DES-11194; No of Pages 9

Desalination xxx (2012) xxxxxx

Contents lists available at SciVerse ScienceDirect

Desalination
journal homepage: www.elsevier.com/locate/desal

Analytical techniques for boron quantication supporting desalination processes:

A review
Ali Farhat, Farrukh Ahmad, Hassan Arafat
Water and Environmental Engineering Program, Masdar Institute of Science and Technology, PO Box 54224, Abu Dhabi, United Arab Emirates

a r t i c l e

i n f o

Article history:
Received 27 October 2011
Accepted 24 December 2011
Available online xxxx
Keywords:
Boron
Analytical techniques
Desalination
ICP-MS
Isotopic analysis

a b s t r a c t
Several studies have been reported over the last two decades to improve the analysis of boron and to determine its
isotopic composition. The isotopic composition of boron is of signicance to SWRO because second pass processes
result in a boron isotopic shift in the permeate, thereby creating a unique process signature. This paper reviews the
different boron detection and quantication techniques ranging from plasma-based techniques, to thermal ionization mass spectrometry (TIMS), and other MS-based and non-MS based techniques. The most recent precision and
detection levels are reported, and the complexity of analysis and sample preparation, as well as the major disadvantages and limitations associated with the measurements of boron and its isotopic composition (e.g., spectral
and isobaric interferences, mass fractionation, and memory effect) are compared among analysis techniques.
While positive-TIMS (PTIMS) has been reported as the most precise, and the negative-TIMS (NTIMS) as the
most sensitive, plasma-based techniques such as multi-collector inductively coupled plasma-mass spectrometry
(MC-ICP-MS) are characterized by their fast speed of analysis and high sample throughput. Several recent
improvements have increased precision and lowered the detection level of the MC-ICP-MS, making it capable of
competing with PTIMS and NTIMS.
2011 Elsevier B.V. All rights reserved.

Contents
1.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.1.
Boron: its occurrence and toxicity . . . . . . . . . . . . .
1.2.
Boron removal in desalination plants . . . . . . . . . . . .
2.
Techniques for boron and boron isotopes analysis . . . . . . . . .
2.1.
Available techniques and their principles of operation . . . .
2.1.1.
Plasma-based techniques . . . . . . . . . . . . .
2.1.2.
Thermal ionization mass spectrometry (TIMS)-based
2.1.3.
Non-MS-based techniques . . . . . . . . . . . .
2.2.
Precision and detection limits . . . . . . . . . . . . . . .
2.3.
Complexity of operation and sample preparation . . . . . .
2.4.
Compliance with regulatory levels . . . . . . . . . . . . .
2.5.
Interferences and limitations . . . . . . . . . . . . . . .
2.5.1.
Spectral and isobaric interferences . . . . . . . . .
2.5.2.
Mass fractionation . . . . . . . . . . . . . . . .
2.5.3.
Memory effect . . . . . . . . . . . . . . . . . .
2.5.4.
Other limitations . . . . . . . . . . . . . . . . .
3.
Boron isotope tracer analysis in applications related to desalination . . .
4.
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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1. Introduction
1.1. Boron: its occurrence and toxicity
Corresponding author.
E-mail address: harafat@masdar.ac.ae (H. Arafat).

Boron is a nonmetallic element, which has ve protons in its nucleus along with ve to six neutrons, resulting in two stable isotope

0011-9164/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2011.12.020

Please cite this article as: A. Farhat, et al., Analytical techniques for boron quantication supporting desalination processes: A review, Desalination
(2012), doi:10.1016/j.desal.2011.12.020

