Talanta 85 (2011) 541–545

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Talanta
journal homepage: www.elsevier.com/locate/talanta

A dispersive liquid–liquid microextraction procedure for determination of boron

in water after ultrasound-assisted conversion to tetrafluoroborate
Lenka Rusnáková a , Vasil Andruch a,∗ , Ioseph S. Balogh b , Jana Škrlíková a
a
Department of Analytical Chemistry, University of P.J. Šafárik, SK-04154 Košice, Slovakia
b
Department of Chemistry, College of Nyíregyháza, HU-4400 Nyíregyháza, Hungary

a r t i c l e i n f o a b s t r a c t

Article history: A novel, simple and green procedure is presented for the determination of boron. The method is based
Received 7 February 2011 on ultrasound-assisted conversion of boron to tetrafluoroborate anion and the formation of an ion pair
Received in revised form 6 April 2011 between BF4 − and Astra Phloxine reagent (R), followed by dispersive liquid–liquid microextraction of
Accepted 11 April 2011
the ion pair formed and subsequent UV–vis spectrophotometric detection. The conversion of boron
to tetrafluoroborate anion is performed in an acidic medium of 0.9 mol L−1 H2 SO4 in the presence of
Keywords:
0.1 mol L−1 F– by means of 10 min of ultrasonication. The extraction of the ion pair formed between
Ultrasound-assisted conversion
BF4 − and R (1 × 10−4 mol L−1 R) is carried out by dispersive liquid–liquid microextraction using 0.5 mL
Dispersive liquid–liquid microextraction
(DLLME)
of amyl acetate (as extraction solvent), tetrachloromethane (as auxiliary solvent) and acetonitrile (as
Green analytical chemistry dispersive solvent) in a ratio of 1:1:2. The absorbance of the coloured extracts obeys Beer’s law in the
Boron range 0.22–18.7 mg L−1 of B(III) at 553 nm wavelength. The limit of detection calculated from a blank test
Water (n = 10) based on 3 s is 0.015 mg L−1 of B(III). The method was applied to the determination of boron in
mineral waters.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction [11], data on the physiological functions of boron are incomplete

and frequently contradictory, and published data are both scarce
Recent years have seen a growing interest in “green chemistry”. and vague. He therefore reviewed the most current references on
Unfortunately, analytical chemistry was, until recently, an excep- the sources, turnover and speciation of boron in the environment
tion [1]. Armenta et al. state that the main principles of green and boron’s possible effects on human health. Based on evidence
analytical chemistry “are to replace toxic reagents, to miniaturize from various laboratories, Nielsen states that boron is a bioactive
and to automate methods, making it possible to reduce dramat- and beneficial element and that some higher animals require it to
ically the amounts of reagents consumed and wastes generated, complete the life cycle [12]. Parks and Edwards summarized the
so reducing or avoiding side effects of analytical methods” [1]. chemistry, occurrence and health effects of boron, along with the
We have previously published articles devoted to automation and existing regulations and guidelines for boron and different methods
miniaturisation of analytical procedures which describe a novel for removing it from drinking water [13]. Minoia and co-workers
dual-valve sequential injection manifold (DV-SIA) for automated focused on boron’s toxicology and health impacts [14,15]. Boron is
liquid–liquid extraction (LLE) [2,3], the application of ultrasound an essential nutrient for the normal growth of higher plants, and
as a replacement for heating [4] and the development of novel dis- the availability of boron in soil and irrigation water is an important
persive liquid–liquid microextraction (DLLME) procedures for the determinant of agricultural production, though if present in excess
determination of various analytes [5,6]. it becomes toxic for plants [16–19].
Although elemental boron has only limited industrial uses, Boron exists in natural waters primarily as undissociated boric
many of its compounds, boric acid and sodium salts of boron in acid along with some borate ions. Soils and sediments can adsorb
particular, are commonly used in a variety of industries, including waterborne boron, though this process depends on boron con-
the production of herbicides, insecticides and fertilizers and the centration and the pH of the water [9]. The natural content of
manufacture of glass, porcelain enamel, ceramic glazes and metal borate in groundwater and surface water is usually quite small,
alloys [7–9]. Argust [7] and Howe [10] reviewed the distribution while boron concentration in fresh water depends primarily on the
[7] and effects of boron in the environment [10]. According to Kot leaching of boron from the surrounding land as well as from indus-
trial and municipal outflows. Boron concentrations in groundwater
have a broad range, from less than 0.3 to over 100 mg L−1 . Average
∗ Corresponding author. concentration in the oceans is 4.5 mg L−1 and ranges in fresh surface
E-mail address: vasil.andruch@gmail.com (V. Andruch). waters from <0.001 to 2 mg L−1 [9]. Conventional drinking water

