al., 2010; Talukdar and Instefjord, 2008), or propyl formate (Bragg et al., 1978; Cayias et al.,
1990; Myal and Wesson, 1981; O’Brien et al., 1978 ; Sheely, 1978).
Among these compounds, propyl formate was one of the first tracers used because of its fast reaction rate (Deans and
Mut, 1997). The low-molecular-weight esters, particularly ethyl acetate, are suitable at temperatures up to 121°C (Deans
and Ghosh, 1994). However, methyl formate is unsuitable because it hydrolyzes too rapidly under reservoir conditions
(Tang and Zhang, 2001).
These esters are always co-injected with non-partitioning tracers, usually alcohols (NPA, IPA, n-propanol, methanol, 2-
propanol) (Cockin et al., 2000; Garnes, 1992; Hernandez et al., 2002b; McGuire et al., 2005; Othman et al., 2007; Stoll et
al., 2010; Tang and Zhang, 2001; Wellington and Richardson, 1994). They are useful for the material balance (to identify
the water that contained the ester, Cockin et al., 2000). They are also used as a backup tracer (n-propanol) (Hernandez et
al., 2002b).
In certain tests, butanol (a partitioning tracer with a K very close to that of the primary tracer, methyl acetate) was also co-
injected with the primary tracer (Tang and Zhang, 2001).
Tracer concentrations (alcohol, ester) are generally analyzed on site by GC methods (Deans, 1978; Dijk et al., 2010;
Hernandez et al., 2002b; Othman et al., 2007; Sheely and Baldwin, 1982; Tang and Zhang, 2001), particularly headspace
gas chromatography (Garnes, 1992).

3.2.2. For PITT

To date, few partitioning tracers have been developed, especially for PITT. This dearth may be explained by the
complexity of their partitioning behavior, which differs by reservoir type.
Before the use of non-radioactive chemicals, the first compounds were radioactive. These compounds were tritiated
alcohols with a higher molecular weight than methanol, ethanol, and propanol; a higher Kow; and a high detectability by
liquid scintillation counting and included tritiated n-butano1 (TNB) (K = 1.3) (Wood et al., 1990) and C14-tagged i-amyl
alcohol (CIA) (Tang ,1992, 1995; Tang and Zhang, 2000).
Since the 1990s, these alcohols have been the most commonly used compounds, but in a non-radioactive form (Cheung
et al., 1999; Lichtenberger, 1991). The following compounds were tested in laboratory and field tests and defined as
suitable partitioning tracers to estimate the SOR: propanol (Tang, 1995), IPA (Kow = 0.04) (Lichtenberger, 1991; Oyerinde,
2004; Tang, 2003a), butanol (Kow = 0.41) (Hutchins et al., 1991), tertiary butyl alcohol (TBA) (Kow = 0.2) (Allison et al.,
1991; Cheng et al., 2005; Du and Guan, 2005; Lichtenberger, 1991; Lliassov et al., 2002; Oyerinde, 2004; Tang, 1995,
2002, 2003a), 2-butanol (Kow = 0.32) (Hutchins et al., 1991), 2-pentanol (Kow = 1.50) (Hutchins et al., 1991), n-pentanol
(Kow = 1.4) (Yoon et al., 1999), hexanol (with Kow = 5.6) (Delshad et al., 2002), n-Hexanol (Kow = 4.6) (Yoon et al., 1999),
1-heptanol (Jin et al., 1997), 2,4-dimethyl-3-pentanol (Hetterschijt et al., 2000), 2,2-dimethyl-3-pentanol (Kow = 12.9)
(Yoon et al., 1999), and 2-ethyl-1-butanol (Kow depends on the experimental conditions).
These alcohols are stable at very high temperatures (between 250°C for n-butanol) (Adams et al., 2004), but some HTO
or SCN- field tests showed that TBA and IPA were partially adsorbed in the reservoir (Lichtenberger, 1991).
In addition, the literature contains contradictory findings on the partitioning behavior of NPA and IPA; NPA and IPA
were also defined as passive tracers and used in SWTT for material balance (Delshad et al., 2002; Jerauld et al., 2010;
Skretinggland et al., 2010; Vilela et al., 1999).
Alcohols such butanol were detected by GC with a thermal conductivity detector (Wood et al., 1990), but their use is
not very interesting because of their high LOD (µg/mL level).
Other compounds detectable by HPLC techniques were tested in 2000 with promising results: 2,6-
bis(trifluoromethyl)benzoic acid, 2,4-bis(trifluoromethyl)benzoic acid, 5-fluoro-2-methyl benzoic acid, p-
(trifluoromethyl)benzoic acid, and 3,5-di(trifluoromethyl)benzoic acid (Chatzichristos et al., 2000).
Phenol was used as a partitioning tracer in the development of a two-dimensional planar flow model (Tang, 2003b).
Methyl-ethyl ketone was also used as a partitioning tracer (Lichtenberger, 1991).
Other partitioning alcohols have been used to locate and quantify non-aqueous phase liquids (Jin et al., 1995) present in
vadose and saturated zones, including 2,2-dimethyl-3-pentanol (Annable et al., 1998) and 2-dimethyl-3-pentanol (Wilson,
1995; Yoon et al., 1999).
Khalil and Oliveira (1999) proposed the use of the sodium derivative of fluorescein and the ester derivative of lower
alcohols for use in the aqueous phase to characterize reservoir studies (fluorescein ester (oil soluble) and oleophilic
fluorescein).
Finally, to develop a cheaper method than PITT, Sinha et al. (2004) successfully investigated the possibility of using the
more soluble organic compounds in oil naturally present (aliphatic acid and alkyl phenols) in crude oil as natural tracers to
estimate oil saturation and swept pore volumes (acid acetic, butyric acid, phenol, o-cresol, 2,4-dimethyl phenol).
Trans-stilbene, analyzed by UV absorption, was also used as a tracer in the oil phase in a core flood test (Shields et al.,
2010).