A. Farhat et al. / Desalination xxx (2012) xxxxxx

forms: 10B (abundance of 19.8%) and 11B (abundance of 80.2%), averaging its atomic weight at 10.81 Da [1]. Boron exists in nature in the
form of boric acid (H3BO3) or borates, mainly sodium borate (Na2B4O710H2O), also known as borax. Boric acid and sodium borates are
considered to be medicinally important compounds and they are classied by the United States Pharmacopeia-National Formulary [2] and
the British Pharmacopeia [3] as two pharmaceutical necessities,
where they are used as antibacterial [4] and antifungal agents [57],
as well as components of dental cement [8]. Despite the fact that
boron exists in fertilizers, where it is described as an essential constituent for the growth of plants and vegetation, boron contamination is
a serious threat to crops, because they are very sensitive to high levels
of boron in the irrigation waters [9]. In animals, high boron concentrations have been observed to affect male reproductive capabilities
[10], unlike in humans where no such negative ndings have been
reported [11].
Boron is detected in surface water and groundwater in various locations around the world, including sea and river waters, where it is
present mainly in the form of boric acid. In seawater, the boron concentration ranges from 0.5 to 9.6 ppm [12], averaging at a value of
4.5 ppm [13,14] to 4.6 ppm [1]. Geographical location and seasonal
effects play a signicant role in the boron concentration in the oceans
and seas. Boron levels in the Arabian Gulf have been reported at
7 ppm [14]. In freshwater, concentrations of boron have been
reported ranging from b0.01 to 1.5 ppm [1] in most cases. For instance, boron levels measured in many US and Canadian surface
water bodies range from 0.01 to 0.4 mg/L, and in UK and Italy river
waters reach 0.9 mg/L. Meanwhile, studies measuring boron levels
in potable water supplies in northern Chile report values from
0.31 mg/L to 15.2 mg/L due to nearby boron-containing soil deposits
[15]. In brackish water, boron levels are generally lower than 5 ppm.
Yet, concentrations might get as high as 23.5 ppm, as in the case
reported by Rahardianto et al. [16]. Hence, the geographic source of
water is the major determinant of these widely variable levels of
boron in the drinking waters.
The 4.5 ppm mean boron level in ocean waters is higher than the
USEPA Health Advisory Committee's maximum boron concentration
of 0.6 ppm in drinking water [17]. In the same vein, the World Health
Organization (WHO, 2004) recommends a stricter goal for the boron
concentration. WHO denes the guideline value of boron concentration in drinking water as 0.5 ppm with the non-observed adverse effect level (NOAEL) of boron in drinking water at 0.3 mg/L [18]. In this
recommendation, WHO considered the maximum tolerable intake in
one day as 0.16 mg of boron per kg body weight [13]. The WHO
guideline value of 0.5 ppm is provisional owing to the lack of detailed
toxicological studies on boron. Thus, it is not a mandatory water quality parameter in the US and it is not yet enforced in the Safe Drinking
Water Act, despite the fact the Boron is classied as a U.S. EPA's
Drinking Water Contaminant Candidate [1]. In the US, only the state
of California issued a regulation with a notication level of Boron exceeding 1 ppm, the same value adopted by the European Union (EU)
[19]. Thus, countries relying on seawater desalination must reduce
the high levels of boron in seawater to below 0.6 ppm before any
water usage by humans and animals, as well as any usage for crop
irrigation.

is gaining signicant attention in membrane desalination where several

specialized boron removal processes and plant congurations have
been tested. Plant congurations evaluated include those using a
second-pass Reverse Osmosis (RO) unit following pH increase to values
above the boric acid pKa [24,25], as well as the ones employing a postRO ion-exchange process with boron-specic resins [26]. Non-RO plant
congurations evaluated for boron removal include electrodialysis desalination using specialized membranes [27] and adsorption membrane
ltration (AMF) [28]. Readers interested in boron removal technologies
from saline water are referred to a recently published detailed review
on this topic [28].
The analysis of boron in feed waters and desalinated waters is of
crucial importance to assessing the effectiveness of boron removal
in desalination. Consequently, this requires the availability of robust
instrumental techniques and analytical methods for monitoring
and quantifying boron and its isotopic composition with signicant
sensitivity, precision, as well as convenience. This paper reviews the different contemporary boron measurement and instrumentation techniques, which include plasma-based techniques, thermal ionization
mass spectrometry (TIMS), and other MS-based and non-MS based
techniques. A comparison of the precision, detection levels, complexity
of operation, sample preparation, and major limitations and interferences among these analytical techniques is detailed. Moreover, the
paper explores boron isotopic ratio analysis as an emerging technique
for evaluating the performance of membrane-based boron removal
processes, and the mixing of waters containing different isotopic ratios
of boron in cases such as aquifer recharge and brine discharge.
2. Techniques for boron and boron isotopes analysis
2.1. Available techniques and their principles of operation
The detection and quantication of boron and its stable isotopes
have been conducted using several different techniques reported in
literature. These techniques are summarized in Table 1. The most
widespread of these are plasma-based techniques, mainly the inductively coupled plasma (ICP) technique [2939], which has recently
been coupled to different types of mass spectrometers (MS) to improve method sensitivity and reliability. Positive thermal ionization
mass spectrometry (PTIMS) [4050] is recognized as the most precise
technique, whereas negative thermal ionization MS (NTIMS) [5160]
is reported for being the most sensitive one. Other non-MS-based
Table 1
Principle of the major boron analyses techniques.
Technique
Plasmabased

ICP-MS

TIMS

1.2. Boron removal in desalination plants

In thermal desalination processes, such as Multi-Stage Flash Desalination (MSF) and Multi-Effect Desalination (MED), where the product
water is reported with Total Dissolved Solids (TDS) values between
5 ppm and 50 ppm [20], the boron problem has never been reported.
The boron problem is exclusively reported in membrane technologies
[21,22], where the membrane rejects most ionic species but fails to prevent the boron from passing through because it is present in its uncharged boric acid form (pKa= 9.2 at 25 C [23]). Thus, boron removal