0039-9140/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.talanta.2011.04.030
542 L. Rusnáková et al. / Talanta 85 (2011) 541–545

treatment methods do not typically remove boron from water [9]. were added, and the volumes were filled up to 1 mL with water. The
According to Council Directive 98/83/EC from 3 November 1998 on solution was thoroughly mixed and then sonicated in an ultrasonic
the quality of water intended for human consumption, the boron bath for 10 min. Then 3.5 mL water and 0.5 ml of 1 × 10−3 mol L−1
content in drinking water must be no more than 1.0 mg L−1 [20]. Astra Phloxine reagent were added, and the solution was again
Boron is a difficult element for analysis [11]. Its analytical chem- mixed well. Next, 0.5 mL of a mixture of solvents containing amyl
istry has been discussed in a number of books and reviews [21–23], acetate as extraction solvent, CCl4 as auxiliary solvent and acetoni-
while variety of methods have been described for boron deter- trile as dispersive solvent in the ratio 1:1:2 (v/v/v) was forcefully
mination in water samples [22,23], a spectrophotometric method injected using a 1 mL glass syringe. The mixture was gently shaken
using azomethine-H being the most common utilised. In addition, 3 times and then centrifuged at 3000 rpm for 2 min., leaving a layer
other methods based on the reaction of boron with a variety of of sediment containing a mixture of amyl acetate and CCl4 at the
organic reagents have also been suggested. The primary drawbacks bottom of each tube. This was removed using a Hamilton syringe,
of these methods are considered the necessity for separating boric inserted into a matched quartz cell, and the absorbance was mea-
acid through distillation as methyl borate or the need for concen- sured at 553 nm.
trated sulphuric acid as a reaction medium. As a result, with boron
determination special attention must be paid on preventing the 2.4. Procedure for real samples
escape of volatile boron compounds and contamination of the sam-
ple by boron from the glass used in the laboratory. One potential A volume of sample up to 0.5 mL, depending on the anticipated
way of developing novel procedures for boron determination could boron content, was placed in a polyethylene test tube. All of the
be a method based on the conversion of boric acid to tetrafluo- required reagents were then added and the determination carried
roborate anion followed by ion pair formation with dye reagents out as described above in Section 2.3.
and the extraction of the ion pair formed into organic solvent with
subsequent spectrophotometric detection [4,21,22,24]. 3. Results and discussion
Despite the existence of numerous methods for boron determi-
nation, we were unable to find a DLLME procedure for its determi- A number of investigators have previously studied the conver-
nation in the literature. The aim of this study was the development sion of boric acid to tetrafluoroborate anion and its application
of a green procedure for boron determination based on ultrasound- to boron determination. Their results are summarised in ref. [22].
assisted conversion of boron to tetrafluoroborate anion, the Thermodynamic calculations for the (H3 BO3 )–F− –H+ system were
formation of an ion pair between BF4 − and Astra Phloxine reagent, carried out by Katagiri et al. [25]. The tetrafluoroborate anion forms
followed by dispersive liquid–liquid microextraction of the ion pair best in an acidic medium. However, at pH > 1, this process is slowed
formed and subsequent UV–vis spectrophotometric detection. due to hydrolysis of BF4 − and the formation of BF3 OH− . Such a result
is unwanted, however, because the mentioned anion forms com-
2. Experimental pounds with dye reagents not extractable by organic solvents. To