3.2.3. Conclusion
The use of partitioning tracers in PITT tests remains complex. In comparison with SWTT methods, PITT methods are
rarer in the literature (Deans and Mut, 1997). Their selection is difficult because an overly long delay compared to the
passive tracer might increase the costs of a tracing test (additional sampling and analysis).
In the 2000s, few chemicals were available and applicable as partitioning tracers, and the data interpretation was largely
qualitative (Guan and Du, 2004).

3.3. Nanoparticles
Since the 2000s, nanotechnology has become very promising in a large number of domains, for both fundamental
research and industrial applications (Kong and Ohadi, 2010; Tillement et al., 2006). Nanoparticles were first studied and
used for medical applications but have become increasingly studied for different applications, such as formation
characterization, enhanced oil recovery methods (Kong and Ohadi, 2010; Metin et al., 2010; Onyekinwu et al., 2010; Yu et
al., 2010a, 2010b), and the SOR determination (Prodanovic et al., 2010), the latter of which is difficult when using
partitioning tracers.
 Nanoparticles, with their unique optical, magnetic, paramagnetic and chemical properties, can contribute to reservoir
description via the development of nano-sensors (Kong and Ohadi, 2010). Obviously, the nanoparticles must be stable in
the reservoir conditions (temperature and pressure) and detectable directly on site.
Because nanoparticles have a nanometer (nm)-level diameter, they are waiting to have a similar behavior like molecules
and migrate easily through the pores in reservoirs without interacting with the rock and through pore throats, even at very
large particle concentrations (Rodriguez et al., 2009). Nanoparticles may have interesting properties for potential
application as water tracers in oil reservoirs (Prodanovic et al., 2010; Rodriguez et al., 2009). However, several
experiments are necessary to understand the transport and retention of nanoparticles in an oilfield environment (with high
salinity, high temperature, etc.) (Yu et al., 2010 b).
Nano-tracers are composed of a core and a coating (McDaniel et al., 2009). The nature of the coating depends on the
application: hydrophilic if the objective is to follow the water phase or hydrophobic if the objective is to reach the non-
aqueous phase (Prodanovic et al., 2010).
The coating, consisting of an inert polymer, surfactant or dispersant (Prodanovic et al., 2010; Zhang et al., 2009) (for
instance, polysiloxane or polyethylene glycol), is necessary to protect the core and to allow the nanoparticles to remain
stable and dispersed in water, without aggregation or adsorption, and to chemically protect the core during the test without
a loss of luminescence intensity (Prodanovic et al., 2010; Rodriguez et al., 2009; Zhang et al., 2009). The adsorption of
polymers to particles enhanced their mobility in both calcite and porous sand media, in which nanoparticles showed similar
migration to an inert tracer (Zhang et al., 2009).
Depending on their intended application, the encapsulating agent can be oils, polymers, or a mixture and can be natural
or synthetic (Malone et al., 2003).
The core can be either organic (fluorophores encapsulated and protected by a shell from tens to hundreds of nanometers
thick) or inorganic (oxides or metals inserted in balls of a few hundred nanometers in diameter). An inorganic core provides
a higher stability (Tillement et al., 2006).
During the experiment, the coating, in contact with the fluids, can break and release an encapsulating agent (e.g., a
fluorescent molecule) used as the tracer. The tracer is diffused in response to the progressive degradation of the polymer
(Malone et al., 2003).
Some core tests using a limestone rock have shown that nanoparticles could be transported through sedimentary rocks,
even those of low permeability (Rodriguez et al., 2009).
To date, several materials have been studied (with HTO as a reference tracer).
Paramagnetic nanoparticles, induced by an imposed magnetic field, are potentially useful (Ryoo et al., 2010). These