Principle of the technique

ICP-OES

PTIMS

NTIMS

Non-MSbased

Spectrophotometry

Nuclear

Ionizing boron into B+ ions then monitors

the wavelength emissions from these excited
ions at its corresponding wavelengths
Ionizing boron into B+ ions, then measuring
B isotopes abundance based on their
mass-to-charge ratio (m/z 10 and 11)
Converting boron into alkali or metal
metaborate cations such as Na2BO2+
(m/z 88 and 89), and Cs2BO2+ (m/z 308
and 309) then measuring their
corresponding m/z
Converting boron into metaborate anions
of BO2 (m/z 42 and 43) then measuring
their corresponding m/z
Adding specic reagents to the boron
samples for color development, then
measuring the absorbance at
wavelengths, respective of the reagent
Bombarding boron with neutrons causing
the production of a-particles and g-particles
that are monitored to measure 10B isotope
abundance

Please cite this article as: A. Farhat, et al., Analytical techniques for boron quantication supporting desalination processes: A review, Desalination
(2012), doi:10.1016/j.desal.2011.12.020

A. Farhat et al. / Desalination xxx (2012) xxxxxx

Fig. 1. Schematic drawing of MC-ICPMS with its different components: plasma torch,
electrostatic analyzer (ESA), magnet, and the multi-collector.

techniques [6165], such as spectrophotometry, are also employed

for boron analysis.
2.1.1. Plasma-based techniques
Plasma is a state of matter similar to gas, described to be an electrically conducting gaseous mixture that is ionized into cations, anions, and electrons with a net charge of zero [66]. Inductively
coupled plasma (ICP) technique is the most widely used plasmabased techniques for boron analysis. ICP is a type of plasma source
formed from electric currents that are caused by electromagnetic induction on a rareed gas such as Argon. Samples are usually prepared
in aqueous phase using steps involving extraction and purication,
and are then introduced into the plasma of the instrument via a nebulizer and spray chamber [67]. The nebulizer is responsible for the
aerosolization of the aqueous sample into ne droplets. However,
since any large droplets formed cannot be further dissociated by the
plasma discharge, a spray chamber is utilized to permit the entrance
of only small droplets into the plasma torch. Other plasma-based
techniques besides ICP, include direct current plasma (DCP) [68,69],
which is less sensitive and requires more maintenance compared to
ICP, as well as microwave induced plasma (MIP) [70] and glow discharge plasma (GDP) [71], which are less commercially available for
general elemental analysis and not widely reported for boron
analysis.
In the ICP method, the boron-containing liquid sample is puried
and pre-concentrated, then atomized (i.e. converting boric acids and

Fig. 2. Schematic drawing the thermal ionization source of PTIMS.

other borates into elemental boron (B)), and ionized into B +, which
is analyzed via different types of detectors. The ICP optical emission
spectroscopy (ICP-OES), also known as ICP atomic emission spectroscopy (ICP-AES), is one type of ICP that detects boron and was published as standard method ISO 11885:1996 (E) [72]. This type of
emission spectroscopy detects electromagnetic radiation emitted
from excited atoms and ions produced by the plasma source, where
the wavelength of the radiation emitted is characteristic of an element. The wavelengths typically monitored for the boron analysis
are 249.678 nm, 249.773 nm [59], and 182.52 nm [73]. This method
was reported for aqueous samples including fresh and saline water
[31,45], as well as solid samples [40,59] including soil, rocks, plant,
and biological samples. The coupling of ICP with a mass spectral detector (ICP-MS), introduced by Gregoire [39], revolutionized the
boron determination with its simultaneous measurement of boron
concentration and its isotope abundance ( 11B and 10B) leading to
lower detection limits and higher sensitivity [67]. Instead of monitoring wavelength-specic emissions of the excited ions as in ICP-OES,
the ICP-MS method measures the ions based on their mass-tocharge ratio (m/z), thus simultaneously measuring boron concentration and its stable isotope abundance.
Congurations involving different types of MS have been developed
to enhance the performance of the ICP-MS instrumental analysis technique. One conguration comprises of combining ICP with a quadruple
MS (ICP-qMS) [38], where the qMS provides higher precision than normal MS. Others include double-focusing magnetic sector ICP-MS, also
referred to as high resolution ICP-MS [34], which reduces the effect of
interferences induced from any mass overlaps, but is complex to operate and maintain and requires a higher capital cost compared to the
ICP-qMS. The conguration utilizing a multi collector MS, known as
multi-collector ICP-MS (MC-ICP-MS) [33], is described as the most
promising ICP-MS technique combining the advantages of superior ionization of ICP with the precision of a double focusing magnetic sector
mass spectrometer with multiple Faraday cups and ion counters [30].
MC-ICP-MS (Fig. 1) overweighs other ICP congurations by its precision, sensitivity and ability to analyze a broader range of elements. Recently, Le Roux et al. [29] and Fietzke et al. [32] used the multiplemultiplier laser-ablation ICP-MS (MM-LA-ICP-MS) and laser-ablation
MC-ICP-MS (LA-MC-ICP-MS), respectively, for in-situ boron isotope
analysis, but these techniques were primarily used for solid samples.
In fact, the different ICP-MS instruments for boron measurement have
been applied to samples ranging from surface and ground water
[3436] to volcanic uids [74], marine carbonates [75,76], and other
geological materials [39].
The ICP techniques are characterized by their fast analyses and
high sample throughput [30,76,77] compared to thermal ionization
MS techniques. In fact, MC-ICP-MS is the most preferred among the
plasma-based technologies due to its high precision and the relatively
small sample size requirements [35,36], allowing it to potentially
compete with the very precise positive thermal ionization mass spectrometry (PTIMS) and the sensitive negative TIMS (NTIMS) boron
analysis techniques [76], albeit at a signicant capital investment
cost.
2.1.2. Thermal ionization mass spectrometry (TIMS)-based techniques
Positive TIMS (PTIMS): PTIMS, which is considered to be the most
precise instrumental analysis technique for measuring boron isotopic
ratios [78], is an MS detection technique working in positive ion mode
to analyze for boron ions generated by a thermal ionization source
(Fig. 2). In PTIMS, the boron in the sample is converted into positively
charged metaborate ions (BO2+) that are not solely present as BO2+,
but exist in the form of alkali or metal metaborate cations (M2BO2+)
[44,79,80]. In fact, this technique requires boron separation from the
sample and this step should be preceded by ofine sample preparation. Subsequent to the separation, an alkali salt (carbonate or hydroxide) is added to form the alkali or metal metaborate complex,