adjust the acidity, it is best to use sulphuric acid, because sulphates,
2.1. Reagents unlike the anions of other strong acids, do not form extractable ion
pairs with the dye reagents. At acidities which are optimal for con-
All solutions used were prepared from analytical grade reagents version, some dye reagents exist in a doubly charged form (HR2+ )
and stored in polyethylene bottles. Ultra pure water from Milli- which is unable to form an ion pair with BF4 − that is extractable by
pore Milli-Q RG (Millipore, USA) was used throughout the work. organic solvents. In addition to the appropriate acidity, an excess
A working solution containing 5 × 10−2 mol L−1 of boron was pre- of fluoride ions is also needed for the most complete conversion of
pared by dissolving 0.3092 g H3 BO3 in water and dilution with boric acid to tetrafluoroborate anion. However, a large excess of flu-
water up to a volume of 100 mL. The 1,3,3-trimethyl-2-[3-(1,3,3- oride anion is also undesirable, because F− is capable of combining
trimethyl-1,3-H-indol-2-ylidene)propenyl]-3H-indolium chloride, with dye reagents to form compounds which can be extracted by
more commonly known as dimethylindocarbocyanine dye or Astra organic solvents. Therefore, conversion in general is performed in a
Phloxine reagent (R), was obtained from Jiacheng–Chem Enter- minimal volume at high acidity and with an excess of fluoride ions,
prises Ltd. (China) and was used without additional purification. though after the conversions, the solution is diluted with water to
A 1 × 10−3 mol L−1 aqueous solution of the reagent was prepared lower the fluoride concentration, and the value of the pH is adjusted
by dissolving 0.0785 g of its chloride salt in several droplets of [22]. The application of dye reagents—which have a wide range for
methanol and subsequent dilution with water up to a volume of their singly charged (R+ ) form—such as Astra Phloxine, seems to
200 mL. A 0.5 mol L−1 aqueous solution of NaF was used to convert offer a better solution because the pH can be adjusted through sim-
H3 BO3 to BF4 − . The pH was set by the addition of 3 mol L−1 H2 SO4 . ple dilution, and no buffer solution is required [4]. The conversion
All solvents used were of analytical grade reagents. of H3 BO3 into HBF4 runs relatively slowly, though applying heat
speeds up the formation of HBF4 [24]. We previously reported a
2.2. Apparatus method for boron determination in which heating was replaced by
ultrasonic irradiation [4] which offers some advantages [4].
A Cary 100 Bio UV–vis spectrophotometer (Varian Inc., USA) and
a Spekol-11 spectrophotometer (Carl Zeiss, Germany) equipped 3.1. Investigation of the dispersive liquid–liquid microextraction
with a matched cell of 1 mm path length were used for spectropho- procedure
tometric measurements. A Sonorex Digitec ultrasonic compact bath
DT 31 (Bandelin Electronic, Germany) was used as source of ultra- The majority of detection techniques commonly require the
sonic energy. Centrifugation was carried out using an MPW-310 initial separation and/or pre-concentration of analytes. Several
centrifuge (Mechanika Precyzyjna, Poland). methods for the pre-treatment of samples, such as cloud point
extraction [26], micelle-mediated extraction [27,28], pressurized
2.3. Calibration of the method LLE [29] and synergistic LLE [30], have appeared in recent lit-
erature. Liquid–liquid extraction, which is among the oldest of
Various amounts of the boron were put into 10 mL centrifugal separation techniques and remains the most commonly utilised,
tubes. Next, 0.2 mL of 0.5 mol L−1 NaF and 0.3 mL of 3 mol L−1 H2 SO4 has limitations, however (if manually performed), primarily due to
 L. Rusnáková et al. / Talanta 85 (2011) 541–545 543