nanoparticles are characterized by a long-term dispersion stability in brines with minimal retention in reservoir rock and
with preferential adsorption at the oil–water interface. When exposed to a magnetic field, paramagnetic nanoparticles
generate sufficient interfacial movements for external detection. Because of their small size, paramagnetic nanoparticles are
mobile even in magnetic fields.
The subsurface applications of super-paramagnetic nanoparticles, ferrofluids, began in the late 1990s through a porous
formation by exposure to a strong magnetic field (Prodanovic et al., 2010).
Optical nanoparticles characterized by the combination of a core of gadolinium oxide (Gd2O3) doped with luminescent
and magnetic rare-earth ions (Tb3+ ions) or organic dyes have been studied (Tillement et al., 2006). These nanoparticles are
ultra-sensitive, multicolored and represent highly photostable luminescent tracers. The use of lanthanides, such as Tb3+,
instead of organic dyes is interesting because of their attractive optical properties and high photostability, suggesting that
they may be appropriate for long-term studies and multi-tracing (Tillement et al., 2006).
Recently, additional materials have been studied. Zinc phosphonate nanoparticles (Zhang et al., 2010), Si-Zn-DTPMP
(diethylene triamine pentakis (methylene phosphonic acid)) were tested in the laboratory in a column containing calcite and
sandstone porous media. These nanoparticles showed reasonable migration in these core materials. Nanometer-sized metal-
phosphonate particles, calcium chloride and zinc chloride, mixed with a basic phosphonate solution were tested in the
laboratory (Zhang et al., 2009).
Carbon nanoparticles (NPs) tested in the laboratory (dolomite core material) showed retardation in comparison with
HTO (Yu et al., 2010b). High-ionic-strength and multivalent ions (Ca2+, Mg2+) could have affected carbon NP
breakthrough.
Thus far, few works have addressed the transport of nanoparticles in reservoir rock formations (Yu, 2010 b).

3.4. Discussion
The selection of tracers with suitable characteristics can be difficult because it depends on the study objectives and the
reservoir characteristics.
Generally, in the case of mature oil fields, artificial tracers are preferable to natural tracers. Among these artificial
tracers, radioactive tracers are not recommended for HSE reasons. Non-radioactive chemical species are clearly preferable.
However, the lack of variety of dyes and chemicals remains a problem. Among chemicals, alcohols, inorganic anionic
ions, and related compounds, scientists have focused on fluorinated compounds for several years because they are generally
more detectable (Adams et al., 2004). Among these compounds, bromide and benzoates have been the most widely used
and are considered reference tracers for geothermal applications (Hirtz et al., 2001). Dyes and alcohols were rejected
because of the observed adsorption phenomena in the rock reservoir, chemical or microbial degradation and interference or
natural contamination, all of which hinder the analysis of these types of tracers.
 Finally, few tracers that meet the selection criteria are currently available for use as water tracers (Huseby et al., 2010).
FBA, with a negligible background noise in the reservoir waters, has seen the broadest use as a passive water tracer. These
compounds can be detected at very low concentrations using a rapid and sensitive technique, by direct injection, and
without sample preparation (UHPLC/MS-MS). Eighteen passive FBA and one partitioning FBA are commercially
available as water tracers (McCarthy et al., 2000).
In comparison with SWTT methods, PITT methods have been less frequently reported (Deans and Mut, 1997). The use
of the partitioning tracer is quite difficult. Its selection must be appropriate because a high degree of retardation in
comparison with passive tracers can considerably increase the costs of the tracing test (as a result of the additional sampling
and analysis required). In the 2000s, few chemicals were available for use as partitioning tracers, and the analysis of the
tracer response curves was still qualitative (Guan and Du, 2004).