Please cite this article as: A. Farhat, et al., Analytical techniques for boron quantication supporting desalination processes: A review, Desalination
(2012), doi:10.1016/j.desal.2011.12.020

A. Farhat et al. / Desalination xxx (2012) xxxxxx

which is then thermally ionized before being introduced into the

mass spectrometer for m/z ltering and measurement [67,81].The
various types of alkali metaborate ions analyzed depend on the alkali
salt used in preparing them. Such alkali or metallic metaborate ions
reported in literature include K2BO2+ [77], Na2BO2+ [79,80,82,83],
Cs2BO2+ [4145,78,8486], Rb2BO2+ [87], and Li2BO2+ [88]. PTIMS is
different from ICP-MS because it analyzes boron in the form of
M2BO2+, rather than an elemental form of boron (B +) as analyzed
by ICP-MS [34]. Initially, sodium metaborate (Na2BO2+ of m/z 88 and
89) was widely used; in fact, two National Institute of Standards
and Technology (NIST) standards, SRM951 and SRM952, were both
certied via monitoring Na2BO2+ in PTIMS [89]. The same is true for
the Central Bureau for Nuclear Measurement (CBNM) standard of
boric acid [90]. However, Na2BO2+ has since been substituted by
Cs2BO2+ (of m/z 308 and 309) [4144] because the latter is more precise and sensitive compared to Na2BO2+, K2BO2+, and Rb2BO2+, all of
which suffer from spectral interferences [67,77,81]. The PTIMS instrumental technique has been applied to aqueous samples [44] (including seawater [63], groundwater [47,82], and volcanic thermal water
[45]), geological samples [45,51,55,91], as well as crop plants [85]
and nuclear materials [83].
Negative TIMS (NTIMS): NTIMS operates in a similar way to PTIMS
but produces and analyzes for metaborate anions (BO2) in a negative
ion mode of operation. At variance with PTIMS, NTIMS requires no alkali salts or metals to be added to the sample as no alkali or metal
metaborate anions are required for mass measurement. Thus, simpler
mass measurements are conducted for 10BO2 and 11BO2, at m/z of 42
and 43, respectively. Developed by Zeininger and Heumann [91] and
Duchateau and De Bievre [92], this technique is characterized by an
ion yield that is 1000 times higher than yields in PTIMS, leading to
higher sensitivity and less sample purication requirements [77].
Barth [55,56] reported a boron isotopic analysis of fresh and saline
water using NTIMS. Furthermore, Barth [57], along with other researchers [52,60], used NTIMS to investigate boron in groundwater
as a tracer, showing that NTIMS is more suitable for aqueous samples
when precision is not of signicance. Other applications of NTIMS
were reported on solid carbonate samples [51,53,58,93], and air samples [54].
2.1.3. Non-MS-based techniques
Spectrophotometric methods for boron determination are simply
based on the addition of specic reagents to aqueous samples for
the development of colored boron complexes, which are then measured using light absorbance at wavelengths corresponding to the
chromophore of the reagent used. These reagents include the red curcumin, measuring its absorbance at 550 nm [94], blue carmine at
605 nm [95], and yellow azomethine-H at 410 nm [96]. USEPA Method 212.3, ASTM Method D3082-03 and AWWA Method 4500-B B are
published standardized methods for boron analysis using the curcumin [97], while AWWA Method 4500-B C and ISO 9390:1990 [98]
are for carmine and azomethine-H respectively. Azomethine-H method is the most commonly employed boron spectrophotometric method,
mainly because it is fast, simple, sensitive, and reported to have the least
interferences among all spectrophotometric methods [67]. This method
has been employed to investigate boron geochemistry in groundwater
[47], seawater [61,63], and geothermal waters [64]. In addition, the