Fig. 1. Effect of the extraction solvent. Conditions for conversion: 1 × 10−3 mol L−1 Fig. 2. Effect of the dispersive solvent. Conditions for conversion: 1 × 10−3 mol L−1
H3 BO3 ; 0.9 mol L−1 H2 SO4 ; 0.1 mol L−1 F− ; 10 min sonication in an ultrasonic bath. H3 BO3 ; 0.9 mol L−1 H2 SO4 ; 0.1 mol L−1 F− ; 10 min sonication in an ultrasonic bath.
Conditions for extraction: 1 × 10−4 mol L−1 Astra Phloxine; 0.5 mL of a mixture of sol- Conditions for extraction: 1 × 10−4 mol L−1 Astra Phloxine; 0.5 mL of a mixture of sol-
vents containing various extraction solvents, tetrachloromethane and acetonitrile vents containing amyl acetate, tetrachloromethane and various dispersive solvents
in 1:1:2 (v/v/v) ratio, l = 1 mm;  = 553 nm. in 1:1:2 (v/v/v) ratio, l = 1 mm;  = 553 nm.

tion of an auxiliary solvent to the extraction solvent in order to

the large volumes of hazardous solvents used [31,32]. As a result,
ensure that the resulting mixture of solvents has a density higher
conventional LLE has been replaced in recent years by disper-
than that of water, thus allowing simple phase separation by cen-
sive liquid–liquid microextraction (originally introduced by Assadi
trifugation. Solvents with a density significantly higher than that
and co-workers [33] in 2006), which has several advantages over
of water, such as dichloromethane, trichloromethane (chloroform),
LLE [34,35]. The primary advantages lie in the fact that DLLME
tetrachloromethane, tetrachloroethylene and chlorobenzene, were
requires only small amounts of organic solvent and that it shortens
tested as auxiliary solvents. The choice of auxiliary solvent was
extraction time considerably due to the large surface area formed
based on the maximum signal which simultaneously offered a min-
between the aqueous and organic phases. The effects of the nature
imal blank test. It is evident from the experimental results that
of the extraction solvent, the auxiliary solvent and the dispersive
tetrachloromethane is the best auxiliary solvent, and it was there-
solvent were studied.
fore selected for further experiments.

3.1.1. Effect of the extraction solvent

3.1.3. Effect of the dispersive solvent
The requirements for extraction solvents in a variety of
The main requirements for a dispersive solvent are its solu-
liquid–liquid extraction approaches are well known and have been
bility in the extraction solvent and its miscibility with water, so
widely discussed [31,36,37]. They can be summarised as follows:
that fine droplets (a cloudy solution) of the extraction solvent can
low solubility in water, high efficiency for extraction of the tar-
form in the aqueous phase. As a result, methanol, ethanol, acetone
get analyte, and minimum extraction of the blank test [5]. The
and acetonitrile are usually tested as dispersive solvents [47]. A
term for the extraction solvents used in DLLME are the same as
series of experiments were carried out similar to that described
for solvents used in conventional LLE [38]. Based on a review of the
in Section 2.3, the difference being that the DLLME procedure was
literature as well as our own experience [4,39–46], it is assumed
performed using various dispersive solvents (methanol, ethanol,
that the aromatic hydrocarbons and acetic esters are in general
acetone, ethylene glycol, acetonitrile, dimethylsulphoxide (DMSO),
the most suitable for extracting ion pairs, because they are usu-
N,N-dimethylformamide (DMFA), and pyridine) and the value of
ally characterised as being very good for such extractions while
analytical response as well as signal-to-noise ratio were then inves-
simultaneously minimising the extraction of simple dye salts (the
tigated. Based on the results (Fig. 2), we concluded that acetonitrile
blank test). Therefore, various organic solvents (water solubility,
is the best dispersive solvent and it was therefore selected for fur-
g/100 mL) from these groups, such as benzene (0.175), toluene
ther experiments.
(0.047), xylene (cca. 0.013), amyl acetate (0.2), butyl acetate (2.3),
and ethyl acetate (7.9), were tested as extractants. The solubility
of the extraction solvent in water is one of the important factors
affecting the volume of sedimented phase [47]. Ethyl acetate was
thus excluded a priori and was not tested.
A series of experiments were carried out similar to that
described in Section 2.3, the difference being that the DLLME pro-
cedure was performed using various extraction solvents, and the
value of analytical response as well as signal-to-noise ratio were
then investigated. Based on the results obtained, which are pre-
sented in Fig. 1, seems to be that benzene, amyl acetate and butyl
acetate are the best extraction solvents. Benzene was thus excluded
because of its toxicity. Due to lower solubility in water, the amyl
acetate was chosen for further experiments.