4. Molecules analytically studied at the laboratory scale

Currently, the lack of chemical tracers prevents the repetition of tracer tests in oilfields already being monitored or the
implementation a tracing test in a reservoir with multiple injecting wells. Thus, the development of new types of water
tracers is increasingly necessary.
The selection of new tracers for reservoir applications requires a careful assessment of the positive and negative
features of potential candidates. Among the main selection criteria (see Section 2.3.1.) (Wu et al., 2008) – stability, passive
behavior, detectability, and toxicity – detectability is key and must be the first parameter considered in the tracer
development phase; very low LOD and LOQ are required to inject very low quantities in the oil reservoirs and hence to
limit the environmental impact (“environmentally friendly” tracers). To prevent a high analytical cost, the aim is to increase
the number of tracers without changing the analytical technique between the current FBA tracers and the new tracers.
Achieving this cost parity is an important consideration for tracing campaigns.
In this investigation, the strategy defined was as follows: 1) consider FBA as “reference water tracers”, 2) use the same
analytical tool, which is sensitive, selective, simple (without sample preparation), rapid and robust, for the simultaneous
detection of different types of tracers used in tracing campaigns, including FBA and other families of tracers. The
UHPLC/MS-MS technique recently developed for the detection of FBA in reservoir waters (Serres-Piole et al., 2011)
addresses all of these analytical criteria: it is rapid (5 min analysis), robust, ultra-sensitive and selective. In addition, this
method is reliable with regard to the representativeness of the results because chemical modifications are not necessary.
Direct injection prevents problems such as losses of some compounds or cross contamination during sample preparation.
The objective here was to propose tracers that are also detectable by UHPLC/MS-MS, by direct injection, with similar
LOD to FBA.
A first analytical study was conducted with molecules already largely used in geothermal applications: NSA.
Next, other molecules, the halogenated boronic acids (see fig. 1), which had never been used as tracers in any discipline
(hydrology, geothermal energy, etc.), were tested for potential use as tracers. These molecules were interesting because
they have similar structures to FBA. The only differences are the acid group (useful for good solubilization) and the
halogenated substituents in the ring. As a result, these molecules are expected to have the same chemical and physical
properties as FBA (thermal stability, passive behavior in the reservoir, etc.).
Although these molecules, which are commercially available, are relatively unknown (with few articles available in
literature), they are of general interest because the presence of an aromatic ring in the molecules allows them to express a
number of isomers with similar characteristics that can be chromatographically separated.
Several analytical techniques in addition to UHPLC/MS-MS were tested in this work to compare their respective
sensitivity, including UHPLC/ICP-MS (presenting excellent performance in terms of sensitivity) and UHPLC/FLD.
For the selection of the MRM (multiple reaction monitoring) transitions for the MS-MS detection of the tested
compounds, a hybrid mass spectrometer ESIqQqTOF (ESI, electrospray source; qQq, triple quadripole; TOF, time of
flight) (QSTAR XL, Sciex Canada) was first used to identify daughter ions of compounds by high-resolution MS with the
direct infusion of individual compound solutions in both modes, negative and positive (20 µl.min-1 (25 µL of the standard
solution + 1000 µL acetonitrile (CH3CN) + 3975 µL ultra-pure water (H2O), 2 µg/mL)). This procedure leads to very
accurate mass measurements for the identification of compounds. ESI-QQQ was applied based on the previously found
daughter ions, and once the setting parameters were optimized, the choice of the MRM transitions was confirmed.

4.1. Experimental
4.1.1. Reagents and chemicals
NSA and standard halogenated boronic acids (purity > 97%) were purchased from Sigma Aldrich. The solvents (HPLC
grade) and products were also purchased from Sigma Aldrich, including acetonitrile (CH3CN, Fluka, LC/MS, 99.9%),
methanol (CH3OH, LC/MS, Chromasolv, 99.9%), formic acid (HCOOH, Fluka, 98%, MS grade), sodium hydroxide
(NaOH, Rectapur, Prolabo, 98% min), ammonium bicarbonate (NH4HCO3, ReagentPlus, 99%), and ammonium acetate
(CH3COONH4, 99%). Ultra-pure water (18.2 MΩ.cm), obtained from a Millipore system (systems Elix 3 and Advantage,
Millipore, Saint-Quentin, France), was used throughout.