curcumin colorimetric method forms the basis of the American Society

of Testing and Materials (ASTM) method D3082 and Standard Methods
4500-B, which measure boron dissolved in aqueous samples. The curcumin method is prone to interferences from nitrate ions and hardness
constituents, even though it can detect boron concentrations as low as
0.1 mg/L or at minimum loading of 0.2 g boron [99]. Furthermore,
other spectrophotometric methods such as the uorimetric methods
are also available to measure the uorescence of samples after the addition of reagents that cause the formation of uorescent boron
compounds.
Non-spectrophotometric methods include the ionometric method,
where boron in the sample is converted into tetrauoroborate (BF4)
which is then measured via selective ion selective electrode. In addition,
boron analysis is of interest in nuclear industry, where boric acid is used
in the primary coolant to control the nuclear reaction, and high boron
concentrations might cause metal oxides to deposit on the fuel rods
[100]. In order to monitor the boron concentration, several nuclear reaction analytical (NRA) methods were reported as powerful independent
measurement technique that can be employed at nuclear reactor sites
with minimal sample preparation. Boron samples in nuclear techniques
are bombarded with neutrons causing the production of -particles and
-particles, one or both of which are monitored to correlate to 10B stable
isotope abundance.
2.2. Precision and detection limits
Table 2 summarizes detection limits and precisions for all mentioned techniques. PTIMS has been widely reported as the most precise
among all instrumental techniques for boron isotope ratio analysis. The
Cs2BO2+ PTIMS method is considered to be the most precise with relative standard deviation (RSD) precisions in the range of 0.20.5
[40,4447,50,59,63,77,86] at detection levels of 0.15 g. Rao et al.
[79,80,83,87] reported boron isotopic ratio with RSD precision values
of 0.242.0 for Na2BO2+ and 0.22.5 for Rb2BO2+. On the other
hand, NTIMS is described as the most sensitive technique, able to detect
boron at concentrations of 110 ng, while PTIMS detection levels are
higher in the range of 0.15 g. Further improvements applied on the
Cs2BO2+ PTIMS method by Nakano and Nakamura [43] and Deyhle
[78] increased the precision and detection by 10-fold, reaching precision values of 0.070.25 (2mean) for 1 g of B, and 0.150.32
(2mean) for 0.1 g of B by the former [43], and 0.06 for 0.1 g
boron by the latter [78]. Below 0.1 g boron, Ishikawa et al. [42]
reported 0.1 precision for 0.050.1 g, and 0.2 for 0.01 g
boron samples [42]. Nonetheless, PTIMS is not yet able to compete
with the sensitive detection capabilities of NTIMS, where 110 ng
boron loadings are reported with comparable precisions of
0.240.8 (2) [5557,93]. ICP-MS, ICP-qMS, and double-focusing
magnetic sector ICP-MS are less precise than PTIMS and NTIMS, with
reported precisions for the plasma-based techniques in the range of
714 for ICP-MS [39,77], 310 for ICP-qMS [80], and 12 for the
double-focusing magnetic sector ICP-MS [34]. However, the introduction of the MC-ICP-MS improved the precision of the plasma-based
techniques. In fact, the most recent publications report precision values
for MC-ICP-MS in the range of 0.20.4 (for 250 ng B [30], for 100 ng B
[35,36], and for 1050 ng B [7476]). This precision range at such low
detection levels (10100 ng) has made MC-ICP-MS very competitive

Table 2
Precision and detection levels of the major boron analyses techniques.
Precision and detection levels

MC-ICP-MS
PTIMS (Cs2BO2+ method)
NTIMS

1000 ng

100250 ng

50100 ng

1050 ng

110 ng

0.070.25 [43]

0.20.4 for 250 ng [30]

0.06 for 100 ng [83]

0.20.4 for 100 ng [35]

0.1 for 50100 ng [42]

0.20.4 [7880]
0.2 for 10 ng [42]

0.240.8 [5557]

Please cite this article as: A. Farhat, et al., Analytical techniques for boron quantication supporting desalination processes: A review, Desalination
(2012), doi:10.1016/j.desal.2011.12.020