3.1.2. Effect of the auxiliary solvent

Since amyl acetate, which was selected as the extraction sol- Fig. 3. Effect of solvents ratio. Conditions for conversion: 1 × 10−3 mol L−1 H3 BO3 ;
0.9 mol L−1 H2 SO4 ; 0.1 mol L−1 F− ; 10 min sonication in an ultrasonic bath. Condi-
vent, has a density lower than that of water, an approach previously
tions for extraction: 1 × 10−4 mol L−1 Astra Phloxine; 0.5 mL of a mixture of solvents
reported on from our laboratory [5,6] and based on the application containing amyl acetate, tetrachloromethane and acetonitrile in various v/v/v ratio,
of an auxiliary solvent was used. This method is based on the addi- l = 1 mm;  = 553 nm.
544 L. Rusnáková et al. / Talanta 85 (2011) 541–545

Table 1
A comparison of spectrophotometric procedures for boron determination.

Author [Ref] Year Extraction solvent Solvent volume, mL Linear range, mg L−1 LOD, mg L−1 Sample

Aznarez et al. [48] 1985 2,2,4-Trimethyl-1,3-pentanediol in chloroform 10 0.05–0.4 0.003 Plants, waters
Wimmer and Goldbach [49] 1999 2-Ethyl-1,3-hexanediol in chloroform 0.05 Up to 3 0.018 Waters, plants
Ramanjaneyulu et al. [50] 2008 2-Ethyl hexane 1,3-diol in chloroform 1 (five times) 80–730 ng 12 ng U–Al–Si alloy
Ramanjaneyulu et al. [51] 2010 2-Ethyl hexane 1,3-diol in chloroform 1 (five times) 0.1–0.8 ␮g 12 ng Zr–Nb alloys
Balogh et al. [24] 2009 Benzene 3 0.03–0.55 0.02 Waters
Škrlíková et al. [4] 2010 Amyl acetate 5 0.1–1.0 0.02 Waters pharmaceuticals
This work 2011 Amyl acetate/CCl4 /acetonitrile 0.5 0.22–18.7 0.015 Waters

Table 2 Table 4
Intra-day and inter-day precision and accuracy data for the determination of boron. Determination of B in mineral waters (MW) (n = 5).

Taken, mg L−1 Intra-day Inter-day Sample Suggested method, mg L−1 Reference method, mg L−1