4.1.2. Standards and samples

 Standard solutions (300 µg/mL) were prepared by dissolving different amounts of compounds (between 15 and 30 mg,
depending on the compound), accurately weighed, in 40 mL of H2O and 10 mL of 3975 µg/mL NH4HCO3 solution. These
solutions were stored at 4°C in the dark for up to four months (the stability of their concentrations after four months of
storage was confirmed within 10%).
Working solutions were prepared by the appropriate dilution of the stock solutions with water. Water samples spiked
with a mixed standard solution at different concentrations (between 0.5 µg/mL and 100 pg/mL) were used for this study.
The samples were filtered through a GHP Acrodisc 13-mm syringe filter (0.2-µm GHP membrane, Pall Life Sciences,
Interchim, France).

4.2. Example applications

4.2.1. NSA, alternative analytical techniques
The comparative study of the different analytical techniques (table 1) for NdSA showed that UHPLC/MS-MS is also
applicable for NdSA, with similar LOD to the FBA, by direct injection (see fig. 2). In addition, as a result of the
optimization of the elution gradient and the selection of specific MRM transitions, this technique enabled the simultaneous
detection of FBA and NdSA in water (data not shown).
The most abundant MRM between the precursor ion and the product ion corresponds to the loss of the SO3- (m/z = 80)
fragment corresponding to the sulfonic group. The optimum transitions monitored are summarized in table 1. In
UHPLC/MS-MS, the selectivity, which is a key factor in preventing false-positive results, is excellent (the retention time of
each analyte in samples was within ± 2 s of the RT of the analyte in the aqueous standard mixture). The positive
confirmation of the target analyte in samples is achieved by the combination of a specific transition and the retention time
relative to the compound.
The analysis by UHPLC/ICP-MS, in which 32S and 34S were monitored, was not appropriate for the detection of NdSA
in water samples: the low ionization degree of the sulfur element (14%) leads to a high LOD.

4.2.2. Halogenated boronic acids

The sensitivity of four compounds (2.5 difluorophenyl boronic acid; 3.5 difluorophenyl boronic acid; 5-bromo-2-
fluorophenyl boronic acid; 5-chloro-2-fluoro phenyl boronic acid) was evaluated by testing different analytical techniques.
This study revealed that these compounds are difficult to detect by direct injection, with LODs similar to FBA and NS
(ng/mL level).
Among the tested techniques, only UHPLC/MS (single mode), with the electrospray in negative mode, allows the
detection of halogenated boronic acids (see fig. 3); this technique leads, by direct injection, to an LOD of between 5 and
300 ng/mL. A preconcentration at the SPE phase would improve the sensitivity by a factor of approximately 20.
The use of neither UHPLC/FLD nor UHPLC/ICP-MS (Bore 10B and 11B monitored, ionization degree of 58%) is
appropriate, even at high concentrations (µg/mL level). High background noise (from the vials of glass containing the bore)
was constant in the case of ICP-MS detection. The use of inert vials (Teflon) with an inert injector and chamber could solve
this problem, but this approach is impractical for routine use.
Halogenated boronic acids are not detectable by UHPLC/MS-MS (in multiple-reaction monitoring mode), even at high
concentrations (µg/mL level). The determination of the MRM transitions by the two instruments showed that the molecular
ion was not detectable, regardless of the compound. Thus, these compounds are characterized by a poor ionization in
comparison to the FBA. Few publications are available about the halogenated boronic acids. Their poor ionization may also
indicate a low reactivity, which would be an advantage in terms of chemical stability but a drawback in terms of analysis by
MS.
Different parameters were studied to try to improve the ionization of the compounds but without success, including
organic solvents constituting the mobile phase (CH3CN and CH3OH), ionization sources (electrospray ionization in
negative and positive mode), the pH value (with ammonium bicarbonate (3975 µg/mL) (pH 7-8), ammonium acetate (pH
4.8), formic acid (AF) (pH 2), and sodium hydroxide (pH 9-10) (sample prepared as follows: 1 mL CH3CN + 4 mL water
with NaOH +25 µL sample)).
A derivatization step comprising the addition of diols before analysis would improve the ionization and hence the
sensitivity, with lower LODs. However, this type of procedure did not correspond with the initial strategy.
Finally, these molecules were not retained as potential water tracers.