A. Farhat et al. / Desalination xxx (2012) xxxxxx

compared to both TIMS (0.240.8 for 110 ng) and PTIMS

(0.10.2 for 10100 ng), especially since MC-ICP-MS is a relatively
faster technique that is characterized by its higher sample throughput.
The major non-MS based technique, ICP-OES, reported 10% precision in quantifying boron concentrations of solid samples [40], and
only 12% for aqueous samples [74]. Furthermore, the spectrophotometric azomethine-H method reported a precision of 210% in the
aqueous samples [47,63] and 5% for the solid samples [45]. Whereas, the nuclear reaction analytical (NRA) method, prompt-gamma
neutron activation, determined boron concentrations with even
higher analytical precision of 515% [46]. The detection limits for
these techniques range from 13 ppb-B for spectrophotometric
methods to 10100 ppb-B in ICP-OES, and 1 ppm-B in the NRA method
[67], depending on type of the reagent and the sample matrix.
2.3. Complexity of operation and sample preparation
MC-ICP-MS outperforms PTIMS, NTIMS, and all other MS-based
techniques in terms of simplicity of operation because of its fast analysis
times and high sample throughput (up to 100 samples per day) [77].
The speed of sample acquisition in MC-ICP-MS has been reported within 4 min per sample for samples containing 250 ng-B to a 0.2 precision [30], compared to 0.254.0 h reported for the TIMS technique
[44,59,80]. Improvements in NTIMS [93] have shortened its sample acquisition time to 20 min, which is still longer than MC-ICP-MS, yet simpler with its fewer sample preparation requirements. As a matter of fact,
to achieve high precision and low detection levels for the aforementioned boron analysis techniques, extensive and laborious sample preparation steps are required for almost all techniques. Sample preparation
procedures involve boron extraction and separation/purication, primarily by ion-exchange resins in order to pre-concentrate boron and
eliminate the effects of the sample matrix [30,50,76,78]. NTIMS is an exception and only requires minimal sample preparation especially for
aqueous samples [56,57], where it entails the addition of freeseawater or Ba(OH)2 + MgCl2 to enhance BO2 formation [80]. Hence,
NTIMS has been recognized as the most suitable technique for water
samples.
2.4. Compliance with regulatory levels
As can be observed, with the exception of the nuclear reaction analytical methods, whose detection limit is 15 ppm with a 15% precision
[67], almost all the above reported techniques for the determination of
boron have their detection limits signicantly below the seawater
boron levels of 4.5 ppm [14] and possess relatively high precision.
More importantly, these detection limits are well below the regulatory
guidance levels for boron of 0.5 and 0.6 ppm [13], as advised by the
WHO and USEPA. Hence, all of the aforementioned techniques can be
applied to ascertain regulatory compliance of aqueous samples.
2.5. Interferences and limitations
Each of the techniques discussed so far for Boron analysis suffers
one or more limitations (Table 3), although in most cases, there are

ways to deal with these limitations. Below is a discussion of these

limitations.
2.5.1. Spectral and isobaric interferences
Each of the MS based techniques described earlier is prone to isobaric interferences owing to the absence of an inline compound separation procedure (e.g., chromatography) prior to mass spectral
analysis. Isobaric interferences occur when the m/z ratios of the target ion and an interfering ion have a difference of less than one unit
[66], making it difcult to separate ions given the resolution of the
mass spectral lter. ICP-MS measuring elemental boron abundance
at m/z 10 and 11 suffers from interference with 12C due to spectral
overlap with 11B [67]. It is not widely reported in MC-ICP-MS, but
others such as 40Ar 4 + (m/z of 10) and 10BH + (m/z of 11) interfering
with 10B and 11B, respectively, are noted [76]. Furthermore, NTIMS
suffers from isobaric interferences of BO2+ at m/z 42 with cyanogens
(CNO ) formed when the samples contain organic materials
[53,80]. In PTIMS, the following isobaric interferences have been
identied: Cs2CNO + with Cs2BO2+ (m/z 308), when HNO3 is present
in the sample, and 88Sr with Na2BO2+ (m/z 88) [77,80]. Wei et al.
[41] used an ionization depressor, 1% H3PO4, to effectively eliminate
isobaric interferences by preventing the formation of Cs2CNO + and
CNO . The CNO interference was also corrected by applying an extrapolation technique described by Kasemann et al. [59].
In techniques measuring light absorbance, several spectral interferences occur with a number of elements because the wavelength
of the investigated boron is near the wavelength of these elements.
Interferences with Fe, Al, Cu, Zn, and Mo are reported in spectrophotometric techniques utilizing the measurement of colored complexes
[101], whereas, in ICP-OES, interferences with Fe, Al, Ni, Cr, Si, and V
are observed [67].
2.5.2. Mass fractionation
This phenomenon occurs due to space-charge effects, which result
in unequal and preferential transmission of the heavier isotope
through the machine parts [80,81]. When the heavier isotopes pass
through the interface, skimmer cone, quadruple mass lter, and the
detector, they are slightly delayed compared to the lighter isotopes.
Therefore, the concentration of the heavier isotope in the measured
results will be reported lower; causing a substantial alteration in the
ratio of the heavier isotope to the lighter isotope. ICP-MS techniques
measure boron by monitoring m/z 10 and 11, while NTIMS monitors
m/z 42 and 43, and with such low masses monitored, mass fractionation is inevitable [30,81]. This is also observed in PTIMS monitoring
Na2BO2+ (m/z 88 and 89) but not in Cs2BO2+ (m/z 308 and 309)
[80]. Yet, the measurement of the total boron concentration in the sample is not signicantly affected by this phenomenon. In any case, such
limitations are corrected by using dened boron isotopic standards
such as SRM 951 and SRM 952 available from NIST, where the drift of
the results of the measured standards from the pre-dened boron isotopic ratios is quantied and corrected to all experimental runs. This is at
variance with matrix induced mass fractionation, which is another type
of mass discrimination effect caused by the sample preparation procedure employed. This is especially observed when using ion-exchange