Determineda , mg L−1 R, % Determineda , mg L−1 R, % MW1 0.56 ± 0.04 0.59 ± 0.02

MW2 2.3 ± 0.2 2.3 ± 0.1
2.2 2.1 ± 0.1 95.5 2.1 ± 0.1 95.5 MW3 7.7 ± 0.3 8.0 ± 0.1
8.8 9.0 ± 0.4 102.3 9.0 ± 0.4 102.3
14.3 14.3 ± 0.2 100.0 14.2 ± 0.2 99.3
17.6 17.5 ± 0.4 99.4 17.3 ± 0.4 98.3
A comparison of the developed procedure with other spec-
a
x±s √t (t = 2.776, P = 0.95), t – Student coefficient for n–1 degrees of freedom; n = 5.
n trophotometric methods reported in the literature is given in
Table 1. The limit of detection (LOD) and linear range of our method
and those of other spectrophotometric methods are comparable.
3.1.4. Effect of solvents ratio The main advantages of the developed procedure are: (1) a much
Besides the effect of the nature of the extraction solvent, auxil- lower consumption of organic solvent and the ensuing reduced
iary solvent and dispersive solvent, the effect of the solvents ratio generation of wastes in comparison with [4,24,48,50,51]; (2) no
was also studied (Fig. 3). A series of experiments was performed need to use benzene in comparison with [24]; (3) the procedure is
in which the ratio of extraction solvent and auxiliary solvent kept faster, as no time is needed for colour development [48–51] and no
constant at 1:1 (v/v), and the proportion of acetonitrile was altered. heating is required [24,48].
Increasing the acetonitrile proportion caused the analytical sig-
nal to noise. The maximum analytical signal was obtained using a 3.2.1. Calibration range
solvents ratio of 1:1:4 (v/v/v); however, the relative standard devi- A calibration plot was constructed from nine data points over
ation of the signal and the value of the blank test were high. The a range of concentrations 0.22–18.7 mg L−1 . The LOD, calculated
ratio 1:1:2 (v/v/v) was therefore selected for further experiments. based on three times the standard deviation of the blank test
(n = 10), was found to be 0.015 mg L−1 of boron.
3.2. Figure of merit
3.2.2. Precision and accuracy
Based on the results obtained, a spectrophotometric method The precision and accuracy of the developed method were
for the determination of boron using the DLLME procedure was checked by performing five replicate determinations of boron at
suggested. The method is based on the reaction of boric acid four concentration levels over two days and then calculating the
with fluoride upon ultrasonication and the resulting formation of relative standard deviation percentage (RSD, %) and the recovery
tetrafluoroborate anion, followed by the dispersive liquid–liquid percentage (R, %). The inter-day and intra-day precision and accu-
microextraction of BF4 − with Astra Phloxine reagent into 0.5 mL of racy results are presented in Table 2 and show good repeatability
a mixture of solvents containing amyl acetate as extraction solvent, of the suggested method.
CCl4 as auxiliary solvent and acetonitrile as dispersive solvent in the
ratio 1:1:2 (v/v/v) and subsequent spectrophotometric detection. 3.2.3. Interferences
The effect of diverse ions on the determination of 4.4 mg L−1
of boron was studied according to the above-described procedure.
Table 3
Effect of foreign ions (4.4 mg L−1 H3 BO3 ).
Tolerance for an ion was taken as a boron:interferent ratio that
caused an error no higher or lower than ±5% (Table 3).
Ion B(III) found, mg L−1 B:interferent ratio Error, %
+
Li 4.3 1:25 −2.3 3.2.4. Application of the method
4.2 1:50 −4.5
The method was applied to the determination of boron in min-
Na+ 4.6 1:3000 4.5
K+ 4.5 1:500 2.3
eral water samples (Table 4), and the obtained results showed
Ca2+ 4.3 1:50 −2.3 sufficient agreement between the determined values from the sug-
4.1 1:100 −6.8 gested and the reference method [52].
Ba2+ 4.3 1:10 −2.3
Mg2+ 4.3 1:20 −2.3
4.1 1:50 −6.8 4. Conclusion
Al3+ 4.2 1:20 −4.5
4.1 1:50 −6.8 To the best of our knowledge, a dispersive liquid–liquid
Cu2+ 4.5 1:10 2.3 microextraction for the determination of boron has been described
Zn2+ 4.5 1:20 2.3
Cl− 4.5 1:1000 2.3
for the first time. The combination of ultrasound-assisted con-
Br− 4.6 1:50 4.5 version with a dispersive liquid–liquid microextraction procedure
SO4 2− 4.3 1:500 −2.3 offers some advantages in comparison with previously reported
NO3 − 4.6 1:100 4.5 methods for boron determination [4,24]. The main advantages of
Fe3+ 4.3 1:20 −2.3
ultrasonication in comparison with conventional heating [24] are
 L. Rusnáková et al. / Talanta 85 (2011) 541–545 545

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