5. Conclusion
Tracers are a very efficient diagnostic tool for the oil industry to obtain information about the characteristics of a
reservoir (interwell connections, heterogeneities, etc.) (Huseby et al., 2009). By providing more detailed information on the
movement of reservoir water, tracers can improve oil recovery efforts. Tracers have proven their effectiveness for more
than 40 years (Bjornstad et al., 1990), but their selection is not always appropriate. To address this issue, a review
providing guidelines for the selection of water tracers in a tracing campaign was proposed as the subject this paper.
An alternative technique to the fluorescence techniques, the UHPLC/MS-MS, was successfully proposed for the
detection of naphthalene sulfonic acids in waters. This original tool had been recently developed for the direct
determination of FBA in reservoir waters (Preud’homme et al., 2010 ; Serres-Piole et al., 2011). With this method, a
sample preparation or chemical modification is not necessary; it allows the detection of FBA and NSA in only 5 min by
direct injection. With a minimum sample manipulation (0.2 µm filtration), this method exhibits an excellent robustness and
is reliable with regard to the representativeness of the results.
New types of chemical tracers were also investigated here, but they were not retained for further study (e.g., on their
stability, passive behavior, etc.) because of their high LOD in all analytical techniques tested.

Acknowledgments
The authors gratefully acknowledge the support for this project from the TOTAL Exploration Production Department.
The authors are very grateful to the LCABIE laboratory, FEDER and Aquitaine Region funds for mass spectrometry
facilities (UPLC Acquity, ICPMS, FLD, TQD MS and XevoTQ MS instruments).
The authors also express their gratitude to the bibliographic department of Total AS for all bibliographic information
and for their participation, which made this study possible.
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Fig. 1. Example of halogenated boronic acids.

Fig. 2. Example of detection of di-NSA by UHPLC/MS-MS.

(15 µL injected).
Fig. 3. Example of detection of halogenated boronic acids by UHPLC/MS.
(10 µL injected).
Table 1: Detection of NSA in water.

Detection parameters

Compounds HPLC/FLD a UHPLC/FLD b UHPLC/MS-MS * UHPLC/ICP-

(excitation (excitation MRM e
MS
and emission and emission transitions Monirored
wavelengths) wavelengths) element
1-NSA 217 / 333
2-NSA 220 / 336
32
1,5-NdSA 218 / 334 223 / 330 286,90 > 206,90 S and 34S
32
1,6-NdSA 224 / 337 223 / 330 286,90 > 206,90 S and 34S
32
2,6-NdSA 225 / 342 223 / 330 287,00 > 206,90 S and 34S
2,7-NdSA 226 / 339
1,3,5-NtSA 224 / 340
1,3,6-NtSA 228 / 342 223 / 330
1,3,6,8-pyrenetetra-NSA 346 / 386

LOD 200 pg/mL 200 – 600 pg/mL 200 – 900 pg/mL c / 10 ng/mL
70 pg/mLd

Techniques compared in the same sample preparation conditions, ie., in ultra-pure water.
* UHPLC/MS-MS (negative electrospray ionization), analysis by direct injection. (See conditions in
Serres-Piole et al., 2011).
a
Data from Rose, 2001 b; Rose et al., 2001 a and 2003.
b
UHPLC/FLD, 10 µL injected.
In UHPLC/FLD, to develop a single method the simpliest as possible applicable for reservoir waters
and allowing the simultaneous detection of the NSA, a compromise was defined: the wavelengths for
excitation and emission were selected to be the same for all the studied NSAs. Only one channel of
wavelength was selected, because it allows to have a better resolution of the peaks, and hence better
signal on noise: The channel 223 / 330 nm leads to signals the less interfered
c
Xevo TQ MS instrument, 15 µL injected.
d
Xevo TQ MS instrument, 50 µL injected.
e
ICP/MS, not matrix dependent.
Highlights

> State of the art of water tracers used in oil field applications > Fluorinated Benzoic Acid (FBA)
broadly used as passive water tracers > Direct determination of the FBA by a simple and fast analytical
technique, UHPLC/MS-MS > Other tracers detectable with the same analytical tool and with low
limits of detection > Naphthalene sulfonic acid (NSA) can also be detected with this technique.