Table 3
Summary of the major advantages and disadvantages on the boron analyses techniques.

Convenience of analysis
Limitations

Interferences

MC-ICP-MS

PTIMS

NTIMS

Very fast
[34,76]
Memory effect and mass fractionation
[30,67]

Slow
[30]
Mass fractionation
(Na-PTIMS)
[77,81]
Cs2CNO+ (with Cs-PTIMS) and
[77,80]

Fast
[53]
Mass fractionation
[42,53]

40
Ar4 + and
[53,76]

10

BH+

88

Sr (with Na-PTIMS)

CNO
[53,59]

Please cite this article as: A. Farhat, et al., Analytical techniques for boron quantication supporting desalination processes: A review, Desalination
(2012), doi:10.1016/j.desal.2011.12.020

A. Farhat et al. / Desalination xxx (2012) xxxxxx

Amberlite IRA-743 resin [76], and cannot be corrected for by using a

dened boron isotopic standard. An exception is NTIMS, which was applied to water samples without the need for ion exchange preparatory
procedure [56].
2.5.3. Memory effect
In spectrometric instruments, boron adheres to the instrumental
components and is retained in the system. This affects the reading of
the instrument for subsequent sample runs, and is dened in literature
as the memory effect [65]. The memory effect is exclusively reported
in plasma-based techniques and causes substantial suppression of 10B
relative to 11B. The memory effect presents a major problem in boron
analyses [67] despite several attempts to minimize it by performing
washouts between runs using NH3, NaF, and Mannitol blanks [80].
The ICP spray chamber is one of the major instrumental components
to which boron adheres to cause the memory effect. Aggarwal et al.
[30] reported using direct injector nebulizer instead of spray chamber
in their ICP to introduce the sample directly into the plasma to minimize
the memory effect, but this approach caused signal intensity to decrease
in half.
2.5.4. Other limitations
Other general limitations are reported in PTIMS which is characterized by its low ionization efciency, requiring laborious sample
preparation for purication [55]. It is also limited by its generation
of its alkali or metallic metaborate (M2BO2+) ion, which is dependent
on the ratio of the metal (M) to the boron (M/B ratio) in the prepared
sample, especially in the case of Cs2BO2+ [80].
3. Boron isotope tracer analysis in applications related to desalination
The removal of boron from seawater or brackish water using
membrane desalination is not a straightforward process. Under neutral feed water pH, boron exists in the form of boric acid, which is a
small and uncharged molecular compound that is poorly rejected by
membranes. However, one of the merits of boron's complicated
chemistry is that the rejection of boron by Reverse Osmosis (RO)
membranes increases with the increase of the pH of the system
above a value signicantly higher than the acid dissociation constant
(pKa) of boric acid (Eqs. (1) and (2)). The elevated pH shifts boric
acid's dissociation equilibrium in the direction of the ionized borate
anion [22], where the borate anion is efciently removed by the membrane because the negatively charged membrane rejects the negatively
charged borate via charge repulsion and prevents its penetration
through the membrane [1].

BOH3 H2 OH BOH4

h i 


 
pKa logKa log H  BOH4 = BOH3

Fig. 3. Distribution of aqueous boron species versus pH in saline water [102].

to a range of 8095% [22], as it is predominantly in the form of borate,

which can easily be removed by RO membranes because it is a
charged, polar molecular molecule [103]. Once the borate is removed,
the permeate is neutralized or blended before distribution to the end
user.
Kloppmann et al. [103] studied the variation of boron isotopic
composition throughout several stages of membrane desalination
plants and reported that boron fractionation is observed in the second
passes (high operating pH at around 9.5), where permeate is enriched
in 11B (Fig. 4). The study observed that no signicant boron fractionation is reported for the rst passes, operating at relatively low pH
values of 66.5, concluding that these isotopic variations are dependent on the pH induced variations of the boron species concentrations. However, the behavior and mechanism of boron speciation
and fractionation related to its removal in second-pass RO still require
deeper investigation. One toolbox for such investigation would be the
stable isotope analysis of boron (11B and 10B) to gain a clearer insight
into the chemical separation and isotopic fractionation occurring during
the boron removal process.
Moreover, this enrichment in 11B of the desalted water causes an
expected depletion of 11B in the produced brine due to mass balance
considerations. These reported fractionations are advantageous in
terms of creating a ngerprinting signature of the desalted water
and the discharged brine.
The importance of water ngerprinting emerges potential contribution of the man-made fresh water to the global water balance.
The desalted water, with its wide utilization including domestic
usage, drinking purposes, and irrigation, is being introduced into
natural systems such as soils, groundwater bodies via articial

Boron speciation in the form of boric acid and borate as a function

of pH is displayed in Fig. 3. The point where the concentration of boric
acid equals the borate concentration is the pKa, and its value, ranging
from 8.4 to 9.5, is affected by the temperature and the ionic strength
or salinity of the feed water [22,102]. As temperature and ionic
strength (salinity) increase, the borate fraction increases and thus
the boron rejection increases.
The RO systems, used for the treatment of seawater and brackish
water, operate traditionally at low pH (66.5) to inhibit scaling, but
since the boric acid penetrates undissociated through these RO membranes, an innovative system of high pH in RO plants has been developed [21,24,25], where a two-pass system of pH adjustment is
installed. The rst pass is operated without pH adjustments to treat
the high salinity water with limited scaling, followed by a second
pass at a pH of 9.510. The second pass RO effectively rejects boron

Fig. 4. Stable isotope fractionation between B(OH)3 and B(OH)4 in terms of 11B () as a
function of operational pH conditions [103]. The value of 11B for both boron species increases
as the pH increases showing a strong fractionation in the heavy isotope of boron while the
average of 11B in seawater is around 39.

Please cite this article as: A. Farhat, et al., Analytical techniques for boron quantication supporting desalination processes: A review, Desalination
(2012), doi:10.1016/j.desal.2011.12.020

A. Farhat et al. / Desalination xxx (2012) xxxxxx

recharge and leaching from irrigation, as well as surface water bodies,

eventually causing changes in the water chemistry and thus in the
ecology. Therefore, backtracking the water origin using the chemical
and isotopic ngerprinting would be of great value, especially in the
case of articial recharge (AR) of the seawater RO (SWRO) desalted
waters into coastal or continental aquifers, where mixing between
desalinated and natural waters is likely occurring [104]. The stable
isotope analysis of boron in water potentially enables the evaluation
of the natural and anthropogenic proportions in groundwater systems
and determination of the source of aquifer water recharge as well as
the salinity origin and the water residence time [60]. As a matter of
fact, the SWRO desalted waters are characterized by a distinctive
boron isotopic composition that can differentiate these SWRO permeate
waters from surface water and meteoric rainwater, where boron isotopes have been reported as useful articial tracers in stressed aquifers
[82]. Therefore, boron isotopes monitoring is considered a successful
tool for evaluating the performance of the articial recharge systems
and assessing the mixing of the man-made fresh waters with the natural water in terms of mixing proportions of the SWRO desalted water
and the degree of its penetration into the groundwater bodies [104].
In addition, this ngerprinting tool can also be applied on the
brine discharged back into the seas or oceans, making use of the depletion of 11B. Since the desalination plants discharge their brine at
relatively short distances from their pumped feed water, the mixing
of the discharge brine with the sea feed water is inevitable. Thus,
studying the boron isotopic composition of these brines as well as
the mixed water in the sea will provide a reliable estimation of the
mixed proportions. Hence, this tool would be of great potential to assess the brine discharge processes and predict the most suitable locations for discharging the brine in SWRO plants.
4. Conclusions
Boron analysis is of interest to numerous areas of research ranging
from nuclear technology, marine biochemistry, and geochemistry, to
environmental sciences, hydrology, and desalination. In seawater desalination, the removal of boron is of paramount concern because it
exists in uncharged form under ambient conditions, allowing it to
pass through desalination membranes. Furthermore, boron has been
shown to be toxic to a number of plant species. Thus, the removal of
boron from saline waters is critical and entails the availability of robust instrumentation and analytical techniques for monitoring
boron levels with considerable sensitivity and precision, as well as
ease of use. The prevailing instrumentation and analytical methods
for boron determination along with their isotopic composition have
been detailed in this study.
NTIMS is recognized as the most suitable for aqueous samples,
especially when the precision of such samples is not of high importance.
Yet, it is difcult to choose a most suitable method because each one is
characterized by its characteristic advantages and disadvantages. Each
of these boron analysis techniques endures several limitations, primarily those associated by the sample matrix, and spectral and isobaric interferences, which render the choice of technique dependant on the
sample type and the degree of complexity acceptable for sample preparation. Several recent developments in MC-ICP-MS have made this
instrumental analysis method competitive with the very precise
PTIMS and very sensitive NTIMS, especially since MC-ICP-MS analysis
is relatively faster and is characterized by a high sample throughput.
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(2012), doi:10.1016/j.desal.2011.12.020